DE1232699B - Process for the production of artificial fiber material - Google Patents

Description

Process for the production of artificial fiber material The present invention relates to a process for the production of fibers from regenerated cellulose, cellulose acetate, polyamide, polyacrylonitrile or polyester by precipitation or melt spinning of mixtures containing the polymer and a compound of the general formula contain, in which R, and R2 are aliphatic or aromatic radicals, members of a common ring or hydrogen and R3 is a metal, an amine, another salt-forming radical, carbamate or the represent, wherein R4 and R5 are the same radicals as R1 and R2.

It is already known from Swiss patent specification 308 243, for the production of shaped structures from regenerated cellulose of the spinning solution to add a soluble salt of an N-substituted dithiocarbamic acid. It will thereby reducing the swelling of the yellow during the manufacture of these structures achieved.

To improve the fiber properties are also used in the British Patent Specification 739 072 sodium and ammonium salts of dithiocarbamic acid in viscose added.

The present invention is based in particular on the object the fibers against fungal attack and various types of biological pests to protect. For this purpose one already has the fabrics made from these fibers Impregnated with various fungicides and pesticides. The impregnation mostly took place with solutions and dispersions. The disadvantage of the known impregnation process is that by washing such fabrics the impregnations immediately or gradually removed.

It has now been found that this disadvantage can be remedied if, for the production of fibers from regenerated cellulose, cellulose acetate, polyamide, polyacrylonitrile or polyester, mixtures are spun by precipitation or melt spinning, which apart from the polymer and a compound of the general formula wherein R1 and R, aliphatic or aromatic radicals, members of a common ring or hydrogen and R3 is a metal, an amine, another salt-forming radical, carbamate or denote represents, where R4 and RS are the same radicals as R ,. and R2 are, additionally contain condensed phosphates.

As compounds of the type indicated above, which are used to combat the Fungal infestation and other pests that can be used are, for example: Thiuram disulfide Dimethyl thiuram disulfide Tetramethyl thiuram disulfide Diethyl thiuram disulfide Tetraethyl thiuram disulfide Tetrapropyl thiuram disulfide Tetraisopropyl thiuram disulfide Tetrabutyl thiuram disulfide dimethyl diphenyl thiuram disulfide dicyclopentamethylene thiuram disulfide N, N'-bis (dimethylamino) thiuram disulfide Tetramethyl thiuram monosulfide tetramethyl thiuram hexasulfide dicyclopentamethylene thiuram monosulfide Dicyclopentamethylene thiuram hexasulfide Sodium methyl dithiocarbamate Sodium dimethyl dithiocarbamate Sodium diethyl dithiocarbamate Iron (III) dimethyl dithiocarbamate Zinc dimethyl dithiocarbamate Zinc diethyl dithiocarbamate selenium diethyl dithiocarbamate tetramethyl thiuramoxide 3,5-dimethyl-4,6-tetrahydro-1,3,5-thiodiazine-2-thione The following can be used as condensed phosphates: alkali salts of condensed phosphoric acids with a degree of polymerization of at least 2. Part of the alkali metal of the alkali salts the condensed phosphoric acids can be replaced by divalent and polyvalent metals be. However, urea phosphate or other corresponding phosphorus-nitrogen compounds can also be used be used. When choosing the proposed compounds of the above general formula, the conditions prevailing in the spinning process must be taken into account. In the case of aqueous spinning solutions, the compound to be used is to be selected so that it can withstand the alkalinity of the solution without substantial decomposition. Using In organic solvents, care must be taken that the compound used is conveniently soluble in the solvent. If you use these substances in melts, it is particularly important to ensure that the temperature prevailing in the melt does not apply survive substantial decomposition.

The additional amounts, calculated on the fiber, are about 0.01 to 10 /, of the above substances in question. However, these limits may apply in special cases also be exceeded.

From the aforementioned Swiss patent specification 308 243 and of British Patent 739 072, the invention differs in that Use of condensed phosphates. Comparative tests have shown that in this way that obtained from the spinning solutions or spinning melts Fiber material against fungal attack and various types of biological pests is much better protected than with thiuram compounds or dithiocarbamates alone. Example 1 Production of viscose rayon or rayon, depending on the cellulose content the viscose spinning solution are 300 to 600 g of tetramethyl thiuram disulfide and in the 3 to Aachen amount of it sodium polyphosphate with the empirical formula NaaP, O "in so Much softened water is stirred in so that the polyphosphate is completely dissolved. This slurry is mixed intensively in 100 kg of viscose spinning solution registered. The viscose stock batch produced in this way is filtered, deaerated and in a constant ratio of 1:50 to 1: 200 in the spinning viscose continuously injected, the metering ratio is to be chosen so that the finished threads contain about 0.08% TMTD (= abbreviation for tetramethyl thiuram disulfide). the Viscose is made into threads or fibers by known processes. .vagsponnen.

a) 200g chopped viscose fibers containing 0.08% TMTD and 0.4% sodium polyphosphate with the empirical formula Na9P702a are mixed with 10 fal of beer wort (1: 1 with water diluted) to which -0.1 was added to a normal suspension of Penicillium simpler (The spore suspension was prepared by floating a slant agar tube with 25 ml of physiological saline solution), added and stored at 30 ° C for 5 days. After this time, no mold infestation could be observed.

b) 500 mg of shredded viscose threads containing 0.08% TMTD and 0.40 /, Sodium polyphosphate with the empirical formula NaeP70 $$ are added with 10 ml of a 3-fold inoculated wort (1: 1 diluted with water and 0.3 ml of a normal Suspension of Penicillium simpler inoculated) and stored at 30 ° C for 5 days. After this time, no fungal attack could be observed.

Comparison: The threads produced without the addition of sodium polyphosphate show a strong in the test according to 1, a) and b) after the time has elapsed Mold growth. Example 2 Production of matted copper reyon or cellulose wool With the titanium dioxide, tetramethyl thiuram disulfide and sodium polyphosphate were in 4 times the amount of thiuram slurried (ball mill) and immediately during production incorporated into the spinning solution. The admixture was made so that the finished Copper fibers contained 0.08% TMTD. The sodium polyphosphate consisted of the same Parts made from pyro-, tripoly- and heptapolyphosphate. The spinning solution modified in this way was spun into threads or fibers using a known process.

a) 200 mg of the copper fiber containing 0.08% TMTD was crushed and with 10 ml of beer wort (diluted 1: 1 with water), the 0.1 ml of a normal suspension of Penicillium simplex was added (the spore suspension was prepared by floating an inclined agar tube with 25 ml of physiological saline solution), added and stored at 30 ° C for 5 days. After this time there was no fungal attack to be observed.

b) 500 mg of the crushed copper fiber was inoculated with 10 ml Beer wort [according to a)] added and stored at 30 ° C for 5 days. After expiration During this time the fibers remained free of fungal attack.

c) 500 mg of the shredded copper fiber was mixed with 10 ml of a 3-fold inoculated wort [according to a)] and stored at 30 ° C for 5 days. To After this time, fungal infestation could be observed.

Comparison: Production of matt copper redyon under the same conditions as described above, only without the addition of the sodium polyphosphate. A test according to a), b) and c) with this fiber showed that in all three cases a strong fungal growth was present after the 5 days. EXAMPLE 3 Production of matt copper redone A mixture of 1 part of tetramethyl thiuram disulfide, 1 part of dimethyl diphenylthiuram disulfide, 4 parts of Kurrol's salt and 4 parts of gray salt is added to the titanium dioxide, mixed intimately in the ball mill and this slurry is then incorporated into the spinning mass. The additives should be adjusted so that the finished threads or fibers contain 0.1% thiuram. The modified spinning mass is spun into threads using a known process.

These copper threads or fibers, woven or knitted fabrics made from them are protected against attack by fungi and bacteria.

a) 200 g of copper redone with a content of 0.05% tetramethyl thiuram disulphide and 0.05% dimethyldiphenyl-thiuram disulphide, 0.4% Kurrol's salt and 0.40 / " Graham salt is crushed and mixed with 10 ml beer wort (1: 1 diluted with water), to which 0.1 ml of a normal suspension of Penicillium simplex was added (the Spore suspension was prepared by floating an agar slant with 25 ml of physiological saline solution), added and stored at 30 ° C for 5 days. After this time, no fungal infestation could be seen.

b) 500 g of shredded copper fibers are mixed with 10 ml of wort (1: 1 diluted with water and inoculated with 0.1 ml Penicillium simplex suspension) and stored at 30 ° C for 5 days. After this time, no fungal growth was possible to be observed.

c) 500 mg of crushed Kupferreyon were mixed with 10 ml of a beer wort (Diluted 1: 1 with water and diluted with 0.3 ml of a normal suspension of Penicillium simplex inoculated) and stored at 30 ° C for 5 days. After this time has elapsed no fungal infestation could be seen yet.

Comparison: If copper rreyon or cellulose wool according to Example 3 is only used without Spun addition of sodium polyphosphates, it turns out that the material is more susceptible to attack by fungi and bacteria. Exams with this Comparative material according to a), b), c) showed in all three cases after 5 days a very strong fungal attack. Example 4 Manufacture of frosted copper fibers In the copper spinning solution according to Example 2, a mixture of 1 part of tetramethyl thiuram disulfide, Incorporated 1 part of tetramethyl thiuram monosulfide and 9 parts of sodium tripolyphosphate in such quantities that the finished spun material in total is approximately 0.110 /, Contains thiuram. The spinning solution is spun into fibers in a known manner.

Comparison: Under the same conditions, only without the addition of sodium polyphosphate spun material is much more susceptible to attack than the material that Contains thiuram and polyphosphate together. Example s production of viscose rayon According to Example 1, the viscose spinning solution is tetraethyl thiuram disulfide and sodium polyphosphate (a mixture of 1 part sodium pyrophosphate and 2 parts Sodium tetrapolyphosphate) incorporated in 4 times the amount of thiuram and the Viscose modified in this way is spun into fibers using a known process.

The thiuram content of the finished threads should be about 0.1 % . The material is more resistant to attack by fungi, bacteria and algae than the comparison material, which was spun under the same conditions without the addition of sodium polyphosphate.

a) 200 mg of shredded viscose rayon fibers containing 0.10%, tetraethyl thiuram disulphide and 0.4% sodium polyphosphate (consisting of 1 part of sodium pyrophosphate and 2 parts of sodium tetrapolyphosphate) are diluted with 10 ml of wort (1: 1 with water) , to which 0.2 ml of a normal suspension of Penicillium simplex was added, and stored at 30 ° C for 5 days. After this time, no mold growth can be observed. In contrast, the material spun without sodium polyphosphate shows strong fungal growth. Example 6 Production of matt viscose cellulose wool The viscose spinning solution is incorporated with zinc dimethyldithiocarbamic acid and 5 times the amount of sodium polyphosphate, based on zinc dimethyldithiocarbamic acid, in such amounts that the finished material contains around 0.10 / "zinc dimethyldithiocarbamic acid. The viscose modified in this way is spun into fibers in a known manner.

The sodium polyphosphate mentioned above is said to be: 2 parts sodium pyrophosphate and 1 part sodium tetrapolyphosphate.

The threads and fibers produced in this way have a significantly higher level Resistance to infestation than the reference material that did not use the Addition of sodium polyphosphates was made.

200 g of crushed viscose cellulose wool containing 0.10 /, dimethyl-dithiocarbamic acid zinc and 0.50 /, sodium polyphosphate (consisting of 2 parts of sodium pyrophosphate and 1 part of sodium tetrapolyphosphate) are mixed with 10 ml of wort (diluted 1: 1 with water) of the 0 , 1 ml of a normal suspension of Penicillium simplex was added, and the mixture was stored at 30 ° C. for 5 days. After this time, no mold growth can be observed.

Comparison: That under the same conditions, but without the addition of sodium polyphosphate Pre-spun comparative material shows a strong test in the corresponding test Mold growth. Example ? Manufacture of polyamide fibers Before polycondensation the monomeric caprolactam is mixed with a slurry, so that 6% water, 0.10 / 0 dimethyldithiocarbamic acid zinc and 0.4% sodium tripolyphosphate incorporated will. The caprolactam modified in this way is known procedure polycondensed and melt-spun. The polyamide threads produced in this way are better protected against infestation than those otherwise under the same conditions, however threads obtained without the addition of polyphosphate.

Claims (1)

Claim: Process for producing fibers from regenerated cellulose, cellulose acetate, polyamide, polyacrylonitrile or polyester by precipitation or melt spinning of mixtures containing the polymer and a compound of the general formula contain, where R1 and R2 are aliphatic or aromatic radicals, members of a common ring or hydrogen and Ra is a metalty, an amine, another salt-forming radical carbamate or den represented, where R4 and R, the same radicals as R, and Ra are, characterized in that mixtures are spun which additionally contain condensed phosphates. Documents considered: German Patent No. 904 700; German Auslegeschrift No. 1079 317; British Patent No. 739 072; Swiss patent Ni. 308 243. When the application was published, comparison tests were laid out.