DE1141973B - Process for reducing the swelling value and increasing the abrasion resistance of structures, such as fibers, threads or fabrics, made of native or regenerated cellulose - Google Patents

Description

It is known, for the production of cellulose derivatives, brought into reactive form cellulose, e.g. cellulose pretreated with strong alkalis, with heterocyclic compounds, which are a or contain several N = C halogen groups, such as cyanuric chloride or cyanuric bromide, to condense. Under certain circumstances, the condensation product can still be combined with compounds containing nitrogen, oxygen or contain sulfur-bonded, replaceable hydrogen atom, e.g. B. with an amine, reacted will. It is also known to esterify or etherify celluloses in the presence of tertiary bases to implement with the said heterocyclic compounds.

Purpose of this process, in which alkali cellulose or acyl or alkyl celluloses with a one or several N = C halogen groups containing compound are reacted, it is above all that Cellulose materials with extensive substitution of the OH groups of the cellulose by cyanuric acid residues to immunize against direct cellulose dyes and to have an affinity for them basic or - after further reaction of the products treated with cyanuric chloride, for example, with amines - to acidic To give dyes. Pre-treatment is a prerequisite for achieving this result of the cellulose material with strong alkalis or a previous esterification or etherification of the Cellulose and the use of a large, at least half the amount of cellulosic material used amount of cyanuric halide for that in an organic solvent Implementation that usually takes several hours and is not inconsiderable Loss of strength of the fiber is associated, which is usually 12 to 26% of the original strength of the cyanuric halide treated fiber.

It has been found that novel, surprising finishing effects, in particular in the sense of a strong reduction in the swelling value and a substantial improvement in the abrasion resistance, can be achieved on structures such as fibers, threads or fabrics made from native or regenerated cellulose by reacting with cyanuric halides, if the dry or moist cellulosic material which does not basified, unlike the above-described known processes, need not be esterified or etherified, at a temperature between 15 and 60 ⁰ C for a period of 1 to 30 minutes, preferably 5 minutes, with an aqueous, on a pH value between 7 and 10, preferably of about 8, maintained solution or suspension of 10 to 100 g, method for reducing the swelling value and for increasing the abrasion resistance

of structures such as fibers, threads
or fabrics, made from native

or regenerated cellulose

Applicant:

Phrix-Werke Aktiengesellschaft,
Hamburg, Stephansplatz 10

Dr. Hans Dolmetsch, Neumünster (Holst.),
has been named as the inventor

preferably 30 to 60 g, per kilogram of treated cyanuric halides of cellulose, then drying and heat treatment at a temperature above 100 ⁰ * C, suitably from 110 to 120 ° C, subjected.

While in the known methods, which aim to immunize the cellulose against direct dyes, the use of strong alkali, a long treatment time and usually a higher temperature, i.e. conditions, are required to achieve the greatest possible substitution of the OH groups of the cellulose by cyanuric acid residues , which cause a rapid elimination of the halogen atoms of the heterocyclic compound, for example a cyanuric halide, so that active chlorine is only retained when a large amount of cyanuric halide is used, according to the invention with very small amounts of cyanuric halide with maximum utilization of the chlorine atoms of the same after only a short time obtained treatment with the dilute aqueous Cyanurhalogenidsuspension by the final heating at a temperature above 100 ⁰ C temperature crosslinking of the OH groups of cellulose, wherein before carrying out this crosslinking reaction, that is, prior to heating , since under the conditions of the invention

209 750/163

According to the process, only a small amount of chlorine atoms are split off, a maximum of unsaponified reactive chlorine atoms is available.

As already mentioned, the method according to the invention allows the water absorption capacity of the To reduce cellulose structures considerably and to increase their abrasion resistance quite significantly, which without Influencing the tensile strength and elongation values is achieved. Compared to the known formaldehyde hardening of cellulose textiles and those containing urea or melamine-formaldehyde resins working finishing process has the advantage that the embrittlement that occurs in these processes of the treated material and the known disorders caused by uneven distribution of the condensation resins which are not directly absorbed from the liquor are definitely avoided can be because the cyanuric halides or other compounds of the triazine series in an alkaline medium are easily bound to the cellulose and so an even absorption from the liquor takes place.

The method according to the invention also offers the possibility of reacting the cyanur ring after or before its coupling to the cellulose with other reactive compounds which either impart desired properties through their binding to the cellulose or in turn can be crosslinked with the cellulose or with each other . Thus, on the treated with a cyanuric halide in the same or a Good Bad additional an amino compound such as urea, melamine, an aliphatic amine od. The like., Allowed to act and the material are then dried at about 100 ⁰ C. In this way it is e.g. For example, it is possible to achieve a very high improvement in the rub resistance with a sufficient reduction in the swelling value or to introduce hydrophobic groups into the cellulose molecule with the aid of the primarily bound cyanuric ring. For this purpose you can z. B. the bonded to the cellulose in the first stage cyanuric ring with a long-chain aliphatic amine, such as heptylamine, oleylamine, stearylamine, etc., couple.

According to a further possible embodiment of the method according to the invention, this can be done with a Treated cyanuric halide suspension and then with an organic amino compound, e.g. B. urea, converted cellulose material with the solution of an aldehyde, for example formaldehyde or glyoxal, treated and then dried and heated to a higher temperature. So here is the amine is linked to the cellulose by means of the cyanuric halide and is formed by acidic aldehyde condensation, at most in the presence of a suitable catalyst, such as ammonium biphosphate, the desired Networking causes, with the result of an extremely large reduction in the source value and a multiplication the rub rate. This mode of operation enables a saving in cyanuric halide and a Dye-like absorption of the nitrogen bodies while avoiding the known squeeze-off difficulties associated impregnation with these and results in a molecular crosslinking that prevents embrittlement.

The method can also be carried out so that one z. B. an amino compound such as urea, melamine, an aliphatic amine od. The like., Is reacted in an aqueous alkaline solution with a cyanuric halide, and the impregnated product to be refined material in a fleet of the resulting reaction product is then dried and heated to above 100 ⁰ C. Here, previously prepared reaction products of suitable compounds with cyanuric halide are subsequently bound to cellulose with the help of the chlorine atom or atoms that are still free.

The treatment with the cyanuric halide suspension can be both dried and spinning-moist Fibers are subjected. The temperature of the

ίο The treatment liquor should not significantly exceed 60 ° C, otherwise the cyanuric halide will decompose. On the other hand, with cooling, a reaction would not occur within a practically useful time. Within the temperature range of from 15 to 6O ⁰ C, a temperature increase of the Cyanurchloridbades results in a substantial acceleration of the reaction, the crosslinking of the OH groups of the cellulose focused more and more on the outer zone of the fiber with increasing temperature, so that it is carried by varying the bath temperature has in hand to achieve a fiber that is uniformly crosslinked over the entire cross-section or a crosslinking in the cladding layer of the fiber.

It is essential to buffer the treatment liquor, e.g. B. by means of borax, since the implementation hydrohalic acid free of cyanuric chloride with cellulose forms and should be avoided that during the reaction of the ρπ-value in the acidic Area turns over. It is also required that, except the cases in which a reaction of the cyanuric halide z. B. with Urea or an amine is carried out, the final heat treatment in the presence of an alkaline Buffer substance, e.g. B. Borax, is made, that is, during the condensation heating on the dried fiber is still buffer substance, because otherwise no implementation z. B. with the hydroxyl groups the cellulose takes place. This condition is fulfilled if the treated with the soaking solution, at most pressed or spun off material is dried without washing.

The material treated with the cyanuric halide liquor can, as said, be freed from the excess of the impregnating liquid by pressing or spinning off before drying, otherwise a correspondingly longer time is required for drying. The heating of the material to be treated to temperatures above 100 ^° C. following drying is preferably carried out at 110 to 120 ^° C.

It can also be applied temperatures up to 16O ⁰ C with correspondingly shorter duration.

Embodiment 1

1 kg cell wool is treated at 20 ⁰ C for 5 minutes with a 20-fold amount of a 2% aqueous solution of borax, in which 60 g of cyanuric chloride dissolved or suspended. The borax solution can also be circulated and kept in contact with the corresponding amount of cyanuric chloride separated by a filter. The cyanuric chloride is completely absorbed by the cellulose from the liquor, the pn value of which is about 8.0, within the specified time. The fiber material is then removed from the liquor and, after the solution still adhering to the surface has been squeezed off or spun off, dried as usual without washing and heated ^{to about 120 ° C. for about 30 minutes.}

The fiber is insoluble and almost non-swellable in cellulose solvents and exhibits the following changes on:

Cyanuric
chloride-
treatment Source value Chafing
strength
T / m
(1.5
Thread km) Tear
strength
g / den strain
wet
° / o Without
With 94
68 184
4300 2.5
2.6 21.6
20.8

Embodiment 2

To equip a cellulose staple fiber with a jacket zone that is insoluble in cellulose solvent one with a cyanuric chloride-borax solution as in Example 1, but at a temperature of Treatment liquor from 40 to 50 ° C.

Embodiment 3

A rayon fabric in linen weave is made according to the method described in Example 1 treated. This makes the material insoluble in cellulose solvents, its swelling value drops from 90 to 78%, while its rub resistance increases from 285 to 940. The tensile strength and elongation of the threads remain practical unchanged.

Embodiment 4

1 kg freshly spun, desulfurized, still moist cell wool is treated at 2O ⁰ C for 5 minutes with a 20-fold amount of a 2% aqueous solution of borax, in which 60 g of cyanuric chloride dissolved or suspended. The fiber material taken from the liquor is freed from excess treatment solution by pressing or spinning, dried without washing and heated ^{to 120 ° C. for about 30 minutes.}

The cyanuric chloride treatment can be followed by an impregnation with a 2% borax containing, usual avivage bath, z. B. based on fatty alcohol sulfate. Like. Follow, whereupon dried and on higher temperature is heated.

The reduction in swelling value achieved and the improvement in rub resistance are based on the summary below emerge:

treatment Source value
% Abrasion resistance
T / m (1.5 thread km) Without cyanuric chloride, without finishing
With cyanuric chloride, without finishing
With cyanuric chloride, with a finishing agent 106
75
78 1500
5 360
10 020

Embodiment 5

1 kg of moist cell spin wool is treated in a suspension of 50 g of cyanuric chloride in a 2% borax solution for 5 minutes at 20 ⁰ C. After the cyanuric chloride has been absorbed, rinsing is carried out for a further 5 minutes with a 5% urea solution buffered with borax to pn 8.0 at 20 ° C. After this solution has been squeezed off or spun off, it is impregnated with a 2.5% strength formaldehyde solution containing 0.2% ammonium biphosphate as a catalyst. After removing the excess, drying is carried out as usual and heating ^{to a temperature of about 120 ° C. for about 30 minutes.}

The fiber has a swell value of 50.2% and a Abrasion rating of 1839 compared to a swelling value of 105% and a abrasion rating of 210 for the untreated, dried fiber.

Embodiment 6

Cellulose fiber material is reacted according to Example 1 with 60 g of cyanuric chloride per 1 kg of cellulose in a borax-alkaline solution. After the cyanuric chloride has been taken up, 30 g of oleylamine, dissolved in acetone, are added to the liquor. After removing the excess liquor, the material is dried and ^{heated to 120 °} C. for 30 minutes. The fiber is now water repellent. Embodiment 7

5 g of urea are dissolved in 20 1 2% borax solution; then are added at 2O ⁰ C with stirring, 60 g of cyanuric chloride, dissolved in acetone added. After the reaction has ended (about 5 minutes), 1 kg of viscose staple fiber made from beech sulphite pulp is added to the liquor and heated to 50 ° C. in order to attach the urea-cyanuric chloride compound to the cellulose. The final condensation is carried out after drying of the fiber by heating at 120 ⁰ C, where adherent Boraxreste intercept the released hydrochloric acid.

The fiber has a swell value of 84% and a rub resistance of 21400 compared to a swell value of 102% and an abrasion index of 4350 for the untreated fiber.

Comparison of the method according to the invention with that of the British patent

Commercially available rayon viscose wool was once made according to the procedure of Example 1 of the British patent 342167 (Experiment A) and the other time treated according to the present Example 1 (Experiment B). A third experiment (C) corresponded to experiment B, but the same amount was used instead of borax Sodium acetate used.

The fiber data can be found in the table below:

Exit cell area Titer
the Wet strength
Rkm Wet stretch
° / o Loop strength
km Source value
% Untreated
A. 2.41
2.74
2.64
2.68 11.5
7.2
12.6
QQ 32.9
17.1
23.0
26.3 5.7
2.3
3.9
4.9 87.1
74.4
71.3 B. C.

This clearly results in a considerable weakening of the fiber by treatment A (with alcoholic KOH, etc.), while the operation of the invention is about an 11% improvement the wet strength provided. Extensibility and loop strength were also retained much better than the method according to the British patent specification.

The process according to the invention with sodium acetate as catalyst (C) occupies a middle position. Although the strength has suffered somewhat, the elongation and loop strength are all the better preserved.

Claims (4)

PATENT CLAIMS: 1. A method for reducing the swelling value and increasing the abrasion resistance of structures such as fibers, threads or fabrics, made of native or regenerated cellulose using cyanuric halides, characterized in that the dry or moist material at a temperature between 15 and 6O ⁰ C for a period of 1 to 30 minutes, preferably 5 minutes, with an aqueous solution or suspension of 10 to 100 g, preferably 30 to 60 g, maintained at a pn value between 7 and 10, preferably about 8 , a cyanuric halides per kilogram of cellulose treated, then drying and heat treatment at a temperature above 100 ⁰ C, preferably at 110 to 12O ⁰ C, subjecting. 2. The method according to claim 1, characterized in that an amino compound such as urea, melamine, an aliphatic amine or the like is applied to the material treated with the liquor containing a cyanuric halide in the same or an additional bath and then drying the treated and heated to a temperature above 100 ⁰ C temperature. 3. The method according to claim 2, characterized in that treated with the liquor containing a cyanuric halide and then reacted with an organic amino compound, if necessary in the presence of a condensation catalyst such as ammonium biphosphate, with the solution of an aldehyde such as formaldehyde or glyoxal, dried and heated to a temperature above 100 ⁰ C temperature. 4. The method according to claim 1, characterized in that the material is treated with a liquor, a reaction product of a cyanuric halide prepared in an aqueous alkaline solution with an amino compound such as urea, melamine, an aliphatic amine or the like, contains. Considered publications:
British Patent Nos. 794 180, 794 181,
167;
French patent specification No. 1107 708. © 209 750/163 12.62