DE1213989B - Process for coloring polyamides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08g

German class: 39 b-22/04

Number:
File number:
Registration date:
Display day:

1213 989
J25837IVc / 39b
May 14, 1964
April 7, 1966

The invention relates to a dyeing process of synthetic, linear polyamides, such as. B. Polyhexamethylene adipamide or polycaprolactam.

It is known that synthetic linear polyamides can be colored in the mass by using any process step prior to final spinning or processing into solid objects incorporates a colorant which is sufficiently stable to be exposed to the action of the molten synthetic Polyamide can withstand. Because of the strongly reducing effect of melted synthetic, linear polyamides, only some organic colorants are satisfactory for bulk coloring thereof. The most notable organic colorants generally used for this purpose are the pigments of the copper phthalocyanine series.

The invention now relates to a method for dyeing synthetic, linear polyamides with Chromium complexes of a monoazo dye of the formula

A-N = N-E

wherein A is a mono- or bicyclic aryl radical, which has a hydroxyl group in the o-position to the azo bond, and E is the remainder of a coupling component represents which in a keto group adjacent to a hydroxyl, amino or enolizable Coupling position, with both A and E at will in addition to those in the o-position for Azo bond, may have other substituents, provided that the molecule does not contain a sulfonic acid, Has carboxylic acid or sulfonamide groups, which is characterized in that these dyes for Bulk coloring can be used. The use of similar dyes for dyeing wool or Polyamides from aqueous liquor are known.

The chromium complexes used in the process according to the invention can be 1,1 complexes, but they are preferably 1,2-complexes, i. i.e. that there is a chromium atom in complex bond with 2 molecules of monoazo dyes, the Monoazo dye molecules can be the same or different.

Examples of mono- or bicyclic aryl radicals that can be represented by A are 2-hydroxyphenyl- or l-hydroxy-2-naphthyl radicals, especially 2-hydroxyphenyl radicals, which can also carry one or more chlorine atoms and / or nitro groups as additional substituents, such as. B. 4- or 5-chloro-2-hydroxyphenyl, 4- or 5-nitro-2-hydroxyphenyl, 4,5-dichloro-2-hydroxyphenyl, 3,5,6-trichloro-2-hy method for dyeing polyamides

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

Munich 5, Müllerstr. 31

Named as inventor:

Alistair Howard Berrie,

Geoffrey Lionel Collier,

Albert Charles Cooper, Blackley, Manchester

(Great Britain)

Claimed priority:
Great Britain May 15, 1963 (19 334),
dated April 23, 1964

hydroxyphenyl, 4-nitro-5-chloro-2-hydroxyphenyl or 5-methoxy-2-hydroxyphenyl radicals.

Examples of coupling components whose radicals are represented by the symbol E in the above formula can be, are in the o-position coupling amines, such as

z. B. 2-naphthylamine, m-phenylenediamine or 1-phenyl-3-methyl-5-aminopyrazole, in particular phenols coupling in the o-position, such as. B. p-cresol, p-chlorophenol, 2-hydroxy-5,6,7,8-tetrahydronaphthalene or 4-acetylaminophenol, naphthols, such as. B. 2-naphthol, 1-acetylammo-7-naphthol, 1-acetylamino-4-naphthol or 6-bromo-2-naphthol, 5-pyrazolones, such as. B. l-phenyl-3-methyl-5-pyrazolone, l- (o-toluyl) - -methyl-5-pyrazolone, 1-phenyl-3-etnoxycarbQnyl-5-pyrazolone or l-phenyl-3- (N-phenylcarbamoyl) -5-pyrazolone, or acetoacetarylamides, such as. B. acetoacet-o-toluidine.

Of particular interest in the process according to the invention are the 1,2-chromium complexes of Dyes with the formula

OH

N = N-B

wherein Y is a hydrogen atom, halogen (especially chlorine atoms) or a nitro or methoxy group,

609 557/356

3 4

«Is 1, 2 or 3 and B means the following, namely to apply linear polyamide, on which one. then

either the colored schnitzel melts and strings

(1) spinning a naphthyl radical with a hydroxyl group into it or making solid objects from it. o-position to the azo group, optionally after loading Optionally, the Rommein with a Disperlieben further substituted, in particular by ^{5 sion of the} colorant in a volatile solution, a methoxycarbonyl group, acetamide group or hydro medium such. B. water or. Alcohol, or with a xyl group, or by grinding the dye with water and

(2) a l-ArVw-methylpyrazole-S-one ^ -yl radical, where ^ei f ™ finely divided synthetic linear polyamide of the aryl radical is from the benzene series and obtained stable dispersion are carried out.

is especially a phenyl or p-toluyl radical, ¹⁰ ^} ^ Z ^^ T®? - ^ "\ ^d T ^bnt i ^st J ^en . ^Patent -

_{the document} 839 712 described. Other preparations,

, ". /, Tr ^. ο / XT ι ι -j \ οι in the said dye before use

(3) a 2-keto-3- (N-arylcarbonamid) -prop-3-yl ^ incorporated rest _the method according to the invention, the worm aryl radical from the benzene series _{werdeQ kmn> are britisclieri} Patent originates

originates. _ig S _{47959 and in the} British patent application

The complexes described in the 4534/61 of the invention.

Processes preferably used are those produced by the process according to the invention

1,2-chromium complexes of dyes of the formula. Dyes have excellent fastness to

_n __ light, rubbing, dry cleaning and the ordinary

ao textile washing treatments.

Since the in the method according to the invention

-N = N - D applied colorants in molten polyamides

are soluble, dispersion throughout the mass is not a problem, and during subsequent

where X is chlorine atoms or a nitro group, 25 spinning processes are no difficulties related

ml, 2 or 3 and D encountered an 1-aryl-3-methylpyrazole-Hch blockage of the spinneret plate *

5-on-4-yl-rest (in which the aryl radical from the benzene- Despite their solubility, the colorants migrate

series originates) or means a naphthyl radical, which, however, does not occur during the pleating of textile fabrics

in o-position to the azo radical a hydroxyl group on the surface, so that the colors in the pleated,

having. 30 textile fabrics show excellent authenticity

Particular examples of chromium complexes that exhibit when rubbing.

The invention is illustrated by the following examples

the 1,2-chromium complexes of 1-phenyl- are illustrated. All parts are given in parts by weight

3-methyl-4- (5'-chloro-2'-hydroxyphenylazo) -5-pyra- depresses.

zolone, i- (5'-chloro-2'-hydroxyphenylazo) -2-naphthol, 35 Examples
l-phenyl-3-methyl-4- (4'-nitro-2'-hydroxyphenylazo) -

5-pyrazolone, 1- (4'-nitro-2'-hydroxyphenylazo) - 1 part of the 1,2-chromium complex of 4- (5-chloro-

2 - naphthol, 1 - (5 '- nitro - 2' - hydroxy - phenylazo) - 2-hydroxyphenylazo) -l-phenyl-3-methyl-5-pyrazolone

2-naphthol, l- (5'-nitro-2'-hydroxyphenylazo) -2-naph- (in the form of the free acid) is dissolved in acetone,

thylamine, l- (3 ', 5', 6'-trichloro-2'-hydroxyphenylazo) - 4 ° and the solution is made with 98 parts of small polyhexa-

Tumbled 2-naphthol, 1- (5'-methoxy-2'-hydroxyphenylazo) methylenediapamide chips. The acetone

2-naphthol, l- (3 ', 5'-Dinitro-2'-hydroxyphenylazo) - is allowed to evaporate in warm air, and the

2-naphthol, l- (4'-chloro-2'-hydroxyphenylazo) -2-naph- chips become evenly with the chromium complex

thol, l- (5'-chloro-2'-hydroxyphenylazo) -2-naphthyl- covered. The schnitzels are made in a conventional

amine, l-phenyl-3-metiiyl-4- (3 ', 5', 6'-trichloro-2'-hy- 45 apparatus melted and spun, with threads

droxyphenylazo) -5-pyrazolone, 1-phenyl-3-methyl- with a very attractive red hue

4 - (5 '- nitro - 2' - hydroxyphenylazo) - 5 - pyrazolon, which has an excellent fastness

1 - Acetylamino - 8 - (5 '- chloro - 2' - hydroxyphenylazo) - washing, rubbing and dry cleaning treatments

7-naphthol, l-acetylamino-8- (5'-chloro-2'-hydroxy- as well as to light,

phenylazo) - 4 - naphthol, 1 - (Γ - hydroxynaphthol- 50 In this example, instead of acetone

2'-ylazo) -2-naphthol or 6-bromo-1- (5'-chloro-2'-hy-alcohol can be used.

droxyphenylazo) -2-naphthol, the mixed 1,2-chromium- The 1,2-chromium complex of 4- (5-chloro-

complexvonl-Phenyl-S-methyM - ^ - chloro ^ -hydroxy- 2-hydroxyphenylazo) -l- (4'-methylphenyl) -3-methyl-

phenylazo) -5-pyrazolone or l- (5'-chloro-2'-hydroxy-5-pyrazolone or its sodium, potassium or

phenylazo) -2-naphthol, or the 1,1-chromium complexes 55 ammonium salt are used,

of l-phenyl-3-methyl-4- (4'-nitro-2'-hydroxyphenyl-..

azo) -5-pyrazolone, 1-phenyl-3-methyl-4- (5'-chlorine- Example 2

2'-hydroxyphenylazo) - 5 - pyrazolone, 1- (5'-chlorine- 1 part of the chromium used in Example 1

2'-hydroxyphenylazo) -2-naphthol or 1- (5'-nitro complex is in the form of an aqueous slurry with

2'-hydroxyphenylazo) -2-naphthol. 60 1 part polyhexamethylene adipamide in the form of a

The aforesaid coloring agent can be mixed by each of the finely divided aqueous paste and the obtained one

in the mass dyeing process known in the syn mixture is mixed with 200 parts of polyhexamethylene adip-

Thetic, linear polyamides are incorporated, amide chips are tumbled. The coated schnitzel

for example by incorporation into the monomers are dried and in a conventional

or prepolymers melted and spun during the polymerization or 65 apparatus, leaving fibers

obtained by pressing into the melt during one with an attractive red shade,

Spinning process. It is advisable to use the dye which has an excellent fastness compared to normal

by rummy on shredded des, synthetic, textile treatments and facing light.

Also, instead of simply mixing the polyhexamethylene adipamide paste with the pulp of the 1,2-chromium complex the two components are ground in a ball mill, making a preparation as described in British Patent 839,712 and as used above will.

Furthermore, the 1,2-chromium complex can be in the form a preparation as above obtained by mixing it with polyhexamethylene adipamide and sufficient formic acid has been obtained with a shearable mass by use of a Baker-Perkins mixer. This method is described in British patent application 4534/61 described.

Example 3

1 part of the 1,2-chromium complex used in Example 1 is in the form of a dry powder mixed with 100 parts of a polyhexamethylene adipamide just made, in the autoclave, which was used for the polymerization. The colored polymer is pressed out in the form of a tape and cooled, cut into cutlets and then melted in a conventional apparatus and spun, with threads with a deep red hue and excellent general fastness can be obtained.

Example 4

Instead of the 1,2-chromium complex used in Examples 1 to 3, the 1,2-chromium complex is used used by l- (5-chloro-2-hydroxyphenylazo) -2-naphthol. The threads obtained are strong Reddish navy blue shade with excellent fastness to washing, rubbing, dry cleaning and light.

Example 5

Instead of the 1,2-chromium complex used in Examples 1 to 3, the 1,2-chromium complex is used ίο of 4 - (4 - nitro - 2 - hydroxyphenylazo) -1 - phenyl-3-methyl-5-pyrazolone used. The threads obtained have a strong bluish-red hue excellent fastness to washing, rubbing, dry cleaning and light.

Example 6

Instead of the 1,2-chromium complex used in Examples 1 to 3, the chromium complex of 4 - (5 - chloro - 2 - hydroxyphenylazo) - 1 - phenyl-3-methyl-5-pyrazolone (as sodium salt) is used.

The threads produced have a deep red color and excellent general fastness properties.

Instead of the sodium complex used in this example, the potassium or ammonium complexes can be used can also be used.

In the following table, column 3 shows the color shades produced by the complexes in column 2 instead of the complex used in Examples 1 to 3. Own all colors excellent fastness to light, rubbing, dry cleaning and washing.

example 1,2-chromium complex Metal complex hue 7th 1,2-chromium complex of 8- (2'-hydroxy-5'-chlorophenylazo) -l-acetylamino-7-naphthol blue 8th 1,2-chromium complex of 1- (2'-hydroxy-5'-chlorophenylazo) -6-bromo-2-naphthol purple 9 1,2-chromium complex of 3- (2'-hydroxy-5'-chlorophenylazo) -l-acetylamino-4-naphthol Dark blue 10 1,2-chromium complex of 2- (2'-hydroxy-5'-chlorophenylazo) -1,5-naphthylenediol blue 11 1,2-chromium complex of α-acetyl - «- (2'-hydroxy-5'-chlorophenylazo) -acetanilide orange 12th 1,2-chromium complex
thoat
1,2-chromium complex of 1- (2'-hydroxy-5'-chlorophenylazo) -2-naphthylamine dull purple 13th
14th 1,2-chromium complex
5-pyrazolone
1,2-chromium complex of methyl-l- (2'-hydroxy-5'-chlorophenylazo) -2-hydroxy-3-naph-
of 1- (2'-hydroxy-3 ', 5', 6'-trichlorophenylazo) -2-naphthol violet
purple 15th
16 1,2-chromium complex
azolone
1,2-chromium complex of l-phenyl-3-methyl-4- (2'-hydroxy-3 ', 5', 6'-trichlorophenylazo) -
of 1- (2'-hydroxy-5'-nitrophenylazo) -2-naphthol Reddish orange
black 17th
18th 1,2-chromium complex of l-phenyl-3-methyl-4- (2'-hydroxy-5'-nitrophenylazo) -5-pyr-
of 1- (2'-hydroxy-5'-nitrophenylazo) -2-naphthylamine Red
dull brown 19th 1,2-chromium complex of 1- (2'-hydroxy-4'-nitrophenylazo) -2-naphthol marine 20th 1,2-chromium complex of 1- (2'-hydroxy-5'-methoxyphenylazo) -2-naphthol blue 21 1,2-chromium complex of 1- (2'-hydroxy-3 ', 5'-dinitrophenylazo) -2-naphthol black 22nd 1,2-chromium complex of 1- (2'-hydroxy-4'-chlorophenylazo) -2-naphthol violet 23 1,1-chromium complex
azolone
1,1-chromium complex of l- (2'-hydroxynaphth-l'-ylazo) -2-naphthol Dark blue 24
25th 1,1-chromium complex of l-phenyl-3-methyl-4- (2'-hydroxy-5'-chlorophenylazo) -5-pyr-
of 1- (2'-hydroxy-5'-chlorophenylazo) -2-naphthol Scarlet fever
violet 26th 1,1-chromium complex
azolone of 1- (2'-hydroxy-5'-nitrophenylazo) -2-naphthol marine 27 of l-phenyl-3-methyl-4- (2'-hydroxy-4'-nitrophenylazo) -5-pyr- Red

Claims (2)

Patent claims: 1. Process for dyeing synthetic, linear polyamides with chromium complexes a Monoazo dye of the formula A-N = N-E wherein A is a mono- or bicyclic aryl radical which is in the o-position to the azo bond Has hydroxyl group, and E represents the remainder of a coupling component which is in a to a position adjacent to a hydroxyl, amino or enolizable keto group, wherein both A and E after removal in addition to those in the o-position to the azo bond, may have other substituents provided that the molecule does not contain sulfonic acids Has carboxylic acid or sulfonamide groups, characterized in that these Dyes can be used for mass coloring. 2. The method according to claim 1, characterized in that that these dyes are used for the mass coloring of monomers or prepolymers of polyamides. Considered publications:
German Auslegeschrift No. 1045 363;
Austrian patent specification No. 190 486. 609 557/356 3.66 © Bundesdruckerei Berlin