DE2322144A1 - DYED POLYESTER AND POLYAMIDE - Google Patents

Description

PATENTANWÄLTE D R. ■ IN GH FINCKE

DiPL-ING. S. ST. "CGE.?

8 M OrJ C hi EM 5 MULLERSTRAS.se 31 2, ί * ΊΑ1 1973

Folder 23 ^ 90 - Dr. K. Case P 25000

Imperial Chemical Industries Ltd, London, Great Britain

Dyed polyesters and polyamides

Priority: May 3, 1972 - Great Britain

The invention relates to colored polyester. Or Polyamide threads. The invention particularly relates to such filaments which have a dispersed polyolefin phase contain.

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According to the invention, a method for producing a polyester or polyamide thread is proposed, which is carried out in that one in the fiber-forming polyester or in the fiber-forming polyamide in the molten state incorporates a smaller amount of a polyolefin in the molten state, wherein a minor amount of a coloring material is dispersed in the polyolefin prior to mixing, and that one then the resulting mixture of polyester or polyamide, polyolefin and colorant is melt-extruded in the form of threads.

The term “polyester” also includes mixed polyesters, the term “polyamide” also includes mixed polyamides and the term "polyolefin" includes • mixed polyolefins.

The polyester can be used before performing the mishandling or the polyamide is in the molten state, as is obtained in a melt phase process, or the polyester or the polyamide can by the up. melting a previously solidified polymer in the molten one State can be obtained, the polymer also produced by a solid-phase polycondensation may have been.

Mixing can be carried out by any convenient method. Examples of this are static mixers or any device that gives a high shear rate (in the case of an already melted one Polymers) and an apparatus in which melting and shearing is effected such as a screw extruder (in the case of a solid polymer).

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The melt extrusion of the mixture is carried out by conventional Measures carried out.

The colorant can be an inorganic pigment such as e.g. Carbon black, titanium dioxide, iron oxide or cadmium sulfide, or a organic pigment or dye found in the polyester or in the polyamide and / or in the polyolefin is soluble, be. In particular, the colorant can be present in the mixture.

Other auxiliaries can be used in admixture for purposes known in the art and in those commonly used Concentrations be present. Examples are stabilizers, anti-inflammatory compounds, antistatic Compounds, antioxidants and optical brighteners.

The threads according to the invention can be drawn by drawing oriented and used in all common textile applications will.

It is believed that the filaments of the invention are a have continuous phase made of polyester or polyamide, in which a discontinuous phase Polyolefin is dispersed in a finely divided state, presumably in the form of fine fibrils.

The proportion of polyolefin should preferably be 0.2 to 16% by weight, based on the total polyester or the total polyamide plus olefin plus colorant. Preferably the proportion of colorant is 10 to 50% by weight, based on on the polyolefin plus colorant.

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A dispersant is advantageously used, to facilitate the degree of dispersion of the polyolefin and the pigment in the polyester or polyamide, or maintain. This can be done in an expedient manner happen that the dispersant is incorporated into the polyolefin in which the colorant is dispersed, before mixing with the polyester or polyamide.

When producing the mixture of polyester or polyamide with the polyolefin and the colorant, the ratio of the melt viscosity of the dispersion of the colorant in the polyolefin to the melt viscosity of the polyester or polyamide should preferably be less than "7: Λ . This ratio can be, for example, up to 0, 3: 1. Preferably the polyolefin content should not exceed 4%. In cases where the polyolefin content exceeds 4%, the ratio of the melt viscosity of the dispersion of the colorant in the polyolefin to the melt viscosity of the polyester or polyamide should preferably not be less than 1.5 = 1. Higher viscosities of colorants in the polyolefin can be achieved by increasing the pigment concentration (if this is permissible) or by using a high molecular weight polyolefin which has a correspondingly higher melt viscosity Mixture of polyester or polyam id, polyolefin and colorant, the mixture is converted into the solid state, for example in granules, before it is melted again and extruded into threads.

The polyester can, for example, polyethylene terephthalate) be, the polyamide can be, for example, nylon-6,6, and the polyolefin can be, for example, polyethylene or polypropylene.

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example 1

Polyethylene masterbatch pellets containing 40% polyethylene with a melt index of 2.0 and 60% titanium dioxide were placed in one half of the compartmentalized feed hopper of a screw extruder (manufactured by Bone Brothers; 5.1 cm inside diameter and "142.2 cm length that is Length to diameter ratio of 28: Ό gauged at 0.833% of the total feed rate with the remainder being gauged into the other half of the feed hopper. It consisted of poly (ethylene terephthalate) granules with an intrinsic viscosity of -0.675 dL / g (melt viscosity at 284 ⁰ C 3300 poise). the extrusion into filaments was carried out by a conventional metering pump. the extrusion temperature was 279 ° C, and the residence time in the molten state was 2 1/2 min. the yarn was at a speed of 792 5 m / min wound and stretched at a stretch ratio of _3? 78th the dispersion of titanium dioxide in the yarn was very good. There were kei all sorts of aggregates. The physical properties of the yarn were comparable to those of a yarn made of polyethylene terephthalate) of the same intrinsic viscosity and with the same content of titanium dioxide, but the titanium dioxide had been added to the bis (β-hydroxyethyl) terephthalate before the polycondensation into the polyester.

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Example 2

One. Polyethylene masterbatch containing 75% polyethylene with a melt index of 7 ^ 0 and 25% carbon black was metered into one half of the compartmentalized feed hopper of a screw extruder (as in Example 1) in an amount of 8% of the total feed rate, the remainder being the other Half of the feed funnel was measured and was made of poly (ethylene terephthalate) with an intrinsic viscosity of C, 675 dL / g. The extrusion ^{temperature was 279 °} C. and the residence time in the molten state was 2 1/2 minutes The yarn was collected at a speed of 792.5 m / min and drawn to a draw ratio of 3.78. The dispersion of the carbon black in the yarns was good. It. no larger aggregates were present. The physical properties of the yarn were comparable to the properties of a poly (ethylene terephthalate) yarn of the same intrinsic viscosity and carbon black content, but the carbon black had been added to the bis (β-hydroxyethyl) terephthalate prior to polycondensation into the polyester.

example

According to a standard ester exchange, polyester polymerization was carried out until the intrinsic Viscosity was 0.60. The vacuum was then broken, and 8% by weight of a polyethylene base mixture were which contained 75% polyethylene and 25% carbon black was added. Then vacuum was applied and the polymerization was continued until an intrinsic viscosity of 0.65 was reached. The black one obtained

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Polyester containing some free polyethylene was spun on a melt spinning line at an extrusion temperature spun from 279 C, obviously none Difficulties arose. However, the stretching was found to be slightly above a stretch ratio of 3.0 as impossible. The highest value; was 3,? 8.

Example 4

A scarlet pigment, PV Fast Red B (CI. Pigment Red 14-9) was piled on nylon 66 chips, which was then melt spun into a 20 ply yarn having a spun denier of 250 decitex. The spun Yarn was fed at a speed of 914.4 m / min and below a draw ratio of 5.2 to one Draw twister drawn. There were frequent cracks in stretching and it was impossible to stretch Take up a spool of thread with a weight of about 1 kg.

example

A dispersion of 20% PV Fast Red B in polyethylene (20% by weight paint in the total mixture) was thereby made that the pigment was added to molten polyethylene and this mixture, in ribbons extruded and cut into schnitzel. 10 parts by weight of the colored polyethylene were with 1 part by weight nylon-11 and 189 parts by weight nylon-66 mixed by mixing in the schnitzel state. The blended polymer was extruded as in Example 4. The spun Yarn was made with a draw ratio of 3.2 and one Stretching speed of 914.4 m / min on a stretching

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twister stretched. The stretching behavior was good. That Drawn yarn was 78 'decitex and had tear strength of 5 »1 g / decitex and an elongation of 31.3%.

Example 6

In this example, a conventionally prepared matte nylon-6,6 was used as the base polyamide. The nylon-6,6 contained 0.3% by weight of titanium dioxide and had a relative viscosity of 40, measured as an 8.4% strength solution of nylon in 90% strength (by weight) formic acid at 25 ^° C. A dispersion of the blue pigment Color Index 74160 (20 parts by weight) in polyethylene a melt viscosity of 284 poise at I7OO ⁰ C (80 parts by weight) was prepared by intensive mixing in 'a Bambury mixer. The obtained dispersion (1 part by weight) and nylon-6,6 (99 parts by weight) were melt-spun using a screw pressure melter. The screw pressure melter used is shown in FIG. 3 of the drawings of BE-PS 775 068. Sufficient shear was provided to achieve good melt mixing. The throughput was 2.7 kg / st at 29o ⁰ C. It was a spinneret plate with 68 holes used, wherein a hole having a diameter of 0.5 mm. The threads obtained were through a

transverse quench flow below the spinneret plate cooled, through a 1.83 m long steam conditioning

pipe passed and at a speed of 905.3 m / min wound up.

The spun filaments were finally drawn to a draw ratio of 3.23 stretched by moving at a speed of 1030.2 m / min over a brake pin with a Diameters of 9> 5 mm were performed, with threads with a

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good appearance and with an even blue color were obtained.

Example 7

This example was basically carried out like Example 1, However, the following exceptions existed. The colorant used consisted of carbon black Type Vulcan 6 (registered trademark). The infusion was made in polyethylene with a melt viscosity of 1700 poise 284 ° C in an amount of 25%, based on polyethylene plus carbon black, dispersed. The carbon black dispersion was in the polyethylene terephthalate) in different concentrations, based on the weight of the poly (ethylene terephthalate) incorporated. The results are given in the table below.

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Tabel

Soot dispersion in
Polyethylene Injection
rate Polyethylene
terephthalate , Il Visco
sity
at 284 ⁰ C Relationship
nis the Extru-
sion viscosity
at 284- ° C "
* 32 see ' 8th% IV Il 3,3OO poise Viscose
activity of
Soot dis
persion
to the vis
kosity
of the poly
esters ver
keep 9500 poise 12% 0.675 It ■
2.9: 1 satisfied
the
putting Il It ti II
- Il
I. Il 20% dd Il l
Il It ti
■ · thread
crack

calculated shear rate in the mixer zone 27 kg / h

With up to 16% of the carbon black dispersion in the polyethylene, based on the weight of the polyalkylene terephthalate S ₃ , the extrusion was satisfactory.

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Example 8

This example was performed according to Example 1, but the difference being that the mixture was passed through a static mixer with 2 ^Λ elements between the extruder and the metering pump. Polypropylene was used as the polyolefin. The carbon black was dispersed in the polypropylene in an amount of 25% by weight based on the polypropylene plus carbon black. The dispersion had a viscosity of 8000 poise (32 sec " ¹ at 284 ° C). The polypropylene dispersion granules and the granules of poly (ethylene terephthalate) which had an intrinsic viscosity of 0.675 (3500 poise) were fed into the screw extruder in a ratio of 4 to 100. Melt extrusion for making filaments was satisfactory, and the spun filaments could be drawn satisfactorily.

Example 9

In this example the dispersion of the colorant in polyethylene to poly (ethylene terephthalate) added, whose polycondensation was carried out to the desired molecular weight until the intrinsic viscosity 0.7 ^ was. After being made by a Melt phase process was · this product did not solidify been. The dye consisted of carbon black, which in polyethylene in an amount of 25%, based on polyethylene plus carbon black, was dispersed to a dispersion with a melt viscosity t? (at 284 ° C 25 sec "') of Ί0.900 poise to manufacture. The PolyCäthylenterephthalat) possessed a Melt viscosity of 5 x 200 poise. The soot dispersion in Polyethylene was continuously poured into a stream of

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molten poly (ethylene terephthalate), namely with a ratio of the flow rates of 8 parts by weight of dispersion to 92 parts by weight of polyethylene terephthalate). The combined stream ran into a static mixer with 14 elements and was exi-ruded into a tape, which was cut into schnitzel. The chips were then again in the manner described in Example 1 Device melted and extruded into threads, as described in Example 1. The melt extrusion for The production of the filaments proceeded satisfactorily, and the spun filaments could be drawn satisfactorily will.

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Claims (10)

2322H4 claims 1. ■ Process for the production of polyester or polyaraid threads, characterized in that a smaller amount of a polyolefin is mixed in the molten state in a fiber-forming polyester or in a fiber-forming polyamide in the molten state, with one in the polyolefin prior to mixing Smaller amount: · a dye is mixed in, and that the resulting mixture of polyester or polyamide, polyolefin_.oJ & fiT dye is then melt-extruded in the form of threads. 2 ". The method according to claim 1, characterized in that that the extrusion is carried out in the form of threads without the mixture of polyester or polyamide, polyolefin and coloring agent is solidified in between. 3- The method according to claim 1 or 2, characterized in that that the proportion of colorant is 10 to 50% by weight, based on polyolefin plus colorant. 4. The method according to any one of claims 1 to 3, characterized in that the ratio of the melt viscosity the dispersion of the colorant in the polyolefin to the melt viscosity of the polyester or polyamide 0.3: "to 7: 1. 309847/1040 5. Method according to one of Claims 1 to 4, characterized in that the proportion of polyolefin is 0.2 to 16% by weight, "based on the total of polyester or polyamide plus polyolefin plus colorant. 6. The method according to any one of claims 1 to 4, characterized in that the proportion of polyolefin 0.2 to 4% by weight, based on the total of polyester or polyamide plus polyolefin plus dye, amounts to. 7. Method according to one of Claims 1 to 4, characterized in that the proportion of polyolefin is 4 to 16% by weight, based on the total of polyester or polyamide plus polyolefin plus colorant, and that the ratio of melt viscosity the dispersion of the colorant in the polyolefin to the melt viscosity of the polyester or polyamide does not is less than 1.5: 1. 8. The method according to any one of claims 1 to 7i characterized in that a dispersant is used to disperse the polyolefin and of the coloring agent in the polyester or polyamide or the degree of dispersion already obtained maintain. 9. Process according to one of Claims 1 to 8, characterized in that the polyester is made from polyethylene terephthalate) and that the polyamide consists of nylon-6,6. 309847/1040 10. The method according to any one of claims 1 to 9 _5, characterized in that the polyolefin consists of polyethylene or polypropylene ". .i ^: .Fl · TCE. :. ·. · ■ {. ·, 309847 / 104G