DE1805263B2 - Nylon-6- compositions of good dye affinity and contng - Google Patents

Abstract

Moulding composition consisting of a mixture of nylon-6 with 20% (or less) by wt. of a polymer with poor colouration properties (e.g. polyethylene, polypropylene, polystyrol or polyester and 0.3-1.5% by wt. of CaCl2. This composition ca nbe produced as threads, films, ribbons or flakes. It will take a drak colouring, with good stability. It can be mixed with polymers of high Young's modulus.

Description

1 2

The invention relates to a process for the production of acceptability for anionic dyes described of molded bodies made from a mixture of a large polymer, these improved in terms of their dyeability Part of polycaprolactam, 20 percent by weight or amides are according to the information in this opposite Polyethylene, polypropylene, polystyrene or posture obtained by polymerizing Polyester and 0.3 to 1.5 percent by weight calcium 5 of the starting materials in the presence of certain derivatives Chloride is carried out by conventional extrusion and optionally by phosphinic acids. This approach is Stretching in a known manner. in so far as this is disadvantageous as the polymerization

As is well known, the aim is to mix it in the presence of foreign substances - those mentioned

'' different types of polymers and fused phosphorus compounds - is accepted,

extrusion of the resulting mixture into filamentary form. One such operation is in the process

gen or thin, film-like objects which are not necessary according to the present invention,

shafts of molded bodies, which mainly consist of the addition of calcium chloride to the polyamide

Polycaprolaktam exist to improve and the pregranulate can be done.

reduce production costs. However, quite a lot of the polycaprolactam in the extruder with it

Series of poly- 15 calcium chloride miscible with the polycaprolactam to form a complex

The disadvantage that it reacts with the compound for the poly is the crystal structure and the

caprolaktam usual, d. H. acidic dyes hardly any degree of freedom of the end groups of the polymer from the

can be colored. Even if they have such equivalent values of the original polymer

be mixed that the characteristic mixed different. This phenomenon can presumably

properties are obtained, the obtained 20 the effect of the present invention is reduced

Shaped bodies with the serious disadvantage are carried out.

that their dyeability is so reduced that they are in fact other calcium salts, such as calcium

Practical value is practically lost. One is therefore sulfate, calcium acetate, calcium oxalate, etc., for the

so far proceeded so that one does not get the part of the further implementation of the present invention

Ren mixed polymers are suitable except for one such.

ring value has decreased that the colorability of the material to be incorporated into the polymer mixture

Object is not adversely affected. the amount of calcium chloride has shown that

The invention is therefore based on the object of not using amounts of less than 0.3 percent by weight Moldings made from mixtures of polycaprolactam and are sufficient because in this case none are noteworthy To create a further polymer which both obtain an improvement in the dyeability of the moldings have better dyeability than can be distinguished. Conversely, proportions of more than th mixing properties such as those made by incorporating 1.5 percent by weight not expedient, since it is true other Polymers, such as those with an apparent that then not just stick together high Young's modulus, etc. are obtained on- in the extruder screen, but also the ways in which they are obtained. 35 nen moldings become stained.

This object is achieved according to the invention by what the content of the other with the polycaprolak process When it comes to the production of moldings from a camouflaged mixed polymer, it doesn’t matter Mixture of a larger part of polycaprolactam, it depends on what level you are working with, as long as that 20 percent by weight or less of polyethylene, poly- polycaprolactam most of the mixture of propylene, Polystyrene or polyester and 0.3 to 1.5 G 40 made. So far, from the point of view of the dye weight percentage Calcium chloride seen from the usual extrudability, the proportion of the further polymer, dating and, if necessary, stretching in a known manner that has been incorporated into the polycaprolactam solved. 'kept half 10 percent by weight. So you can

From Japanese Auslegeschrift 14 831/1962 a process has already become known, for example by spinning a mixture, in which polycaprolactam and polyethylene terephthalate do not contain a polyamide-polyethylene mixture with CaCl ₈ treated fibers with a high Young's modulus when delt is obtained. The treatment is carried out by adding the proportion of the polyethylene terephthalate in the solution of the mixture in a CaCl _a methanol solution. mix is less than 10 percent by weight. This process is technically not entirely in contradiction to it, since the addition of calcium supplements, as-by the "dissolution of the polychloride improves the dyeability of the moldings according to the amide, a reduction in the degree of polymerization. Invention, the proportion is possible furthermore follows what a subsequent post-polymerization with the poly-aid of benzoyl peroxide to be mixed with the polycaprolactam is necessary.
The treatment in turn causes an oxidative decomposition. The invention is therefore associated with a noticeable settling of the polyamide, as a result of which considerable technical progress is associated, since this results in a reduction in strength. Another disadvantage of low cost moldings with better dyeability of this known five-step process lies in the fact that the film formation can be obtained with simultaneous removal of the solvent, which in the ren polymers, that is, with one that has a large number of fine holes 60 in Young's modulus, or the like, in a sheet obtained. Based on these facts, what happens by adding only foils or films made from polycaprolactam and another polymer to a mixture using the known method before low strength, low gloss and rough surface - the melting and extrusion 0.3 to 1, 5 weight areas available. percent calcium chloride added. Moreover, through

In the method of the invention, on the other hand, such an improvement in the colorability occurs.

does not show the disadvantages described. of the moldings and the durability of the dye

Tn the Australian patent specification 261 521 practice achieved that a deep color is possible and

fiber-forming linear polyamides with improved responsiveness to the migration of dyes

certain treatments, such as B. the laundry, due to discoloration is extremely low.

The invention will be described in more detail below with the aid of a few examples. Tn the examples all percentages are based on weight.

Example 1

To a well-blended mixture of granulated polycaprolactam (relative viscosity = 3.5) and 15 weight percent of granular polypropylene were added 0.3 weight percent calcium chloride, and the mixture was melted at 260 ⁰ C. The resulting spinning melt was extruded through a spinning head with 15 holes (diameter of the holes 0.5 mm) into a water bath. The threads were drawn in a hot bath at a temperature of 98 ° C. to 3 times their original length, whereby threads with 900 den (den number of the monofilament 60) were obtained. The threads obtained were treated several times in a scorerol bath (No. 400) with a concentration of 9 g / l at a bath ratio of 1:50 and then at 70 ^° C. for 20 minutes. The threads were then treated using an acidic dye (, Ltd. solar Orange, Sumitomo Chemical Co.) dyed at a ratio of 3% of dye, and 3% of ammonium acetate, wherein the ratio of the impregnating bath 1: 100, the bath temperature was 90 ⁰ C and the pH of the bath. 4

For comparison purposes, the same mixture of granulated polycaprolactam and polypropylene was used, however treated in a similar manner without the addition of calcium chloride. In Table 1 below are the results of the comparative experiments are shown. It can be seen that the manufactured according to the invention Products compared to the comparison samples a considerable improvement in color affinity and the Exhibited washfastness of the colors.

40

45

Table 1 Color affinity
(7o) Fastness to washing
of the colors Moldings the 2nd Class
1st Class According to the invention
Comparative samples 900
900 43
35

Table 2 Fastness to washing
of the colors Moldings 3rd grade
1st Class. 5
According to the invention
Comparative samples ... Color affinity
(%) 44
35

Example 3

Granulated polycaprolactam (η _η ι = 3.5) was mixed with 20 percent by weight of granulated polystyrene. As in Example 1, threads were also produced from two corresponding polymer mixtures, that is to say from one which contained 1.5 percent by weight of calcium chloride and from the other to which no calcium chloride had been added. The results of the corresponding comparative tests are shown in Table 3. This table clearly shows the superiority of the moldings according to the invention.

Table 3 Fastness to washing
of the colors Moldings 3rd grade
1st Class According to the invention
Comparative samples ... Color affinity
(7o) 43
28

In all of the experiments used herein, color affinity was measured using a spectrophotometer measured. The wash fastness of the paint was determined in accordance with JISL 1045 MC-2.

Example 2

Granulated polycaprolactam with a relative viscosity of 3.5 was made with 15 weight percent mixed with granulated polyethylene. To this, 1.0 percent by weight calcium chloride was added. That The resulting mixture was made into threads under the same conditions as in Example 1. Further became the same mixture but not containing calcium chloride under the same conditions as in Example 1 processed. The results of the comparative experiments are shown in Table 2 below. This clearly results in the essential improvement in the color affinity and color fastness of the invention Molded body. Example 4

To a mixture of granulated polycaprolactam (r / rei = 3.5) and 10 weight percent granulated polyethylene terephthalate (rj _re i = 0.72) 1.0 weight percent calcium chloride was added, the mixture ^{melted at 280 0} C and through a nozzle with a A lip length of 300 mm and a lip width of 0.7 mm were extruded into a film with a thickness of 30 μ, cooled and solidified.

The film was cut into strips and ^{stretched on hot rollers at 145 °} C. to 3.5 times the original length, whereby tapes with 700 denier each were obtained. For comparison purposes, the same mixture, but not containing calcium chloride, was treated in a similar manner. Table 4 shows the results of the corresponding comparative tests.

Table 4 Fastness to washing
of the colors Moldings 4th grade
3rd grade According to the invention.
Comparative samples ... Color affinity
(%) 42
26th

Claims (1)

Claim: Process for the production of moldings from a mixture of a larger part of polycaprolactam, 20 weight percent or less polyethylene, polypropylene, polystyrene or polyester and 0.3 to 1.5 weight percent calcium chloride by conventional extrusion and optionally Stretching in a known manner.