DE2641043B2 - Bulk dyeing of polyamides - Google Patents

Description

It has been found that the benzoxanthene and benzothioxanthene dyes known from DE-OS 24 47 024, page 3 ff of the following general formula (1) surprisingly excellent Have temperature stability and, above all, are stable in the reducing polyamide melt and retain their high fastness properties, making them advantageous for dyeing synthetic polyamides in bulk.

The present invention thus relates to methods for dyeing synthetic polyamides in the Mass, in which one has a dye of the formula (1)

B- (D),

- (W) ₁ .

(D

or

-CH ₂ -CH ₂ -CH-CH ₂ -

CH,

or a cyclohexylene radical or a radical of the formula

- NH—, —NH — SO ₂ -

used in the form of the free acid or in the form of the water-soluble salt, or the use of the dyes of the formula (1) in the form of the free acid or a water-soluble salt for dyeing of synthetic polyamides in bulk.

The individual formula elements of formula (1) have the following meaning:

X is an oxygen or sulfur atom,
Ri, R2, R3 and R ₄ are identical or different and each is a hydrogen atom, a halogen atom, of which in particular a chlorine or bromine atom, the hydroxy, the nitro, an alkyl group of 1 to 4 carbon atoms, of which preferably the Methyl or ethyl group, or an alkoxy group of 1 to 4 carbon atoms, of which the methoxy or ethoxy group is preferred,
B is an alkylene radical of 1 to 6 carbon atoms, such as

- CH ₂ -, —CH ₂ —CH _{2 --—}

-Q-CH ₂ -, --O - CH ₂ -CH ₂ -

25th

30 or a three-bonded nitrogen atom or a benzene or naphthalene nucleus or a benzyl radical, the aromatic nuclei of which can be substituted by 1 or 2 substituents from the group consisting of alkyl or alkoxy of 1 to 4 carbon atoms and chlorine and / or 1 or 2 alkylene radicals of Can contain 1 to 4 carbon atoms to which the radical W can be bonded,

D is a bivalent or trivalent benzene or naphthalene radical or a carboxylic acid ester, carboxamide or acyl radical of an aromatic carboxylic acid with one or two benzene rings or one aliphatic carboxylic acid with up to five carbon atoms, for example formic acid, acetic acid, Valeric acid or benzoic acid or naphthoic acid, or an aliphatic sulfonic acid amide radical with up to five carbon atoms or an aromatic sulfonic acid amide radical with one or two benzene rings, preferably of the benzene series, for example phenylsulphonic acid or p-toluenesulphonic acid, or a sulfonamido or carbonylamido radical, in particular a radical of the formula

-O - CO - R, --NH - CO - R,

-NH-SO ₂ -R, —N (alkyl) —SO ₂ -R,

-CO —NH-R ooer - CO-N (alkyl) - R,

- N (alkyl) —CO - R,
-SO ₂ -NH-R,

- SO ₂ N (AIlCyI) -R,

in which alkyl represents an alkyl radical from 1 to 4 C atoms, preferably for the methyl or ethyl group and R is a branched or straight-chain alkyl radical from 1 to 6, preferably from 2 to 4 Carbon atoms, or the phenyl radical, which by 1, 2 or 3 Siubstituenten from the group chlorine, methyl,

Ethyl, methoxy and ethoxy can be substituted, or an alkylenephenyl radical of the formula

-CH ₂ -CH

or

-CH ₂

W as a water-solubilizing residue that can be bonded to B or D is the sulfonic acid residue, the sulfato group (-OSO ₃ H), thiosulfate- (-SSO ₃ H), phosphato- (OPO ₃ H ₂ ), phosphonic acid ( -PO (OH) ₂ ) or phosphonic acid half-ester group -PO (ORsXOH), in which R5 is a lower alkyl or benzyl radical,
m is 1 or 2 and
π is O or 1.

In particular, those compounds of the formula (1) are particularly interesting and are preferred suitable for mass coloring of synthetic PoK amide, have the following formula residues:

Ri or R ₂ or R ₃ is a methyl or methoxy group, in the other case a hydrogen atom, and R4 is hydrogen, or R ;, R ₂ , R ₃ and R »are each a hydrogen atom,

X is an oxygen or sulfur atom,

the remainder of the formula

-iB- (D) J

together form an alkylene radical of 1 to 6 carbon atoms, preferably of two carbon atoms, or one Remainder of the formula

- alkylene — CO - N - alkylene—

Alkvi

where alkylene is an alkylene radical of 1 to 6 carbon atoms and alkyl is an alkyl radical of 1 to 4 carbon atoms, preferably the methyl or ethyl radical, means

W stands for the sulfonic acid group, for the sulfato, phosphato or thiosulfate radical, and
w is 1 or 2.

Particularly advantageous and preferred of these are those compounds of the formula (1) for which Ri, R ₂ , R ₃ , R ₄ and X and W have the meanings just mentioned, π is zero, m = 1 and B the meaning initially given for formula (1), in particular

However, 2ü re the meaning of a phenylene group or naphthylene group with one or two terminal ends Alkylene radicals of 1, 2 or 3 carbon atoms, preferably the radical of the formula

Alkylene -

-NH

-Alkylene - (- -f-

-Alkylene - (- - (J-alkylene

- alkylene - O - CO

-CH ₂

or

CH,

has, particularly preferably and advantageously, however, the meaning of an alkylene group of 1 to 6 carbon atoms, thereof preferably 1.2 or 3 carbon atoms

However, the dyes of the general formula (2) in the form of have proven to be particularly outstanding free acid or a water-soluble salt

CH ₃ O

in which B is a radical of the formula

-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -

or

CH ₂

and W is the thiosulfato or phosphato group, but especially the sulfo group or sulfato group is.

Water-soluble salts of the dyes of the formula (1) are preferably the alkali salts, in particular the Sodium and potassium salts, as well as the ammonium salts; they can also be advantageously in the form of Alkaline earth, such as calcium salts, and as salts of

aliphatic amines such as methylamine, ethylamine, cyclohexylamine, ethylenediamine, hexamethylenediamine or amino fatty acids.

In particular, spin dyeing is referred to as mass coloring Understood.

In accordance with the present invention, polyamide polymers of aliphatic hydrocarbons are used for bulk dyeing or lower alkylene benzenes, each having 1 or 2 amino and / or carboxylic acid groups contain, suitable, such as polyamides from ε-caprolactam, from 1,12-amino-undecanoic acid or from Adipic acid and hexamethylenediamine. These polyamides can also be modified in such a way that they are additionally contain free amino groups or free carboxy groups, furthermore in such a way that they carry free sulfonic acid groups (see the German Patent 16 94 164 and US-PS 33 28 341, 31 42 662, 30 39 990 and 31 84 436).

Bulk dyeing or spin dyeing is carried out in a known manner. This is how you go with the The present invention most advantageously assumes that you get polyamide granules or polyamide chips first with a dye of the formula (1) or a powdery or granular dye preparation of this The dye of the formula (1) is mixed (so-called "breading process") and this mixture is then heated and melts. The dye preparations used here contain the dye of the formula (1) or its water-soluble salt together with a commercially available salt suitable for this in a known manner thermoplastic carrier material, which is sufficiently compatible with the polyamide. Such thermoplastic Carrier materials are z. B. low molecular weight polyethylene, polypropylene, powdered polyamide or polyalkylene glycol; if necessary, a dispersant is added (cf. also DE-OS 23 41 000).

Furthermore, the mass dyeing according to the present invention can advantageously be carried out by first dyeing the surface of the polyamide chips in the usual manner in an aqueous dyebath using the exhaust process and this surface-colored polyamide mass being fed to the actual mass and spin dyeing by melting recommended for the spin-dyeing of polyamide-6, as polyamide-6 or 8 to 10% after the polymerization oligomers which are extracted in the production of fibers and filaments from the granules by washing several times with hot water, this includes washing process, a surface color of the Polyamide granules or chips are connected using the dyes of the formula (1) according to the invention. 1 to 1: In this exhaust process, the polyamide granules or -chipmaterial at a liquor ratio of about 1 is inked 4 at boiling temperature until sufficient bath exhaustion to increase the absorption rate and the Aufziehgrades dyeing advantageously in the weakly acidic to neutral medium, at at a pH from 3 to 7, in particular 4 to 6.5, preferably using acids and / or buffer substances such as weak or medium-strength organic acids or phosphoric acid, or fibficber buffer substances such as sodium acetate, ammonium acetate, mono- and di-sodium phosphate die in this dye bath The amount of dye used can vary within wide limits; it depends on the desired color depth. An average depth of color is obtained, for example, if a dyebath containing about 0.06% by weight of dye is used using a liquor ratio of about 1: 3. The coloring of the polyamide granulate or the polyamide chips can also take place above 100 ° C, for example at 130 ° C under pressure in a pressure dyeing vessel.

Dyeing processes of this type for mass and spin dyeing are known and are for example in the German Offenlegungsschrift No. 23 45 123 and 23 45 124, in German Auslegeschriften No.

ίο 17 94 122 and 19 03 235 as well as in the sample card no. P 44 I from Hoechst AG.

The thus prepared surface-stained polyamide granules or chips or after the above-mentioned "Panierverfahren" mixed with dye or dye preparation of polyamide granules are then added to a homogeneous melt at a temperature up to about 270 to 29o ⁰ C under homogeneous distribution of molecularly / disperse heated dissolving dye of the formula (1). The molten polyamide mass colored in this way can be processed further by customary methods, for example by injection molding or spinning. During further processing in the spinning process, the colored polyamide granulate or chip material can also be melted and spun directly in the spinning systems themselves, for example in grate spinning systems or in extrusion spinning systems.

Instead of "clear" polyamide material with no admixtures, you can also use Use titanium dioxide matted polyamide material.

The mass dyeings and dyed fiber materials produced in the manner according to the invention draw are characterized by a high level of brilliance and very good fastness to use and manufacture, such as, for example high and very good light, washing, acid, water, rubbing, ironing, alkali, alkaline and acidic Fastness to perspiration, chlorine bath water, peroxide bleach, dry cleaning, shampooing, thermosetting and solvent fastness. In addition, the very good color build-up and the extraordinary color strength are those according to the invention to mention the dyes used. Furthermore, they can be used with those suitable for mass coloring selected blue dyes in connection with the method according to the invention, highly brilliant green colorations achieve that have excellent coloristic properties.

The following examples serve to illustrate the invention.

example 1

In one with stirrer and heating and cooling device

The staining vessel provided is made of polyamide-6 granules at a liquor ratio of about 1: 2 with 0.2% by weight, based on the granules used Dye of the formula

CH ₃ O

in the form of its sodium salt and 0.5% by weight Ammonium acetate, based on the granules used, at 98 to 99 ° C within 90 to 120 minutes up to colored almost completely exhaustion of the dye liquor.

N-Cl-I ₂ -CII ₂ -SO ₃ H

10

The polyamide granulate is then rinsed warm and cold with water, dried and in the usual way spun on an extruder-type spinning machine; then the threads are drawn. You get such a spun-dyed thread with a greenish yellow shade, which has a high level of brilliance with very good Has fastness to use, of which in particular the light fastness, the perspiration fastness, the washing and peroxide bleaching fastness as well as the shampooing, solvent- and thermosetting fastnesses are to be emphasized. In addition, the dye in the Polyamide mass has excellent thermal stability.

Example 2

Instead of the dye used in Example 1, 0.3% by weight, based on the dye used Granules of the benzothioxanthene dye of the formula

by means of 1000 g of polyamide 6,6 granules with
finely ground dye of the formula

2 g one

t CH ₁ O

N-CH ₂ -CH ₂ -SO ₃ H

IO

mixed. The granulate coated in this way is then coated on the melt spinning plant by means of an extruder melted homogeneously and spun into threads. The spun-dyed threads thus obtained correspond the spin dyeings produced according to Example 1 in shade and fastness.

Examples 4-10

In a manner analogous to that described in one of the above Examples 1 to 3, mass or Spin dyeings also with the general formula (3) described in the table below achieve appropriate dyes.

25th

When used in the form of the sodium salt, one also obtains brilliant, yellow, spun-dyed threads Nuance with very good fastness properties as indicated in Example 1.

Example 3

In a roller barrel, small amounts of a wetting agent customary for mass coloring are added.

They also produce strong, highly brilliant colorations with a greenish yellow shade with good ones Maintain light and wet fastness properties.

Example R ₅

-A-

- W

- OCH, —H —H

- H - H - O 6th -OCH ₃ - H - H 7th -OCH ₃ - H - H 8th -OCH ₃ - H - H 9 -CH ₃ -CH ₃ - H 10 -CH ₃ - H - H Ϊ1 - H - H - H

-OCH ₃

-CH ₂ -CH ₂

-CH ₂ -CH ₂ - -CH ₂ -CH ₂ - -CH ₃ -CH ₂ -O-CO-VV

-CH ₂ -CH ₂ -CH ₂ - - CH ₂ - CH ₂ - -CH ₂ - CH ₂ - -CH ₂ - CH ₅ - -SO ₂ -CH, --CH, - -

OSO ₃ H

-SO ₃ H
-OPO (OH) ₂

-SO ₃ H

-SO ₃ H
-SO ₃ H
-SO ₃ H
-SO ₃ H

Claims (2)

Palent claims: 1. Use of dyes of the general formula (1) (W) _n (D with the following meaning :. X is an oxygen or sulfur atom, Ri, R ₂ , R3 and R ₄ are identical or different and each is a hydrogen atom, a halogen atom, of which in particular a chlorine or bromine atom, the hydroxy, the nitro, an alkyl group of 1 to 4 carbon atoms, of which preferably the methyl or ethyl group, or an alkoxy group of 1 to 4 carbon atoms, of which preferably the methoxy or Ethoxy group, B is an alkylene radical of 1 to 6 carbon atoms, in particular 10 15th 20th 25th -CH ₂ -, -CH ₂ -CH ₂ - -CH ₂ -CH ₂ -CH-CH ₂ -CH ₃ 30th 35 or a cyclohexylene radical or a radical of the form! - NH-, --NH-SO ₂ - - NH - 0-CH ₂ -, -0-CH ₂ -CH ₂ - or a trivalent nitrogen atom or a benzene or naphthalene nucleus or a benzyl radical, their aromatic nuclei by 1 or 2 substituents - from the group consisting of alkyl or alkoxy of 1 in each case up to 4 carbon atoms and chlorine can be substituted and / or 1 or 2 alkylene radicals of 1 to 4 May contain carbon atoms to which the remainder W may be bonded, D is a bivalent or trivalent benzene or naphthalene radical or a carboxylic acid ester, carboxamide or acyl radical of an aromatic carboxylic acid with one or two benzene rings or an aliphatic carboxylic acid with up to five carbon atoms, for example formic acid, Acetic acid, valeric acid or benzoic acid or naphthoic acid, or an aliphatic sulfonic acid amide radical with up to five carbon atoms or an aromatic sulfonic acid amide radical with one or two benzene rings, preferably of the benzene series, for example phenylsulfonic acid, or the p-toluenesulfonic acid, or a sulfonamido or Carbonylamido radical, in particular a radical of the formula -0 - CO - R,
-NH-SO ₂ -R,
-CO —NTH —R or - NH-CO —R, - N (alkyl) —SO ₂ -R, - CO- N (alkyl) - R, - N (alkyl) —CO-R,
-SO ₂ -NH-R, - SO ₂ N (alkyl) —R, in which alkyl for one, alkyl radical of 1 to 4 carbon atoms, preferably for the methyl or Ethyl group and R is a branched or straight-chain alkyl radical from 1 to 6, preferably of 2 to 4 carbon atoms, or the phenyl radical which is selected by 1, 2 or 3 substituents from the Group chlorine, methyl, ethyl, methoxy and ethoxy can be substituted, or an alkylenephenyl radical the formula -CH ₂ -CH -CH W as a water-solubilizing residue, which can be bonded to B or D, is the sulfonic acid residue, the sulfato group (-OSO ₃ H), fhiosulfato - (- SSO3H), phosphato- (-OPO ₃ H ₂ ), phosphonic acid (-PO (OH) ₂ ) or phosphonic acid half-ester group- pe -PO (OR ₅ XOH) ₁ we-in R _{5 is} a lower'- alkyl or benzyl radical , fnistl or 2 and π is 0 or 1, in the form of the free acid or in the form of water-soluble salts for dyeing synthetic polyamides in bulk. 2. Use of dyes of the general form! (1) (see claim 1) for spin dyeing of synthetic polyamides.