US3775050A - Process for facilitating postponement of fixation using reactive carbonate dyestuffs - Google Patents

Abstract

A new class of dyestuffs that contains a carbamate structure to which there is attached an N-hydroxymethyl group has been prepared. These new dyestuffs were prepared through combination of certain dyestuffs with the hydroxyl group of hydroxyalkyl carbamates. Methylolation of the carbamate moiety renders the dyestuffs reactive under acidic conditions to cellulosic and other textile materials containing reactive hydrogens.

Description

United States Patent [1 1 Kullman et al.

[4 1 Nov. 27, 1973 PROCESS FOR FACILITATING POSTPONEMENT 0F FIXATION USING REACTIVE CARBONATE DYESTUFFS Inventors: Russel M. Kullman, Metairie;

Robert M. Reinhardt, New Orleans, both of La.

The United States of America as represented by the Secretary of Agriculture, Washington, DC.

Filed: May 13, 1971 Appl. No.: 143,176

Related US. Application Data Division of Ser. No. 751,697, Aug. 6, 1968, abandoned.

Assignee:

US. Cl. 8/41 R, 8/1 A, 8/1 E, 8/1 K, 8/1 P, 8/1 UA, 8/39, 8/54.2, 260/153, 260/146 T, 260/249, 260/208 Int. Cl. C09b 62/80, C09b 62/82 Field of Search 8/41 R, 54.2; 260/153, 146 T, 249, 208

[56] References Cited UNITED STATES PATENTS 3,152,111 10/1964 Taber 260/153 3,218,310 11/1965 Benz et al. 1 260/154 3,248,370 4/1966 Stanley s 260/199 3,261,827 7/1966 Boresch eta1.... 260/163 3,501,259 3/1970 Long 8/18 Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. Ives Attorney-R. Hoffman et al.

[5 7] ABSTRACT 9 Claims, No Drawings 1 PROCESS FOR FACILITATING POSTPONEMENT OF FIXATION USING REACTIVE CARBONATE DYESTUFFS This application is a division of application bearing Ser. No. 751,697, filed Aug. 6, 1968, now abandoned.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to dyestuffs useful in dyeing cellulosic textiles. Specifically this invention relates to a wide variety of dyes which are generally applied to cotton and other cellulose containing textiles from acid media, to the preparation of the said wide variety of dyes, and to the application of these newcolorants to cotton and other cellulose'containing textiles. Morespecifically, this invention relates to dyestuffs which are converted from alkaline reactive dyes to derivatives of the same dyes that are reactiveunder acidic conditions.

The instant invention teaches-to those who would practice the invention that the dyestuffs produced by the method of the instant invention (1) can be applied from acidic medium, (2) can be stored indefinitely with the selected catalyst incorporated in the solution and without the dyestufi sufi'ering decomposition, and (3) when applied to cellulosic textiles the fixation of the colorant onto the textile can be postponed indefinitely.

The advantage to (l) the application of the dyestuff from acidic medium is that a dye whichis normally applied from basic medium can be converted to application in acid medium in order to incorporate a preferred acid catalyst. The advantage to (2) being able to store the prepared dye bath is that if a solution containing all the ingredients is stored without this advance to the state of the art the dye-stuff may suffer decomposition, whereas a solution prepared by the method of the instant invention would have excellent shelf life. One advantage to (3) postponement of the fixation of colorant onto the cellulosic textile is that if the stored textile contains an impregnated colorant which is not fixed said colorant can be removed without harm of any sort to the fabric.

The science and technology of textile dyeing have advanced so that dyestuffs are available which are reactive with the textile material so as to produce a covalent bond between the textile substrate and the dyestuff. A number of reactive dyes for cellulosics are well known to those skilled in the textile processing art. Among these are chloro-pyrimidine, chloro-triazine, vinyl sulfone, and acrylamide type reactive dyes, all of which are applied to the cellulosic textile under alkaline conditions.

In the prior art we find few reactive dyes available for application under acidic conditions. Chromophorecontaining derivatives of epoxy, aziridinyl, and triazinone compounds (see U.S. Pat. No. 3,152,111) have been described which can be applied under acidic catalysis to color cellulosics. The reactive functions in these dyes are similar to those found in certain textile finishing agents. Problems associated with each type of functions are well known to those skilled in the art, namely, water and storage stability for epoxy and aziridinyl compounds and the relatively poor durability of triaginone finishes.

In the prior art-we find that inventor Stanley discloses in U.S. Pat. No. 3,248,379 a somewhat related dyestuff. On cursory view of the cited dye structure the unskilled may indicate a kinship of the Stanleydye, column 1, lines 51-54, to the structure of the dyes of the instant invention; however, the structures are different, as shown below.

The instant invention:

x-NCH.01-i

C OORO Dye X can be H or a CH OH group R alkylene or substituted alkylene R- alkyl U.S. Patent 3,248,379:

DyC-N-CH2OH The instant invention discloses a carbamate with the colored moiety attached to the ester portion of the molecule, whereas U.S. Pat. No. 3,248,379 discloses the colored moiety attached to the amide portion of the molecule. v

The main object of the instant invention is to provide a new class of dyestuffs containing an N-hydroxymethyl-substituted carbamate in which the chromophoric moiety is attached through the ester group of the carbamate structure.

The second object of the instant invention is to provide stability against hydrolysis of a dyestuff in the presence of water.

The third object of the instant invention is to provide for postponement of fixation of a dyestuff applied to a substrate.

Other objects and further scope of the applicability of the instant invention will become apparent upon reading the detailed description throughout the specification. As an example, rather than the dye moiety, the moiety could readily comprise other substituent groups capable of imparting select properties, such as bacterithe substrate.

In accordance with this invention, dyestuffs of the fa lszxias m la has bs a i sw re wherein Z is a colored moiety derived from a chromophore-containing chlorotriazine, dichlorotriazine, vinyl sulfone, difunctional vinyl sulfone, vinyl sulfonamide, chloroquinoxaline, trichloropyrimidine, or acrylamide; B is an alkylene or substituted alkylene group; A is an oxygen or sulfur atom; X is hydrogen atom, a-

CH OH group, or a CH OR group in which R is a hydrogen atom, a CH;- group, or a H RT ML QTY??? a wherein A is an oxygen or sulfur atom, and

B is an alkylene or substituted alkylene group and x l or more. Some examples are:

ll ll HOCHQCHZOCNHL; HOCH2CH2CH2OCNH2, and

HOCH2CHCHzOCNH2.

These carbamates can be prepared by substantially any of the known processes for producing such compounds. ln one such route, they can be prepared by reaction of ammonia with ethylene carbonate, substituted ethylene carbonate, or the thio derivatives.

Colored moieties suitable for use in the preparation of dyestuff by this invention are derived from compounds that contain but are not limited to the following type structures:

HOgB

wherein R is a member of the group consisting of HSO -dye-OCH;Cl-i

H s o c u cntososH and q i H NaSO -dyeN-CH CH2.

HF L and R is a member of the group consisting of CH =CH, CH Cl-l Ol-l, CH CH OSO H, --CH CH,X (wherein X is any halogen) and CH C- l-l,OCH

wherein R is a member of a group consisting of NaSO dye-NH-, a halogen, or

and X is a halogen selected from a group consisting of chlorine, bromine, or fluorine atoms. The manner in which the halotriazines are made does not in any way limit their utility in this invention. Some examples of chlorotriazines are given below but the invention is not limited to these examples:

17H: 5011 E 011- N I, t H Cla N NH 0 N N PURPLE SOaH OH EH:

N N 11033 NH- -Cl N ORANGE N-- -0l H BLUE The only limiting requirement of such colored moieties is that they contain a functional group reactive to the hydroxyl group of the carbamate structure.

In preparing the dyestuffs of the invention, the desired color-containing moiety is attached to the hydroxy carbamate by reaction to form the intermediate as shown hereunder.

where Z is the color-containing'moiety, Y is a group reactive to --OH, B is an alkylene or substituted alkylene group, x=l or more, and A is an oxygen or sulfur atom.

Conveniently, the reaction is accomplished by adding to one mole of the hydroxy carbamate, a measured amount of the dyestuff in the absence of water and then 4 II II zoaocmn 01110 ZOBOClIlCHzOH ln forming the N-hydroxymethyl-substituted carbamate dyestuffs, it is preferable to carry out the reaction at a temperature above 20C. The resultant dyestuff is then acidified to a pH of 6.0 or less.

The new reactive dyestuffs of the invention are especially suited for the coloration of cellulosic textile materials such as cotton, linen, and viscose rayon. Textile material containing a substantial amount of cellulosic fiber blended with other fibers also may be treated by the process of this invention.

The dyestuffs are applied by treating the textile material in an aqueous solution (which may be thickened as a printing paste) in the presence of an acidic or latent acidic material such as zinc nitrate, magnesium chloride, zinc fluoborate, zinc chloride, and the like. The acidic catalyst may be added to the dye bath prior to, simultaneously with, or after the addition of the dyestuff.

Dyeing in the presence of latent acidic catalyst preferably is carriedout at elevated temperatures, for example, between about 60 and 200C in order to improve the exhaustion and fixation of the dyestuff. It is preferable to heat cellulosic materials at 120C or higher for a short period of time after application of the dyestuff and latent acidic catalyst. The textile material may be dried if desired and stored for prolonged periods prior to dyestuff fixation. In this manner it becomes possible to readily remove the dyestuff and reapply.

To summarize, the present invention provides (1) a new class of reactive colorants, (I!) a method of preparing these new colorants, and (III) a process comprising postponement of fixation when these new colorants are applied to cellulosic textiles. More specifically the invention can be described as.

W l. dyestufis of th e general formula.

wherein Z is a chromophore-containing moiety, B is an alkylene or a substituted alkylene group, A is an oxygen or sulfur atom, and X is a hydrogen atom or a methylol group;

II. a method of converting dyestuffs which are generally reactive with hydroxyl groups under basic conditions to dyestuffs capable of reacting with hydroxyl groups under acidic conditions, comprising.

a. mixing a selected dyestuff with hydroxyalkyl carbamate in a weight to weight ratio of about 1:3, and adjusting the pH to about 8 to 10,

b. heating the mixture for about from 40 to 2880 minutes at temperatures about from 25 to C, using the longer periods of time with the lower temperatures, to obtain the dyestuff intermediate,

c. cooling the intermediate to about 25C (room temperature),

d. mixing the cooled intermediate of (c) with about from 2.3 to 4.6 parts of a 36.3% formaldehyde solution (a molar ratio of about from 1:1 to 1:2

of hydroxyalkyl carbamate to formaldehyde),

e. adjusting the pH of the mixture of (d) to about from 8 to 10,

f. heating the adjusted mixture for about from 30 to 45 minutes at about lC to obtain the new reactive dyestufi', and allowing the mixture to cool to about 25C,

g. adjusting the pH of the final mixture to below 7, l

ll 7 Z-OBO-C-N-CHzOH wherein Z is the chromophore-containing moiety, B is an alkylene or a substituted alkylene group, A is an oxygen or sulfur atom, and X is a hydrogen atom or a methylol group,

b. centrifuging the wet, impregnated textile to remove excess liquid,

c. drying the wet, impregnated material for about 7 minutes at about 60C,

d. storing the dry, impregnated, cellulosic textile for about from 0 to 70 days at ambient temperatures, and

e. heating the stored, dry, impregnated, cellulosic textile for about from 3 to 4 minutes at about 160C to effect fixation.

The detailed dscription and specific examples while indicating preferred embodiments of the instant invention are provided only to illustrate the invention and should not be construed as limiting the scope of the instant invention in any manner whatever. Numerous changes and modifications within the spirit of the invention will become apparent to those skilled in the art.

EXAMPLE 1 3.5 grams of a yellow chromophore containing a dichlorotriazinyl group (Cl Reactive Yellow 4) of the formula having two active chlorine atoms are added to 10.5 grams (0.1 mole) of hydroxyethyl carbamate and to this mixture is added sodium hydroxide solution to make a pH of 8-10. The solution is heated on a steam cone for 40 minutes, then cooled to obtain the intermediate. There is then added 8 grams (0.1 mole) of neutralized 36.3% formalin and the mixture is heated 30 minutes on a steam cone, cooled to room temperature, and allowed to stand 16 hours. The solution is adjusted to below pH 7 with 6N hydrochloric acid and allowed to stand until ready forapplication.

To the above solution is added 76 ml distilled water and 4 ml of 25% zinc nitrate hexahydrate solution. An

80 X 80 cotton printcloth (Sample 1) is thoroughly saturated with the solution, centrifuged to remove excess liquid, then dried 7 minutes at 60C and heated 3 minutes at 160C for fixation, washed, and dried.

3.5 grams of the yellow chromophore containing chlorotriazinyl group (Cl Reactive Yellow 4), the starting material, is added to a solution containing 92.5 ml distilled water and 4 ml of 25% zinc nitrate hexahydrate solution. The solution is acidified with 6N hydrochloric acid and applied to an 80 X 80 cotton printcloth (Sample 2) as done for Sample 1. The fasteners of the dye in Sample 1 was much greater than that of the colorant of Sample 2.

EXAMPLE 2 The procedure of Example 1 is repeated using as a starting material a red chromophore containing a chlorotriazinyl group (Cl Reactive Red 7) of the formula with one active chlorine atom. The fasteners of the dyeing to washing of the carbamate dyestuff is once again greater than that of the colorant from which the new dyestuff is prepared.

EXAMPLE 3 3.5 grams of C1 Reactive Violet 4 of the formula 0 HNCOCH H035 0011201128 0 N-N containing a monovinyl sulfonyl group is added to 10.5 grams (0.1 mole) of hydroxyethyl carbamate and to this mixture is added sodium hydroxide solution to obtain a pH 8-10. The ingredients of the solution were allowed to react for 48 hours at 25C to obtain the intermediate. 16 grams (0.2 mole) of 36.3% formalin at pH 10 is then added and the mixture is heated 45 minutes on a steam cone and the solution cooled. 82 ml of distilled water is added and the pH adjusted to 5.7 with a solution of hydrochloric acid and then 4 ml of 25% zinc nitrate hexahydrate solution is added. The procedure to treat Sample 1 was followed for Sample 5.

3.5 grams of Cl Reactive Violet 4, the starting material is added to 92.5 ml of distilled water and the pH adjusted to 5-6 with solution of hydrochloric acid. 4 ml of 25% zinc nitrate hexahydrate solution is then added. The solution is then applied to Sample 6 following the procedure for Sample 5. The fastness of the dye of Sample 5 to washing is much greater than that of the colorant from which the new dyestuff is prepared (Sample 6).

EXAMPLE 4 The procedure of Example 3 is repeated using Cl Reactive Black 5 of the basic chromophoric structure a difunctional colorant with reactive vinyl sulfone groups, as a starting material. The fastenss of the dyeing to washing of the new carbamate reactive dyestuff on fabric is greater than that of the colorant from which it is prepared.

EXAMPLE 5 The solution of Example 2 containing the new dyestuff and zinc nitrate catalyst is stored in a stoppered glass flask for 15 months then it is applied to cotton printcloth following the procedure of Example 1. After drying at 60C for seven minutes two portions of sample are removed and the remaining portion is heated four minutes at 160C. One portion of the dried sample is washed and dried with the portion heated to 160C. The fastness of the dyeing to washing is far greater for the portion heated at 160C than the other portion. This illustrates the stability of the new dyestuffs in the presence of water and acidic catalyst over prolonged periods of time. It also illustrates the ease of removal of the dye prior to fixation at an elevated temperature. It also shows that the reaction to cause chemical union between the dyestuff and the cellulose occurs at elevated temperature and that fastness is not achieved until this chemical union occurs.

The third portion, dried only, was stored weeks then cut into two parts. One part was heated four minutes at 160C to effect dye fixation. The remaining part of the dried sample is washed and dried with the part heated to 160C. The fastness of the dye to washing is far greater for the part heated at 160C than the other part. Further, the fastness of the dye to washing is the same as the sample heated to 160C immediately after drying. l

EXAMPLE 6 The procedure of Example 5 was repeated using the solution of Example 4 which is stored for months in presence of water and acidic catalyst. The fastness of dyeing to washing was again greater for the heat fixed sample compared to the non-heat fixed sample.

We claim:

1. A process for facilitating postponement of fixation of a reactive dyestuff applied to a cellulosic textile, comprising:

a. impregnating a cellulosic textile with an aqueous solution containing an acidic catalyst selected from the group consisting of zinc nitrate, magnesium chloride, zinc fluoborate, and zinc chloride, and a dyestuff of the general formula wherein Z is the chromophore-containing moiety, 8 is an alkylene or substituted alkylene group, A is an oxygen or sulfur atom, and X is a hydrogen atom, a CH OH group, or a --CH OR group in which R is a hydrogen atom, a CH group, or a group;

b. centrifuging the wet, impregnated, cellulosic textile to remove excess liquid;

c. drying the wet, impregnated, cellulosic textile for about 7 minutes at about 60 C.;

d. storing the dry, impregnated, cellulosic textile for about from 0 to days at ambient temperatures; and

e. heating the stored, dry, impregnated, cellulosic textile for about from 3 to 4 minutes at about C. to effect fixation.

2. The process of claim 1 wherein Z is derived from a chromophore-containing monochlorotriazine, B is an ethylene group, and X is a hydrogen atom.

3. The process of claim 2 wherein the chromophorecontaining monochlorotriazine is Cl Reactive Red 7 dye.

4. The process of claim 1 wherein Z is derived from a chromophore-containing dichlorotriazine, B is an ethylene group, and X is a hydrogen atom.

5. The process of claim 4 wherein the chromophorecontaining dichlorotriazine is Cl Reactive Yellow 4 dye.

6. The process of claim 1 wherein Z is derived from a chromophore-containing monovinyl sulfone, B is an ethylene group, and X is a methylol group.

7. The process of claim 6 wherein the chromophorecontaining monovinyl sulfone is CI Reactive Violet 4 8. The process of claim 1 wherein Z is derived from a chromophore-containing difunctional vinyl sulfone, B is an ethylene group, and X is a methylol group.

9. The process of claim 8 wherein the chromophorecontaining difunctional vinyl sulfone is CI Reactive Black 5 dye.

P940550 UNIT S? 51123 PATEZIJT I Patent No. 3,775,050 Dated November 27. 1973 Inventor(s) Russell M. H. Ku1lman and Robert M. Reinhardt It is certified that error appears in the above-identified patent and that said Letters Patent arc.- hcrcby corre ,:tcd as shovm below:

The first inventor's name should be corrected to read as follows:

' RUSSELL M. H. KULLMAN The Title should be corrected to read as follows:

Process for Facilitating Postponement of Fixation Using Reactive Carbamate Dyestuffs Column 3, line 8, change "chrmophore" to chromophore Column 7, line 36, change "dscription" to description Column 8, line 29, change "fasteners" to fastness Line 40, "N-N" should be N=N Column 9, line l0, change "fastenss" to fastness Signed and sealed this 5th day of November 1974.

(SEAL) Attest: v

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents

Claims (8)

1. 2. The process of claim 1 wherein Z is derived from a chromophore-containing monochlorotriazine, B is an ethylene group, and X is a hydrogen atom.
2. 3. The process of claim 2 wherein the chromophore-containing monochlorotriazine is CI Reactive Red 7 dye.
3. 4. The process of claim 1 wherein Z is derived from a chromophore-containing dichlorotriazine, B is an ethylene group, and X is a hydrogen atom.
4. 5. The process of claim 4 wherein the chromophore-containing dichlorotriazine is CI Reactive Yellow 4 dye.
5. 6. The process of claim 1 wherein Z is derived from a chromophore-containing monovinyl sulfone, B is an ethylene group, and X is a methylol group.
6. 7. The process of claim 6 wherein the chromophore-containing monovinyl sulfone is CI Reactive Violet 4 dye.
7. 8. The process of claim 1 wherein Z is derived from a chromophore-containing difunctional vinyl sulfone, B is an ethylene group, and X is a methylol group.
8. 9. The process of claim 8 wherein the chromophore-containing difunctional vinyl sulfone is CI Reactive Black 5 dye.