EP1560894A2 - Process for incorporation of uv-luminescent compounds in polymeric materials - Google Patents

Process for incorporation of uv-luminescent compounds in polymeric materials

Info

Publication number
EP1560894A2
EP1560894A2 EP03795792A EP03795792A EP1560894A2 EP 1560894 A2 EP1560894 A2 EP 1560894A2 EP 03795792 A EP03795792 A EP 03795792A EP 03795792 A EP03795792 A EP 03795792A EP 1560894 A2 EP1560894 A2 EP 1560894A2
Authority
EP
European Patent Office
Prior art keywords
process according
formula
compound
component
denotes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03795792A
Other languages
German (de)
English (en)
French (fr)
Inventor
Véronique Hall-Goulle
Stefan Koller
Luc Nueffer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP03795792A priority Critical patent/EP1560894A2/en
Publication of EP1560894A2 publication Critical patent/EP1560894A2/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004—General aspects of dyeing
    • D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/90—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in organic solvents or aqueous emulsions thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the present invention relates to a process for the preparation of UV luminescent polymeric materials and their uses.
  • It is therefore an object of the present invention to provide a dyeing composition comprising a substance which is invisible to the unaided eye but yields a strong luminescence under UV exposure and which composition can be used for all conventional dyeing applications of polymeric materials including textiles such as wool, silk, cellulosic materials, natural and synthetic fibres as well as for the mass dyeing of polymeric materials including those used in textile and plastic applications.
  • component (a) is a compound of formula I
  • Ch " is a negatively charged ligand containing at least one UV absorbing double bond
  • n denotes 3 or 4
  • m denotes a number from 0 to 4
  • m denotes a number from 0 to 4
  • L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4,
  • m denotes 1 and L is a single-charged cation.
  • component (a) is a compound of formula II, III or IV
  • Ln represents a lanthanide
  • n denotes 3 or 4
  • m denotes a number from 0 to 4 in case n is 3
  • m denotes a number from 0 to 4
  • L is a neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand or, in case n is 4,
  • m denotes 1 and
  • L is a single-charged cation
  • R 2 is hydrogen or C C 6 alkyl
  • R T and R 3 are each independently of the other hydrogen, d-C ⁇ alkyl, CF 3l C 5 -C 24 aryl or
  • the compounds of formula I, II, III or IV can basically contain any neutral monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand 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, phosphine-oxide derivative (trialkyl or triaryl), triazine, bistriazine, oxazole, bisoxazole, oxazoline, bisoxazoline and substituted derivatives thereof and all relevant (poly)N-oxide derivatives of above cited ligands.
  • n denotes 3 and L is a nitrogen-containing ligand.
  • L can be a polychelating ligand, like for example 4,4'-bipyridyl
  • the compounds of formula I, II, III and IV include multimetallic chelates, such as for example the compounds of formula XIII and XIV, containing two M -(diketone) 3 or M -(carboxylate) 3 units connected via a bidentate ligand:
  • L as single-charged cation can be basically any metal cation (e.g. Li ⁇ K + , Na + ), unsubstituted or substituted ammonium (e.g. NH 4 + , polyalkylammonium) or any protonated or alkylated monodentate or polydentate ligand as described above.
  • metal cation e.g. Li ⁇ K + , Na +
  • unsubstituted or substituted ammonium e.g. NH 4 + , polyalkylammonium
  • any protonated or alkylated monodentate or polydentate ligand as described above.
  • Preferred positively charged ligands are piperidinium, ammonium, alkylammonium, dialkylammonium and, in particular, trialkylammonium.
  • Triethylammonium is especially preferred.
  • R , R 5 and Re are each independently of the other hydrogen, halogen, d-C 6 alkyl, C 5 -C 24 aryl, C 6 -C 24 aralkyl, CrC 6 alkoxy, amino, dialkylamino or a cyclic amino group and R 7 is hydrogen, C C 6 alkyl, C 5 -C 24 aryl, C 6 -C 24 aralkyl or vinyl.
  • Alkyl groups as substituents R ⁇ to R 7 can be straight chain or branched. 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.
  • Alkoxy groups as substituents R to R 6 can be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.
  • C 5 -C 24 aryl groups are phenyl, tolyl, mesityl, isityl, diphenyl, naphthyl and anthryl. Phenyl is preferred.
  • Heteroaryl group preferably contain 4 or 5 C atoms and one or two heteroatoms selected from O, S and N. Examples are pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl or chinolyl.
  • Aralkyl groups as substituents R to R 7 can be, for example, benzyl, 2-phenylethyl, tolylmethyl, mesitylmethyl and 4-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.
  • Halogen atoms as substituents R 4 to R e are preferably fluorine, chlorine or bromine, but in particular chlorine.
  • 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 wherein P , R 5 and R 6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N + (R 7 ) 3 .wherein R 7 is CrC 6 alkyl.
  • Preferred components (a) are compounds of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm or Nd.
  • Ri and R 3 are methyl, t-butyl, n-pentyl or phenyl.
  • R 2 in formula II is preferably hydrogen.
  • component (a) are the compounds of formula XIII to CVI:
  • lanthanide chelates may contain
  • pyridine aminopyridine, pyrrolidinopyridine, methylpyridine, methoxypyridine, pyridine-N-oxide, bipyridine, phenanthroline, imidazole or any other derived or similar N, O or S containing mono- or polydentate ligand in place of DMAP piperidinium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, pyridinium or any other similar N containing protonated species in place of Et 3 NH +
  • the compounds of formula I, II, III and IV are known, for instance from WO 96/20942 and from CR. Hurt et al., Nature 212, 179-180 (1966), or can be prepared by methods known per se.
  • 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 rare earth metal chelate. Further reaction with the monodentate or polydentate nitrogen-, oxygen- or sulfur-containing ligand L thus yielding 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.
  • component (b) may be water, an organic solvent, a mixture of two or more organic solvents or a mixture of water and one or more organic solvents.
  • component (b) is water, one or more water-miscible organic solvents or a mixture of water and one or more water-miscible organic solvents.
  • Suitable organic solvents include alcohols, glycols, ether alcohols, sulfoxides, amides, amines, heterocyclic solvents, ketones, ethers, esters, nitriles and aliphatic, cycloaliphatic and aromatic hydrocarbons.
  • 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 monoethylether, polyethyleneglycol dimethyether, ethoxybutanol, 2-butoxyethanol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetone, 2-butanone, diethylether, di-n-propylether, tetrahydrofurane (THF), ethyl acetate, ethyl propionate, acetonitrile, pyridine, n-pentane, n-hexane, cyclohexane, benzene and toluene.
  • the water-miscible organic solvent is preferably an aliphatic alcohol, etheralcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrile, aliphatic polyether or aliphatic sulfoxide.
  • compositions according to the invention may, in addition to components (a) and (b), comprise one ore more colorants (c).
  • Suitable colorants are the well-known pigments and dyes including mixtures of different pigments and dyes.
  • compositions according to the present invention the amounts of components (a) and (b) and where appropriate (c) and/or further ingredients (d) can vary within wide ranges.
  • compositions according to the present invention consist of component (a).
  • further ingredients (c) and/or (d) may also be added together with (a) in order to give simultaneous supplementary propertie(s) to the polymeric material in addition to the UV-luminescence.
  • compositions For a dyeing process, preferred compositions contain 0.01 to 20.0 %, more preferably 0.05 to 10 % and in particular 0.1 to 5.0 %, by weight of component (a) and 80.0 to 99.99 %, more preferably 90.0 to 99.95 % and in particular 95.0 to 99.9 %, by weight of component (b), based on the total amount of components (a) + (b).
  • the amount of component (c) depends on the type of substrate as well as on the specific pigment or dye. Advantageous amounts will generally be 0.01% to 15% by weight and especially 0.1% to 10% by weight, of colorant based on the weight of fibre.
  • compositions according to the invention are e.g. 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 of ordinary skill in the art.
  • the components of the composition can be combined and mixed in a suitable mixer or blender.
  • compositions according to the invention are useful for impregnating manufactured natural, artificial and especially synthetic hydrophobic materials, especially textile materials.
  • Textile materials composed of blend fabrics comprising such manufactured natural polymer or synthetic hydrophobic fiber materials can likewise be impregnated with the formulations of the invention.
  • Useful manufactured natural polymer textile materials 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 terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane; polycarbonates, for example those formed from ⁇ , ⁇ -dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; or fibres based on polyvinyl chloride or polyamide.
  • linear aromatic polyesters for example polyesters formed from a terephthalic acid and glycols, particularly ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hydroxymethyl)cyclohexane
  • polycarbonates for example those formed from ⁇ , ⁇ -dimethyl-4,4'-dihydroxydiphenylmethane and phosgene
  • fibres based on polyvinyl chloride or polyamide are especially linear aromatic polyesters, for example polyesters formed from a terephthal
  • polyester fibres are exhaust dyed from an aqueous dispersion in the presence of customary anionic or nonionic dispersants with or without customary carriers at temperatures between 80 and 140°C, preferably between 120 and 135°C.
  • Cellulose acetate is preferably dyed at between 60 to 85°C and cellulose triacetate at up to 115°C.
  • the formulations used according to the invention are useful for dyeing by the thermosol, exhaust and continuous processes and for printing processes.
  • the exhaust process is preferred.
  • the liquor ratio depends on the apparatus, the substrate and the make-up form. However, the liquor ratio can be chosen to be within a wide range, for example in the range from 4:1 to 100:1 , but it preferably is between 6:1 to 25:1.
  • the textile material mentioned may be present in the various processing forms, for example as a fibre, yarn or web or as a woven or loop-formingly knitted fabric.
  • the luminescent lanthanide chelates of the invention are likewise useful for mass-dyeing of plastics.
  • the invention further relates to a process for the preparation of luminescent plastics characterized in that the plastics material is extruded in the presence of 0.01 - 10.0 % by weight, based on the amount of plastics material, of a compound of formula I, II, III or IV.
  • Plastics useful for mass dyeing include for example dyeable high molecular weight organic materials (polymers) having a dielectric constant > 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.
  • PC polycarbonate
  • PS polystyrene
  • PP polypropylene
  • PMMA polymethyl methacrylate
  • ABS acrylonitrile/butadiene/styrene
  • 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 polybutylene terephthalate (PBTP); polycarbonates, for example polycarbonates formed from ⁇ , ⁇ -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).
  • PET polyethylene terephthalate
  • PBTP polybutylene terephthalate
  • polycarbonates for example polycarbonates formed from ⁇ , ⁇ -dimethyl-4,4'-dihydroxydiphenylmethane and phosgene
  • polymers based on polyvinyl chloride or polyamide for example nylon 6 or nylon
  • 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, polymethyl methacrylate (PMMA), polypropylene (PP) or polystyrene (PS).
  • PMMA polymethyl methacrylate
  • PP polypropylene
  • PS polystyrene
  • the plastics are dyed for example by mixing the luminescent lanthanide chelate according to component (a) into these substrates using roll mills or mixing or grinding apparatus whereby the lanthanide chelates are dissolved or finely dispersed in the plastic.
  • the plastic with the admixed dyes is then processed in a conventional manner, for example by calendering, pressing, extrusion, spread coating, spinning, casting or injection moulding, whereby the dyed material acquires its ultimate shape.
  • the mixing of the components can also be effected directly prior to the actual processing step, for example by continuously metering solid, for example pulverulent, lanthanide chelates and a granulated or pulverulent plastic and also optionally additional substances such as for example additives simultaneously directly into the inlet zone of an extruder where the mixing-in takes place just prior to the processing.
  • additional substances such as for example additives simultaneously directly into the inlet zone of an extruder where the mixing-in takes place just prior to the processing.
  • prior mixing of the lanthanide chelates into the plastic is preferable, since more uniformly impregnated substrates are obtainable.
  • the invention further relates to luminescent textile fibre and to luminescent plastic prepared by the process described above.
  • the present invention makes it possible to incorporate colourless or coloured hidden marks into various colourless, white, pale coloured or dark coloured substrates, which can be revealed under UV exposure.
  • the claimed process is particularly useful for the manufacture of security fibres or security threads that can be applied to fiduciary documents or other materials.
  • Security fibres are incorporated in fiduciary documents or other materials for the purpose of ensuring identification, an authentication, a protection against forgery, imitation or falsification.
  • Security threads are continuous threads or strips of film introduced into fiduciary documents for the same purpose as security fibres.
  • infant documents denotes papers, such as papers for bank notes, cheques, shares , bills, stamps, official documents, identity cards, passports, record books, notes, tickets, vouchers, bulletins, accounting books as well as credit, payment, access or multifunctional cards, and similar documents which necessarily involve a high degree of security.
  • security fibres or security threads can be accomplished by known methods as described, for example, in U.S. Patents Nos. 4,655,788, 5,759,349 and 6,045,656, EP-A 185 396 and EP-A 1 013 824.
  • Incorporation of the lanthanide chelate compound can be carried out by conventional dyeing or printing processes.
  • Suitable fibres for the claimed process can be obtained from wood or vegetable pulp, cellulose pulp, cotton, linen or synthetic fibres.
  • paper fibres or synthetic fibres are used.
  • the process according to claim 1 is used for the preparation of anti-counterfeit documents, cards, cheques or banknotes.
  • the compositions according to the invention distinguish from analogous prior art compositions by outstanding luminescence quantum yield, long-lasting luminescence and high luminescence intensity.
  • the impregnation of a cellulosic bobbin (0.75kg cotton thread 40tex) is performed at 35°C for 20 min in an alternated circulation dyeing apparatus (Callebault de Blicquy) (3 min cycle) with a liquour ratio of 1 to10.
  • the liquour contains 4.5% of the compound of formula XVII
  • the impregnation of a silk thread (10g) is performed at 25°C for 10-60 min in the same liquour and liquour ratio to textile material as described in Example 1. After treatment, centrifugation and air-drying of the thread reveals strong red-orange fluorescence under UV light.
  • High temperature dyeing of a polyester (PES) filament (135°C, 60min)
  • a PES filament (10g) is introduced in a 250mL bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
  • High temperature dyeing (HTD) of a velvet PES fabric (135°C, 60min)
  • a velvet PES fabric (10g) is introduced in a 250ml bottle tight against leakage, containing
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
  • a white velvet PES fabric (10g) is introduced in a 250mL bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • the dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex XV
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated velvet PES fabric is white and exhibits a strong green fluorescence under irradiation at 254nm.
  • High temperature dyeing of a polyamide (PA) tricot (135°C, 60min)
  • a PA tricot (10g) is introduced in a 250mL bottle tight against leakage, containing 200mL of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated PA tricot exhibits a strong red-orange fluorescence under irradiation at 365nm.
  • High temperature dyeing of a PA tricot (135"C, 60min)
  • a white PA tricot (10g) is introduced in a 250ml bottle tight against leakage, containing
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated PA tricot is white and exhibits a green fluorescence under irradiation at 254nm.
  • High temperature dyeing (HTD) of a transparent colourless PA thread (135°C, 60min)
  • a transparent colourless PA thread (10g) is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated transparent PES thread exhibits a strong red-orange fluorescence under irradiation at 365nm.
  • a homogenised mixture of polypropylene granules (200g) and compound XVII (2g) is introduced in the fusion chamber (200°C) of a 3mm cable extruder. After cooling in a water bath, the thus obtained rigid cable is cut into granules again, which are in turn introduced in the fusion chamber (230°C) of a filament extruder.
  • the thus obtained transparent multifilament thin polypropylene thread ( ⁇ dtex) exhibits a strong red-orange fluorescence upon excitation at 365nm.
  • Titanium dioxide together with compound XVII.
  • High temperature dyeing of a coloured PES thin thread (135"C, 60min)
  • Pigment Black 7 is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated thin cyan PES thread is cyan and exhibits a strong green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
  • High temperature dyeing of a coloured PES thin thread (135°C, 60min)
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated thin black PES thread is black and exhibits a strong green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
  • High temperature dyeing of a coloured PES thin thread (135°C, 60min)
  • Pigment Yellow 147) - is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated thin yellow PES thread is yellow and exhibits a strong green-yellow fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
  • High temperature dyeing (HTD) of a PES filament (135°C, 60min)
  • a PES filament (10g) is introduced in a 250ml bottle tight against leakage, containing 200ml of dyeing bath (i.e. bath ratio 1 to 20).
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated PES filament exhibits a strong red-orange fluorescence under irradiation at 365nm.
  • High temperature dyeing (HTD) of a PES filament (135°C, 60min)
  • a white PES filament (10g) is introduced in a 250m! bottle tight against leakage, containing
  • the dyeing bath is prepared as a mixture of the following two solutions : o a NMP suspension (5 to 30ml) containing 2% of the lanthanide complex
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated white PES filament is white and exhibits a pink-red fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
  • High temperature dyeing (HTD) of a PES filament (135°C, 60min)
  • a white PES filament (1 Og) is introduced in a 250ml bottle tight against leakage, containing
  • the dyeing bath is prepared as a mixture of the following two solutions : o a solvent-based solution (5 to 30ml) containing 3-5% of the lanthanide complex
  • Cibatex AB 45 (Ciba Specialty Chemicals)
  • the bottle is installed in a rotating high temperature dyeing autoclave with a starting bath temperature of 70°C.
  • the temperature is then raised to 135°C over 30 min and kept stable for further 1 hour.
  • the treatment temperature is finally decreased down to 40°C over 15 min, after which the thread is removed from the bottle, rinsed for 5 min with warm water (35°C), spin dried and finally dried with hot air (90-105°C).
  • the thus treated white PES filament is white and exhibits a green fluorescence under irradiation at 254nm and no fluorescence under irradiation at 365nm.
  • High temperature dyeing (HTD) of PES (135°C, 60min)
  • Transfer printing with UV fluorescent lanthanide chelates is performed by using transfer printing formulations containing one or more UV fluorescent lanthanide chelates. These formulations are prepared in a similar way 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 disperse dye(s).
  • a polymer mixture (e.g. copolymerised polyamide Akulon ® , supplied by Akzoplastiks) is distributed to three extruders and the granules are melted.
  • the melts indicated for the outer components of the thread are each mixed with 3 % by weight of a compound of formula
  • Co-extrusion of the lanthanide chelate(s) with one or more dyes or pigments provides coloured threads which are similarly fluorescent under UV light.
  • a security thread is prepared by extrusion of a polyamide melt containing 3 % by weight of a 1:1 mixture of a compound of formula (XVII) and a compound of formula (XV). Upon irradiation of UV light of different wavelengths red and/or green fluorescence is observed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
EP03795792A 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials Withdrawn EP1560894A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03795792A EP1560894A2 (en) 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP02405931 2002-10-30
EP02405931 2002-10-30
EP03405448 2003-06-20
EP03405448 2003-06-20
EP03795792A EP1560894A2 (en) 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials
PCT/EP2003/011638 WO2004039913A2 (en) 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials

Publications (1)

Publication Number Publication Date
EP1560894A2 true EP1560894A2 (en) 2005-08-10

Family

ID=32232211

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Application Number Title Priority Date Filing Date
EP03795792A Withdrawn EP1560894A2 (en) 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials

Country Status (10)

Country Link
US (1) US20060046050A1 (tr)
EP (1) EP1560894A2 (tr)
JP (1) JP4381377B2 (tr)
KR (1) KR101076621B1 (tr)
AR (1) AR041843A1 (tr)
AU (1) AU2003298093A1 (tr)
CA (1) CA2502038A1 (tr)
MX (1) MXPA05004229A (tr)
TW (1) TW200418952A (tr)
WO (1) WO2004039913A2 (tr)

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DE502005005905D1 (de) * 2005-10-26 2008-12-18 Alcan Tech & Man Ltd Gegenstand mit einem aufgedruckten Bild
FR2906393B1 (fr) * 2006-09-21 2008-12-19 Inst Nat Sciences Appliq Procede de marquage d'un materiau comprenant au moins une matrice minerale et materiau correspondant
KR100773089B1 (ko) 2007-04-30 2007-11-05 씨엠에스테크놀로지(주) 감마선에 감응하는 폴리 가교형 프탈로시아닌 화합물 및 그를 포함하는 잉크 조성물
ITMI20080572A1 (it) * 2008-04-02 2009-10-03 Colograf S R L Contenitore in legno decorato.
ATE522581T1 (de) * 2008-05-09 2011-09-15 Nanocms Co Ltd Gammastrahl-empfindliche phthalocyanin-verbindung eines polyvernetzten typs und tintenzusammensetzung damit
WO2010075003A1 (en) * 2008-12-16 2010-07-01 The University Of Akron Lanthanide ion complexes and imaging method
FR3021979A1 (fr) * 2014-06-04 2015-12-11 Commissariat Energie Atomique Procede de marquage d'un fil textile par un element fluorescent, fil textile obtenu par le procede de marquage et utilisation dudit fil textile pour tisser un vetement
US9851341B2 (en) 2014-06-27 2017-12-26 Eastman Chemical Company Fibers with chemical markers used for coding
US9972224B2 (en) 2014-06-27 2018-05-15 Eastman Chemical Company Fibers with multicomponent fibers used for coding
US9863920B2 (en) 2014-06-27 2018-01-09 Eastman Chemical Company Fibers with chemical markers and physical features used for coding
CN107083237A (zh) * 2017-05-06 2017-08-22 中北大学 一种邻菲罗啉配基功能化聚合物‑稀土配合物发光材料
CN107022096B (zh) * 2017-06-01 2020-03-27 厦门大学 具有近紫外激发功能高光透过性复合醋酸纤维素膜的制备
PL3584088T3 (pl) * 2018-06-19 2021-05-04 Borealis Ag Kompozycja poliolefinowa zapewniająca znakowanie z wykorzystaniem fluorescencji

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FR2566440B1 (fr) * 1984-06-22 1988-07-22 Jalon Michel Fibres de securite et autres matieres rendues luminescentes par un procede de teinture, leurs procedes de realisation et leurs applications
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TW200418952A (en) 2004-10-01
CA2502038A1 (en) 2004-05-13
JP2006504883A (ja) 2006-02-09
AR041843A1 (es) 2005-06-01
AU2003298093A8 (en) 2004-05-25
KR101076621B1 (ko) 2011-10-26
US20060046050A1 (en) 2006-03-02
JP4381377B2 (ja) 2009-12-09
KR20050084907A (ko) 2005-08-29
WO2004039913A2 (en) 2004-05-13
MXPA05004229A (es) 2005-07-05
WO2004039913A3 (en) 2004-07-01
AU2003298093A1 (en) 2004-05-25

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