Патент USA US2406004код для вставки
Patented Aug. 20, 1946 2,406,004 ~ UNITED STATES PATENT" OFFICE 1} MONOAZO COMPOUNDS ‘Joseph B. Dickey and James G. McNally,'Roch- . ester, N. Y., assignors to Eastman Kodak Com pany, Rochester, N. Y., a corporation of New Jersey No Drawing. Application May 20, 1942, Serial No. 443,718 .6 Claims. (01. 260—205) - This invention relates to new azo dye com .2 , . tate, cellulose formate, cellulose propionate‘ or pounds and their application to the art of dyeing. cellulose butyrate and the hydrolyzed as well: as We have discovered that dyeings which can be discharged to a clear white can be obtained by dyeing a suitable textile material with a dye the unhydrolyzed mixed organic acidesters of having the formula: cellulose such as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such'as methyl cellulose, ethyl cellulose - or benzyl cellulose. ‘ While our invention will ‘be alkyl ' described more particularly ingconnection: with the dyeing of cellulose‘ acetate, silk, it will- be understood that it is applicable to the Idyeing ‘of the other textile materials'which have been in / R—N=N—R1—N \ _ . v R: _ v wherein R stands forv the residue of a benzene “nucleus containing an NHz group inpara posi “tion; to the azo bond shown and a . R4 group, wherein R3 stands for a member selected - .from the group consisting of hydrogen and an .alkyl group and R4 stands for a member selected from the groupconsisting of an alkyl group .and a benzene nucleus, in 'ortho or meta position to sulting from the development operation have the formula: ‘ a benzene nucleus and R2 stands for a member selected from the group consisting of any alkyl group and a benzene nucleus, diazotizing the _ . T 1 25 ‘ . . alkyl D~N=NV—_B—N=N—_R1—N/‘> ' " dye on the ?ber and developing with a developer r ' dyeings can be obtained.‘ The use of components, such as '2-hydroxy-3-carboxynaphthalene, yield ing dischargeable navy'vblue to black shadesap pears to‘ be of greatest importance-since these .20 shades are in demand and dyes which» can. yield . them are highly desirable. The disazov dyes re the azo bond shown, R1 stands for the residue of , ' 15 ?ber yellow, scarlet, violet, navy blue’ and black / .—SQ2N component. ' ponent used to develop the diazotized dye' on‘ the Ra ' dicated hereinbefore. _ ' Dependingupon' the particular developer/com -» I ' R2 wherein D stands for the residue of a developer component, B stands for the residue of a benzene I So far as we are aware both the monoazo dye nucleus containing a, compounds and the disazor dye compounds re sulting from the development operation consti tutenew compounds. Accordingly, it isan ob ‘Y » . ~ I ~. R3 ‘~——SO2N/ ject of our invention to provide new azo dye R4 compounds. Another object is to provide dye group and wherein R1, R2,, Rsand R4 have the ings on textile materials which are of good fast- ~ 35 meaning previously assigned to them. ness to light and washing and which can’ be dis charged to a clear white. A particular object is to provide cellulose acetate textile materials dyed navy blue or blackshades of good fastness to light and washing and which are dischargeable The dye compounds of our invention possess properties which make them of unusual indus trial importance. The free amino dye. com‘ pounds combine ,good speed of ‘dyeing with ‘good exhaustion and for the most part can be applied to'a, clear white. _ , ‘ ' to the ?ber at. a temperature as low as 60". C. ~ The dyeing process of our invention appears Further, generally speaking, these free amino to, be particularly of, value in. connection with dye compounds possess good solubility in water the production of navy blue to black shades on .anddo lnot gum'on heating with steam; When cellulose acetate textile materials. However, the .45 vdiazotized on the ?ber and coupled with a’ de dye compounds‘of our invention are applicable to veloper component, such as 2-hydroxy-3-car the coloration of organic derivatives of cellulose boxynaphthalen'e, desirable shades of color are in general as well as'to other textile’ materials obtainedwhichare of good fastnessto ‘light and such as nylon, wool and silk. Our invention washing and which arereadily dischargeable to a seems to be of greatest utility in connection with 50v clear white. _Ready_ dischargeability to a clear the coloration of cellulose acetate and nylon white is a very important property vfor a‘ dye to textile materials. possess. Typica1 organic derivatives of cellulose include ?thehydrolyzed as well as the unhydrolyzed cel lulose organic acid esters such ‘as cellulose ace ' V y '. >. ; . ‘q ‘ The qualities above enumerated,- as previously 55 noted, makethe-dye compounds of'our- inven tion vvery valuable commercially; Rapid dyeing 2,406,004 ‘ 4 3 at low temperatures coupled with good exhaus the dye compound formed tends to coagulate as a gummy mass unless it is well stirred to keep the product broken up. 11.3 grams, which is 67.45% of the theoretical yield of 4'-amino-2'-sulfone tion are qualities of utmost importance in jig dyeing operations which normally are conducted at temperatures of 60-65° C. Thus dye com pounds, which dye rapidly at temperatures of methylamidobenzeneazo - 4 - dimethylaminoben 80-85° C. and which .are otherwisesatisfactory .zeneis obtained in the form ofsmall?nely formed but whichposses's poora?inity forthe?ber at red-orange crystals. The dye compound formed Gil-65° C. have little or no utility for present day commercial jig dyeing operations. Accordingly,’ the discovery of dye compounds which .dye. is recovered by ?ltration, washed with water and '.' dried. ' do not form gummy deposits.randlwhichxyield. By substituting an equivalent gram molecular weight of 4’-nitro-2’-sulfonemethylamidoben zeneazoeei-diethylaminobenzene for the starting wdye'compound'aof the example 4'-amino-2'-sul dyeings of excellent fastnesslto light and'w'ashing ‘fonemethylamidobenzeneazo - 4 - diethylamino and which are readily dischargeable to white constitutes an important as well as unexpected benzene is obtained. This dye ‘compound is like wise obtained as red-orange crystals and has prop ‘ rapidly at low temperatures, which exhaust well, which have excellent solubilityin water; which _ technological advance. ' ’ erties substantially the same as the dye compound Concentrations, for example, from 1/a% to 3%,’ by weight of the dye tothe material undergoing dyeing can be employed-in the initial dyeing op eratic-n,iprettyuorangewellow dyeings being ob of the example. _ I V ExampZeZ 20 23 grams of ‘i’-nitro-'2’-sulfonethylamidoben zeneazo '-4-di-c- hydroxyethylaminobenzene are heated in 100 cc. of ethyl alcohol in a reaction vessel to boiling. A solution 0158 grams of‘fused tained. For the development operation follow ling1thediazotization of ‘the free ‘amino dye com .pounduon Jthe ?benan excess of. the developer ‘component is ordinarilyv employed. The in tensity of shade-obtained varies depending on theiamount‘of the free ‘amino ‘dye-absorbed by :the ?ber: in the vinitiali'd'yeing‘operation. To 'iThus'it ‘is seen that the'intensity of the sgiade 60% sodium sul?de in 18 cc, of water is'then added in small portions because the reduction re action proceeds very vigorously. After all of the sul?de solution has been added, the reaction mix ture is boiled for 45-60 minutes and then poured through a filter paper into two liters of cold water which is vigorously stirred.‘ 13 grams, which is 65% of the theoretical amountiof £4’-'amino-2" sulfonethylamidobenzeneazo-4-di <- ,8 -ilhydroxy ethylaminobenzene is recovered by ?ltration as increases" with an‘increase in the amount :of_' the 3:) well formed orange crystals. The dye compound illustrate, when 12 -<hydroxyi3i-carboxynaphtha llenetis the developer ‘component 'at lower con centrations, the icolor "appears navy ‘blue ’ but as the concentration increases the intensity of the color‘ increases until :thecolor appears black. ‘free-‘aminordyeiappliedto the ‘?ber. ‘ 7 obtained is washed with'water and dried. -~ ‘Themonoazo"dyefcompoundsiof ‘our invention Example 3 can ' be ‘prepared by‘v reducing the corresponding ‘nitro dye compounds to the 1free amino ‘form. ‘Thus > 4 ' - ' amino-2 'l-sulfonemethylainidobenzene -az‘o-4-zdimethylaminobenzene ‘having the ,ior 'mul'az " ' - Id ' H.N_<I;;I rink <3: 34CH: I /H . ‘ SOgN 'CHt' " f can be prepared by reducing . . ' aminobenzene are'placed in a reaction vessel to getherwith 200cc; of ethylalcohol and the mix ture resulting'is heated to boiling. 8 grams of fused 60% sodium sul?devin 18‘cc.>of water is 1then added in small portions to prevent the reduc tion-reaction from being too vigorous. vAfter all of ‘the sul?de ~'solution has been added the re action mixture is re?uxed for 45-60 minutes and then'poured through a'?lter paper into 2 liters of ‘coldrwaterl which is being stirred'vigorously. 17.5 \ CH3 / OrN 23.9 grams of 4'-nitro-2'-sulfonethylamidoben zeneazo-Z-chloro - 4 - (ethyl, ?-hydroxyéthyD grams, which is 82% of the theoretical amount of '4'-a-mino - 2' -' sulfonethylamidobenzeneazo' - 2 _ I v 7 . 80% ‘ CH: chloro-'4-‘(ethyl, ‘p-hydroxyethyl) ‘aminobenzene ‘is obtained after ?ltration of the'reaction mixture in the form of wel1iormed red-orange crystals. ‘The dye --compoundiobtained is washed with . CH3 ' ‘The preparationof the monoazo nitro compounds is'illustrated in our U- saPatent 2,261,175‘, issued water and dried. 'November4,i194l, wherein a ‘considerable num ‘1, 2 and 3; the following monoazo dyes of our in vention can be prepared. In naming the dye berofsuch compounds isdisclosed. 'v .. ' The following. examples illustrate ‘the ‘invention: . . . ‘Example 1 . ‘117.’? grams‘ of '4i-nitro-2'esulfonemethylamido benzeneazo-iledimethylaminobenzene are ‘heated 65 in 100>ccrof ethyl ealcoholto boiling. A solution of‘ 8 .gram-s'off60% sodium sul?de fusedwith 2 :gramsof sulfurin 20 cc. of'water is then added in‘ small portions because the reduction reaction Following the procedure described in Examples compounds tabulated hereinafter,v the numbering indicated in connection with the dye 4'-amino-2' sulfonemethylamidobenzeneazo - 4 - dimethyl aminobenzene has been followed. , 1-.‘ 4'-'amino- 2' -sulfone-/3-hydroxyethylamido lbenzeneazo#l-dimethylaminobenzene. 2. 4' - amino-2'-sulfone-p-methoxyethylamido benzeneazo-4-dimethylaminobenzene. . 3. 4’ - amino-2‘-sulfone-;8-methoxyethylamido ‘which take‘siplace is ‘very vigorous. After all of ' "0 benzeneazo-4-diethylaminobenzene. \the‘sul?de reaction mixture has been added, the 4.- 4"- amino-2"-sulfone-p-methoxyethylamido resulting reaction mixture is re?uxed for 45460 "minuteslafter-lwhich’ it is'p'oured through a ?lter paper- into two liters of cold‘water'which is stirred benzeneazo-‘i- (ethyl, ?-hydroxyethyl) -aminoben— lvigorously. Vigorous :s'tirring is required‘ because benzeneazo-4-di-p-hydroxyethylaminobenzene. zene. .' , V . '5. 4’ - amino-2'-sulfone¢;3—methoxyethylamido ‘ 32,406,004 7 "1‘. .4’ efamino' :12‘ J-- sulfonem‘ethylamidoben - -- ."Whil? .a'considerable number of compounds il illustrating the monoazo dye‘compounds of our invention have been vgiven, ‘it is to be clearly understood that the compounds disclosed are il lustrativeand not limitative of the invention. Thus, .any of the nitrobenzene-sulfoneamide compounds disclosed herein'can be diazotized and coupled with any of the coupling components in zeneazoeéledimethylaminobenzene. -. ‘ 2. 4’ - amino - 2' - sulfonethylamidobenzene - azo-4-di-p-hydroxyethylaminobenzene. ' 3. 4' - amino - 2’ - sulfonethylamidobenzene — azo - 2 - chloro-li- (ethyLe-hydroxyethyl) -amino benzene. - ' a 4.4’ - amino - .2’ - sulfonemethylamidoben - dicated herein to yield 'monoazo , dyes which zeneazo-4-diethylaminobenzene. can be converted in accordance with the Procedure described in‘Examples 1, 2 and 3 to yield the monoazo dye compounds of our invention. :The monoazo dye compounds of the invention ' > 5. 4’ - amino .- 2’ - ,sulfonephenylami'doben zeneazo - 4 - (ethyLe - hydroxyethyl) - amino benzene. ' 6. 4' - amino - ,3' - sulfonethylamidobenzene - azo-4-dimethylaminobenzene, can bezapplied to the textile material such as an 7. 4'.- amino - 3' -_sulfonethylamidobenzene organic derivative of cellulose textile material 15 by methods well known in the art. They may be azo-4-di-p-hydroxyethylaminobenzene. 8. 4’ - amino - 3' -sulfonethy1amidobenzene applied, for example, from an aqueous solution azoei-(methylphenyl) -aminobenzene. orsuspension of the dye or dyes. In this method 9. 4' - amino - 3' - sulfon‘ethylamidobenzene the dye is ?nely ground and ordinarily inti mately admixed'with a dispersing or solubilizing 20 azo-‘l-di-B-hydroxyethylaminonaphthalene. agent such as soap, sodium sulforicinoleic acid - 10. 4' - amino - 2' - sulfonethylamidobenzene azo-4-di~p-hydroxyethylaminonaphthalene. ,orrsodium lignin-sulfonate and dispersed in water to ‘form an aqueous dyebath. The material-to be ll. 4’ - amino - 6’ - chloro - 2’ - sulfonemeth — y1amidobenzeneazo-4-dimethylaminobenzene. dyed is then added to the dyebath thus prepared 12. 4’ - amino - 2’ - sulfonedimethylamidoben and dyeing is conducted at a temperature of 25 zeneazo-ll-di-?-methoxyethylaminobenzene. 50:85". C. until complete. In accordance with the usual dyeing practice, the material to be dyed will When the above compounds are diazotized and ‘ordinarily be added to the dyebath at a tempera coupled with 2-hydroxy-3-carboxynaphthalene, ture lower than that at which the main portion navy blue to black dyeings are obtained; when of the dyeing is to be effected, a, temperature ap 30 coupled with I-phenyI-B-methyl-S-pyrazolone, proximating 45-55" C., _for example, following which thetemperature of the dyebath is raised to "that selectedfor carrying out the dyeing opera yellow dyeings are_obtained’;_when_coupled with tion. Usually one to two hours is su?icient for the dyeing ‘operation. As this method of dyeing and modi?cations‘ of it arewell known to those ‘skilled'in the artto which this invention is di 35 e-naphthol, scarlet dyeings are obtained; when coupled with 1-diepehydroxyethylamino-2¢meth oxy-S-methylbenzene, violet dyeings are obtained and when 1e?rv-dihydroxypropyl-Z-methyltet rahydroquinoline is the developer component navy blue dyeings are ‘obtained. 1 The monoazo dye von the ?ber can be diazotized rected, further discussion is believed unnecessary. The monoazo dye compounds Of the invention ‘are principallyof importance in connection with 40 in accordance with‘ the procedure described here inafter. Itwill be understood, however, that any so-called developed dyeing operations. In this other suitable method can be used. method of dyeing the monoazo dye (or dyes) is Diazotization of the monoazo dye on the ?ber diazotizedom the ?ber and the diazonium com pound resulting is coupled with a compound ,After the material has been rinsedafter dye known as a developer compound. These‘ latter ing, it is diazotized in a hath made up as fol compounds are well known to those skilled in the lows: For each 10 grams of cloth, one gram of .art asa considerable‘number of them are dis sodium nitrite is dissolved inra mixture contain closed in the prior art. Representative developer ing_2 grams of concentrated (35 %) hydrochloric compounds arejgiven hereinafter but no attempt ‘acid and 300 v(Bo/‘of water. The diazotization .has been made to givean exhaustive list. It will 50 treatment is‘ given for ,30-45-minutes at a tem be apparent that compounds of the general char perature of ‘about'20b C’. Upon ‘completion of the .acter. as those indicated can also be employed. diazotization reaction, the fabric is removed and . ,Developer compoundsthat canbe employed in vthoroughly rinsed'with water following which it is ready for development. clude 2-hydroxy - 3 - carboxynaphthalene, 1 _phenyl-S~methyl-5-pyrazolone, phenol, a cresol such as p-cresol, v13-naphthol,,arylamides of 2-hy ,droxy-3-carboxynaphthalene such as the anilide, the m-nitroanilide or’ the p-methoxyanilide The development operation of the invention will be illustrated in connection with 2ehydroxy 3-carboxynaphthalene. Generally speaking, the developing operation will be carried out in a moderately acid medium although in certain derivatives, 1 - di - e- hydroxyethylamino - 2 pmethoxy-?~methylbenzene, N-di-B-hydroxyethyl aminobenzene, N-‘(ethyL e-hydroxyethyl) -amino 60 cases it may be deemed more desirable to carry benzene, N-13,11-dihydroxypropyltetrahydroquino line, 1-b,'y-vdihydrogpropyl-2-methyltetrahydro ,quinolineand 1-B-hydroxyethyl-2? - dimethyl ‘tetrahydroquinoline. I The colors - obtainable when representative monoazo dyes of our invention are applied to cel— lulose acetate textile materials, diazotized on the ?ber and then developed with various represen tative developer compounds are givenhereinafter. ‘ Twelve monoazo dyes are ?rst listed and the col ors obtained when they are yd‘iazotized and de out the development operation in a slightly al kalinev medium. ‘ a Following thediazotization treatment, the ma terial is developed, preferably immediately?n a bath made up as follows: ‘for every 10 grams of ‘cloth, 10 cc. of a 5% stock solution of Z-hydr'oxy S-naphthoic acid and 1 cc. of glacial aceticlacid are added to 300 cc. of Water. The stock solu »tion of. 2-hydroxy-3enaphthoic acid is made by dissolving 10 grams of 2-hydroxy-3-naphthoic acid inlOO .cc. of 5% .NaOH and then adding 100 cc. of water. " The cellulose acetate cloth from veloped with the developer compounds indicated the diazotization treatment is entered in the de are given in the paragraph immediately follow- , v veloping bath.ats~30°jC; and "the temperature is gradually raised to 60° (Lover a 30 minute-ipei ing. 2,406,004 10 riod at which temperature the bath is kept for another 30 minutes. Following this treatment, selected from the group consisting of hydrogen, a lower alkyl group, a lower alkoxyalkyl group and a lower hydroxyalkyl group, R4 and R5 each stands for a member selected from the group con The developing bath made up as described CI sisting of a lower alkyl group, a lower alkoxy above has a pH of approximately 4.0. By increas alkyl group, a lower hydroxyalkyl group and a the cellulose acetate silk is removed, washed well with water and dried. ing the amount of acetic acid, the pH will be low ered and the shade obtained on the fabric will be greener. If the pH is raised by decreasing the monocyclic group of the benzene series, X1 stands for a member selected from the group consisting Using the above procedure, navy blue to black ber selected from the group consisting of hydro of hydrogen, a lower alkyl group, an acetamino amount of acid added a redder shade is obtained. 10 group and a chlorine atom, X2 stands for a mem shades can be obtained depending upon the con gen and a lower alkoxyl group, 2Q stands for a centration of the monoazo dye on the ?ber. The member selected from the group consisting of colors obtained are readily discharged to sub hydrogen, a lower alkyl group, a lower alkoxyl stantially a pure white by the usual reduction 15 group, a chlorine atom and a bromine atom, and discharges such as, for example, the monozinc X4 stands for a member selected from the group salt of the formaldehyde sulfoxylic acid (Ron consisting of hydrogen and a lower alkyl group galite). and wherein at least one of X3 and X4 must be While the development operation has been 11 lustrated in connection with the use of 2-hy droxy-3-carboxynaphthalene, it will be under hydrogen. 20 stood that it can be carried out in a similar man ner using one of the other developer components indicated herein. That is, the pH of the devel oper bath can be about 4.0 although as previous 25 ly indicated the pH is not restricted to this value. The shade obtained will vary somewhat depend ing upon the pH of the developer bath. If de sired, the dyeing can be topped by treating with 2. The azo compounds having the formula: R5 I /Rz SO2—N\H wherein R2, R3 and R5 each stand for a lower alkyl group. 3. The azo compounds having the formula: a direct dye of another shade. Also the develop ment operation can be effected using more than one developer compound. To illustrate, the di azotized ?ber can be developed with both 2-hy droxy-3-carboxynaphthalene and 1-phenyl-3 methyl-5-pyrazolone at the same time. Although the use of the dye compounds of our H invention has been described more particularly in connection with cellulose acetate, it will be wherein R2 and R5 each represents a lower hy understood that they can be applied to the other droxyalkyl group and R3 represents a lower alkyl textile materials named herein by the methods group. described or by methods similar thereto. Fur 4. The azo compound having the formula: ther, while the disazo dye compounds of our in CH: 0 H2 0 H vention have been shown as being prepared on / HgN the ?ber, it will be understood that the diazo N=N —N\ tized monoazo dyes can be coupled with the de 45 CHgCHzOH | C2115 veloper components without being applied to the S OzN ?ber and if this is done the disazo dyes are ob tained per se. Normally the disazo dye is formed H on the ?ber. Coupling components wherein the benzene or 50 naphthalene nucleus contains an amino group which is substituted with a phosphorus grouping can be prepared as described in our copending 5. The azo dye compound having the formula: application Serial No. 225,198, ?led August 16, 1938. 55 We claim: 1. The azo compounds having the formula: X4 | X3 I X1 I 6. The azo dye compound having the formula: CgHs R5 60 l 3 R' X1 R: H.N@_N=N@_N/ O f) H \CgH5 SOaN R4 wherein R2 and R3 each stands for a member JOSEPH B. DICKEY. JAMES G. MCNALLY.