DE1769730A1 - Process for dyeing metal-modified polyolefin fibers - Google Patents

Description

Process for dyeing metal-modified polyolefin fibers The invention relates to a process for dyeing metal-modified polyolefin fibers with anthraquinone dyes of the general formula in which X is a nitro or amino group, W is a hydrogen, chlorine or bromine atom, R is a hydrogen atom or a lower alkyl group and n is an integer from 1 to 4. The object of the invention is to create a method for dyeing metal-modified fibers, in particular polyolefin fibers, in particular polypropylene fibers modified with an aluminum compound, with a blue color, excellent clarity and lightfastness.

As a means for improving the low color affinity of polypropylene fibers, a method has been proposed in which chelating metallic salts such as fatty acid salts of aluminum, nickel, zinc and the like are incorporated into polypropylene fibers to form dyeable metal-modified polypropylene fibers and then the fibers be colored with such dyes which are in the position to form a chelate ring with the above metals.

The dyes according to the invention are valuable for the lightfast dyeing of such metal-modified fibers and have a surprising effect, especially when they are applied to aluminum-modified fibers.

As can be clearly seen from the above formula (1) , the dyes according to the invention have a characteristic chemical structure in which an aryl group is present between the imino group in the -position of the antrachinoma and the benzene ring. Compounds to which the AllWlgruppe; e, ie compounds in which an @ .nalin group is bound in a position, are not able to give a true blue coloration when used for staining, but rather give a greenish-blue coloration. In contrast, the dyes according to the invention give a true blue coloration due to the fact that they have the alkyl group. Furthermore, because of the presence of the alkyl group, the dyes according to the invention have improved properties with regard to uniformity and improved lightfastness. Furthermore, the halogen atom in the / G position in the dyes according to the invention is particularly effective when X is an amino group. I. E. the halogen atom contributes to the improvement of the color affinity and light fastness.

The dyes according to the invention are produced as follows: 4.8 Dinitro-1,5-dihydroxyanthraquinone is made with an amine compound of the general formula in which 8 and n have the same meaning as in formula (1) to produce the dyes of the general formula in the round n has the same meaning as in formula (1). Aeuh by converting t, 8-diasino-1,5.-ditydroxyanthraohinon'vit eine®, chloride of the common loroel In the 8 and n the meaning given in the table above, the tasbotoffe are the general torrrel obtained, in which R and n @ have the meaning given above . By analogizing the dyes dor formula (5) , the dyes of the general formula received, in the hal. stands for chlorine or bromine atom and R and n have the meaning given above. According to the invention, the coloring is carried out by bringing an effective amount of the above paraffin into contact with metal-modified polyolefin fibers in an aqueous suspension. Before the dye is used, the dye is expediently subjected to a so-called comminution treatment by a suitable process consisting, for example, of dissolving the dye in 90 to 93% sulfuric acid at low temperature. Placing in ice water, followed by filtering and washing in order to obtain a cake that is ground together with a cationic or anionic dispersant. For dyeing metal-modified polypropylene drums with the disperse dyes of the invention, the basic procedure consists in dispersing the dye finely divided in the above manner at a bath ratio of 30 to 50 times based on the fibers, the pH to 3 to 6 in the presence of a suitable anionic or nonionic surfactant, dyeing the fibers for 20 to 90 minutes at 100 ° to 1200 ° C. and then washing the dyed fibers with water, followed by cleaning with soap or hydrosulfite. It is also possible to perform the staining by the oogenannte-thermosol method, which consists in daß.man the aqueous dispersion to which a non-ionieches, ° o.berflächenaktives agent was added, and stock response nacheTrocknung Troeknungs a heat treatment during undergoes three minutes at about 13,000. The invention is explained in more detail aneohliseeend by the following feiepiele, in which parts and Prosentäxtss on 11Seven words bind. Ibtepial 1 50 parts of 4,8-dinitxo-1,5-dihydroxranthraquinone were suspended in 500 parts of chlorobenzene. Further, 20 parts of sodium carbonate were added to the suspension , whereupon 25 parts of benzylamine were added dropwise at 120 ° C. with stirring . The dropping in took about an hour. The reaction was allowed to proceed at the same temperature for the following one to two hours . There was water to the Reaktionsgemise6'htnzugegeben, and chlorobenzene was removed therefrom by steam distillation. The precipitate was filtered, washed with water, then with dilute hydrochloric acid and again with water and dried. 48 parts of a dye of the following structural formula were obtained: A portion of the above p ulverföreigen dye was "dissolved in 20 parts of 90% sulfuric acid at a temperature below 100C and the solution was poured into 200 parts of water. The precipitate formed was trated -Dabei fil, washed with Wagner and with o , 5 parts Natriuadinaphthy: eetiarnultnaat ground so 'was formed a 100 IgE rarbeteffpaatn a portion of the thus obtained processed to a fine paste ended dyes was dispersed in 500 parts of water, to which 0.25 parts of a nonionic surfactant prepared.. from nonylphenol and ethylene oxide, and 0 "2 Tolle Essigsilurs von 60H9 for the production-the color bath were added. 10 parts nodifiziertea polypropylene containing 092 wt. I4 aluminum (it was basic kluainiuestearat mono- verleibt) were immersed in this dye bath, which was tenperetur then raised to 120 ° C. The staining was carried out for one hour, after which the colored rabbits were washed with water. The fibers were then heated for 20 minutes at 85 ° C. in 500 parts of water, in de® 0.25 part of "Monogen" (sulfates of higher alcohol; registered trade name of the Datchi Kogyo Company, Japan), 0.5 part of sodium hydroxide and 0.5 part of sodium hydrosulfite was dissolved , followed by washing with water . The dyed product obtained had a clear navy blue color and its lightfastness was 6, and the numerical rating of dry cleaning, cleaning, nitrogen oxide gas, washing and peeling of the surface color was 5. The product was in all cases also resistant to sublimation. Example 2 In the same way as in the preparation of the dye according to Example 1, except that the benzylamine was replaced by 28 parts of p-phenylethylamine , a dye of the following formula was prepared. The above dye was used for dyeing aluminum- modified polypropylene fibers, wherein the essential chen a gleiohwertigee Ergebnie, t were obtained as in Example. Example 3 In the same way as in the preparation of the dye according to Example 1, except that the benzylamine was replaced by 35 parts of 1-phenyl-3-aminobutane , a dye of the following structural formula was prepared. The above dye was used to dye aluminum- modified polypropylene fibers , with a result substantially equivalent to that in Example 1 being obtained . Example -4 In the same way as in the preparation of the dye according to Example 1, except that the benzylamine was replaced by 28 parts of p-xylylamine, a dye of the following formula was prepared. The above dye was used to dye aluminum-modified polypropylene fibers, with a result substantially equivalent to that in Example 1 being obtained. Example 5 50 parts of 4,8-diamino-1,5-dihydroxyanthraquinone were suspended in 400 parts of o-dichlorobenzene. 20 parts of sodium carbonate and 100 parts of benzyl chloride were then added to the suspension, and the system was reacted for eight hours at 140 ° C. and then subjected to steam distillation. The precipitate was filtered, dried and pulverized to obtain 64 parts of dye (A) represented by the following formula . 50 parts of the dye (A) were dissolved in 250 parts of glacial acetic acid, and then 25 g of bromine were added to the solution at 50.degree. After stirring for two hours at the same temperature, the reaction mixture was poured into Waeeer. After filtering and washing the precipitate with water, 57 parts (bromine content: 17%) of the dye were obtained. (B) received. The structural formula of the dye (B) was as follows: This dye (B) was used for dyeing aluminum-modified polypropylene fibers to give a product dyed in a clear blue color and excellent in light fastness. The dye (B) had compared with the dye (A), who was not brominated better Eigenschaf- th respect Anfärbaffinität and fastness. Example_ 6 50 parts of the dye obtained in Example 1 were suspended in 1000 parts of water. 6 parts of sodium hydroxide and 50 parts of sodium sulfide were added and the suspension was heated at 90 ° C. for one hour. The nitro group was reduced to the amino group, and the same dye as the dye (A) of Example 5 was obtained.

Claims (2)

C claims process for dyeing polyolefin fibers, characterized .gekennzeichnet, DAB one anthraquinone of the general formula .- in which X is a nitro or amino group, W is a hydrogen, chlorine or bromine atom, R is a hydrogen atom or a lower alkyl group and n is a whole number from 1 to 4, is applied to metal-modified polyolefin fibers. 2) procedure according to Claiml, characterized in that the metal-modified polyolefin fibers aluminum-modified polypropylene fibers used ..--.