CA2502038A1 - Process for incorporation of uv-luminescent compounds in polymeric materials - Google Patents

Process for incorporation of uv-luminescent compounds in polymeric materials Download PDF

Info

Publication number
CA2502038A1
CA2502038A1 CA002502038A CA2502038A CA2502038A1 CA 2502038 A1 CA2502038 A1 CA 2502038A1 CA 002502038 A CA002502038 A CA 002502038A CA 2502038 A CA2502038 A CA 2502038A CA 2502038 A1 CA2502038 A1 CA 2502038A1
Authority
CA
Canada
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.)
Abandoned
Application number
CA002502038A
Other languages
French (fr)
Inventor
Veronique 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
Individual
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 Individual filed Critical Individual
Publication of CA2502038A1 publication Critical patent/CA2502038A1/en
Abandoned legal-status Critical Current

Links

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

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)

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 Incorporation of UV-luminescent Compounds in Polymeric Materials The present invention relates to a process for the preparation of UV
luminescent polymeric materials and their uses.
There is a need for furnishing textiles with covert effects, which may act as security markings, as special effects or as decorations that only become visible under UV irradiation.
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.
The invention relates to a process for the preparation of luminescent polymeric fibres characterised in that the fibres are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.
Preferably, component (a) is a compound of formula I
Lm-Ln3+(Ch-)n (I), wherein Ln represents a lanthanide, 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, in case n is 3, m denotes a number from 0 to 4 and 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.
More preferably, component (a) is a compound of formula II, III or IV
3+
Lm Ln R~ ~ R3 (II), O O
n Lm Ln3+ R~~O (III), I IO
n Lm Ln3+(R~-O7" (IV), wherein 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 and 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, R2, is hydrogen or C,-Cealkyl, and R~ and R3 are each independently of the other hydrogen, C,-Csalkyl, CF3, C5-Cz4aryl or C4-C24heteroaryl.
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.
Particularly preferred are compounds of formula I, II, III or IV wherein n denotes 3 and L is a nitrogen-containing ligand.
Since 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:
/ /
3i / \ / ~ 3r Eu-N -Eu ~ I ~ I (X111), 3 ~ v 3 / /
I Eu3~ N / ~ -Tb3 XI
3 ~ 0 3 When n denotes 4, L as single-charged cation can be basically any metal cation (e.g. Li+, K+, Na+), unsubstituted or substituted ammonium (e.g. NH4+, polyalkylammonium) or 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.
Particularly preferred are compounds of formula I, II, III or IV wherein L is a compound of formulae V to XII
/ R4 R4 ~ ~ Rs N~ (V), ~ ~ ' (VI), R N ~ Rs a N
(VII), ~> (VIII), N
I
R6 R~
R Rs Ra i~ i~Rs (IX), a N ~ ~ N (X), N N
Rs /
w R4 / ~ Rs (XI), R4 ~~ \N ~ ~ ~ (XII), N iN N /
or a cation of the formula H-N+(R7)s, wherein R4, R5 and Re are each independently of the other hydrogen, halogen, C,-Csalkyl, C5-C24aryl, C6-Cz4aralkyl, C,-Cealkoxy, amino, dialkylamino or a cyclic amino group and R~ is hydrogen, C,-Cgalkyl, CS-C24aryl, Cs-Cz4aralkyl or vinyl.
Alkyl groups as substituents R~ to R~ 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 R4 to Rg can be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.
Examples of C5-Cz4aryl 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 R4 to R~ 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 R4 to Re 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 wherein R4, R5 and R6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N+(R~)3.wherein R, is C~-Csalkyl.
Preferred components (a) are compounds of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm or Nd.
Furthermore, compounds of formula II and III are preferred, wherein R, and R3 are methyl, t-butyl, n-pentyl or phenyl.
RZ in formula II is preferably hydrogen.
Particularly preferred as component (a) are the compounds of formula XIII to CVI:
/ /
3+ ~ ~ ~ \ 3+
Eu-N N-Eu \ I ~ I (X111), 3 ~ V 3 O O O O
/ / (1..13C')3C~C(CH3)3 EU3~ N ~ \ N-Tb3+ ~ ~~ ( ) XIV
3 ~ ~ 3 O O
H3CN ~ \N-Tb3+ ((HaC)aC ~ C(CH3)3la (~), H3CN ~ \N-pys+ ((H3C)3C ~ C(CH3)3) (XVI), H3CN ~ \N-Eu3+ \ I I (XVII), v O O
H3CN ~ \N-Eu3+ ( H3C' ~ 'CH3 )3 (XVIII), I / N/Eu3+ ~ I ~ I (XIX), / N ~ v s ~ I o 0 I \1 iN~
I N/Eua+
O
(HSCz)ZNH Eua+ \ I \ I (XXI), \ v O O

3+
HC C
(H5C2)ZNH Tb ( a )a \ C(CH3)3 (XXII), O O

Tb (HaC)aC \ C(CHa)a ~ (XXIII), Tba+ ~ H3C\ ~ 'CHa ~ (XXIV), 3+
a 3 O O O O
Sma+ / /
Sma+ ( H3C CHa 1 ~ , \ ~ (XXVI), /3 ( ) \ 3 O O O O
a+ /
a. ~ ) Sm (HaC)aC \ C(CHa)a'a (XXVII), Sm \ \ CHa a (XXVIII , O O
a+ /
Sm \ I CF (XXIX), Sma+ ~ ~ CF (~), O O a a S ~~ a a / /
Tba+ \ I \ I (~I), Tba+ \ I CH (XXXII)~
\ \/ a ~ a 3 O O O O
Tba+ \ I CF (XXXIII), Tba+ ~ CF (XXXIV), 3 3 S ~~ 3 3 O O O O
1 Eu3+ / /
Eu3+ ~ H3C' ~ /CH3 13 (~)~ \ \ \ I 3 (~I), ~O \~O' O O
3+
3+ ~ ) EU (H3C)3C' ~ 'C(CH3)313 (XXXVII), Eu \ I \ -CH3 3 (XXXVIII , ~O \'O~ I O O
/
Eu3+ \ ~ CF (XXXIX), Eu3+ ~ ~ (XXXX), \ 3 3 S \ CF3 3 O O O O
/ /
Dy3+ ~ H3C CH3 1 XXXXI , Dy3+ \ ~ \ ~ (III), /3 ( ) \ 3 O O O O
3+ /
Dy3+ ~ (H3C)3C~C(CH3)3 ~ (XXXXIII), DY \ I \ -CH3 ~O ~O~ 3 p O
Dy3+ \ I CF (~)~ DY3+ / ~ CF (XXXXVI), \ 3 S ~~ 3 3 / /
s+ Nd3+ ~ I (XXXXVIII), Nd ~ H3C\ ~ /CH3 13 (XXXXVII), \ \ \ s ~O \~O' I O O
g+ /
3+ ~ ( ) Nd (H3C)3C~C(CH3)3~s (XXXXIX), Nd \ ( \ -CH3 3 L , ~O 'OI O O
Nd3+ \ ~ CF (LI), Nd3+ ~ ~ CF (LII), \ 3 S ~ ~ 3 3 O O O O
Some preferred derivatives of structures of type II and III, derived from the above drawn preferred structures of type I, are compiled in the table below:

-g_ L DMAP DMAP DMAP DMAP DMAP E>aNH Et3NH E13NH E13NH E13NH

Ln Tb Eu Sm Dy Nd Tb Eu Sm Dy Nd Ch-H~C~CH3 LIII XVIIILXII LXVIIILXXIIILXXIX LXXXIVLXXXIX LXXXXV CI
~

o 00 (H~C)~C~C(CH~~XV LVIIILXIIIXVI LXXIV XXII LXXXV LXXXX LXXXXVICII
~

o 00 I \ I LIV XVII LXIV LXIX LXXV LXXX XXI LXXXXI LXXXXVIICIII

LV LIX LXV LXX LXXVI LXXXI LXXXVILXXXXIILXXXXVIIICIV
\ I
CH

a \
O O

LVI LX LXVI LXXI LXXVIILXXXIILXXXVIILXXXXIIILXXXXIXCV
\ I
cF

\
O O

LVII LXI LXVIILXXIILXXVIIILXXXIIILXXXVIIILXXXXIVC CVI
CFa -O O

DMAP: 4-dimethylaminopyridine Further suitable 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 Et3NH+
For certain applications it is recommendable to use a combination of different lanthanides, for example Eu and Tb. Such a mixture increases the degree of security of the hidden colourations, the sophistication of the security level and multiplies the coding possibilities.
The compounds of formula I, II, III and IV are known, for instance from WO
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, _g_ 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.
Accordingly, 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.
Preferably, 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, nitrites 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 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 nitrite, aliphatic polyether or aliphatic sulfoxide.
Particularly preferred water-miscible organic solvents are ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofurane (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile, polyethyleneglycol dimethyether and dimethylsulfoxide (DMSO).

The 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.
In the 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.
For a mass-dyeing process, the compositions according to the present invention consist of component (a). Optionally, further ingredients (c) and/or (d) may also be added together with (a) in order to give simultaneous supplementary properties) to the polymeric material in addition to the UV-luminescence.
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.
Further ingredients (d) which may be present in the compositions according to the invention are e.g. optical brighteners, biocides, bactericides, fungicides insecticides and fragrance.
The compositions containing at least one lanthanide chelate can be prepared by any suitable method known to those of ordinary skill in the art. For example, the components of the composition can be combined and mixed in a suitable mixer or blender.
The 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 a,a-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; or fibres based on polyvinyl chloride or polyamide.
The formulations according to the invention are applied to the textile materials according to known dyeing processes. For example, 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.
Accordingly, 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. 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 polybutylene terephthalate (PBTP); polycarbonates, for example polycarbonates formed from a,a-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).
Very 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, polymethyl methacrylate (PMMA), polypropylene (PP) or polystyrene (PS).
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. In general, however, 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.
The expression "fiduciary 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.
The manufacture of 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.
Preferably, paper fibres or synthetic fibres are used.
In a particularly preferred embodiment 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 following Examples illustrate the invention.
Ink Composition A:
Concentrate of compound XVII in 1,2-propylene glycol HsC /~~\ pub / /
N-( H,N-EuHz I I (III) j \ \ \

1 g of compound VII I is dissolved in 99 g of 1,2-propyleneglycol under heating at 100°C for 1 hour. The clear yellow solution is allowed to cool down and after filtration (clarification) provides the stable Ink Composition A which exhibits an intense red luminescence under UV
light. This concentrate can be further used in either solvent based or aqueous based conventional or high-tech (ink jet) printing formulations for paper, textile, leather, wood, plastic or other compatible substrates.
Example 1:
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 Biicquy) (3 min cycle) with a liquour ratio of 1 to10. The liquour contains 4.5% of the compound of formula XVII
H3CN ~ \N-Eu3i \ I I (XVII) v hl3C ~~ 3 in 2-butoxy-ethanol.
After treatment, centrifugation and air-drying of the bobbin, strong red-orange fluorescence is observed under UV light.

Example 2:
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.
Example 3:
The impregnation of a patchwork fabric containing several distinct bands of synthetic, artificial, natural (vegetal and animal) fibers (20g) is performed at 25°C for 10-60 min in the same fiquour and liquour ratio to textile material as described in Example 1.
After treatment, centrifugation and air-drying of the patchwork reveals on most fibers strong red-orange fluorescence under UV light.
Equivalent results are obtained from similar processes using other lanthanide complexes, exhibiting other emission wavelength under irradiation in the UV (e.g.
terbium, dysprosium, samarium, neodymium).
Example 4:
High temperature dyeing (HTD) of a polyester (PES) filament (135°C, 60min) A PES filament (10g) is introduced in a 250mL bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex of formula XVII dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g/I of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/l sodium hydrogencarbonate 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.

Example 5:
High temperature dyeing (HTD) of a velvet PES fabric (135°C, 60min) A velvet PES fabric (10g) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 of formula XVII dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g11 of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4811 sodium hydrogenocarbonate 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.
Example 6:
High temperature dyeing (HTD) of a velvet PES fabric (135°C, 60min) A white velvet PES fabric (108) is introduced in a 250mL bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex XV
H3CN J ~N-Tb3+ ((H3C)3C~C(CH3)3~ (XV) dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6811 of Univadin DP (Ciba Specialty Chemicals) ~ 2.58/1 of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.48/1 sodium hydrogencarbonate 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.
Example 7:
High temperature dyeing (HTD) of a polyamide (PA) tricot (735°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).
The dyeing bath is prepared as a mixture of the following two solutions o a solvent-based solution (5 to 30mL) containing 3-5°I° of the lanthanide complex XVII dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g/l of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4gi1 sodium hydrogencarbonate 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.
Example 8:
High temperature dyeing (HTD) of a PA tricot (135°C, 60min) A white PA tricot (10g) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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°I° of the lanthanide complex XV dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6gi1 of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogenocarbonate 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.
Example 9:
High temperature dyeing (HTD) of a transparent colourless PA thread (135°C, 60min) A transparent colourless PA thread (10g) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex XVII dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g/I of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogenocarbonate 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.
Example 10:
Incorporation of XVII in polyamide (PA) by mass-dyeing process Extruded Ultramid B3K in the presence of 2% of the lanthanide complex XII for 2 min at 260°C results in red-orange fluorescence upon irradiation at 365nm.
Example 11:
Incorporation of XVII in polystyrene (PS) by mass-dyeing process Extruded Polystyrol H165 in the presence of 2% of the lanthanide complex XVII
for 5 min at 300°C results in red-orange fluorescence upon irradiation at 365nm.
Example 12:
Incorporation of XVII in polypropylene (PP) by mass-dyeing process 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 (8dtex) exhibits a strong red-orange fluorescence upon excitation at 365nm.
Example 13:
Incorporation of XVII in polypropylene (PP) by mass-dyeing process Similar process and resulting fluorescent properties are obtained with simultaneous use of Titanium dioxide together with compound XVII.
Example 14:
Incorporation of XVII in poly(methylmefhacrylate) (PMMA) by mass-dyeing process Extruded Plexiglas 6N in the presence of 2% of the lanthanide complex XVII for 5 min at 260°C results in red-orange fluorescence upon irradiation at 365nm.
Example 15:
Incorporation of XVII in acrylonitrileibutadieneistyrene-copolymer (ABS) by mass-dyeing process Extruded Terluran 877M in the presence of 2% of the lanthanide complex XVII
for 5 min at 220°C results in red-orange fluorescence upon irradiation at 365nm.
Example 16:
High temperature dyeing (HTD) of a coloured PES thin thread (135°C, 60min) A thin cyan PES thread (10g) - previously mass-dyed with a mixture of Irgalite Blue GLGP
(C.I. Pigment Blue 15:3), titanium dioxide (C.I. Pigment White 6) and carbon black (C.I.
Pigment Black 7) - is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex XV dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing .. ~ 0.6g/I of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogencarbonate 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.
Example 17:
High temperature dyeing (HTD) of a coloured PES thin thread (135°C, 60min) A thin black PES thread (10g) - previously mass-dyed with a pigment mixture containing titanium dioxide (C.I. Pigment UVhite 6) and carbon black (C.I. Pigment Black 7) - is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex XV dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g11 of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogenocarbonate 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.
Example 18:
High temperature dyeing (HTD) of a coloured PES thin thread (135°C, 60min) A thin yellow PES thread (108) - previously mass-dyed with Filester Yellow RNB(C.I.
Pigment Yellow 147) - is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex XV dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.68/1 of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/l of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4811 sodium hydrogencarbonate 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.
Example 19:
High temperature dyeing (HTD) of a PES filament (135°C, 60min) A PES filament (108) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5% of the lanthanide complex (HSCZ)ZNH Eu3.
(m>, O O

w dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170mt-) containing ~ 0.6g/I of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogenocarbonate 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.
Example 20:
High temperature dyeing (HTD) of a PES filament (135°C, 60min) A white PES filament (10g) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 NMP suspension (5 to 30m1) containing 2% of the lanthanide complex 3i N/Eu ~ O ~3 ( /~
I O
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6g/I of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4g/I sodium hydrogenocarbonate 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.
Example 21:
High temperature dyeing (HTD) of a PES filament (735°C, 60min) A white PES filament (10g) is introduced in a 250m1 bottle tight against leakage, containing 200m1 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 30m1) containing 3-5°l° of the lanthanide complex (HSC2)ZNH Tb3' (H3C~3C~C(CH~3 (XXII), IOI 'O

dissolved in NMP
o an aqueous solution at pH=4.5 (195 to 170m1) containing ~ 0.6gi1 of Univadin DP (Ciba Specialty Chemicals) ~ 2.5g/I of Cibatex AB 45 (Ciba Specialty Chemicals) ~ 0.4gi1 sodium hydrogenocarbonate 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.
Example 22:
High temperature dyeing (HTD) of PES (135°C, 60min) All above experiments of High Temperature Dyeing are also realised without using NMP, by a similar preparation method to that of Disperse Dyes, and by replacing the Disperse Dye with the UV fluorescent lanthanide chelate to be applied.

Example 23:
Transfer printing with UV fluorescent lanthanide chefates 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).
Example 24:
Preparation of a multi-component security thread 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 (XVII) in such a way that it dissolves homogeneously in the polyamide melt.
After extrusion of the multi-component threads a security thread is obtained the edge strips of which fluoresce under UV light whereas the central strip does not show any fluorescence.
Co-extrusion of the lanthanide chelate(s) with one or more dyes or pigments provides coloured threads which are similarly fluorescent under UV light.
Example 25:
Preparation of a multi-component security thread As described in Example 24, 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.

Claims (20)

What is claimed is
1. A process for the preparation of luminescent polymeric fibres characterised in that the fibres are treated with a composition comprising (a) one or more luminescent lanthanide chelates containing three or four organic anionic ligands having at least one UV absorbing group and (b) one or more solvents.
2. A process according to claim 1 characterized in that component (a) is a compound of formula I
Lm-Ln3+(Ch-)n (I).
wherein Ln represents a lanthanide, 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, in case n is 3, m denotes a number from 0 to 4 and 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.
3. A process according to claim 1 characterized in that component (a) is a compound of formula II, III or IV
Lm-Ln3+(R1-O]n (IV), wherein 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 and 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, R2, is hydrogen or C1-C6alkyl, and R1 and R3 are each independently of the other hydrogen, C1-C6alkyl, CF3, C5-C24aryl or C4-C24heteroaryl.
4. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, III or IV wherein n denotes 3 and L is a nitrogen-containing ligand.
5. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, 111 or IV wherein L is a compound of formulae V to XII
or a cation of the formula H-N+(R7)3, wherein R4, R5 and R6 are each independently of the other hydrogen, halogen, C1-C6alkyl, C5-C24aryl, C6-C24aralkyl, C1-C6alkoxy, amino, dialkylamino or a cyclic amino group and R7 is hydrogen, C1-C6alkyl, C5-C24aryl, C6-C24aralkyl or vinyl.
6. A process according to claim 5 characterized in that component (a) is a compound of formula II wherein L is a compound of formula V, VI, VII, VIII, IX, X, XI or XII wherein R4, R5 and R6 are hydrogen, methyl, amino, pyrrolidino or dimethylamino or L is a cation of the formula H-N+(R7)3.wherein R7 is C1-C6alkyl.
7. A process according to claim 2 or 3 characterized in that component (a) is a compound of formula I, II, III or IV wherein Ln is Eu, Tb, Dy, Sm or Nd.
8. A process according to claim 3 characterized in that component (a) is a compound of formula II or III wherein R1 and R3 are methyl, t-butyl, n-pentyl or phenyl.
9. A process according to claim 3 characterized in that component (a) is a compound of formula II wherein R2 is hydrogen.
10. A process according to claim 3 characterized in that component (a) is a compound of formula XIII to LII
11. A process according to claim 1 or 2 characterized in that component (b) is water, one or more water-miscible organic solvents or a mixture of water and one or more water-miscible organic solvents.
12. A process according to claim 11 characterized in that the water-miscible organic solvent is an aliphatic alcohol, etheralcohol, glycol, aliphatic ketone, carboxylic acid ester, carboxylic acid amide, aliphatic nitrite, aliphatic polyether or aliphatic sulfoxide.
13. A process according to claim 11 characterized in that the water-miscible organic solvent is selected from the group consisting of ethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, acetone, 2-butanone, ethyl acetate, tetrahydrofurane (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), acetonitrile, polyethyleneglycol dimethyether and dimethylsulfoxide (DMSO).
14. A 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 components (a) + (b).
15. A process according to claim 1 characterized in that the formulation contains additionally (c) one or more colorants.
16. 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 polymeric material, of a compound of formula II or III according to claim 3.
17. A luminescent textile fibre prepared by the process according to claim 1.
18. A luminescent plastic prepared by the process according to claim 16.
19. A process according to claim 1 wherein the polymeric fibres are paper fibres or synthetic fibres.
20. The use of the process according to claim 1 for the preparation of anti-counterfeit documents, cards, cheques or banknotes.
CA002502038A 2002-10-30 2003-10-21 Process for incorporation of uv-luminescent compounds in polymeric materials Abandoned CA2502038A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP02405931 2002-10-30
EP02405931.3 2002-10-30
EP03405448 2003-06-20
EP03405448.6 2003-06-20
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
CA2502038A1 true CA2502038A1 (en) 2004-05-13

Family

ID=32232211

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002502038A Abandoned CA2502038A1 (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 (en)
EP (1) EP1560894A2 (en)
JP (1) JP4381377B2 (en)
KR (1) KR101076621B1 (en)
AR (1) AR041843A1 (en)
AU (1) AU2003298093A1 (en)
CA (1) CA2502038A1 (en)
MX (1) MXPA05004229A (en)
TW (1) TW200418952A (en)
WO (1) WO2004039913A2 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE413282T1 (en) * 2005-10-26 2008-11-15 Alcan Tech & Man Ltd ITEM WITH A PRINTED IMAGE
FR2906393B1 (en) * 2006-09-21 2008-12-19 Inst Nat Sciences Appliq METHOD OF MARKING A MATERIAL COMPRISING AT LEAST ONE MINERAL MATRIX AND MATERIAL THEREFOR
KR100773089B1 (en) 2007-04-30 2007-11-05 씨엠에스테크놀로지(주) Poly cross linked phthalocyanine compounds and ink compositions comprising said compounds
ITMI20080572A1 (en) * 2008-04-02 2009-10-03 Colograf S R L DECORATED WOODEN CONTAINER.
EP2116578B1 (en) * 2008-05-09 2011-08-31 NANOCMS Co., Ltd. Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same
WO2010075003A1 (en) * 2008-12-16 2010-07-01 The University Of Akron Lanthanide ion complexes and imaging method
FR3021979A1 (en) * 2014-06-04 2015-12-11 Commissariat Energie Atomique METHOD FOR MARKING A TEXTILE YARN WITH A FLUORESCENT ELEMENT, TEXTILE YARN OBTAINED BY THE MARKING METHOD AND USE OF SAID TEXTILE YARN FOR WEAVING A GARMENT
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
US9851341B2 (en) 2014-06-27 2017-12-26 Eastman Chemical Company Fibers with chemical markers used for coding
CN107083237A (en) * 2017-05-06 2017-08-22 中北大学 A kind of ligand functionalized polymer rare earth complex luminescent material of Phen
CN107022096B (en) * 2017-06-01 2020-03-27 厦门大学 Preparation of high-light-permeability composite cellulose acetate membrane with near-ultraviolet excitation function
PL3584088T3 (en) * 2018-06-19 2021-05-04 Borealis Ag Polyolefin composition providing marking by fluorescence

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH656656A5 (en) * 1980-05-30 1986-07-15 Gao Ges Automation Org SECURITY PAPER WITH AUTHENTICITY CHARACTERISTICS IN THE FORM OF LUMINESCENT AND ABSORBENT SUBSTANCES.
DE3122470C2 (en) * 1981-06-05 1985-09-05 GAO Gesellschaft für Automation und Organisation mbH, 8000 München Security paper and process for making the same
FR2566440B1 (en) * 1984-06-22 1988-07-22 Jalon Michel SECURITY FIBERS AND OTHER MATERIALS MADE LUMINESCENT BY A DYEING PROCESS, THEIR PROCESSES AND THEIR APPLICATIONS
DE3446861A1 (en) * 1984-12-21 1986-07-10 GAO Gesellschaft für Automation und Organisation mbH, 8000 München SECURITY DOCUMENT WITH THE SECURITY THREAD STORED IN IT AND METHOD FOR THE PRODUCTION AND AUTHENTICITY TESTING OF THE SECURITY DOCUMENT
FR2603043B1 (en) * 1986-08-19 1988-11-10 Petrel Sarl SECURITY MARKING, MATERIALS PROVIDED WITH SECURITY MARKS, APPARATUS FOR REVEALING THE SECURITY MARK
BE1007071A3 (en) * 1993-04-28 1995-03-07 Philips Electronics Nv Optical systems.
WO1996020942A2 (en) * 1995-01-06 1996-07-11 Ciba Specialty Chemicals Holding Inc. Triboluminescent lanthanideiii complexes
US5837042A (en) * 1996-06-10 1998-11-17 Videojet Systems International, Inc. Invisible fluorescent jet ink
US5759349A (en) * 1995-12-14 1998-06-02 Westvaco Corporation Lumen loading of hygienic end use paper fibers
US6045656A (en) * 1998-12-21 2000-04-04 Westvaco Corporation Process for making and detecting anti-counterfeit paper
US6402986B1 (en) * 1999-07-16 2002-06-11 The Trustees Of Boston University Compositions and methods for luminescence lifetime comparison
AU2003206918B2 (en) * 2002-02-26 2007-12-06 Ciba Specialty Chemicals Holding Inc. Ink compositions containing lanthanide complexes

Also Published As

Publication number Publication date
AU2003298093A1 (en) 2004-05-25
EP1560894A2 (en) 2005-08-10
JP2006504883A (en) 2006-02-09
AU2003298093A8 (en) 2004-05-25
TW200418952A (en) 2004-10-01
WO2004039913A2 (en) 2004-05-13
WO2004039913A3 (en) 2004-07-01
KR101076621B1 (en) 2011-10-26
JP4381377B2 (en) 2009-12-09
MXPA05004229A (en) 2005-07-05
KR20050084907A (en) 2005-08-29
US20060046050A1 (en) 2006-03-02
AR041843A1 (en) 2005-06-01

Similar Documents

Publication Publication Date Title
JP4532907B2 (en) Ink composition containing lanthanide complex
CA2502038A1 (en) Process for incorporation of uv-luminescent compounds in polymeric materials
EP2215184B1 (en) Organic fluorescent compositions
CN103502222B (en) There is the chromophore of perfluoroalkyl substituents
Qi et al. Smart photochromic fabric prepared via thiol-ene click chemistry for image information storage applications
KR20080011322A (en) Dye mixtures
Sadeghi‐Kiakhani et al. Functionalization of poly (amidoamine) dendrimer‐based nano‐architectures using a naphthalimide derivative and their fluorescent, dyeing and antimicrobial properties on wool fibers
CN109652064B (en) Special fluorescent anti-counterfeiting material and preparation method and application thereof
EP1794136B1 (en) Aryl-ureido benzoxazinone compounds
CN100362078C (en) Process for incorporation of UV-luminescent compounds in polymeric materials
WO2007028734A1 (en) Dihydroquinophenanthrine dione and tetrahydroquinophenanthrine dione fluorescent whitening agents
RU2618742C2 (en) Polymer bound vat dyes
ES2229146T3 (en) USE OF PIGMENTS TO DYE BY DISPERSION FROM A WATERPROOF.
US3870519A (en) S-triazine derivatives as ultraviolet protecting agents
ES2291471T3 (en) USE OF PIGMENTARY COLORS FOR DYING BY DISPERSION IN AQUARIUS MEDIA.
JP2741782B2 (en) Cationic compound and method of dyeing substrate using the same
US5225563A (en) Photochromatic compound, a method for its preparation, and articles which contain it
JP2810737B2 (en) Cationic compound and method of dyeing substrate using the same
Choi et al. Anti-counterfeiting fiber system with near-infrared wavelength selectivity based on photothermal and thermochromic dyes
JPH0623317B2 (en) Cationic compound and substrate dyeing method using the same
RU2010900C1 (en) Method for producing bulk-dyed triacetate or polycapronamide fibers
JPH03170560A (en) Cationic compound and dyeing of substrate with the same
JPS63227879A (en) Method for enhancing photochemical stability of dyed polyester fiber article
JPS6172066A (en) Coumarine compound

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued
FZDE Discontinued

Effective date: 20111021