Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-2-
R2
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-3-
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,
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-4-
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-5-
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 (~),
H3C
H3CN ~ \N-pys+ ((H3C)3C ~ C(CH3)3) (XVI),
H3C
H3CN ~ \N-Eu3+ \ I I (XVII),
v
H3C
O O
H3CN ~ \N-Eu3+ ( H3C' ~ 'CH3 )3 (XVIII),
0 OO
I / N/Eu3+ ~ I ~ I (XIX),
/ N ~ v s
~ I o 0
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-6-
I \1
iN~
I N/Eua+
O
(HSCz)ZNH Eua+ \ I \ I (XXI),
\ v
O O
4
3+
HC C
(H5C2)ZNH Tb ( a )a \ C(CH3)3 (XXII),
O O
4
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-7-
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:
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-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
0 0
LV LIX LXV LXX LXXVI LXXXI LXXXVILXXXXIILXXXXVIIICIV
\ I
CH
a
\
O O
LVI LX LXVI LXXI LXXVIILXXXIILXXXVIILXXXXIIILXXXXIXCV
\ I
cF
3
\
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,
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
_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).
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-10-
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-11-
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-12-
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-13-
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-14-
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 \ \ \
H3C 3
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-15-
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-16-
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)
I3
H3C O O
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-17-
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)
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-18-
~ 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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-19-
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).
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-21-
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
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-22-
(HSCZ)ZNH Eu3.
(m>,
O O
4
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),
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-23-
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
4
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.
CA 02502038 2005-04-08
WO 2004/039913 PCT/EP2003/011638
-24-
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.
