DE2641043C3 - Bulk dyeing of polyamides - Google Patents

Description

It has been found that the benzoxanthene and benzothioxanthene dyes of the general formula (1) below known from DE-OS 24 47 024, page 3 ff, surprisingly have excellent temperature stability and are especially stable in the reducing polyamide melt and their high fastness properties maintained so that they Lt advantageously suitable for the dyeing of synthetic polyamides in the mass.

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

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 components of the formula (1) have the following meanings:

X is an oxygen or sulfur atom,
Ri, R2, Rj and R4 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 I to 6 carbon atoms, such as

or

is -CH ₂ -CH ₂ -CH-CH ₂ -

CH ₃

or a cyclohexylene radical or a radical of the formula

- NH -. —NH - SO, -

-CH ₂

-C ^- H ₂ -CH ₂

- O —CH ₂ —CH ₁ -

or a trivalent nitrogen atom or a benzene

r> 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 1 to 4 carbon atoms f can hold on

-10 which the rest of W can be tied,

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 4-, 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 sulfonyl 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 hereof

-O-CO-R.
-NH-SO ₂ -U.
-CO -NH-R or

- N11 - C O - R.

--N (AIkyli-Si) - -R.

- NlAlkyD — CO - R.
-SO ₂ -NII-R.
- SO-Nl Alkvi) - R.

in which alkyl is an alkyl radical of I to 4 carbon atoms, preferably the methyl or ethyl group and R is a branched or straight-chain alkyl radical of I to 6, preferably 2 to 4 carbon atoms, or the phenyl radical which is replaced by I, 2 or 3 substituents from the group chlorine, methyl,

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

CH ₁ -CH ₁

or

-CH ₂ -I

W as a water-soluble residue that can be bonded to B or D is the sulfonic acid residue, the sulfato group (-OSO ₃ H), thiosulfato- (-SSO ₃ H), phosphato- (OPO ₃ H ₂ ), phosphonic acid (-PO (OH) ₂ ) or phosphonic acid half-ester group -PO (ORjXOH), in which R5 is a lower alkyl or binzyl radical,
measure 1 or 2 and
/ 7 is O or 1.

In particular, those compounds of the formula (1) are particularly interesting and are preferred suitable for bulk dyeing of synthetic polyamides, which 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 Ri, R ₂ , R ₃ and R ₄ are each a hydrogen atom,

X is an oxygen or sulfur atom,

the remainder of the formula

4B- (D) _n ]

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

NH

Alkvle.i -

-NH-

■ -NU-

-Alkylene — CO - N —alkylene -

Alkyl

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

W stands for the sulfonic acid group, for the sulfato, phosphato or thiosulfate radical, and
m 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 given at the beginning for formula (1), but in particular the meaning of a phenylene group or naphthylene group with one or two terminal alkylene radicals of 1, 2 or. Carbon atoms, preferably the radical of the formula

-CU,

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 "-orm" have proven to be particularly outstanding free acid or a water-soluble salt

CH ₁ O

- B - W

in which B is a radical of the formula

-CH ₂ -CH, -. - CH ₂ -CH ₂ -CH ₂ -

Alkvlen— \ - -H--

\ lMlen - ■ '-; * - Alkvlen

D (O

and W 'Jie thiosulfato or l'hosphato group, but in particular is the sulfo group or sulfato group.

Water-soluble salts of the dye: of the formula (1) are preferably the alkali salts, in particular those Sodium and potassium salts, as well as the ammonium salts; Furthermore, sit can be advantageous 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.

Bulk coloring is understood to mean, in particular, spin coloring.

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 made from f-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 are free Carry sulfonic acid groups (see German Patent 16 94 164 and US-PS 33 28 341. 31 42 662. 30 39 990 and 31 84 436).

r »:. w ί · Λ- \ ι -j: "c: fü_i ...: ι:"

L / IC 1 * 1 (1331.1 Ol L / Ull £ VJt.rt. UIt- .JJ / II11 Il Q I UUt Ig WMU III

carried out in a known manner. This is most advantageously believed to be the case in the present invention. that polyamide granules or polyamide chips are first mixed with a dye of the formula (1) or a powder or granular dye preparation of this dye of the formula (1) mixed (so-called "Breading process") and this mixture is then heated and melted. The dye preparations used for this contain the dye of the formula (1) or its water-soluble salt together with one commercially available thermoplastic carrier material suitable for this in a known manner, which is with tolerates polyamide sufficiently. Such thermoplastic carrier materials are, for. B. low molecular weight Polyethylene, polypropylene, powdered polyamide or polyalkylene glycol; if necessary, one uses Dispersants too (cf. also DE-OS 23 41 000).

Furthermore, the bulk coloring according to the present invention can advantageously be so be carried out that you first polyamide chips in a conventional manner in an aqueous dyebath after The exhaust process dyes the surface and this surface-colored polyamide mass of the actual Mass and spin dyeing supplied by melting. This dye-proof is especially for spin dyeing of polyamide-6 is recommended because polyamide-6 still contains 8 to 10% oligomers after polymerisation the production of fibers and threads from the granulate by washing it several times with hot water extracted contains. This washing process can result in surface coloring of the polyamide granulate or chips are connected using the dyes of the formula (I) according to the invention. at In this exhaust process, the polyamide granulate or chip material is made with a liquor ratio of approx 1: 1 to 1: 4 at cooking temperature up to sufficient Bath exhaustion colored. To increase the winding speed and the degree of absorption, it is advantageous to dye in a weakly acidic to neutral medium, see above at a pH of 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 more commonly Buffer substances such as sodium acetate, ammonium acetate. Mono- and di-sodium phosphate. The amount of dye used in this dyebath can be varied within wide limits fluctuate: it depends on the desired color depth. A medium color depth is obtained, for example, when using a liquor ratio of about 1: 3, about 0.06% by weight of dye containing dye bath used. - The coloring of the polyamide granulate or the polyamide chips can also take place above 100 ° C, so at 130 ° C below > Print 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.

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

The surface-colored polyamide granules or chips produced in this way or those according to the abovementioned "breading process" with dye or

r. Dye preparation of mixed polyamide granules are then added to a homogeneous melt at a temperature up to about 270 ° to 290 ⁰ C under a homogeneous distribution of molecularly / disperse u.- ~ i_- i?, .- u_ _"n rr _Aa. Anw c _nrmn i i \\ _αρ ι, λ ·, ι n; <"d IU ^ IIUI.11 I aiUJlutlt.J WW ■ wiiti" .i yt / ".fftiir.f. % - * % - ■ **

: <> colored, melted polyamide mass can after customary processes, for example by injection molding or spinning, are processed further. In the The colored polyamide granulate or chip material can also be processed in the spinning process

:> Spinning plants themselves, such as in grate spinning plants or in extrusion spinning systems, melted and spun directly.

Ans?, I! E of without admixtures "Clear" polyamide material can also be used with

i "Use titanium dioxide matted polyamide material.

Those produced in accordance with the invention Bulk dyeings and dyed fiber materials are characterized by a high level of brilliance and very good Usage and manufacturing fastness. as in-

r. 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. Next to it is the very good color structure

j "and the extraordinary color strength of the to mention the dyes used. Furthermore, they can be used with those suitable for mass coloring selected blue dyes in connection with the process according to the invention, highly brilliant green

j> achieve colors that are excellent in terms of color Have properties.

The following examples serve to illustrate the invention.

example 1

In one with stirrer and heating and cooling provision

The dyeing vessel provided is a polyamide-6 granulate with a rotting ratio of about 1: 2 with 02 % by weight, based on the granulate used, of the dye of the formula

CH ₃ O

V /

N-CH: -CH; -SO; H

A.
O

dyed in the form of its sodium salt as well as Op wt .-% of ammonium acetate, based on the granule, at 98 to 99 ^C C within 90 to 120 minutes to almost complete exhaustion of the dyebath

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-tanned thread with a greenish yellow shade, which has a high level of brilliance with very good Has the fastness to use, of which in particular the light fastness, the perspiration fastness, the washing and Perot. * Fastness to bleaching as well as the shampooing, solvent and thermosetting fastnesses are to be emphasized. In addition, the dye in the Polyamide compound has excellent thicimostability.

Example 2

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

N-CH-CH; -SO ₁ H

Example 3

In a roller barrel, small amounts of a normal netting used for mass coloring are added

by means of 1000 g of polyamide 6.6 granules with
finely ground dye of the formula

2 g one

CII ₁ O

K)

Nt Ih-C II, -SO, Il

mixed. An Rxtruder is then used on the Melt spinning plant the granulate coated in this way is melted homogeneously and spun into threads. The spun-dyed threads thus obtained correspond to the spun-dyed threads produced according to Example 1 in Nuance and authenticity.

Examples 4-10

ιϊΐ οΜαιΓ / gCr * «C! 5C,, ViC! ίΐ CimCm ^ uCr Οι ^ ΟΓϊ ^ ΟΓϊίϊΠΓι, ΟΓΊ

Examples 1 to 3 described, can be mass or Spin dyeings also with the general formula (3) described in the table below achieve appropriate dyes.

used in the form of the sodium salt, m Also spun-dyed threads in brilliant, yellow nuan.e with very good fastness properties of the in Example 1 given.

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

R :,

- W

4 -OCH _; - H - II -CH ₃ -C

- H [J - OCH. -CH ₃ - CH, - - OCH. - H - H -CIIr- CH; - - OCH - M - H CFI- '■ - X -OCH-. - H LI - CH, - CH _: -CH ■) -CH -CH ₃ - H -CH CH; - 10 -CH ₃ - H - H - CH; - CH ₂ - 11th - H - H - H -CH CH--

SO _: -CII; -Dl · - -OSOJI

- SO. H

-OPO (OH ,;

S · ■. - '_ ς for 11

- SO-.H

- SO.H

- SO ₃ H

Claims (1)

Patent claims: 1. Use of dyes of the general form! (I) IO with the following meaning :. X is an oxygen or sulfur atom, Ri, R ₂ , R3 and R4 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 from 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, in particular JO -CH ₂ -. -CH ₂ -CH, - -CH ₂ -CH ₂ -CH-CH: - CH ₃ - O-CO-R. -NH-CO -R. -NH-SO ₂ -R. —N (alkyl) —SO ₂ - - CO —Nil —R or - CO-N (AIkVl) - in which alkyl for an 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 ClI, -t -CU, - W as a water-solubilizing residue attached to B or D may be bonded is the sulfonic acid residue. or a cyclohexylene radical or a radical of the formula - HH-, -NH-SO ₂ - -NH -NH - O - CH ₂ -, --O - CH ₂ --CH ₂ - or a trivalent 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 alkyl or alkoxy group of 1 to 4 carbon atoms and chlorine and / or 1 or 2 alkylene radicals of 1 can contain up 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 lengths 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 benzenes, preferably of the benzene series, for example phenylsulphonic acid or the p-toluenesulfonic acid, or a sulfonamido or Carbonylamido radical, in particular a radical of the formula -N (AIkVl) -CO-R.
R. -SO ₂ -NH-R.
■ R. —SO ₂ N (, \ ikyl) —R. is by 1, 2 or 3 Si 'substituents from the Group chlorine, methyl, ethyl, methoxy and ethoxy can be substituted, or an alkylenephenyl radical the formula the sulfato group (-OSO ₁ H), thiosulfato - (- SSO ₃ H), phosphato (-OPO ₃ H ₂ ), phosphonic acid (-PO (OH) /) or phosphonic acid half-ester group- pe -PO (OR ₅ XOH), where Rs is a lower alkyl or benzyl radical, ro is 1 or 2 and π is O or I, in the form of the free acid or in the form of the water-soluble salts for dyeing synthetic Polyamides in bulk, 2, Use of dyes of the general formula (1) (see claim 1) for spin dyeing synthetic polyamides.