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Publication numberUS3617173 A
Publication typeGrant
Publication dateNov 2, 1971
Filing dateJun 24, 1968
Priority dateJun 24, 1968
Publication numberUS 3617173 A, US 3617173A, US-A-3617173, US3617173 A, US3617173A
InventorsHildreth John David, Wehner Philip
Original AssigneeToms River Chemical Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
2-benzoylanthraquinone dyes for polyester fibers
US 3617173 A
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Description  (OCR text may contain errors)

United States Patent John David Hildreth Bramhall, England; Philip Wehner, Cranmoor Manor, NJ. [211 App]. No. 739,146

[22] Filed June 24, 1968 [72] Inventors [45] Patented Nov. 2, 1971 [73] Assignee Toms River Chemical Corporation Toms River, NJ.

Continuation-impart of application Ser. No. 386,735, July 31, 1964, now abandoned.

[54] Z-BENZOYLANTHRAQUINONE DYES FOR POLYESTER FIBERS 3 Claims, No Drawings [52] 0.8. CI 8/39, 8/21 ,C, 260/372, 260/377 [51] Int. Cl D06p l/20 [50] Field of Search 260/376,

[56] References Cited UNITED STATES PATENTS 2,937,190 5/1960 Straley et al. 260/377 X '3,21 1,755 10/1965 Fitzpatrick et a1 260/376 FOREIGN PATENTS 661,045 11/1961 Great Britain 260/376 OTHER REFERENCES H. A. Lubs, Chemistry of Synthetic Dyes and Pigments (1955)pp.4l7419.Copyin260377 Primary Examiner Donald Levy Assistant Examiner-T. .1. Herbert, Jr.

Attorneys-Harry Goldsmith, Joseph G. Kolodny, Bryant W.

Brennan and Edward J. Sites ABSTRACT: Dyeings and printings are produced on fibrous materials of aromatic polyesters, especially polyethylene terephthalate, by using as dyestuff a 2-benzoylanthraquinone of the formula:

if i

' water solubilizing group.

Z-BENZOYLANTIIRAQUINONE DYES FOR POLYESTER FIBERS This application is a continuation-in-part of our application Ser. No. 386,735, filed on July 31, 1964, now abandoned.

BACKGROUND OF THE INVENTION Polyester fibers present particular dyeing problems, arising at least in part out of the hydrophobic nature of such fibers. In the dyeing of polyester fibers, the class of dyes known as disperse dyestuffs has come to have the widest application. These dyestuffs are essentially water-insoluble products applied in a finely divided condition from a dispersion. In the application of such dyestuffs, the dyeing difficulties associated with polyester fibers have been met by the development of special methods for the application of disperse dyes to the fibers. Ofthese methods, the one known as the Pad/Therrnofix method has become of increasing importance since it is particularly adapted for high-speed, continuous dyeing operations. In this method, a fabric is padded by passing it through an aqueous suspension of the dyestuff and squeezing the fabric between closelyset rollers in order to remove excess dye liquor. The dyestuff is only loosely attached to the fiber at this point. The dyestuff is then fixed on the fiber by subjecting the material to a short, intensive heat-treatment at elevated temperatures of the order of about l-220 C. It is evident that a dyestuff, in order to be suitable for application by this method, must be fast to sublimation or else it will wholly or partially volatilize from the fiber during the heat-treatment step. The result of such sublimation will be a loss of color value on the polyester fiber and, ifa union dyeing operation is being carrier out, the staining of the other fibers, such as cotton, which may be present in the blend.

SUMMARY OF THE INVENTION In accordance with the present invention, it has been discovered that valuable dyeings and printings are produced on fibrous materials of aromatic polyesters, especially polyethylene terephthalate, by using as dyestuff a 2- benzoylanthraquinone of the formula:


l O X DESCRIPTION OF THE PREFERRED EMBODIMENT Many of the 2-benzoylanthraquinones employed in the practice of the present invention are known compounds and can be prepared according to known procedures, as for example, the processes of U.S. Pat. No. 2,499,003 and Berichte 51, 1233 (1918). Others of the 2-benzoylanthraquinones employed are novel compounds and the preparation and utilization of these novel compounds are specifically disclosed herein.

For dyeing, the said dyestuffs are preferably used in a finely divided form and the dyeing is carried out in the presence ofa dispersing agent, such as sulfite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents. Before dyeing, it is generally of advantage to convert the dyestuff or dyestuffs to be used into a dyestuff preparation which contains a dispersing agent and the finely divided dyestuff(s) in such a form as to yield a fine dispersion when the preparation is diluted with water. Dyestuff preparations of this kind can be made by known methods, for example, by grinding the dyestuff(s) either in dry or wet form with or without the addition ofa dispersing agent.

The dyestuffs used in the invention are especially suitable for dyeing by the so-called thermofixation or Pad/Thermofix method, in which the fabric to be dyed is impregnated advantageously at a temperature not exceeding 60 C. with an aqueous dispersion of the dyestuff, which may containing l to 50 percent of urea and a thickening agent, especially sodium alginate, and the fabric is squeezed in the usual manner. The squeezing is preferably carried out so that the goods retain 50 to percent of their weight of dye liquor.

The dyestuff is fixed by subjecting the impregnated fabric to a heat treatment at temperatures above 100 C., for example, at a temperature ranging from -220 C., it being of advantage to dry the fabric prior to this treatment, for example, in a current of warm air.

The thermofixation mentioned above is of special interest for the dyeing of mixed fabrics of polyester fibers and cellulose fibers, especially cotton. In this case, in addition to the dyestufi to be used in the process of the invention, the padding liquor contains a dyestuff suitable for dyeing cotton, for example, a direct dyestuff or vat dyestuff, or a so-called reactive dyestuff, i.e., a dyestuff capable of being fixed on cellulose fibers with the formation of a chemical bond, for example, a dyestuff containing a chlorotriazine or chlorodiazine residue. In the latter case it is of advantage to add to the padding liquor an agent capable of binding acid, for example, an alkali carbonate, alkali phosphate, alkali borate or alkali perborate, or a mixture of two or more of these agents. When vat dyestuffs'are used, the paddedfabric must be treated, after the heat treatment, with an aqueous alkaline solution ofa reducing agent of the kind used in vat dyeing.

The dyeings produced on polyester fibers by the process of the invention are advantageously given an after-treatment, for example, by heating them with an aqueous solution of. a nonionic detergent.

Instead of applying the dyestuffs in the process by impregnation, they maybe applied by printing. For this purpose, a printing color is used which, in addition to the usual printing assistants, such as wetting and thickening agents, contains the finely dispersed dyestuff, if desired, in admixture with one of the aforesaid cotton dyestuffs, and, if desired, in the presence of urea and/or an agent capable of binding acid.

There are obtained by the practice of the present invention strong dyeings or prints of attractive shade and good color buildup having excellent fastness properties, especially a good fastness to sublimation and to light. Another advantage resides in the fact that the dyestuffs employed in the present invention are produced more economically than available commercial blue dyestuffs of similar fastness properties.

The term polyester defines synthetic polymeric polyesters, such as the highly polymeric linear polyesters, the molecules of which have recurring monomeric units connected by ester linkages. Dibasic acids, for example, aromatic acids, such as terephthalic acid, diphenyl-4,4'-dicarboxylic acid and/or diphenylsulfone-4,4 '-dicarboxylic acid and dihydroxy compounds, for example, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and/or butylene glycol, as well as other diols, such as l,4-cyclohexyldiol can be used as the monomers to form the polymeric polyesters. Typical commercial examples of such fibers are DACRON, TERYLENE, FORTREL, TREVIRA, TERLAN- CA, KODEL, VYCRON, etc. They are disclosed, for example, in U.S. Pat. No. 2,901,466 and British Pat. Nos. 578,079; 579,462; 588,497 and 596,688.

The present invention is, of course, equally applicable to the dyeing of blends of polyester fibers and cellulosic fibers. The latter term includes native cellulose, such as linen or, more particularly, cotton, as well as regenerated cellulose, such as viscose or cuprammonium rayon.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise specified.

Example 1 l6 g. of l-amin-2benzoyl-4-bromoanthraquinone is added to 230 g. by volume of amyl alcohol, and 30 g. of p-toluenesulfonamide, 20 g. of sodium acetate and 0.12 g. of copper acetate are then added. The mixture is heated with stirring to reflux l 34 C.) and held at reflux temperature for a period of 12 hours, the color very quickly changing from a reddishorange to a very deep violet. The reaction mixture is cooled to room temperature, then suction-filtered and washed twice with 50 g. by volume portions of amyl alcohol. Residual solvent is removed by steam distillation and the product again filtered and dried. The dye, l-amino-2-benzoyl-4-ptoluenesulfanamidoanthraquinone, is obtained in a yield of l8 g. and in the form of dark violet platelike crystals.

Example 2 Ten g. of the dyestuff of example 1 are brought to a state of fine dispersion by milling in a ball mill with 3.0 g. of the condensation product of naphthalene-Z-sulfonic acid with formaldehyde, and 37 g. of water.

Amounts of this preparation, sufficient to provide a concentration of 1.5, 3.0 and 6.0 grams of dyestuff per liter of dye bath, are finely dispersed in water containing 10.0 g. of sodium alginate per liter and the resultant pad liquor is brought to a temperature of25 C.

Polyethylene terephthalate fabric is then padded with the above liquor and mechanically squeezed to a 65 percent pick up. The padded material is then air dried and developed by dry heat curing in an electrically heated, hot-air dryer for l minute at 200 C. The dyed fabric is scoured for minutes at the boil in a solution containing 3 percent of sodium di-iso-butylnaphthalene monosulfonate and 5 percent sodium carbonate and then dried. A bright violet dyeing is obtained, characterized by good penetration and excellent fastness to light and excellent sublimation fastness.

Among other known Z-benzoylanthraquinones which can be employed according to the present invention, there can be mentioned lp-toluenesulfonamido-Z-benzoylanthraquinone, lamino-4-p-chloro-benzamido-Z-benzoylanthraquinone, the anthraquinone vat dyes of the formula l,2,4-l-l N (ROC) (R'OCNH) C H O where R is an aryl group having six l2 C atoms and R is an aryl or alkaryl group with not more than 12 C atoms as disclosed in British Pat. No. 663,383, the anthraquinone vat dyes of U.S. Pat. No. 2,567,82] corresponding to British Pat. No. 663,383, particular examples comprising those instances wherein R is naphthyl, and particularly phenyl and substituted phenyl, such as tolyl, halophenyl and alkoxyphenyl, and the COR moiety represents the radical of an aromatic or aliphatic-aromatic carboxylic acid containing at most [3 carbon atoms and which may contain substituents in the aromatic nucleus such as the residue of benzoic acid.

When the above dyestuffs are employed in the procedure of example 2 in lieu of the specific dyestuff recited in example 2, dyeings of desirable shade ranging from orange to blue-violet are obtained having good to excellent light and sublimation fastness and penetration characteristics.

In addition to the known dyestuffs referred to in the preceding paragraph and the foregoing example, the novel 2- benzoylanthraquinone hereinafter discussed can also be em ployed. In general, the novel dyestuffs ofthe present invention have the formulas ooa where R is lower alkyl, R is phenyl, naphthyl, diphenyl, halophenyl, halo-naphthyl, halo-diphenyl, alkyl-phenyl henyl alkyl-naphthyl, and alkyl-diphenyl, alkoxy-phenyl, alkylnaphthyl and alkoxy-diphenyl; and X is anilino, toluidino, lower alkylsufonamido, benzenesulfonamido, lower alkylbenzenesulfonamido, halobenzenesulfonamido, or lower alkoxybenzenesulfonamido; and


where R is the same as above, but also hydrogen; R' is the same as above; and X is anilino, toluidino, lower alkylsulfonamido, benzenesulfonamido, halobenzenesulfonamido or lower alkoxy-benzenesulfonamido.

Examples 3 6 The procedure of example 1 is repeated except that the sulfonamide reactant listed in the table below under the column entitled Sulfonamide" is used in place of the p-toluene-sulfonamide employed in example 1 in the amount given under the column entitled Grams" to give the 2-benzoylanthraquinone dyestufflisted under the column entitled Dyestuff.

sulfonamidounthruquinune When dispersed in the conventional manner described in example 2 and applied to polyethylene terephthalate fibers, these dyestuffs gave dyeings of bright violet shades characterized by excellent sublimation and light fastness and by good penetration properties.

Example 7 lamino-2-benzoyl-4-p-toluidinoanthraquinone Ten g. of lamin0-2-benzoyl 4-bromoanthraquinone, 20.0 g. anhydrous sodium acetate, 11.7 g. p-toluidine, 0.12 g. copper acetate and 150 g. by volume of amyl alcohol are heated with stirring at reflux for 12 hours, the color changing to a dark blue.

At the end of the above time period, the reaction mixture is cooled to room temperature, filtered, washed with ethyl alcohol and then water, and then dried.

The product, lamino-2-benzoyl-4-p-toluidinoanthraquinone, is obtained in yield of 8 g.

When dispersed and applied to polyethylene terephthalate by the procedure of example 2, lamino-Z-benzoyl-4-ptoluidinoanthraquinone gave dyeings of a bluish-grey shade having good light and sublimation t'astness and good penetration characteristics.

Example 8 The procedure of example 7 is repeated except that 10.4 g. of aniline is employed in place of ptoluidine. The product. l amind-2benzoyl-4-anilinoanthraquinone is obtained in a yield of7 g.

When dispersed and applied to polyethylene terephthalate by the procedure of example 2, l-amino-Z-benzoyl- 4anilinoanthraquinone gave dyeings of a blue shade having good light and sublimation fastness and good penetration characteristics Examples 9 -l4 The procedure of example 1 is repeated except that the reactants listed in the pertinent columns in the Table below in which R is a member selected from the group consisting of hydrogen, lower alkyL-and sulfonyl, R is a member selected from a group consisting of phenyl, naphthyl, diphenyl, halophenyl, halo-naphthyl, halo-dipheynl, alkyl-phenyl, lower alkyl-naphthyl, lower alkyl-diphenyl, alkoxy-phenyl, lower alkoxy-napthyl and lower alkoxy-diphenyl, and X is a member selected from a group consisting of anilino, toluidino, lower alare employed in the indicated quantities to provide the kylsulfonamldo' benezenesulfonamldo' lower k dyestuffs listed in column 5 benezenesulfonamldo, loweralkoxybenzenesulfonamido,

TABLE Example Sulfonamide Grams Reactant Grams Dyestuff 9 p-Toluenesulfom 29.0 l-methylamino-lbenzoylA-bromoun- 16,0 l-methylaminwZ-benzoyH-ptoluenesulfonamidoanumldc. thraquinone. thruquluone.

10 Bengguesulfona- 27.0 .do 16.0 1-rnehylamino-2benzoyl-4-benzcnesnllonamldounthrnmi e. qu none.

11 p-Chlorobenzene- 33.0 LEOthYIEIDiHO-irbOIlZOYlA-bIOlIlO- 16.0 1-methyiamino-ZbenzoylA-p-chlorobenzenesullonsulfonamide. anthraquinone. amidoanthrnquinone.

12 p-Methoxybenzene- 32.0 .....(10 16.0 l-methylamino-2'benzoyl4-p-methoxybenzonesullousullonamlde. amidoanthrnquinone.

13 r p-Toluenesulfona- 28.0 1-am1no-2-(p-chlorobonzoyl)-4-bromm 16.0 1-nmino-2-(p-chlorobenzoyl)4-p-toluenesulfonamidomide. anthraquinone. anthraquinone.

14 p-ToluenesulIona- 26.0 1-arnino-2-(3',4'-dlchlorobenzoyl)- 16.0 l-amino2-(3',4-dichlorobenzoyl)-4-p t,oluenesuifonumimide. i bromoanthraqiztlnone. doanthraquinone.

When dispersed and applied to polyethylene terephthalate by the procedure of example 2, the 2-benzoylanthraquinone dyestuffs of column 6 gave blue-violet dyeings having excellent light and sublimation fastness.

We claim:

1. Polyester fiber dyed with an anthraquinone compound of the formula 0 NHR COR

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2937190 *Mar 10, 1958May 17, 1960Eastman Kodak CoCarbamylanthraquinone compounds and materials dyed therewith
US3211755 *Sep 27, 1963Oct 12, 1965Toms River Chemical Corp1-amino-2-benzoyl-4-hydroxy anthraquinone
GB661045A * Title not available
Non-Patent Citations
1 *H. A. Lubs, Chemistry of Synthetic Dyes and Pigments (1955) pp. 417 419. Copy in 260 377
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4977134 *Jul 21, 1989Dec 11, 1990Minnesota Mining And Manufacturing CompanyLightfastness, heat fastness
US4988664 *Jul 21, 1989Jan 29, 1991Minnesota Mining And Manufacturing CompanyThermal transfer imaging using alkylcarbonylamino-anthraquinone dyes
US5034547 *Jul 21, 1989Jul 23, 1991Minnesota Mining And Manufacturing CompanyColorfastness
US5302577 *Mar 29, 1993Apr 12, 1994Basf AktiengesellschaftTransfer of anthraquinone dyes
EP0409638A1 *Jul 20, 1990Jan 23, 1991Minnesota Mining And Manufacturing CompanyAnthraquinone dyes having alkylsulfonylamino substituents
EP0567829A1 *Apr 13, 1993Nov 3, 1993BASF AktiengesellschaftProcess for transfer of anthraquinone dyes
U.S. Classification8/676, 8/679, 8/675, 552/251
International ClassificationC09B1/28, C09B1/36, D06P1/16, C09B1/00, D06P1/20, C09B1/32
Cooperative ClassificationD06P1/20, C09B1/32, C09B1/36, C09B1/28
European ClassificationD06P1/20, C09B1/32, C09B1/28, C09B1/36
Legal Events
Jan 21, 1982AS03Merger
Effective date: 19811022
Jan 21, 1982ASAssignment
Effective date: 19811102
Effective date: 19811022