MXPA05004229A - Process for incorporation of uv-luminescent compounds in polymeric materials. - Google Patents

Abstract

The invention relates to a process for the preparation of luminescent textile fibres characterized in that the fibres are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.

Description

PROCESS FOR THE INCORPORATION OF UV LUMINESCENT COMPOUNDS IN POLYMERIC MATERIALS FIELD OF THE INVENTION The present invention relates to a process for the preparation of UV luminescent polymeric materials and their uses.

BACKGROUND OF THE INVENTION There is a need to provide textiles with protective effects, which can act as safety markers, as special effects or as decorations that only become visible under UV irradiation.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a dye composition comprising a substantial one which is invisible to the naked eye but produces a strong luminescence under UV exposure and composition which may be useful for all conventional dyeing applications of polymeric materials including textiles such as wool, silk, cellulosic materials, natural and synthetic fibers as well as for the massive insertion of polymeric materials including those used in textile and plastic applications.

DETAILED DESCRIPTION OF THE INVENTION The invention relates to a process for the preparation of luminescent polymer fibers characterized in that the fibers are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one group that absorbs UV and (b) one or more solvents. Preferably, component (a) is a compound of formula I Lm-Ln3 + (Ch ") n (I), where Ln represents a lanthanide, Ch" is a negatively charged ligand containing at least one double bond that absorbs UV, n denotes 3 or 4, m denotes a number from 0 to 4, in the case where n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or polydentate ligand containing nitrogen, oxygen or sulfur or , in the case where n is 4, m denotes 1 and L is a cation of a single charge. More preferably, component (a) is a compound of formula II, III or IV where Ln represents lanthanide, n denotes 3 or 4, m denotes a number from 0 to 4 in the case where n is 3, m denotes a number from 0 to 4 and L is a neutral monodentate or a polydentate ligand containing nitrogen, oxygen or sulfur or, in the case where n is 4, m denotes 1 and L is a single charge cation, R2 is hydrogen Ci-C¾ alkyl, and Ri and R3 are each independently of each other hydrogen, Ci-C6 alkyl, CF3, C5-C aryl; or C4-C2 heteroaryl. The compounds of formula I, II, III or IV can contain basically any neutral or polydentate monodentate ligand containing nitrogen, oxygen or sulfur, such as, for example, unsubstituted or substituted pyridine, pyrazine, piperidine, quinoline, aniline, bipyridine, phenanthroline, terpyridine, imidazole, benzimidazole, bisimidazole, bisbenzimidazole, pyrimidine, bipyrimidine, naphthyridine, alkylamine, dialkylamine, trialkylamine, alkylene polyamine, dioxane, dimethylsulfoxide, dimethylformamide, (trialkyl or triaryl) phosphine oxide derivative, triazine, bistriazine, oxazole, bisoxazole, oxazoline, bisoxazoline and substituted derivatives thereof and all the relevant (poly) N-oxide derivatives of ligands mentioned above. Particularly preferred are the compounds of formula I, II, III or IV where n denotes 3 and L is a nitrogen-containing ligand. Since L can be a polyacrylate ligand, such as for example 4,4'-bipyridyl, the compounds of formula I, II, III and IV include multimetal chelates, such as for example compounds of formulas XIII and XIV, which contain two units of M111- (diketone) 3 or M I- (carboxylate): ¾ connected via a bidentate ligand: When n denotes 4, L as a cation of a single charge can be basically any metal cation (for example Li +, K +, Na +), unsubstituted or substituted ammonium (for example NH + r polyalkylammonium) or any monodentate or polydentate ligand protonated or rented as described above. Preferred positively charged ligands are piperidinium, ammonium, alkylammonium, dialkylammonium and, in particular, trialkylammonium. Triethylamine is especially preferred. Particularly preferred are the compounds of formula I, II, III or IV where L is a compound of formulas V to XII or a cation of the formula H-N + (Ri) 3, where R4, R5 and R6 are each independently of each other hydrogen, halogen, Ci-C6 alkyl, C5-C24 aryl, C6-C2 aralkyl, alkoxy Ci-C6, amino, dialkylamino or a cyclic amino group and R7 is hydrogen, Ci-Ce alkyl, C5-C24 aryl, C3-C24 aralkyl or vinyl. The alkyl groups as substituents Ra to R7 can be straight or branched chain. Examples which may be mentioned are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl and isohexyl. The alkoxy groups as substituents R4 to R6 may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy. Examples of C5-C2 aryl groups; phenyl, tolyl, mesityl, isityl, diphenyl, naphthyl and anthryl. Phenyl is preferred. The heteroaryl group preferably contains 4 or 5 carbon atoms and one or two heteroatoms selected from O, S and N. Examples of pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazine, pyrimidinyl, pyridazinyl, indolyl, purinyl or quinolyl. The aralkyl groups as substituents R4 to R7 can be, for example, benzyl, 2-phenylethyl, tolylmethyl, mesitylmethyl and -chlorophenylmethyl.

Suitable dialkylamino groups are, for example, diethylamino, diisopropylamino, di-n-propylamino, N-methyl-N-ethylamino and, in particular, dimethylamino or pyrrolidino. Suitable cyclic amino groups are pyrrolidino and piperidino. The halogen atoms as substituents R4 to Rs are preferably fluorine, chlorine or bromine, but in particular chlorine. Preferred compositions according to the invention contain as component (a) a compound of formula II wherein L is a compound of formula V, VI, VII, VIII, IX, X, XI or XII where R4, R5 and R6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N + (R7) 3. where R? is Ci-C alkyl. The preferred components (a) are compounds of formula I, II, III or IV where Ln is Eu, Tb, Dy, Sm or Nd. In addition, the compounds of formula II and III are preferred, wherein R x and R 3 are methyl, t-butyl, n-pentyl, or phenyl. R2 in formula II is preferably hydrogen. Particularly preferred as component (a) are the compounds of formula XIII to CVI: ? (XXXVI), N (XXXXVI I), (XXXXVIII).

Some preferred derivatives of structures of type II and III, derived from the aforementioned preferred structures of type I, are compiled in the following table: uv XVII LXIV LX1X LXXV LXXX XXI LXXXXI l_XXXXVII Clll LV ux LXV LXX LXXVI LXXXI LXXXV1 LXXXX1I LXXXXVIII CIV LVI LX LXVI LXXI LXXVII LXXXII LX XVII LXXXXIII LXXXXIX cv LVII LXI LXVII LXXII L XVIII LXXXIII LXXXVIII LXXXXIV C CV1 DMAP: 4-dimethylaminopyridine Additional lanthanide chelates may contain • pyridine, aminopyridine, pyrrolidinopyridine, methy1pyridine, methoxypyridine, pyridine-N-oxide, bipyridine, phenanthroline, imidazole or any other mono- or polydentate ligand containing N, 0 or S derived or similar from DMAP, piperidinium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, pyridinium or any other protonated species having N, similar, instead of Et3 H * For certain applications, it is advisable to use a combination of different lanthanides, for example Eu and T. This mixture increases the degree of security of concealed placements, the sophistication of the level of security and multiplies the possibilities of coding.

The compounds of formula I, II, III and IV are known, for example, from O 96/20942 and from C.R. Hurt et al., Nature 212, 179-180 (1966), or can be prepared by methods known per se. For example, a ligand such as acetylacetone, benzoylacetone, dibenzoylmethane, dipivaloylmethane, salicylic acid, valeric acid or caproic acid can be reacted under suitable conditions with a rare earth metal halide such as a lanthanide trichloride to produce the ground metal chelate. weird. The additional reaction with the monodentate or polydentate ligand containing nitrogen, oxygen or sulfur L thus produces the rare earth metal chelate compounds of formula I, II, III and IV. The luminescent lanthanide chelate can be applied as a powder, as a solution or as a dispersion. Accordingly, component (b) can be water, an organic solvent, a mixture of two or more organic solvents or a mixture of water and one or more organic solvents. Preferably, component (b) is water, one or more organic solvents miscible in water or a mixture of water and one or more organic solvents miscible in water. Suitable organic solvents include alcohols, glycols, ether alcohols, sulfoxides, amides, amines, heterocyclic solvents, ketones, ethers, esters, nitriles and aliphatic, cycloaliphatic and aromatic hydrocarbons. Examples of suitable organic solvents are methanol, ethanol, n-propanol, isopropanol, n-butanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monoethyl ether, polyethylene glycol dimethyl ether, ethoxy butanol, 2-butoxyethanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), direthylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, 2-butanone, diethyl ether, di-n-propyl ether, tetrahydrofuran (TF), ethyl acetate, ethyl propionate, acetonitrile, pyridine, n-pentane, n-hexane, cyclohexane, benzene and toluene. The water-miscible organic solvent is preferably an aliphatic alcohol, ether alcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatic sulfoxide. Particularly preferred water-miscible organic solvents are ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofuran (THF), dimethylformamide (DMF), direthylacetamide (DMA), N-mepyrrolidone. (NMP), acetonitrile, polyethylene glycol dimethyl ether and dimethylsulfoxide (DMSO). The compositions according to the invention can, in addition to components (a) and (b), comprise one or more dyes (c). Suitable dyes are well-known pigments and dyes, including mixtures of different pigments and dyes. In the compositions according to the present invention the amounts of the components (a) and (b) and where appropriate (c) and / or additional ingredients (d) may vary within wide ranges. For a mass staining process, the compositions according to the present invention consist of component (a). Optionally, additional ingredients (c) and / or (d) can also be added together with (a) to give supplementary properties simultaneously to the polymeric material in addition to the UV luminescence. For a dyeing process, the preferred compositions contain from 0.01 to 20.0%, more preferably from 0.05 to 10% and in particular from 0.1 to 5.0%, by weight of the component (a) and from 80.0 to 99.99%, so more preferable from 90.0 to 99.95% and in particular from 95.0 to 99.9%, by weight of component (b), based on the total amount of components (a) + (b). The amount of the component (c) depends on the type of substrate as well as the specific pigment or dye. Advantageous amounts will generally be from 0.01% to 15% by weight and especially from 0.1% to 10% by weight, of dye based on the weight of the fiber. The additional ingredients (d) which may be present in the compositions according to the invention are, for example, optical brighteners, biocides, bactericides, fungicides, insecticides and fragrance. Compositions containing at least one lanthanide chelate can be prepared by any suitable method known to those skilled in the art. For example, the components of the composition can be combined and mixed in a suitable mixer or combiner. The compositions according to the invention are useful for impregnating artificial, especially synthetic, natural synthetic hydrophobic materials, especially textile materials. Textiles composed of combined fabrics comprising these natural or synthetic polypropylene hydrophobic fibers can likewise be impregnated with the formulation of the invention. The natural polymeric textiles made useful are especially wool, cotton, silk, cellulose acetate and cellulose triacetate.

Synthetic hydrophobic textile materials are especially linear aromatic polyesters, for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of 1,4-bis (hydroxymethyl) -cyclohexane terephthalic acid; polycarbonates, for example those formed from a, a-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; or fibers based on polyvinyl chloride or polyamide. The formulations according to the invention are applied to the textile materials according to the known dyeing processes. For example, the polyester fibers are extensively dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants, as or without carriers customary at temperatures between 80 and 140 ° C., preferably between 120 and 135 ° C. The cellulose acetate is preferably dyed at between 60 to 85 ° C and the cellulose triacetate at 115 ° C. The formulations used according to the invention are useful for dyeing by thermal, continuous and continuous processes and for printing processes. The exhaustive process is preferred. The liquor ratio depends on the apparatus, the substrate and the way of manufacturing. However, the liquor ratio "can be chosen so that it is within a wide range, for example in the range of 4: 1 to 100: 1, but is preferably between 6: 1 to 25 ,: 1. The material The aforementioned textile may be present in different processing forms, for example as fiber, yarn or net or as a woven or knitted fabric forming curls The luminescent lanthanide chelates of the invention are probably useful for the mass staining of plastics Accordingly, the invention also relates to a process for the preparation of luminescent plastics characterized in that the plastic materials are extruded in the presence of 0.01-10.0% by weight, based on the amount of the plastic materials, of a compound of Formula I, II, III or IV Plastics useful for mass staining include, for example, organic materials of high molecular weight (polymers), dyeable, which have a constant d iellecica 2.5, especially polyester, polycarbonate (PC), polystyrene (PS), polypropylene (PP), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN! or acrylonitrile / butadiene / styrene (ABS). Preference is given to polyester and polyamide. Particular preference is given to linear aromatic polyesters obtainable by polycondensation of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane, for example polyethylene terephthalate (PET) or terephthalate. of polybutylene (PBTP); polycarbonates, for example polycarbonates formed from a, cr-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; polymers based on polyvinyl chloride or polyamide, for example nylon 6 or nylon 6.6, polystyrene (PS) or polypropylene (PP). Particular preference is given to plastics based on linear aromatic polyesters, for example those formed from terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane, methacrylate of polymethyl (PMMA), polypropylene (PP) or polystyrene (PS). The plastics are dyed for example by mixing the luminescent lanthanide chelate according to component (a) in those substrates using roller mills or mixing or grinding apparatuses whereby the lanthanide chelates are dissolved or dispersed finely in the plastic. The plastic with the mixed dyes is then processed in a conventional manner, for example by calendering, pressing, extrusion, spray coating, centrifugal casting, pouring or injection, whereby the dyed material acquires this final shape. The mixing of the components can also be carried out directly before the actual processing step, for example by continuously metering solid lanthanide chelates, for example pulverulent, and a granular or powdery plastic and also optionally additional substances, such as, for example, additives, Simultaneously, directly in the entrance area of an extruder where mixing takes place just before processing. In general, although it is preferred to first mix the lanthanide chelates in the plastic, since impregnated substrates can be obtained more uniformly. The invention also relates to luminescent textile fibers and luminescent plastics prepared by the process described above. The present invention makes it possible to incorporate colored or colorless occlusal markings on various colorless, white, pale-colored or dark-colored substrates, which can be developed under UV exposure. The claimed process is particularly useful for the manufacture of security fibers or security threads that can be applied to fiduciary documents or other materials. The security fibers are incorporated into fiduciary documents or other materials for the purpose of ensuring identification, authentication, protection against forgery, imitation, or reproduction.

Security threads are continuous threads or strips of film inserted into fiduciary documents for the same purpose as security fibers. The term "fiduciary documents" denotes papers, such as papers for bank notes, checks, stocks, invoices, stamps, official documents, identity cards, passports, record books, notes, tickets, vouchers, newsletters, accounting books as well as credit, payment, access or multifunctional cards, and similar documents that necessarily imply a high degree of security. The fabrication of security fibers or security threads can be effected by known methods as described, for example, in US Patents Nos. 4,655,788, 5,759,349 and 6,045,656, EP-A 185 396 and EP-A 1 013 824. The incorporation of the lanthanide chelate compound can be carried out by conventional dyeing or printing processes. The fibers suitable for the claimed process can be obtained from wood or vegetable pulp, or cellulose pulp, cotton, linen or synthetic fibers. Preferably, paper fibers or synthetic fibers are used.

In a particularly preferred embodiment, the process according to claim 1 is used for the preparation of documents, cards, checks or anti-falsification bank notes. The compositions according to the invention are distinguished from analogous prior art compositions by the quantum yield of outstanding luminescence, durable luminescence and high luminescence intensity. The following examples illustrate the invention.

Composition of Ink A ^ Concentrate of compound XVII in 1,2-propylene glycol 1 g of compound VIII is dissolved in 99 g of 1,2-propylene glycol under heating at 100 ° C for 1 hour. The light yellow solution is cooled and after filtration (clarification) provides the stable A-ink composition which exhibits an intense red luminescence under UV light. This concentrate can also be used in any conventional or high-tech printing (solvent-based) or water-based print formulations such as paper, textile, leather, wood, plastic or other compatible substrates.

Example 1: The impregnation of a cellulosic coil (cotton thread of 0.75kg of 40tex) is carried out at 35 ° C for 20 min in a stamping apparatus with alternating circulation (Callebault de Blicquy) (3 min cycle) with a ratio of liquor from 1 to 10. The liquor contains 4.5% of the compound of formula XVII in 2 -butoxy-ethanol. After treatment, centrifugation and air drying of the coil, a strong orange-red fluorescence is observed under UV light.

EXAMPLE 2 The impregnation of a silk thread (10g) was carried out at 25 ° C for 10-60 min in the same liquor and the ratio of liquor to textile material as described in Example 1. After treatment, centrifugation and Air-drying of the strand reveals a strong red-orange fluorescence under UV light.

Example 3: The impregnation of a patch fabric containing several different bands of synthetic, artificial, natural (vegetable and animal) fibers (20g) at 25 ° C for 10-60 min in the same liquor and liquor ratio was carried out. to textile material as described in Example 1. After the treatment, the centrifugation and air-drying of the patch reveals in most fibers a strong red-orange fluorescence under UV light. Equivalent results are obtained from similar processes using other lanthanide complexes, which exhibit another emission wavelength under UV radiation (eg, terbium, dispros io, sama io, neodymium).

Example 4: High temperature staining (HTD) of a polyester filament (FES) (135CC, 60 min) A filament of PES (10g) is introduced into a 250mL leak-tight bottle containing 200ml of staining bath ( that is, a bath ratio of 1 to 20). The dyebath is prepared as a mixture of the following two solutions: 0 a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex of formula XVII dissolved in NP ° an aqueous solution at pH = 4.5 (195 to 170ml) containing • 0.6g / l of Univadin DP. { Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (90 ~ 105 ° C). The filament of PES thus treated exhibits a strong red-orange fluorescence under irradiation at 365nm.

Example 5: High temperature staining (HTD) of a PES velvety cloth (135 ° C, 60 in ^) A velvety PES fabric (lOg) is introduced. It is a leak-tight 250mL bottle, containing 200ml of staining bath . {ie, a bath ratio of 1 to 20). The dye bath is prepared as a mixture of the following two solutions: ° a solvent-based solution (5 to 30ml) containing 3-5% of the complex. lanthanide of formula XVII dissolved in NMP ° an aqueous solution at pH = 4.5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (90-105 ° C). The PES filament thus treated exhibits strong reddish-orange fluorescence under irradiation at 365 nm.

Example 6: High temperature staining (HTD) of a PES velvety cloth (135 ° C, 60min) A velvety PES fabric (10g) is introduced. This is a leak-tight 250mL bottle, containing 200ml of staining bath ( that is, a bath ratio of 1 to 20). The staining bath is prepared as a mixture of the following two solutions: 0 a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV dissolved in NMP ° an aqueous solution at pH = 4.5 (195 to 170ml) which contains · 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally decreased to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried with hot air (90-105 ° C). The velvety PES fabric thus treated is white and exhibits a strong green fluorescence under irradiation at 254 nm.

Example 7: High temperature staining (HTD) of a polyamide tricot. { 135 ° C, 60min) A PA tricot (lOg) is introduced into a leak-tight 250mL bottle containing 200ml of staining bath (ie, a bath ratio of 1 to 20). The dye bath is prepared as a mixture of the following two solutions: ° a solvent-based solution (5 to 30 ml) containing 3-5% of the lanthanide complex of XVII dissolved in NMP 0 an aqueous solution at pH = .5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Ciba Specialty Chemicals) · 2.5g / l of Cibatex AB 45 (Ciba Specialty 23 Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a high temperature autoclave, rotating, with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally decreased to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried with hot air (90-105 ° C). The PA tricot thus treated exhibits a strong red-orange fluorescence under irradiation at 365 nm.

Example 8: High temperature staining (HTD) of a polyamide tricot (135 ° C, 60min) A white PA tricot (lOg) is introduced into a 250mL leak-tight bottle, containing 200ml of staining bath (en say, a bathroom relationship-- from 1 to 20). The dyebath is prepared with a mixture of the following two solutions: ° a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex of formula XVII dissolved in NMP or an aqueous solution at pK =. 5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Giba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with a bath temperature of 70 ° C. The temperature is then raised to 125 ° C for 30 min and is stable for 1 more hour. The treatment temperature is finally reduced to G ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with 35 ° C hot water), dried by centrifugation and finally dried by hot ( 90-105 ° C). The PA tricot thus treated exhibits a green luorescence under irradiation at 254 nm.

Example 9: High temperature staining (HTD) of a transparent colorless PA strand (135 ° C, oGniinJ A transparent colorless? A strand (lOg) is introduced into a leak-tight 250mL bottle, containing 200ml of water bath. staining (ie, a bath ratio of 1 to 20).

The staining bath is prepared with a mixture of the following two solutions: ° a solvent-based solution (5 to 30 ml) containing 3-5% of the lanthanide complex of formula XVII dissolved in NMP 0 an aqueous solution at pH = 4.5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally decreased to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried with hot air (90-105 ° C). The strand of PES trtansparente thus treated exhibits a strong fluorine under irradiation at 365nm.

Example 10: Incorporation of XVII in polyamide (PA) by a massive staining process The Ultramid B3K extruded in the presence of 2% of the lanthanide XII complex for 2 min at 260 ° C results in a reddish-orange fluorescence after irradiation at 365nm.

Example 11: Incorporation of XVII in polystyrene (PS) by a massive staining process Polystyrol H165 extruded in the presence of 2% of the lanthanide XII complex for 5 min at 300 ° C results in a red-orange fluorescence after irradiation to 365nm.

Example 12: Incorporation of XVII into polypropylene (PP) by a massive dyeing process A homogenized mixture of polypropylene granules (200g) and a compound XVII (2g) is introduced into the melting chamber (200 ° C) of an extruder of jrr.m. After cooling in a water bath, the rigid cable thus obtained is cut into granules again, which in turn are introduced into the melting chamber (230 ° C) of a filament extruder. In this way a polypropylene, clear, transparent fiber (dtex of 8) is obtained, exhibiting a strong red-orange fluorescence after excitation at 365 nm.

Example 13: Incorporation of XVII into polypropylene (PP) by a massive staining process A similar process and resulting fluorescent properties are obtained with the simultaneous use of Titanium dioxide together with compound XVII.

Example 14: Incorporation of XVII in poly (methyl methacrylate) (PMMA) by a massive staining process The 6N Plexiglas extruded in the presence of 2% lanthanide complex XVII for 5 min at 260 ° C results in a red fluorescence o- orange after irradiation at 365 nm.

Example 15: Incorporation of XVII into acrylonitrile / butadiene / styrene (ABS) copolymer by a bulk staining process The Terluran 877M extruded in the presence of 2% lanthanide XVII complex for 5 mm at 220 ° C results in a red fluorescence -Autumn after irradiation at 365nm.

Example 16: High temperature staining (HTD) of a thin strand of colored PES (135 ° C, 60min) A thin strand of PES cyan (lOg), previously stained in bulk with a mixture of Irgalite Blue GLGP (CI Pigment Blue 15: 3), titanium dioxide. { C.I. Pigment White 6) and black smoke. { C.I. Pigment Black 7) - is introduced in a leak-tight 250ml bottle, containing 200ml of staining bath (ie bath ratio 1 to 20). The dyebath is prepared as a mixture of the following two solutions: ° a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide XV-compost dissolved in NMP ° an aqueous solution at pH = 4.5 (195 to 170ml) which contains · 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (90-105 ° C). The thin strand of PES thus treated exhibits a strong green fluorescence under irradiation at 254 nm and does not fluoresce under irradiation at 365 nm.

Example 17: High emperature staining (HTD) of a thin strand of colored PES (135 ° C, 60min) A thin strand of black PES (10g), previously stained in bulk with a pigment metal containing titanium dioxide ( CI Pigment White 6) and carbon black (CI Pigment Black 7) - is introduced in a leak-tight 250ml bottle, containing 200ml of staining bath (ie bath ratio 1 to 20). ? 1 dye bath is prepared as a mixture of the following two solutions: ° a solvent-based solution (5 to 30 ml) containing 3-5% of the lanthanide complex XV dissolved in NMP or an aqueous solution at pH = 4.5 ( 195 to 170ml) containing 0.6g / l of Univadin DP (Giba Specialty Chemicals) 2. 5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) 0.4g / l sodium hydrogen carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (90-105 ° C). The thin black strand of PES thus treated exhibits a strong green fluorescence under irradiation at 254 nm and does not exhibit fluorescence under irradiation at 365 nm.

Example 18: High temperature staining (HTD) of a thin strand of colored PES (135 ° Cr Omin) A thin strand of yellow PES (10g), previously stained massively with Yellow Filester RNB ÍC.I. Pigment Yellow 147) - is introduced into a 250ml leak-tight bottle containing 200ml of staining bath (ie bath ratio 1 to 20). The dyebath is prepared with a mixture of the following two solutions: 0 a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV dissolved in NMP ° an aqueous solution at pH = 4.5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a high-temperature autoclave, rotating, with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally lowered to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried hot pelaire ( 90-105 ° C). The thin yellow strand of PES thus treated exhibits a strong red-orange f uorescence under irradiation at 254 nm. and does not exhibit fluorescence under irradiation at 365nm.

Example 19: High temperature staining (HTD) of an S filament (135 ° C, 60min) A filament of PES (10g), is introduced in a 250ml celia leak-tight, containing 200ml staining bath (ie bath ratio 1 to 20). The dye bath is prepared as a mixture of the following two solutions: 0 a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex dissolved in NMP ° an aqueous solution at pH = 4.5 (195 to 170mi) containing • 0.6g / l of Univadin DP (Giba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The Or treatment temperature is finally decreased to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (90-105 ° C). The PES filament thus treated exhibits strong reddish-orange fluorescence under irradiation at 365 nm.

Example 20: High temperature staining (HTD) of a PES filament (135CC, 60min) A filament of white PES (10g), is introduced into a 250ml leak-tight bottle, containing 200ml of staining bath (ie bath ratio 1 to 20). The dyebath is prepared as a mixture of the following two solutions: ° a suspension of NMP (5 to 30nil) containing 2% of the wool complex 0 an aqueous solution at pH = 4.5 (195 to 170ml) containing • 0.6g / l of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Cibatex AB 45 (Ciba Specialty Chemicals) • 0.4g / l of sodium acid carbonate The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 125 ° C for 30 min and remains stable for 1 hour more. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally air dried. hot (90-105 ° C). The white filament of PES treated in this way exhibits a pinkish luorescence or under irradiation at 254 nm and without fluorescence under irradiation at 365 nm.

Example 21: High temperature staining (HTD) of a PES filament. { 135oC, bOmin) A filament of white PES (lOg), is introduced into a leak-tight 250ml bottle, containing 200ml of staining bath (ie bath ratio 1 to 20). Beino staining is prepared with a mixture of the following two solutions: ° a solvent-based solution (5 to 30ml) which contains 3-5% of the lactide or comole dissolved in NMP ° one. aqueous solution at pK = 4.5 (195 to 170ml) containing • O.Gg/1 of Univadin DP (Ciba Specialty Chemicals) • 2.5g / l of Ci atex AB 45 (Ciba Specialty Chemicals) • 0.4g / l Sodium Carbonate Acid The bottle is installed in a rotating high temperature autoclave with an initial bath temperature of 70 ° C. The temperature is then raised to 135 ° C for 30 min and remains stable for 1 more hour. The treatment temperature is finally reduced to 40 ° C for 15 min, after which the strand is removed from the bottle, rinsed for 5 min with hot water (35 ° C), dried by centrifugation and finally dried by hot air (S0-105 ° C>.) The white strand of PSS thus treated exhibits a green fluorescence under irradiation at 254 nm and does not exhibit fluorescence under irradiation at 365 nm.

Example 22 High temperature staining (???) of PES (135 ° C, 60 nun) All the previous experiments of Stain to Alca Temperature are also made without using NMP, by a method of 1 of the Dispersed Dyes, and replacing the Scattered Tint with the lanthanide chelate fluorescent to the UV to be applied.

Example 23: Transfer printing with fluorescent lanthanide chelates to UV is effected using transfer printing formulations containing one or more UV-fluorescent lanthanide chelates. Such formulations are prepared in a manner similar to conventional transfer printing formulations, either by using one or more lanthanide chelates in place of disperse dyes, or by using one or more lanthanide chelates in addition to the dispersed dyes.

Example 24: Preparation of a safety strand of multicomponent is a polymeric mixture (for example poiiamide cocol imanized AJulon * distributed by Akzoplastiks) The grinds indicated by the external components of the strand are each mixed with 3% by weight of a compound of formula (XVII) in such a way that it dissolves homogeneously in the poiyamide melt. After the extrusion of the multicomponent strands, a safety strand is obtained from the edge strips from which they fluoresce under UV light while the central strip shows no fluorescence. The coextrusion of the lanthanide chelates with one or more dyes or pigments provides colored strands which are fluorescent simulated under UV light.

Example 25: Preparation of a single-component safety strand As described in Example 24, a safety strand was prepared by extrusion of a melt of pcliamide containing 3% by weight of a 1: 1 mixture of a compound of formula (XVII). ) and a compound of formula (XV). After irradiation of UV light of different wavelengths a red and / or green fluorescence was observed.

Claims (20)

1. CLAIMS 1. A process for the preparation of luminescent polymeric fibers, characterized in that the fibers are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one group that absorbs u and y (b) one or more solvents.
2. 2. The process according to claim 1, characterized in that component (a) is a compound of formula I Lm-Ln3 '(Ch) n (I), where Ln represents a lanthanide, Ch "is a negatively charged ligand. that contains at least one double bond that absorbs UV, n denotes 3 or 4, m denotes a number from 0 to 4, in the case where n is 3, m denotes a number from C to 4 and L is a neutral monodentate or polydentate ligand containing nitrogen, oxygen or sulfur or, in the case where r is 4, m denotes 1 and L is a single charge cation 3. The process according to claim 1, characterized in that the component (a) is a compound of formula II, III or IV where Ln represents lanthanide, n denotes 3 or 4, m denotes a number from 0 to 4 in the case where r: is 3, ra denotes a number from 0 to 4 and L is a neutral monodentate or a polydentate ligand that contains nitrogen, oxygen or sulfur or, in the case where n is 4, m denotes 1 and L is a cation of a single shell, R2l is hydrogen C1-C alkyl, and Ri and R3 are each independently yes hydrogen, C1-di alkyl, CF3, C5-CS arium; or C-C2 heteroaryl. 4. The process according to claim 2 c 3, characterized in that component (a) is a compound of formula I, II, III or IV where n denotes 3 and L is a ligand containing nitrogen. 5. The process according to claim 3, characterized in that component (a) is a compound of formula I, II, III or IV where L is a compound of formulas V to XII or a cation of the formula H-N + (3 / where R, R5 and R5 each independently of each other hydrogen, halogen, CL-C6 alkyl, C aryl; -C24, C3-C4 arachidyl, alkoxy or R7 is hydrogen, Ci-C6 alkyl, aryl of C -Cz.lf C ara-C24 araiquil or vinyl 6. The process according to claim 13, characterized in that the component (a) is a compound of formula II, wherein L is a compound of formula V, VI, VII, VIII, IX, X, XI or XII where ¾, R5 and R ~ are hydrogen, methyl, amino, pyrrolidino or dirne- i lamino or L is a cation of the formula H-N + (R7) 3, where R- is alkyl of CL-C5 7. The process according to claim 2 or 3, characterized in that component (a) is a compound of formula I, II, III IV where Lr is Eu, Tb, Dy, Sm or Nd. The process according to claim 3, characterized in that component a) is a compound of formula II or III where R L and R :. they are methyl, t-butyl, n-pencilo or phenyl. 9. The process according to claim 3, characterized in that the component a) is a compound of formula II wherein R2 is hydrogen. The process according to claim 3, characterized in that component (a) is a compound of formula XIII to LII (H3C), CX (?,), ?? Tb, C (CH,), (XXII). o o '(XXIV). L 1. G? O "" '"). Tb" ((xxxiv) (XXXVI), (XXXXIV). (XXXXVI), H3C- -CH, (XXXXVII). O O (XXXXVIII). Nd 11. The process according to claim 1 or 2, characterized in that the component (b) is water, one or more organic solvents miscible in water or a mixture of water and one or more organic solvents miscible in water. 12. The process according to claim 11, characterized in that the organic solvent miscibie in water is an aliphatic alcohol, ether alcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatic sulfoxide . 13. The process according to claim 11, characterized in that the organic solvent used in water is selected from the group consisting of ethane, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofuran ( THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (MMP), acetomtril, polyethylene glycol dimethyl ether and dimethylsulfoxide (DMSO). The process according to claim 1, characterized in that the formulation contains 0.01 to 20.0% by weight of component (a) and 80.0 to 99.99% by weight of component (b), based on the total amount of the components (a) + (b). 15. The process according to claim 1, characterized in that the formulation additionally contains (c) one or more colorants. 16. The process for the preparation of luminescent plastics, characterized in that the plastic material is produced in the presence of 0.01 - 10.0% by weight, based on the amount of polymeric material, of a compound of formula II or III in accordance with claim 3. 17. A luminescent textile fiber characterized in that it is prepared by the process according to claim 1. 18. A luminescent plastic, characterized in that it is prepared by the process according to claim 16. 19. The compliance process according to claim 1, characterized in that the polymeric fibers are paper fibers or synthetic fibers. 20. Use of the process according to claim 1, for the preparation of documents, cards, checks or anti-counterfeit bank notes.