DE1282226B - Process for the production of dyed regenerated cellulose fibers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY.

GERMAN

PATENT OFFICE

EDITORIAL

Int. CI .:

DOIf

German class: 29 b -3/26

Number: 1282 226

File number: P 12 82 226.3-43 (J 20910)

Filing date: November 27, 1961

Open date: November 7, 1968

The invention relates to a method for mass dyeing viscose rayon.

It is known to produce dyed viscose rayon by adding viscose solution, which is fine Contains particles of phthalocyanine pigments, spun. If in this process polychlorophthalocyanines green tones are obtained, which are because of their dullness and dichroism are not very appealing.

It has been found that the use of certain polybromochlorophthalocyanines in bulk dyeing of Viscose delivers very appealing yellowish green tones without any dichroism.

The subject of the invention is thus a method for producing dyed regenerated cellulose fibers, in a conventional viscose solution containing fine particles of one or more copper polybromochlorophthalocyanines contains wherein the total number of halogen atoms is at least 15 and at least six of the halogen atoms are bromine atoms, as usual ao spun.

When carrying out the method according to the invention, a viscose solution containing fine particles of copper polybromochlorophthalocyanine in a usual manner by squeezing through as the holes of a spinneret are spun into threads beneath the surface of a spinning bath liquid. the Threads can then be desulphurized, bleached and spun in any viscose thread for treatment usual way to be treated. For example, the threads can be treated with a desulfurized aqueous solution of sodium sulfide, sodium hydroxide, sodium carbonate or sodium sulfite and then bleached with sodium hypochlorite, washed and, if necessary, oiled.

Viscose solution containing fine particles of copper polybromochlorophthalocyanine can be suitably used can be obtained by mixing viscose solution with a finely dispersed aqueous suspension of copper polybromochlorophthalocyanine, as obtained by colloid milling (e.g. gravel milling) an aqueous paste of copper polybromochlorophthalocyanine in the presence of a dispersant such as disodium dinaphthyl methane - ^ - sulfonate, can be obtained. The best results are obtained using a finely dispersed one aqueous suspension of copper polybromochlorophthalocyanine, wherein at least 90% of the particles a Have a diameter of less than 3 μ, preferably less than 1 μ.

Copper polybromochlorophthalocyanines which are suitable for use in the process according to the invention can be made as follows:

Method of making colored
Regenerated cellulose fibers

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

8000 Munich 5, Müllerstr. 31

Named as inventor:

John Mitchell,

David Tough,

Manchester, Lancashire (UK)

Claimed priority:
Great Britain from December 2, 1960,

dated November 1, 1961 (41517)

Copper phthalocyanine is stirred with sodium bromide and aluminum chloride at a temperature between 155 and 165 ^° C. until the mass is liquid. Chlorine gas is then passed through the melt with stirring until no further weight gain can be detected. During the first 3 hours, the temperature was increased to about 190 ^° C. and kept at this temperature during the further introduction of the chlorine gas. The total chlorination treatment occurred within about 24 hours. The product, which contains between 15 and 16 helogen atoms per molecule, is isolated by cooling the reaction mixture, pouring it into dilute hydrochloric acid, filtering, washing and drying. The relative proportions of chlorine and bromine in the product depend on the proportions of the reactants. 104 parts of copper phthalocyanine, 168 parts of sodium bromide and 437 parts of aluminum chloride give a product that contains 7.2 bromine atoms and 8.5 chlorine atoms, while 78 parts of copper phthalocyanine, 225 parts of sodium bromide and 583 parts of aluminum chloride give a product that contains 12.5 bromine atoms and 3 , Contains 0 chlorine atoms. By replacing some of the chlorine with bromine, the proportion of the bromine substituent is increased, and conversely, by replacing some of the sodium bromide with sodium chloride, the proportion of the chlorine substituent is increased.

809 630/663

Claims (1)

3 4 According to the process according to the invention, the dispersion obtained in this way has greater color Regenerated cellulose fibers in a very attractive yellow starch, and the viscose yarn is more strongly colored, Lich green shades are colored, which an _R. · Ι ο excellent fastness to washing, sweat, e ι s ρ ι e dry cleaning and bleaching, compared to the 5 parts used in Example 1 instead of the 15 parts Textile finishing treatments and light-sensitive copper polybromochlorophthalocyanines can use 15 parts show no dichroism. Used with high levels of copper polybromochlorophthalocyanines gender number of bromine atoms in the copper poly- containing the following amounts of bromine and chlorine Bromochlorophthalocyanines will contain yellower shades: ^hold ·,,, “. . ,. ,., - ". ^{,, 10} a) 6.0 bromine atoms and 9.7 chlorine atoms (the pigment In the following examples, parts relate to _{vnrd obtained} essentially according to the instructions Weight. _of example 9 of British patent specification 925 266), B e i s ρ i e 1 1 b) 8.1 bromine atoms and 7.8 chlorine atoms (Example 4 ", _.,". ,, ,, ',,, · · of British patent specification "925 266), 15 parts copper polybromochlorophthalocyanine with 15 _{c) 125} bromine atoms and 3.0 chlorine atoms (Example 6 a content of 7 2 bromine atoms and 8.5 chlorine - _{the British} patent specification 925 266), atoms, which according to the procedure of Example 3 _{d) 15 0} bromine atoms and 0.6 chlorine atoms (Example 7 British Patent 925 266 has been obtained _{from British} Patent 925 266).
was, 5 parts of Dmatnumdinaphthylmethane-p-sulfonate and 75 parts of water are ground colloid to 20 The above examples describe the coloring of at least 90% of the particles are smaller than 3 microns. The viscose rayon with a series of copper poly- The paste obtained is separated from the gravel and replaced by bromochlorophthalocyanines, in which the number Adding water diluted to 100 parts. Bromine atoms is between 6.0 and 15.0 (the latter is 15 parts of the pigment dispersion described above, a practically completely brominated product), the total number of halogen atoms in a viscose solution with a 7.75% content of -cellulose being at least 15 with constant stirring. In each case one receives stated until a homogeneous mixture is obtained. take yellowish green tones without any dichroism. The mixture is degassed for 2 hours under vacuum with excellent fastness to light, washing, and then pressed at 45 ° C using sweat, dry cleaning and bleaching. With a gear pump with an output of 0.6 cm ^3/30 rising bromine in Polybromchlorphthalo-rev. a spinneret with 60 holes made of jecyanine makes the color tones increasingly yellow. Although 0.075 mm diameter is used in a spinning bath, compared to 15 parts of polybromochlorophthalene consisting of an aqueous solution containing cyanine in each example, 10% sulfuric acid, 20% Glauber's salt and 1% can of course be obtained by using a smaller amount of copper-zinc sulfate , and the yarn produced in this way is wound up and spools up. The speeds of the gear pump and, by using a larger amount of the darker bobbin, are tuned to achieve threads of color tones. Receives 5 denier. The yarn is desulfurized by using the same method in each of the examples it is used at 70 to 80 ° C by a l% is ^e aqueous spinning process, the invention is not Sodium sulfite solution leads, bleached by limiting it to the procedure described, and it Any known spinning process can optionally be used at 20 ° C. by means of an aqueous sodium hypochlorite solution with 0.35% content of available chlorine can be applied. it is washed well with water and dried. The disodium di-Das used in all examples Yarn is colored in a pleasant yellowish naphthyl methane / S-disulfonate can be caused by other disgreens Color with very good fastness to light, 45 persion media can be replaced, z. B. especially Na washing, Sweat, dry cleaning and bleaching trium oleyl sulfate, sodium oleyl p-anisidine sulfonate, li and without any dichroism. gninsulfonic acids, octylphenol ethylene oxide condensate If necessary, the yarn can be desulfurized, sat and cetyl alcohol-ethylene oxide condensate. by keeping it at 70 to 80 ° C by a 1% although the best results are as in the examples aqueous sodium sulfide solution (described in place of the sulfite 50, when using finely dispersed solution) leads. : aqueous suspensions of copper polybromochlorine _R. . , - phthalocyanine are obtained, in which at least α ei ei / 90% of the particles have a diameter smaller than 3 μ Instead of the 15 parts used in Example 1, yellowish green shades are obtained without di-copper polybromochlorophthalocyanine, 15 parts of 55 chromophthalocyanine are also used when using dispersions of a copper polybromochlorophthalocyanine, larger particle sizes are obtained,
which 11.4 atoms of bromine and 3.6 atoms of chlorine per _D ,
Contains molecule and mentansprucü according to the instructions in Example 5:
British Patent 925,266 is obtained. The process for making dyed viscose yarn is dyed in a more yellow-cellulose fiber, characterized by a distinctive green tone with very good fastness to light, characterized by using a conventional viscose solution, washing, sweating, dry cleaning and bleaching the fine particles of one or more several copper and completely free of dichroism. contains polybromochlorophthalocyanines in which If in this example the copper polybromochlorine- the total number of halogen atoms is at least 15 phthalocyanine paste is ground colloid until it is 65 and at least six of the halogen atoms are bromine At least 90% of the particles are atoms smaller than 1 μ in diameter, spun as usual. When the application was announced, 1 color sample was displayed with an explanation. 809 630/663 10.68 © Bundesdruckerei Berlin