US3377129A - Process for the dyeing of polyethylene glycol terephthalate-type polyester fibers - Google Patents

Description

United States Patent ()fi ice 3,377,129 PRQCESS FOR THE DYEING F POLYETHYLENE GLYCUL TEREPHTHALATE-TYPE POLYESTER FlBERS Hans E. Wegmiiller and Werner Bossard, Riehen, Switzerland, assignors to .l'. R. Geigy A.G., Basel, Switzerland No Drawing. Original application Aug. 17, 1964, Ser. No. 390,232, now Patent No. 3,341,512, dated Sept. 12, 1967. Divided and this application Jan. 12, 1967, Ser No. 623,785 Claims priority, application Switzerland, Sept. 9, 1963, 11,094/63 5 Claims. (Cl. 8-41) ABSTRACT OF THE DISCLOSURE Polyethylene glycol terephthalate-type fibers and materials made therefrom are excellently dyed with a new group of dyestuffs which correspond to the formula Y1 3 oo-N\ o o- NOz wherein X is lower alkoxy or phenoxy, Y is H, lower alkyl, lower alkoxy, Cl, Br or N0 and R is lower alkyl or lower alkoxyalkyl.

The present application is a division of copending application, Ser. No. 390,232, filed August 17, 1964.

This invention relates to the dyeing of polyethylene glycol terephthalate type fibers with new, difiicultly watersoluble dyestuffs suitable for the dyeing of such fibers and of textile materials made therefrom, as well as to the aforesaid fibers and textile materials which have been dyed with the aid of these dyestuffs.

Dyeing as used in this specification and in the appended claims also comprises pad-dyeing and printing.

In the dyeing of polyethylene glycol terephthalate ty pe textile polyester fibers and fabrics made therefrom, it has been a special problem that dyeings with disperse dyes which are fast to light and sublimation, and at the same time satisfactorily reserve cellulose and natural polyamide fibers, especially cotton or wool, are difiicult to obtain, because those dyestuffs which promise to fulfill the above requirements, often do not draw sufiiciently on the aforesaid terephthalate type fibers, and/or lack depth of color; on the other hand, dyestuffs which draw satisfactorily on the last-mentioned fibers often lack some or all of the first-mentioned properties.

It is also known that non-sulfonated disperse dyes of the benzene-azo-barbituric acid series, especially when substituted at the benzene nucleus, e.g. by alkoxy or aryloxy radicals, and dyestuffs of the benzene-azothiobar-bituric acid series, especially those which are substituted at the benzene nucleus by a nitro group, are valuable dyes for hydrolyzed and also for unhydrolyzed cellulose acetate, cellulose propionate and others, as well as for mixed organic acid esters of cellulose.

Generally, the disperse dyes falling under the second of the above series, cannot be used for the dyeing of polyethylene glycol terephthalate fibers because they do not withstand the conditions of dyeing of the latter fibers, especially in the so-called high temperature dyeing process 3,377,129 Patented Apr. 9, 1968 which requires dyeing at temperatures above C. under excess pressure, while on the other hand the known disperse dyes of the first-menti0ned benzene-azo-bar-bituric acid series generally lack drawing power and/or depth of color in dyeings 0n polyethylene glycol terephthalate fibers to such an extent that they are not commercially useful for dyeing these fibers.

Polyethylene glycol terephthalate type polyester fibers as used in this specification and the appended claims, comprise such well known terephthalate and iso-phthalate fibers as Terylene, Kodel, Vycron and the like.

The term lower as used in this specification and in the appended claims in connection with alkyl or alkoxy means that these radicals have from 1 to 4 carbon atoms.

Other specific problems are created in the well-known high-temperature dyeing of polyethylene glycol terephthalate type fibers, namely, above 100 C. under pressures above atmospheric, especially when the use of swelling agents is to be dispensed with. Under these high temperature conditions many otherwise satisfactory disperse dyes fail to show satisfactory drawing power on the aforesaid fibers. In these cases, there is danger that the dyestuff particles in aqueous dispersions of such disperse dyes will agglomerate and excess of dyestutf which has not properly drawn on the fibers, will be deposited thereon and will thus detrimentally influence the fastness properties of the resulting dyeings on polyethylene glycol terephthalate fiber materials, especially fastness to crocking and to organic solvents.

We have now found that dyes of the formula wherein R represents lower alkyl or lower alkoxy-lower alkyl, X represents lower alkoxy, especially methoxy or ethoxy, or phenoxy, and Y represents hydrogen, lower alkyl, especially methyl or ethyl, lower alkoxy, especially methoxy or ethoxy, chlorine, bromine or nitlo, are distinguished as polyterephthalate fiber dyes because they possess excellent drawing power on these fibers equally in the carrier dyeing process, below 100 C. with the use of swelling agents as well as under the conditions of the high temperature processoutlined above. The dyeings obtained therewith possess very good fastness to light and to sublimation, to crocking and to organic solvents; they reserve cotton and Wool well; moreover in mixture with blue dyestuffs they yield dyeings of level green shades, an advantage which is lacking in many of the known disperse polyterephthalate fiber dyes.

These good dyeing properties of the dyestuffs of Formula IE on polyethylene glycol terephthalate type fibers are particularly unexpected, since the aforesaid dyestuffs are of no practical value as cellulose ester dyes, for they do not possess any practically useful drawing power on such fibers.

The compounds of Formula IB are produced by coupling the diazonium salt of an amine of the formula wherein X is as precedingly defined, with a coupling component of the formula (III) wherein Y and R are as precedingly defined, with malonic acid, advantageously in an inert organic solvent such as chloroform, in the presence of an agent which splits off water, e.g. in the presence of phosphorus oxychloride, or by reactionof the above N,N-disubstituted urea with cyanoacetic acid to form the corresponding cyanoacetyl urea, conversion of this in an alkaline medium to form the 4-aminouracil and saponification of the imino group to the x0 group, e.g. with boiling diluted hydrochloric acid.

The diazonium salt of an amine of Formula II is coupled with the coupling component of Formula III by the usual methods, preferably in a mineral acid to weakly acid aqueous medium, in particular at a pH of 4 to 4.5. If the coupling is made in a :mineral acid medium, the acid is advantageously buffered, e.g. with alkali metal salts of low fatty acids.

The dyestuffs according to the invention are brought into afinely dispersed form by millingwith dispersing agents. Suitable dispersing agents are, e.g. anionic dispersing agents such as alkylaryl sulfonates, condensation products of formaldehyde and naphthalene sulfonic acids, lignin sulfonates, or non-ionogenic dispersing agents .such as fatty alcohol polyglycol ethers. Advantageously mixtures of the anionic and non-ionogenic dispersing agents mentioned are used.

When so prepared, the dyestuffs according to the invention are suitable for the dyeing of polyethylene glycol terephthalate type fibers from an aqueous dispersion.

Polyglycol terephthalate fibers are dyed with aqueous dispersions of the dyestuffs according to the invention preferably at temperatures of over 100" C. under pressure above atmospheric,.preferably at 0.5 to 4 atmospheres excess pressure. Dyeing can also be performed, however, under ambient pressure at the boiling point of the dyebath in the presence of carriersv such as phenylphenol, polychlorobenzene compounds or similar auxiliaries, or pad dyeing can be performed on the foulard followed by thermo-fixing at 180-210 C.

On the fibers mentioned, the dyestuffs according to the invention produce greenish yellow, yellow and orange dyeings which have excellent fastness to washing, milling, sublimation, light, rubbing, perspiration, solvents, crossdyeing, decatizing, gas fading and industrial fumes. In addition, vegetable and animal fibers, particularly cotton or wool, are very well reserved by the dyestuffs according to the invention. Also, they can be evenly dyed with the usual commercial carriers. Good and evenly penetrated dyeings are obtained with these dyestuffs even on closely woven fabric or tightly twisted yarns.

The following non-limitative examples illustrate the invention. Where not expressly otherwise stated, parts and percentages are given by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is that of grams (g.) to milliliters (ml.).

Example 1 A fine suspension of 16.8 parts of 1-amino-2-nitromethoxybenzene in 500 parts of water, 60 parts of 36% hydrochloric acid and 5 parts of cetyl polyglycol ether is diazotised in the usual way at 05- by the addition of 6.9 parts of sodium nitrite. The diazonium salt solution is clarified and, at 0-5", is added to a solution of 21.8 parts of 1-phenyl-3-methyl.barbituric acid in 800 parts of water and 200 parts of acetic acid. The pH of the coupling bath is then raised to 4-4.5 by the addition of sodium acetate. On completion of the coupling, the yellow precipitate formed, the composition of which corresponds to the formula is filtered off, washed with a lot of water and dried in vacuo at 6070. After milling with the sodium salt of a condensation product of naphthalene-Z-sulfonic acid and formaldehyde, the dyestuff so obtained dyes polyglycol terephthalate fibers from an aqueous dispersion, optionally in the presence of a carrier such as the sodium salt of o-phenylphenol, in pure yellow shades. The dyeings have very good fastness to washing, rubbing, light and sublimation.

Dyestuffs which have similar properties are obtained if the diazo components given in Column 2 of the following Table I are coupled under the conditions described in the above example with the equimolecular amount of one of the coupling components given in Column 3.

barbituric aeid.

Example 8 2 parts of'the dyestuff prepared according to Example 1 are dispersed in 4000 parts of water. 20 parts of the sodium salt of o-phenylphenol as swelling agent as well as 20 parts of diammonium sulfate are added to this dispersion which is then used to dye 100 parts of polyethylene glycol terephthalate yarn for minutes at to 98. The dye liquor is almost completely exhausted. The dyeing is rinsed with water and then after-treated for 15 minutes at 80 with 12 parts of 30%-sodium hydroxide solution and 4 parts of octylphenyl polyglycol ether in 4000 parts of water. Finally the dyed material'is again thoroughly rinsed with water and dried.

In this manner, a yellow dyeing is obtained which is fast to washing, light and sublimation.

When, in the above example, the 20 parts of the sodium salt of o-phenylphenol are replaced by 20 parts of one of the following commercially available swelling agents, namely 20 parts of -o-phenylphenol emulsion, or

20 parts of p-chlorophenoxyethanol emulsion, or

20 parts of dichlorobenzene emulsion, or

20 parts of cresotic acid methyl ester emulsion, or by 20 parts of a 1:1 emulsion of terephthalic acid dimethyl ester and benzanilide,

while all other conditions are the same as in the above example, yellow dyeings of equal quality are obtained.

When, in the above example, the 100 parts of polyethylene glycol terephthalate yarn are replaced by 100 parts of polyethylene glycol isophthalate yarn or ,100 parts of polycyclohexanediol terephthalate fibers and dyeing is performed under the same conditions as before, yellow dyeings of equal quality are obtained.

Dyeings of similarly good quality are obtained when, in the above example, the 2 parts of the dyestufi" prepared according to Example 1 are replaced by 2 parts of the dyestuff prepared as described in Examples 2 to 7.

Example 9 A fine suspension of 16.8 parts of 1-amino-2-nitro-4- methoxy-benzene in 500 parts of water, 60 parts of 36%- hydrochloric acid and 5 parts of cetyl polyglycol ether is. diazotized in the usual Way at to by the addition of 6.9 parts of sodium nitrite. 1

Separately 25.3 parts of 1-(3-ch1orophenyl)-3-methylbarbit-uric acid are dissolved in 300 parts of water by the addition of 8 parts of sodium hydroxide. The alkaline 1-(3'-chlorophenyl)-3-methyl-barbituric acid solution is added dropwise at 0 to 5 to the prepared diazonium salt solution. Then the pH-value of the coupling bath is adjusted to 4 to 4.5 by the addition of sodium acetate. On completion of the coupling reaction, the yellow precipitate corresponding to the formula CO-N N02 CH3 is separated by filtration, washed with water and dried in vacuo at 70 to 80. 10 parts of the coupling product thus obtained are brought into fine water-dispersible form by milling them together with the sodium salt of a condensation product of naphthalene-Z-sulfonic acid formaldehyde and 10 parts of a lignin sulfonate. The aqueous dispersion of the dyestutf worked up in this manner is very stable and when used in particular for dyeing polyethylene glycol terephthalate slubbings, yarn and fabrics at 125 to 130 under pressure, it has no tendency to precipitate.

The 1-(3-chlorophenyl)-3-methylbarbituric acid used as coupling component in this example is prepared, for instance, by reacting N-(35-chlorophenyl)-N'-methyl-urea with cyanoacetic acid to form the corresponding cyanoacetyl urea, converting the cyano-acetyl urea with sodium hydroxide to form l-(3-chl0rophenyl)-3-methyl-4-aminouracil and then splitting oif the amino group in diluted boiling hydrochloric acid. Pure 1-(3'-chlorophenyl)-3- methyl-barbituric acid having a melting point of 162 to 163 is obtained from the crude product by crystallization from ethanol.

Dyestuffs of similar properties are obtained when the diazo components listed in Column 2 of the following Table II are reacted under the conditions described above with one of the coupling components mentioned in Col-- umn 3 and when the resulting coupling products are brought under the above-described conditions into fine water-dispersible form.

TABLE II Shade on poly- Ex. Dlazo component Coupling component ethylene-glycol N o. tereph th alatc fibers 10. 1 amin0-2-nitro-4 1-(2-1nethylphenyl)- Yellow.

methoxybenzene. SqniethyI-baIbituric 8C1 11 do 1-(3,4-dichlor0phenyl)- Do.

3-rnethyl-barbituric acid. 12 do 1-(4-brom0phenyl)-3- Do.

methoxypropyl-barbituric acid. 13 lo 1-(4-chl0ropheny1)-3- D0.

ethyl-barbituric acid. 14.- -do 1(3-rnethylpheny1)-3- D0.

n-propyl-barbituric acid. 15. e l-amin02-nitro-4- 1-(3-n1ethylphenyl) -3- Do.

ethoxy-beuzene. mettihyl-barbituric acl 16 .do 1-(3-nitrophenyl)-3- Do.

methyl-barbituric acid. 17 do 1-(2-methyl5-chloro- Do.

phenyD-dmethylbarbiturio acid. 18 do 1(2,4-din1ethyl- Do.

phenyD-tl-Inethylbarbituric acid. 19. 1. do 1-(2 methoxyphenyl)-3- Do.

methyl-barbituric acid. 20. 1-an1in0-2-nitro-4- 1-(z-n1ethylphenyl)-3- Do.

phenoxy-benzene. meghyl-barbituric aci 21 do 1(3-chlorophenyl)-3- Do.

methyl-barbituric acid.

Example 22 3 parts of the dyestuif prepared according to Example 20 are dispersed in 4000 parts of water. 2 0 parts of the sodium salt of o-phenylphenol as swelling agent as well as 20 parts of diammonium sulfate are added to the dispersion which is then used to dye for 90 minutes at 95 to 98, 100 parts of polyethylene glycol terephthalate yarn. The dyeing is rinsed and then aftertreated for 15 minutes at with 12 parts of 30%-sodium hydroxide solution and 4 parts of octyl phenyl polyglycol ether in 4000 parts of water. Subsequently, the dyed yarn is again thoroughly rinsed with water and dried. In this manner, a pure yellow dyeing is obtained which has a very good fastness to light When, in the above example, the 100 parts of polyethylene glycol terephthalate yarn are replaced by 200 parts of a blended fabric consisting of cotton and polyethylene glycol terephthalate (ratio 1:1), while the other conditions are maintained, the polyethylene glycol terephthalate threads are dyed in the same pure yellow as above while the cotton threads are very well reserved.

The dyestuffs descn'bed in the other examples have similar good qualities in reserving cotton when used to dye a blended cotton/polyethylene glycol terephthalate fabric.

' Example 23 3' parts of the dyestuif prepared according to Example 10 are dispersed in 4000 parts of water. 20 parts of the sodium salt of o-phenylphenol as swelling agent as well as 20 parts of diammonium phosphate are added to this dispersion which is then used to dye for minutes at to 9'8. 200 parts of a blended fabric consisting of 55% of wool and 45% of polyethylene glycol terephthalate. The dyeing is rinsed with Water and then aftertreated for 15 minutes at 60 with 4 parts of octylphenyl polyglycol ether in 4000 parts of water. Then the dyed fabric is again thoroughly rinsed with water and dried. Under these conditions, the polyethylene glycol terephthalate fibers of the blended fabric are dyed in a pure yellow shade 'while the woollen portion is well reserved.

The dyestuifs described in the other examples have similar good properties in reserving the woollen part when used for the dyeing of blended wool/polyethylene glycol terephthalate fabrics.

7 Example 24 0.5 part of the dyestulf obtained according to Example 9 are dispersed in 1000 parts of water in a pressure dyeing apparatus. 0.3 part of oleic acid N-methyltauride, 0.5 part of the sodium salt of a condensation product of naphthalene-Z-sulfonic acid and formaldehyde, 2 parts of diammonium sulfate as well as 0.1 part of 85%-formic acid are added to this dispersion.

parts of densely wound polyethylene glycol terephthalate yarn are introduced at 50, the closed bath is heated within minutes to 125 to 130 and is maintained at this temperature for another 45 minutes while the goods are being dyed under pressure. The dyebath is well exhausted. The dyeing is rinsed with water, soaped and dried. A yellow dyeing is obtained which has good fastness to washing, rubbing, perspiration, light, sublimation and solvents, and which is free from any visible dyestuif residue.

Similar good results are obtained when, in the above example, the 0.5 part of the dystuff prepared according to Example 9 is replaced by 0.5 part of the dyestuffs prepared according to the Examples 10 to 21 and dyeing is performed under the conditions described above on polyethylene glycol terephthalate, polycyclohexane diolterephthalate or polyethylene glycol isophthalate slubbings, yarn or fabric.

Example 25 Polyethylene glycol terephthalate fabric is printed on a printing machine at 25 with a liquor of the following composition:

parts of the dyestuff prepared according to Example 14 finely dispersed in 300 parts of water 40 parts of urea 400 parts of crystal gum thickener and 200 parts of a 10% aqueous p-phenylphenol emulsion The printed fabric is steamed for minutes at and then soaped, rinsed wth water and dried.

A yellow colored printing is obtained good fastness to washing, rubbing,light and sublimation.

A printing of similar good quality is obtained-when in the above example the 200 parts of 10% p-phenylphenol emulsion are replaced by 200 parts of water and. the.

Example 26 Polyethylene glycol terephthalate fabric is impregnated on a foulard at 40 with a bath of the following, composition:

20 parts of the dyestulf prepared according to 19, finely dispersed in- Example 7.5 parts of sodium alginate 20 parts of triethanolamine 20 parts of octylphenyl polyglycol ether and 900 parts of water.

The fabric is squeezed to about 100% moisture content, dried at 100 and then fixed for 30 seconds with air at a temperature of 210. Thedyed goodsare then rinsed with water, soaped and dried. Under theseconditions, a

which has very.

yellow dyeing is obtained which is fast to washing, rubhing, light, and sublimination.

We claim:

1. A process for the dyeing of polyethylene glycol terephthalate-type polyester fibers, comprising dyeing the aforesaid fibers with an aqueous dispersion of a dyestuff of the formula wherein X is lower alkoxy or phenoxy, Y is H, lower alkyl, lower alkoxy, Cl, Br or. N0 and R is lower alkyl or lower alkoxyalkyl.

2. A process according to claim 1, wherein the dyestuff is the dyestuff of the formula 3. A process according to claim 1, wherein the dyestuff is the dyestuff of the formula I CO- N02 4. A process according-to claim 1, wherein the dyestuff is thedyestuff of the formula CON I a 5. A process according to claim 1, wherein the dyestulf is the dyestuff of the formula NORMAN G. TORCHIN, Primary Examiner. T, J. HERBERT, JR., Assistant Examiner.