UVACTIVE RAIN ADVICE CELLULOSE FIBERS

The invention is on the area of the lumineszierenden cellulose fibers. The dye of rain advice cellulose is accomplished generally according to the usual methods of the Textilfärberei for flake, yarns, surface fabrics and Gewirke with water-soluble coloring materials or Kepenfarbstoffen. Coloring during the spin process against it is so far only possible with pigments, since these color bodies do not remain enclosed in for the viscose rayon fiber solubility in water or organic solvents to show and thus with the following wash processes (chemical fibre textile industry, Bd 34/86 (1984) number 6.444). If one wants to brighten rain advice cellulose fibers up optically, then nouns Aufheller are added to the wash baths, which follow the spin process, which fluoreszieren within a broad UV range ton with approximately 250 - 360 Nm radiation absorb and within the visible range with approximately 420 - 440 Nm. If one uses water-soluble optical Aufheller, then the finished fibers show bad wash genuinenesses, which means that the desired effect is only from temporally limited duration. In addition the light fastness level must be called insufficient. As the further disadvantage of these organic UVactive compounds their price is to be regarded. If UVactive pigments are included into the fiber, results frequently a fiber with the self-color of the effective substances or however fibers, which appear as very white white to blaustichig for the human eye. The US4,655,788 A describes a procedure for the production of lumineszierender fibers using for example organic, water-soluble, lumineszierenden materials. Here the auxiliary materials are added to the dyebath for the fibers. In accordance with GB609 197 A are added to a Spinnlösung for artificial fibers, like cellulose derivatives, before extruding inorganic fluorescent pigments, e.g. zinc sulfide or Cadmiumwolframat, and the manufactured molded articles with a fluorescence coloring material are colored following, so that they exhibit both in the visible light and in UV light an intensive color. In chem. Abstr. 122 (1995) No. 190705s are descriptive four different fluorescent rain advice cellulose films, those by mixing a cellulose solution with fluorescent inorganic substances, e.g. Zn2 SiO4: Mn were manufactured. The Fluoreszenzspektren, the fluorescence intensities, examines, became which crystallinity degrees and the mechanical characteristics of the films. The Japanese patent publication 87-327866 describes the additive of Yttriumoxysulfid, but has this pigment the disadvantage that it loses during the meal procedure on particle sizes of smaller 1 p.m its ability of the luminescence, since this effect depends on the crystal structure of the connection. In addition the sulfur portion is not sufficiently steady in the molecule to the sour spin process, the following desulphurisation procedures and the oxidative process steps, which a viscose rayon fiber goes through according to standard. Task of the available invention was it to place a procedure for the production of a nichffarbigen rain advice cellulose fiber for the order which avoids the disadvantages described above. In addition a synthetic material is desired, which only in a very much limited spectral region of approximately 10 - 20 Nm to fluorescence to stimulate is. The task is solved surprisingly by adding certain inorganic phosphors to the viscose rayon mass and following spiders into a sour coagulating bath. Article available invention are lumineszierende rain advice cellulose fibers, containing or several inorganic phosphors from group phosphates, oxides, Wolframate, Sitikate and aluminates Erdalkatimetatle, which Nebengruppenetemente or the set tones the ground connections as well as the halides Alkaliund of alkaline earth metals, which are endowed with one or more activators from the group a Mn2*, Mn " * Sb3., Sn2., Pb2., Cu*, Ag+ and the rare ground connection, in a quantity from 0,01 to 5 Gew. - %, preferably 0.2 to 3 Gew. - %, related to the cellulose content of the spin mass before the precipitation and deformation, whereby the inorganic phosphors possess a middle particle size of smaller than 1 t m, in particular 0.5 to 0.7 p.m. By the term inorganic phosphors are synthetically won, inorganic, to understand crystallized connections which are qualified, after Energieabsorption in the ultraviolet, Röntgenoder visible spectrum to shine. During this procedure called Photolumineszenz the wavelength of the emission maximum is large as those the absorbed radiation. Generally the lucency is only acquired by activation, i.e. by installation (doping) RK 409,377 B by small quantities of crystal-strange ions (activators) into the crystal lattice of the inorganic compound (base material). Particularly preferential inorganic phosphors are calcium phosphates, zinc silicates, strontium phosphates, alkaline-earth silicates, Silikateund of aluminates the rare ground connection, Wolframate of the alkaline earth metals, zinc oxides and oxides the rare ground connection. Particularly preferential activators are Eu2÷, Eu3., Sb3., Mn2÷, Ag*, Cu*, Sn2. and Tb”. Are from special interest the following phosphor activator combinations: Zinc salts with Mn2., Cu+ or Ag* as activators; Barium magnesium aluminate, Ba (AI, mg) 11 O19: Eu2; • • 2+ Strontlumalumlnat, SrAI2 04: European Union; Yttriumoxid, Y2 03: Eu3*; Calciumhalophos3+ 2+. - chamfer, Cas (PO) 4) 3 (F, CI): Self-service, Mn; StrontJummagnesJumorthophosphat, (SR, mg) 3 (PO4) 2: Sn2*; Zinc. • • 2+ • • 3+ sdJkatZn2SiO4: Mn; Cermagneslumalummat, Ce (mg, AI) 12,019: Tb. It was shown that activated base materials can be stimulated also in a cellulose matrix energetically and when irradiation “bright” to work. This is above all therefore Qberraschend, since most inorganic phosphors are acid unstable and were not it to be expected that these connections drink that strongly spin process without prejudice to project. The phosphors emit light in narrow wave bands of the visible spectral area, the near ultraviolet and the infrared. The production of phosphors and their doping with activators is actually admits and in the literature describes already variously, so for example in UIImann, encyclopedia of technical chemistry, (publishing house chemistry, Weinheim, New York) 4th Aufl. Bd. 16, page 180 fr. (1978). The subject of the available invention is also a procedure for the production of lumineszierenden rain advice cellulose fibers, characterized by that one adds the inorganic phosphor of the viscose rayon mass endowed with the activator and in the viscous pin procedure fibers spinnt, or by adding the phosphor of a cellulose draw and from the password to fibers spinnt, as for example in the cuprous procedure, the Lyocellverfahren and the procedure over low Celluloseether substituted. The cellulose in a suitable organic solvent one draws, for example N-Methylmorpholinoxid/water, which phosphor in dispersed form of the password added, and the mass directly to fibers versponnen. The phosphors according to invention show a good compatibility with the viscose rayon. The additive takes place in a quantity from 0,01 to 5 Gew. - %, preferably 0.2 to 3 Gew. - %, related to the cellulose content of the spin mass, before the precipitation and deformation. The following examples serve the invention for the elucidation. The term of parts corresponds to parts by weight. Example 1 into a operatingusual spin viscose rayon with a cellulose content of 8,9%, an alkali content of 5% and a viscosity of 38 Kugelfatlsekunden with 30°C is introduced an inorganic phosphor. One proceeds as follows: 4,48 parts Yttriumoxid, endowed with europium, particle size smaller 1 I m are dispersed in 10 parts water and mixed with 436 parts of spin viscose rayon. This Vormischung is stirred into 2522 parts of spin viscose rayon. After dern degassing the spin mass in operatingusual viscous pin procedures into a sulfur-sour, Natriumund zinc sulfate haltiges bath to fibers versponnen, drawn in sour baths, cut, washed, prepared and dried. It will receive a fiber, which when irradiation with light the wave-long 254 Nm a red luminescence color, but no self-color exhibits. Example 2 one works according to the data of the example 1 and interferes 3%, related to the cellulose mass in the viscose rayon, barium magnesium aluminate, which is endowed with europium, into the spin mass. After further processing after the process steps usual for spinviscous a fiber RK will receive 409,377 B I0 from modiflzierter viscose rayon, which shows 254 Nm a blue luminescence color when irradiation with light of the wavelength, without being even colored. Example 3 one works according to the data of the example 1 and mixes 1% cerium magnesium aluminate, which contains terbium as activator, into the spin mass. After execution of the further usual process steps a fiber will receive, which shines when irradiation with light of the wavelength 254 Nm with a green luminescence color. Examples 4 to 6 one in each case 2% of the phosphor in the following specified work according to the data of the example 1 and mix: Activator too. 4. Calcium halo phosphate • Sb3+ Strontiummagnesiumorthophosphat' Sn” 6. zinc silicate: Mnz+ luminescence color: light blue rotor course gr0n.