DE2312260A1 - PROCESS FOR MANUFACTURING GRANULATES IMPRAEGNATED WITH COLORS OR ADDITIVES FROM LINEAR POLYAMIDES OR POLYESTERS - Google Patents

Description

CiBA-GElGY AG, CH-4002 Basel

Dr. F. Zumstein »en. - Dr. E. Arsmann

R.Kocii: ^ -: l? Ircsr - Dip !. r'Y: yc. u. hjhc

Dr. F. 2'JMCi-; in 'ju'n.

Patent attorneys

8 monks 2, Brcuhdusitroßa 4 / III

Case 3-8066-68 / +
Germany

Process for the production of granules from linear polyamides or impregnated with dyes or additives Polyesters

A method often described in the patent literature for bulk coloring linear polyamides and polyesters is the so-called powdering or breading process. It consists in getting granules of the plastics mentioned dusted with a dye or pigment powder

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(breaded) and the breaded granules transferred into a melt and the melt into structures such as fibers, Foils or tapes deformed. However, this method is associated with major disadvantages, especially when it is used in Large technical scale is carried out, where the granules are pneumatically conveyed, with a large Part of the dye is blown off, which not only causes high losses of dye, but also rapid clogging the filter results. In order to remedy this disadvantage, attempts have also been made to bind the dye by means of a binder to fix to the granules, however, a foreign substance gets into the polyamides or polyester, which is on the mechanical properties of the dyed material, especially when it comes to fibers, unfavorable can affect.

It has now been found that non-dusting granules made of linear polyamides or polyesters and impregnated with powdered dyes or additives are obtained in a simple manner if the granules are ■ at temperatures between 30-20O ⁰ C with dyes or additives ^{above 100 0} C melt intimately mixed in a high-speed rotating mixer until dyes or additives are fixed or dissolved on the granules and the mixture is allowed to cool if necessary.

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Linear polyamides which are suitable for the present process are the polyamides made from ^ -caprolactam (PA 6), from undecanolactam (PA 11) from hexamethylenediamine and adipic acid (PA 6,6) or from hexamethylenediamine and Called sebacic acid (PA 6,10). The linear polyesters used are preferably polyalkylene terephthalates, such as they are obtained by polycondensation of terephthalic acid or its ester, containing an alkylene glycol 2-10 C atoms, but especially polyethylene terephthalate.

Granules are understood as meaning polymer particles which are produced by cutting, breaking or similar comminution methods of extruded or calendered polyamides or polyesters.

There is a comparatively wide range of options available for the selection of the dyes. There are both substrate-soluble as well as pigments that are insoluble in the substrate, as long as they can be distributed finely enough »As pigments Both inorganic and organic come into consideration, for example cadmium sulfides, iron and Chromium oxides, ultramarines, cobalt pigments, carbon black, titanium dioxide, phtaloeyanines, quinacrodones, 2,4-di- (2'-hydroxynaphtyl) -6-pyrenyl-1,3,5-triazine, as well as individual vat dyes,

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such as perylenetetracarboxylic acid diimides or anthrimide carbazoles. Examples of substrate-soluble dyes are certain metal complexes of azo dyes, in particular 1: 2 chromium complexes of water-insoluble monoazo dyes and also disperse dyes of the azo or, in particular, the anthraquinones, such as alkyl and cycloalkyl baths Arylaminoanthraquinones, Phenylmercaptoanthraquinones or Anthraquinone Acridones.

It is expedient to use about 0.1-5 parts of dyestuff to 100 parts of granules.

Instead of pure dyes, preparations can be used, i.e. compounds of medium or higher molecular weight, which withstand the processing temperatures of polyamides and polyesters and the dye in finer Distribution contain, for example abietic acid esters, alkaline earth salts of higher fatty acids, e.g. magnesium behenate, Vinyl chloride-vinyl acetate copolymer or polyterpene resins. These preparations contain expedient about 30-60% dye.

Examples of additives are optical brighteners, both substrate-soluble and substrate-insoluble Called stabilizers.

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Mixtures of different dyes or mixtures of dyes with additives can also be used.

Various high-intensity mixers can be used to mix the granules with the dyes or additives, or a mixing device with a rotating shaft that has transversely arranged blades or other mixing elements. Examples of a suitable mixing device are the mixers marketed by the company Papenmeier, Detmold under the name Papenmeier mixer and the mixers marketed by the company Rheinstahl Maschinenbau, Kassel, under the name Henschel fluid mixer. The best speed range is between 300-3000 revolutions per minute, which, depending on the device, corresponds to peripheral speeds of 4-35 m / sec. It is advisable to start the mixing process at the lower limit of the speed range, i.e. at about 300 revolutions per minute, and increase the speed over a period of about 30 seconds / min. further to the final value, which is between 1800 and 2600 revolutions per minute. These high speeds are maintained for the greater part of the time required for coloring. It is assumed that when the granules hit the mixer blade, the local temperature is so high that plastic

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fication of the surface occurs, creating a good fixation or solution of the dye particles is made possible.

Depending on the type of dye or additive used and the intensity of the mixture, the duration of the mixing can be approximately 1/2 minute to 60 minutes, preferably 3-20 minutes, until the dye has fixed.

The granules obtained are characterized by good quality Abrasion resistance. They can be made into fibers, films or tapes or into injection-molded articles in the usual way be deformed. Uniform colorations are obtained.

The granules obtained according to the invention have the advantage over the granules colored by the normal dry mixing method (dry tumbling) that the adhesion of the color body particles is much greater and that losses during transport (eg pneumatic transport) can be avoided. This means a substantial improvement in the utilization of the substance.

Furthermore, the granules obtained according to the invention have the advantage that the mass-colored structures obtained therewith, for example threads, with the same amount of dye , have one

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better dispersion of the dye and thus connectedness _χ have the greater color strength. In the case of polymer-soluble products, an improvement in solubility can be determined, ie with the same grain size of the starting product, the same dissolving time and temperature, the proportion of undissolved particles in the products made from granulate that was colored according to the invention is smaller than, for example in the case of mass-dyed threads produced from granules dyed by the dry tumbling method.

example 1

A commercially available linear polyester (polyethyleneterephthalate) in granulate form (rectangular cross-section approx. 4 mm 5 mm 2 mm) is introduced into an intensive mixer (Papenraeier system) whose jacket is heated (steam r * s 1.5 atti) for 3 minutes _# einge- was on. 1% phenylenetetracarboxylic acid di (p-methoxyphenylimide) is then added to the granulate (7 kg), the mixer is closed and the mixing process is started. This is done as follows: 2 minutes of mixing at 600 rpm, then 2 minutes at 1200 rpm, then 1800 rpm until there is no dust inside the mixer.

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-ο-

education is more evident. The time required to fix the pigment on the granulate is 12 minutes, the initial temperature 30 ° C and the final fixing temperature 124 ° C. After the end of the fusing process, the heating of the mixer is switched off and the cooling switched on (water). The coated granulate is then stirred at 600 rpm with ongoing cooling until its temperature falls below the limit of 50 ^° C., duration 18 minutes.

The end product of this mixing operation is a granulate coated with the pigment used, in which the Pigment is fixed in the surface, so that abrasion can only be achieved with the use of greater forces.

These pigment-coated granules can be used without difficulty e.g. used for the production of mass-dyed continuous yarn, e.g. the pigment distribution of the threads spun on an Inventa melt spinning line is better than the threads whose starting granulate is made after the so-called "dry tumbling" or "powder process" has been colored.

The textile properties of the threads mentioned above show normal values. This shows that neither the polymer nor the color body is damaged during the mixing process

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Example 2

The procedure according to example 1 is repeated. Deviating from this, the operation of the mixer is changed as follows: After filling in the granulate, the heating of the mixer (jacket heating, steam 1.5 atli) is switched on and the granulate is heated until it reaches a temperature of 80 + 5 ° C. During this heating process, the granules are stirred at 600 rpm for 10 seconds at intervals of 50 seconds each. After reaching the temperature of 80 ⁰ C, after about 15-20 minutes (the time depends on deir granular form (bulk density) ab)., The mixing process is analogous to Example 1 was carried out, as is the KUhlvorgang. The process data are achieved during the mixing process mixing time (= fixing time) 11 Minutes, KUhlzeit 18 Minutes, initial temperature of 80 ⁰ C, Fixierendtemperatur 186 ° C.

As far as the properties of the granules colored by this method are concerned, as well as those made from them mass-colored threads, the findings of example 1 apply.

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The procedure according to example 2 is repeated. Different of these, hexadecachloro copper phthalocyanine is used as the pigment. The data obtained during the procedure are: mixing time (= fixing time) 8 minutes, cooling time 19 minutes

V-

grooves, initial temperature 80 ° C, final fixing temperature 168 ° C. .-

With regard to the granulate, processing and For thread properties, the findings of Example 1 apply.

Example 4

The procedure according to example 1 is repeated. In contrast to the example, 2,6-BI- (2'-hydroxynaphthyl) -4-pyrenyl-1,3,5-triazine, which is soluble in the polyester, is used instead of a pigment. The process data obtained are: mixing time (= fixing time) for 15 minutes, KUhlzeit 11 Minutes, beginning tempera door 30 ⁰ C, Fixierendtemperatur 135 ° C.

In addition to the fixation of color particles described in Example 1, the granulate shows a partial dissolution of the applied dye in the outer layers of the granulate grains. In the manufactured from this granulate

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- '11 -

For th mass-dyed polyester threads, the dye is useful solved. Otherwise, the statements made in Example 1 apply.

Example 5

The procedure according to example 4 is repeated. In deviation, however, instead of the mixing process according to example 1, the mixing process according to example 2 is used. Process data: mixing time (= fixing time) 8 minutes, cooling time 19 minutes, initial temperature 80 ⁰ C, ^{final fixing temperature 149 0} C.

For the granulate, processing and thread properties what was said in example 3 applies.

Example 6

The procedure according to Example 5 was repeated. Deviating from this, 2.5% (= 175 g) of that in polyester are largely soluble vat dye obtainable by melting sulfur of aminomethylbenzanthrone for coating of the granulate is used. Process data: mixing time (= fixing time) 6 minutes, cooling time 16 minutes, initial temperature 79 ° C, final fixing temperature 170 ° C. ...; .-.

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With regard to the granulate, processing and thread properties, the findings of Example 3 apply.

Example 7.

The procedure according to example 1 is repeated. Different of which a pigment preparation is made up of 50% made from ß-copper phthalocyanine and 50% from Mg-behenate. Process data: mixing time (= fixing time) 9 minutes, cooling time 35 minutes, initial temperature 81 ° C, final fixing temperature 136 ° C.

With regard to the granulate, processing and thread properties, the findings of Example 1 apply.

Example 8

The procedure according to example 1 is repeated. Different a pigment preparation consisting of 1/3 of the. Glycerol ester of hydrogenated rosin u, 2/3 made of carbon black puts. Process data: mixing time (= fixing time) 12 minutes, cooling time 13 minutes, initial temperature 25 ° C, final fixing temperature 110 ° C.

With regard to the granulate, processing and thread properties the statements of example 1 apply.

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Example 9

The procedure according to example 8 is repeated. In contrast to this, the granulate is filled in at room temperature without the jacket heating being used for preheating. Process data: mixing time (= fixing time) 13 minutes, cooling time 14 minutes, initial temperature 20 ° C, final fixing temperature 112 ⁰ C.

With regard to the granulate, processing and thread properties the statements of example 1 apply.

Example 10

The procedure in Example 1 is repeated. Different of which ß-copper phthalocyanine was used as pigment The mode of operation of the Papenmeier mixer has been changed as follows: Filling granulate and pigment into the unheated mixer, closing the mixer and starting the mixing process, 30 see mixing at 600 rpm, then mixing during '30 see increase to 2600 rpm and maintain this speed until no more dust formation can be seen in the mixer is. The mixing time (= fixing time) is 3 minutes, the initial temperature 24 ° C, the final fixing temperature 45 ° C.

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With regard to the granulate, processing and thread properties the statements made in example 1 apply.

Example 11

The procedure according to example 10 is repeated. In contrast to this, the substrate-soluble 2,6-di- (2'-hydroxynaphthyl) -4-pyrenyl-1,3,5-triazine (17 _O ) is used instead of a pigment. Process data: Mixing time (= fixing time) 2 1/2 minutes. Initial temperature 21 ° C, final fixing temperature 42 ° C.

With regard to the granulate, processing and thread properties the statements made in example 2 apply.

Example 12

The procedure according to Example 10 is repeated. Deviating from this, 2.5% aminodibenzanthrone was used. Process data: Mixing time (= fixing time) 8 minutes. Initial temperature of 30 ⁰ C, Fixierendtemperatur 112 ° G. In contrast to Example 110, the water cooling of the mixer was switched on after the end of the fixing process and the coated granulate was cooled with stirring (600 rpm) until a temperature of 50 ^° C. was reached. Cooling time 14 minutes.

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With regard to the granulate, processing and thread properties the findings of example 4 apply.

Example 13

The procedure according to example 12 is repeated. In contrast to this, 3% of a pigment preparation consisting of 1/3 of carbon black and 2/3 of the glycerol ester of hydrogenated rosin was used as the color body. Process data: mixing time (= fixing time) 3 minutes, cooling time 7 minutes. Starting temperature 26 ° C, end temperature 65 ⁰ C.

With regard to the granulate, processing and thread properties the statements made in example 1 apply.

Example 14

The procedure according to example 11 is repeated. Deviating from this, the substrate weight is from 7 kg to 70 kg elevated. Because a larger mixer is used for this experiment was (volume 150 1), the speeds changed during mixing as follows: start-up for 30 seconds at 480 rpm, then increase to 960 rpm and keep the speed until the fixation is finished. The circumferential speeds achieved

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- Ib -

The capacities are in the range of those for the 7 kg batches used mixer. Process data: Mixing time (= fixing time) 9 minutes. Starting temperature 25 ° C, end temperature 54 ° C.

With regard to the granulate, processing and thread properties the statements of example 4 apply.

Example 15 *

The procedure according to Example IA is repeated. Different of this, the granulate weight increases from 7 kg to 70 kg

a preparation increased and as a dye / from each 0.5% 2,6-di- (2 * -hydroxynaphtyl) -4-pyrenyl-1,3,5-triazine and 0.5% 1,5-dihydroxy-4-nitro-8-anilinoanthraquinone

used. Also unlike the Beispiell4 a cooling operation was necessary, which in a cooling mixer (300 1 volume) reached with stirring (120 rev / min) performed wurde'bis the granule temperature 50 ⁰ C. Process data: Mixing time (= fixing time) 3 minutes. Cooling time 4 minutes. Start temperature 44 ° C, fixation temperature 75 ⁰ C.

With regard to the granulate, processing and thread properties the statements of example 4 apply.

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Example 16

The procedure according to example 12 is repeated. Deviating from this, instead of a non-matted one, a matted granulate of a linear polyester (0.4% ^ iO ₂ ) ^{and anste} H ^{e e} ^ - ~ nes color body 0.2% of the optical brightener of the formula -

used. Process data: Mixing time (= fixing time) 8 minutes. Cooling time 10 min. Starting temperature 26 ° C, fixing temp. 84 '

After the fixation, the product was partially dissolved in the surface of the granulate or was similar on the surface fixed with a pigment. The quality of the fixation corresponded to that described in Example 1. The one with a brightener coated granulate could be processed into continuous yarn without difficulty.

Example 17

The procedure according to example 10 is repeated. Deviating from a frosted linear polyester was used in place of the non-matted substrate, and instead of a color solid 0.17 _o of the heat stabilizer of formula

₃ ) ₃ C

HO- (TjY- CH ₂ PO (OC ₂ H ₅ ) ₂ ) C

used.

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Process data: Mixing time (? = Fixing time) 4 minutes. At first temperature to 33 ° C, fixing temperature to 51 ° C.

The product was firm on the surface of the granules fixed. The coated granulate could be processed into continuous yarn without difficulty.

Example 18

A commercially available linear polyamide (polyamide-6) in granulate form (round cross-section, diameter 2 ram, length 3 mm) is introduced into an intensive mixer (Papenmeier system), the jacket heating (steam 1.5 atli) in front of the E-inflillen fttr Was switched on for 3 minutes. 1% 2,6-di- (2'-hydroxynaphthyl) -4-pyrenyl-1,3,5-triazine is then added to the granulate (7 kg), the mixer is closed and the mixing process is started. This proceeds as follows: 2 minutes of mixing at 600 rpm, then 2 minutes at 1200 rpm, then 1800 rpm until no more dust formation can be detected inside the mixer. The one needed to fix the pigment on the granulate. Takes 12 minutes, the initial temperature of 30 ⁰ C, the Fixierendtemperatur 122 ° C. After the end of the fusing process, the heating of the mixer is switched off and the cooling switched on (water). Thereafter, the coated granulate is kept with ongoing cooling

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600 rpm stirred until its temperature falls below the limit of 50 ° G, duration 16 minutes.

In addition to a fixation of color particles, the granulate shows a partial dissolution of the applied dye in the outer layers of the granules. In the out of this In mass-dyed polyester threads produced in granules, the dye is practically dissolved. Otherwise, the im Example 1 made observations.

Show the textile properties of the aforementioned threads normal values. This shows that neither the polymer nor the color body is damaged during the mixing process occurs.

Example 19

The procedure of Example 18 is carried out with the same amount of polyamide-6 (polycaprolactam) granules (round cross-section 0 2 mm, length 3 mm) with 70 g (= 1%) 4,4'-diamino-l, l'-dianthraquinonyl repeated. The times and temperatures of the mixing process are as follows: Coating time 14 minutes, cooling time 12 minutes, initial temperature 35 ° C, final fixing temperature 122 ° C.

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The granulate obtained can be easily converted into polyamide 6 continuous yarn, for example on the Inventa melt spinning system mentioned above to process. As for the quality of the fixation of the 'pigment on the granulate and the properties of it As far as produced mass-dyed threads are concerned, the statements made in Example 1 apply.

Example 20

The procedure according to example 18 is repeated. Deviating from this, the operation of the mixer is changed as follows: After filling in the granulate, the heating of the mixer (jacket heating, steam nj 1.5 atm) is switched on and the granulate is heated until it reaches a temperature of 80 + 5 ° C. During this heating process
the granules are stirred at 600 rpm for 10 seconds at intervals of 50 seconds each. After reaching the temperature of 80 ⁰ C, after about 15-20 minutes (the
Time depends on the granulate form (bulk density), the mixing process is carried out as in Example 1, as is the cooling process. The process data are achieved during the mixing process mixing time (= fixing time) 8 minute, cooling time 19 minutes, start temperature 80 ⁰ C, Fixierendtemperatur 149 ° C.

As far as the properties of the granules colored by this method are concerned, as well as those made from them

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mass-dyed threads, the findings of example 18 apply.

Example 21

The process according to Example 20 is repeated, wherein

as substrate polyamide-6 granulate and as

Pigment ^l 4,4-diamino-l, l'-dianthraquinonyl is used, the data that obtained by the process are: mixing time (= fixing time) 11 Minutes, Klihlzeit 18 Minutes, initial temperature of 80 ⁰ C, Fixierendtemperatur 168 ° C.

With regard to the properties of the granules and the thread, the statements made in Example 20 apply.

Example 122

The procedure according to example 20 is repeated. In contrast to this, polyamide 6 granules are used as the substrate Substrate-soluble dye of the 1: 2 chromium complex of the monoazo dye the formula

COOH

HO-C

co;

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used. Process data: mixing time (= fixing time) 8 minute, Klihlzeit 22 Minutes, initial temperature of 80 ⁰ C, Fixierendtemperatur 159 ° C.

The remarks apply to the properties of granules and threads according to example 18.

Example 23

The procedure according to Example 19 is repeated. Deviating from this, a pigment preparation consisting of 507 _o ß-copper phthalocyanine and 50? _{o used} from Mg-behenate. Process data: mixing time (= fixing time) 9 minutes, cooling time 35 minutes, initial temperature 81 ° C, final fixing temperature 136 ° C.

With regard to the granulate and thread properties, the statements of Example 19 apply.

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Example 24

The procedure according to Example 18 was repeated. In contrast to this, the size of the batch was reduced to 5 kg, VA of the substrate-soluble 1: 2 chromium complex of the monoazo dye of the formula

COOH

N = NC - C-CH ₃

used and the mode of operation of the Papenmeier mixer changed as follows: Pour granules and color bodies into the unheated mixer and start the mixing process. Premix for 30 seconds at 600 rpm, then run the mixer up to 2600 rpm for 30 seconds and maintain this speed until no more dust formation can be seen in the mixer. The mixing time (= fixing time) is 3 minutes, the initial temperature 24 ⁰ C ^ dLe fixing end temperature 45 ° C.

With regard to the granulate, processing and thread properties the statements made in example 18 apply.

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B e i s. Ρ i e 1 25

The procedure according to Example 24 was repeated. In contrast to Example 24, VL β-Cu-phthalocyanine were used as the colored bodies. Process data: Mixing time (= fixation time) 8 minutes, .. Start temperature at 34 ° C, fixation temperature 91 ° C. Because of the high Fixierendtemperatur fixation was different from "Example 24 after switched on the water cooling of the mixer and the coated pellets while cooled (600 U / min) with stirring, was reached until a temperature of 5O ⁰ C. Cooling time 12 minutes. .. -.-- ..

With regard to the granulate, processing and thread properties the findings of example 19 apply.

Example 26

The procedure according to Example 24 was repeated. In contrast to this, 2% of a preparation consisting of 40% a-Cu-phthalocyanine and 60% a polyterpene resin was used. Process data:. Mixing time (= fixing time) of 4 minutes • initial temperature 30 ° C, Fixierendtemperatur 50 ⁰ C.

With regard to the granulate, processing and thread properties the statements of example 19 apply.

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Example 27

The procedure according to Example 2 5 was repeated. Deviating from this, instead of a non-matted, a matted linear polyamide (0.4% TiO ₂ ) and instead of a dye 0.2% of the optical brightener of the formula were used as the substrate

- N

C ₂ H ₅ NH

so

CH4 = approx

3 ~ r

used. Process data: mixing time (= fixing time) 4 minutes, cooling time 10 minutes. Start temperature 30 ⁰ C. Fixing end ^{temperature 87 0} C.

The brightener was partly dissolved in the surface Part fixed. The quality of the fixation originated from that described in Example 19. The one coated with brightener Granules could be processed into continuous yarn without difficulty.

Example 28

The procedure according to Example 27 was repeated. Deviating from this, 0.1% was used instead of the optical brightener a light protection agent of the formula

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(CH ₃ )

O, OC ₀ H.
P-

used for the coating and the cooling process required in Example 27 after the fixation was omitted. Process data: Mixing time (= fixing time) 4 minutes. Initial temperature 17 ⁰ C. Fixing temperature 44 ° C.

The product was fixed on the surface of the granulate, whereby the quality of the fixation corresponded to that described in Example 19. The coated granules could be used without difficulty can be processed into continuous yarn.

B e i s ρ i e 1 29

The procedure according to Example 28 was repeated. In contrast to this, instead of the light stabilizer used there, 0.57o of a heat stabilizer of the formula was used

C (CH ₃ ) ₃

) gKHCOC ₂ H ₄ -

C (CH ₃ ) ₃

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used. Process data: Mixing time (= fixing time) 4 minutes. Initial temperature 24 ⁰ C, final fixing ^{temperature 54 0} C.

With regard to the granulate and processing properties, the statements in Example 28 apply.

Example 30

The procedure according to Example 24 is repeated. In contrast to this, a linear polyamide of the polyamide-11 type (poly-GJ-undecanolactam) is used as the substrate to be colored. Vorfahrpnsdaten: mixing time (= fixing time) 13 minutes, cooling time 13 minutes. Starting temperature 28 ° C, end temperature 80 ⁰ C.

As far as the properties of the granules colored by this method are concerned, as well as those made from them mass-dyed threads, the findings of example 18 apply.

Example 31

The procedure according to example 30 is repeated. Deviating from this, the substrate to be colored becomes a linear one Polyamide of the type polyamide-12 (poly-lauryl lactam) is used. Process data: mixing time (= fixing time) 13 minutes, Cooling time 11 minutes. Initial temperature 37 ° C, end temperature 72 ° C. 3Ö9839 / 0905

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As for the properties of the dyed by this method As far as granules are concerned, as well as those of the mass-colored ones produced from them. Threads, the findings of the apply Example 18.

Example 32

The procedure according to Example 30 is repeated. Notwithstanding this, a polyamide 6,6 granulate (polyhexamethylene adipate) is used as the substrate and as the dye YL of the 1: 2 chromium complex of the monoazo dye of the formula

N = NCC-CH ₃ HO-C N

used. Process data (= fixing time) 8 minute, cooling time 12 minutes, the top temperature door 25 ⁰ C, Fixierendtemperatur 76 ° C.

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Example 33

The procedure of Example 1 is repeated. Different a pigment preparation consisting of 50% of the Disazo pigment of the formula

-NHCO

and 50% of a vinyl aromatic marketed by Esso under the trade name Escorez 7403 Hydrocarbon resin.

Example 34

The procedure is as indicated in Example 1, but a preparation consisting of 50% hexadecachloro copper phthalocyanine is used and 50% from one under the trade name Escorez 4110 from Esso on the market brought Polj ^ terpenharzes.

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Example 35

The procedure is as indicated in Example 1, but a preparation consisting of 50% carbon black and 50% from one from the Goodyear company under the trade name Pliolite VT-L commercial copolymer made of vinyl toluene and butadiene.

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Claims (5)

CIBA-GEIGY AG Claims Process for the production of colored granules from linear polyamides or polyesters, characterized in that that the granules at temperatures between 3O-2OO ° C with pigments or polymer-soluble dyes are intimately mixed in a high-speed rotating mixer until the surface of the granulate particles plasticized and the pigments or dyes are fixed on the granules and the mixture is allowed to cool if necessary. 2. The method according to claim 1, characterized in that 100 parts of the granules 0.1-5 parts pigment or dye used. 3. The method according to claims 1 and 2, characterized in that there is a mixer with a Speed range of 300-3000 revolutions per minute used. 4. The method according to claims 1 to 3, characterized in that the mixing time is 3-20 minutes amounts to. 309839/090 CIBA-GEIGYAG * "- 5. The according to claims 1 to 4 available Granules. 3 0 9839/0905