US3355243A

US3355243A - Process for the dyeing of polyacrylonitrile fibers

Info

Publication number: US3355243A
Application number: US374233A
Authority: US
Inventors: Bindler Jakob; Durr Emanuel
Original assignee: JR Geigy AG
Current assignee: Novartis AG
Priority date: 1963-06-11
Filing date: 1964-06-08
Publication date: 1967-11-28
Anticipated expiration: 1984-11-28
Also published as: AT256767B; GB1017942A; NL6406567A; BE649078A; CH401900A; ES300841A1; DE1267658B

Description

United States Patent Office 3,355,243 PROCESS FOR THE DYEING F POLYACRYLO- NITRILE FIBERS Jakob Bindler, Riehen, and Emanuel Durr, Arlesheim,

Basel-Land, Switzerland, assignors to J..R. Geigy, A.G.,

Basel, Switzerland N0 Drawing. Filed June 8, 1964,.Ser. No. 374,233 Claims pri0rity, application Switzerland, June 11, 1963, 7,284/63 19 Claims. (Cl. 8-55) The present invention concerns a process to attain level dyeings on copolymeric acrylonitrile and especially on acrylic fibers having color saturation values in the range from about 2.5 to 6.5, the dye liquors used therefor as well as, as industrial product, the uniformly dyed material.

Hitherto, in order to dye polymeric or copolymeric acrynonit'rile by the exhaustion method with basic dyestuffs and in level shades, a dye liquor has been used which, in addition to basic dyestuffs, contained as dye assistants tertiary, monoor bis-quaternary organic nitrogen compounds having at least one higher alkyl radical per molecule. As a rule, these assistants detrirnentally affect the fastness to light of the dyeings obtained and block the fibers, i.e. as soon as a portion thereof has been drawn onto the fiber, they reduce the absorption power of the vfiber both for further basic dyestuff and for further dye assistant. This blocking effect on the fiber makes the re dyeing and in particular the cross dyeing of a shade already attained very much more difficult. Since the blocking effect caused by the known dye assistants on the polyacrylonitrile fiber affects the individual basic dyestuffs present, for instance, in a conventional mixed dye in different degrees, it is also generally impossible to attain or reproduce a desired shade with usually preferred mixtures of 'basic dyestuffs. Finally the blocking effect has a varying influence on'the rate at which the basic dyestuffs draw onto the aforesaid type of fibers which, in practice, easily leads to uneven distribution of the dyestulf. Moreover, since the hitherto used dye assistants which have drawn onto the fiber are. very diflicult to remove, this blocking effect is generally irreversible.

' It has now been found that polymeric, and especially copolymeric acrylonitrile fibers can be dyed in level shades while avoiding the above disadvantages by dyeing these materials in anacid, preferably organic acid and more particularly an acetic acid, dyebath which contains the basic dyestuffs and a polyamine, which latter has three or more, preferably 3 to quaternized basic nitrogen atoms, a polyglycol ether chain and at least one lipophilic substituent, whereafter the dyeing process is completed in known manner.

The polyamines usable in the dyeing treatment accordingto the invention are, in. particular, polyalkylene polyamine compounds the alkylene components of which are :preferably of from 2 to 3 carbon atoms each, e.g. 1,2-

ethylene, or 1,2- or 1,3-propylene radicals; the number of amino-nitrogens in these amines ranges from 3 to 5 and is preferably 3; forexample, diethylenetriamine, tri- 3,355,243 Patented Nov. 28, 1967 ethylenetetramine, tetraethylenepentamine or dipropylenetriamine are compounds from which the polyamines usable according to the invention are derived. The latter polyamines further contain as lipophilic substituent an 5 alkyl or alkenyl radical having, particularly, 14 to 20 carbon atoms. Examples of such radicals are the tetradecyl, hexadecyl, octadecyl or eicosyl or the oleyl radical. The polyglycol ether chain of the polyamines usable according to the invention has about 10 to 50, and preferably from 15 to 20 alkyleneoxy groups; these are mainly ethylene oxy groups and there may be present in the chain a minor portion, preferably from one to two individual propyleneoXy or styreneoxy groups.

These polyamines are obtained by adding the desired alkylene oxide component and if desired also minor amounts of styrene oxide to the polyamine having at least one lipophilic radical and three or more nitrogen atoms. The addition products thus obtained are then quaternized to form the product to be used according to the invention with an ester derived from a low aliphatic or araliphatic alcohol and a strong acid, e.g. with dimethyl or diethyl sulfate, ethyl chloride or ethyl bromide, or benzyl chloride, arylsulfonic acid alkyl esters such as p-toluene sulfonic acid methyl or ethyl ester, chloroacetic or bromoacetic acid methyl or ethyl ester or chloropropionic or bromopropionic acid methyl or ethyl ester.

For instance, N octadecyl diethylenetriamine condensed with ethylene oxide and permethylated with dimethyl sulfate to a product containing a polyglycol ether chain having 15 to 2'0 ethyleneoxy groups has an excellent levelling action.

The basic dyestuffs used according to the invention are advantageously of the following dyestuif classes: thiazines, oxazines, diphenylmethanes, triphenylmethanes,

" rhodamines, azo, anthraquinone dyestuffs and, preferably,

monoazo, methine and azamethine dyestuffs, which all contain onium groups, the onium groups being mainly ammonium groups.

As copolymeric acrylonitrile fibers, those fiber materials are used, the fiber-forming substance of which consists of a synthetic long-chain polymer comprising at least by weight of acrylonitrile and which possess suflicient dyesites to impart to the fibers a color saturation value above 2, and especially in the range of about 2.5 to 6.5. The acid groups of copolymer effecting the afiinity of the dyestulf are mainly the carboxylic acid, carboxylic acid amide or hydroxy groups as well as the sulfonic acid group.

The balance is essentially derived from vinylpyridines and other monomers copolymerizable with acrylonitrile which are described, for instance, in Canadian Patent 557,597, issued May 20, 1958.

Suitable acrylic fibers which satisfy the above require- 3 the invention when mixed with other fibers, e.g. with cellulose or polyamide fibers, in particular, however, with wool.

These fibers are dyed by the exhaustion process from short, concentrated dye baths (goods-to-liquor ratio of 1:5) as well as from long dye baths (goods-to-liquor ratio of 1:100) at a temperature of preferably 60 to 100 C. The finished fibers are then rinsed and dried.

Depending on the depth of shade desired, the dosage of the aforesaid polyamine dye assistant in the dye bath ranges between 1 and 2% calculated on the weight of the goods. Deep dyeings require less levelling agent than light shades.

The acid reaction of the liquor is preferably adjusted by addition of organic acid, in particular formic acid, acetic acid or tartaric acid. For instance, to secure pH- values of the dye bath of preferably 3.5 to 5, 80%-acetic acid is added in amounts of 2 to and in particular 4 to 6%, calculated on the weight of the goods to be dyed in the bath. The dyeings obtained according to the invention on the above described types of acrylic fiber materials are very level and fast to light. They can easily be re-dyed or cross-dyed.

The inventive process for dyeing polymeric and especially copolymeric acrylonitrile fibers has among others the following advantages over similar known processes: It does not block the fibers; it affords a better dyestuif yield, especially in deeper shades; an overdosage of the polyamine used according to the invention does not decrease the dyestuif yield; the process permits an easy crossdyeing of light shaded parts to deeper shades and does not adversely influence the fastness of dyeings obtained with basic dyestuffs.

The color saturation value mentioned in this specification and in the appended claims is the theoretical saturation value of usable acrylic fibers with a basic dyestuff of average afiinity for such fibers, expressed in grams of dyestuff per 100 grams of fiber (viz, Surean, Progrs raliss dans la teinture des fibres Acryliques, Teintex, June 1961).

The following non-limitative examples illustrate the invention. The temperatures are given therein in degrees centigrade. C.I. means Colour Index, Second Edition, 1956, published by The Society of Dyers and Colourists, Bradford, England and The American Association of Textile Chemists and Colorists, Lowell, Mass, USA.

4 liquor (liquor ratio 1:50) which contains 0.7% of C.I. Basic Yellow 19, i.e. dyestuff of the formula onto 0.3% of C.I. Basic Red 22, i.e. dyestuff of the formula LHa and 2% of C.I. Basic Blue 41, i.e. dyestulf of the formula as Well as 5% of acetic acid (100%), 10% of sodium sulfate and 2% of the condensation product of 15 to 20 equivalents of ethylene oxide with N-octadecyl diethylenetriamine, quaternized with dimethyl sulfate, all percentages being calculated on the weight of the fibers. The liquor is heated to 80 within 10 minutes and then the temperature is raised at the rate of half a degree centigrade per minute to the boil. The material is left in the liquor for 2 hours at this temperature and then the liquor is allowed to cool to within 30 minutes. The material so dyed is then taken out of the dyebath, and rinsed first with lukewarm and then with cold water.

The hanks of polyacrylonitrile are dyed a very level grey color, and have good fastness to light. The dyeings can easily be cross-dyed.

When the condensation product of 15 to 20 equivalents of ethylene oxide with N-octadecyl diethylenetriamine quaternized with dimethyl sulfate is replaced in the above example by corresponding amounts of the dye assistants listed in Table I below and otherwise the procedure described in the above example is followed, then dyeings having similarly good properties are obtained.

TABLE I Dye assistant condensation product of X mol of ethylene oxide with 1 mol of polyamine, quaternized No.

X Alkylene oxide Polyamine Quaternizing agent Ethylene oxide 1540 plus propylene Dimethyl sulfate.

oxide. 15-20 Ethylene oxide Diethyl sulfate. 15-20 do Benzyl chloride. 15-20 do Toluene sulfonic acid methyl ester.

20 do 0 Dimethyl sulfate. 12 do N-oleyl-triethylenetetramine Do. do N-hexadecyl-tetraethylenepentamine Do. 15-20 do N-octadeeyl-dipropylenetriamine Do. 18 20 Ethylene oxide plus styrene N-octadecyl-diethylenetriamme Do. oxide.

When the same rocedure as in Exam le 1 is followed EXAMPLE 1 P P but, instead of the, in all, 3% of the dyestuif mixture given in Example 1, corresponding parts of the dyestuffs listed in Column 11 of Table II are used, then dyeings of the shades given in Column HI of that table are obtained, which have similar satisfactory properties.

-T.ABLE H I 11 III N o. Dyes'tufi Shade on polyacrylonitrile fibers 11 0.1. Basic Blue 49 Blue.

12 0.1. Basic Red 14 Red.

/CHCHzCl LOMF N s f CH C a H3 13 0.1. Basic Yellow 13 Yellow.

a... s 14 0.1. Basic Green 1 (42040) Green.

15. Deorlin Light Yellow 4RL Yellow.

(CH3) aN-CHr-O ON=N-'|C 16..." Deorlin Light Blue BL Blue.

P o NNI s0.cm-

CH; e I

NH- -0 cmcmmcmm 17 0.1. Basic Blue 5 (42140).. Do.

18..... 0.1. Basic Blue 44 Do.

I O NH:

CH3 804-0 13 Y el/ "5 o fNH -a-e0 GZEhCHiN' CH2 A 19; L 0.1. Basie Bluezl. 42025 Do.

.20... 1051. Basic" Green16 Olive.

(GEM-1 (0301-! TABLE IICnt7lnued I II 111 i No. Dyestufi Shade on polyacrylonltrile fibers 21 C.I. Basie Orange 21 (48035) Orange. I

22 C.I. Basie Orange 22 (48040) D0.

23.... 0.1. B11510 Red 13 (48015) Pink.

24-- C.I. Basic Violet 7 (48020) Red-violet.

25 C.I. Basie Violet 20 Blue-violet.

CH;N=C O 01H;

OHaSOa 26. C.I. Basie Violet 21 Violet.

CH; omoo o-oH=oH-N-oomom o1- H: N

27. C.I. Basie Yellow 12 (48065) Yellow.

28. C.I. Basic Yellow 20 D0.

C H: JCH;

CCH=CH--HN- OCH: Cl 69/ I? CHzO CH;

29 0.1. 48013 Q. Pink.

30. C.I. B8510 Blue 6 (51175) Blue.

31. 0.1. Basic Yellow 3 (41005) Yellow.

32. C.I. Basie Green 4 (42000) Green.

33. C.I. B51810 Red 1 (45160) Red.

34-.-" C.I. Basic Yellow 19, C.I. Basic B1116 41 (1:1) Green.

N=N-N-NO1 01- 09 N 2 and OHZO om0H=-o11 ZnGh- (1:1 GB 1 C a EXAMPLE 35 in. This solution is added to a solution of g. of sodium 3 grams (g.) of C.I. Basic Blue 41, i.e. dyestufi of the formula v are pasted at room temperature with 5 g. of 80%-acetic acid. Then 250 milliliters (m1) of hot water are poured sulfate and 2 g. of an adduct, quaternized with dimethyl sulfate, of mols of ethylene oxide and 2 mols of styrene oxide to N-octadecyl diethylene-triamine in 1250 ml. of water. After heating the liquor thus obtained to 60, a polyacrylonitrile fabric containing about 15% of dyesites-atfording copolymer, e.g. a Dralon fabric, is introduced. The liquor is heated within 10 minutes to 80 and then at a rate of half a degree per minute up to 98". It is maintained at this temperature for 2 hours, whereupon it is allowed to cool within minutes to The fabric; dyed in this way is rinsed several times in 40-warm Water and in cold water, then treated with an aqueous solution of 4 g./liter of an antistatic cationactive fatty acid imidazoline derivative, and finally dried.

A level, deeply blue dyeing is obtained.

We claim:

1. A process for the production of level dyeings on copolymeric acrylonitrile fibers having dyesites corresponding to a color saturation value above 2, comprising dyeing this material with an acid dye liquor which contains at least one basic dyestuff and, as dye assistant, a polyamine the molecule of which consists of a polyalkene polyamine moiety having from three to five quaternized basic nitrogen atoms, a polyglycol ether chain of from 10 to 50 ethyleneoxy groups and at least one lipophilic substitucnt, and steaming and rinsing the resulting dyeing.

2. A process according to claim 1, wherein the dye assistant is a permethylated N-octadecyl-diethylene triamine which contains a polyglycol ether chain having to ethyleneoxy groups.

3. A process as defined in claim 1, wherein the pH of the dye liquor is within the range between 3.5 and 5.

4. An acid dye liquor for use in the production of level dyeings on copolymeric acrylonitrile fibers having dyesites corresponding to a color saturation value above 2, said acid dye liquor containing at least one basic dyestuif for coloring said fibers and, as dye assistant, a polyamine the molecule of which consists of a polyalkene polyamine moiety having from three to five quaternized basic nitrogen atoms, a polyglycol ether chain of from 10 to 50 ethyleneoxy groups and at least one lipophilic substituent.

5. A dye liquor as defined in claim 4, wherein the pH of said liquor at introduction of said fibers is within the range between 3.5 and 5.

6. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 15 to 20 equivalents of ethylene oxide with N-octadecyl diethylenetriamine quaternized with dimethyl sulfate.

7. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 20 mols of ethylene oxide and 2 mols of styrene oxide With N-octadecyl diethylenetriamine, per mol of the latter, quaternized with dimethyl sulfate.

8. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 15 to 20 mols of ethylene oxide and 1 mol of propylene oxide with 1 mol of N-octadecyl-diethylenetriamine, quaternized with dimethyl sulfate.

9. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 20 mols of ethylene oxide with 1 mol of N-octadecyl-diethylenetriamine, quaternized with dimethyl sulfate.

10. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 12 mols of ethylene oxide with 1 mol of N-oleyl-triethylenetetramine, quaternized with dimethyl sulfate.

11. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 15 mols of ethylene oxide with 1 mol of N-hexadecyl-tetraethylenepentamine, quaternized with dimethyl sulfate.

12. A process as defined in claim 1, wherein said polyamine dye assistant is the condensation product of 15 to 20 mols of ethylene oxide with 1 mol of N-octadecyldipropylenetriamine, quaternized with dimethyl sulfate.

33. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 15 to 20 equivalents of ethylene oxide with N-octadecyl diethylenetriamine quaternized with dimethyl sulfate.

14. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 20 mols of ethylene oxide and 2 mols of styrene oxide with N-octadecyl diethylenetriamine, per mol of the latter, quaternized with dimethyl sulfate.

15. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 15 to 20 mols of ethylene oxide and 1 mol of propylene oxide with 1 mol of N-octadecyl-diethylenetriamine, quaternized with dimethyl sulfate.

16. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 20 mols of ethylene oxide with 1 mol of N-octadecyldiethylenetriarnine, quaternized with dimethyl sulfate.

17. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 12 mols of ethylene oxide with 1 mol of N-oleyl-triethylenetetramine, quaternized with dimethyl sulfate.

18. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 15 mols of ethylene oxide with 1 mol of N-hexadecyltetraethylenepentamine, quaternized with dimethyl sulfate.

19. A dye liquor according to claim 4, wherein said polyamine dye assistant is the condensation product of 15 to 20 rnols of ethylene oxide with 1 mol of N-octadecyl-dipropylenetriarnine, quaternized with dimethyl sulfate.

References (Jited UNITED STATES PATENTS 2,769,684 11/1956 Geigy et al 884 X 2,891,835 6/1959 Matter et al. 855 2,967,755 1/1961 Keller 8-84 3,273,954 9/1966 Wachsmann et al. 884 X FOREIGN PATENTS 355,457 8/1961 Switzerland.

NORMAN G. TORCHIN, Primary Examiner. J. TRAVIS BROWN, Examiner.

T. J. HERBERT, Assistant Examiner.

Claims

1. A PROCESS FOR THE PRODUCTION OF LEVEL DYEINGS ON COPOLYMERIC ACRYLONITRILE FIBERS HAVING DYESITES CORRESPONDING TO A COLOR SATURATION VALUE ABOVE 2, COMPRISING DYEING THIS MATERIAL WITH AN ACID DYE LIQUOR WHICH CONTAINS AT LEAST ONE BASIC DYESTUFF AND, AS DYE ASSISTANT, A POLYAMINE THE MOLECULE OF WHICH CONSISTS OF A POLYALKENE POLYAMINE MOIETY HAVING FROM THREE TO FIVE QUATERNIZED BASIC NITROGEN ATOMS, A POLYGLYCOL ETHER CHAIN OF FROM 10 TO 50 ETHYLENEOXY GROUPS AND AT LEAST ONE LIPOPHILIC SUBSTITUENT, AND STEAMING AND RINSING THE RESULTING DYEING.