U.S. patent application number 12/598767 was filed with the patent office on 2010-07-01 for functionalized nanoparticles.
This patent application is currently assigned to CIBA CORPORATION. Invention is credited to Didier Bauer, Christian Cremer, Leonhard Feiler, Martin Muller, Thomas Ruch, Wolfgang Schlenker.
Application Number | 20100162494 12/598767 |
Document ID | / |
Family ID | 39705848 |
Filed Date | 2010-07-01 |
United States Patent
Application |
20100162494 |
Kind Code |
A1 |
Muller; Martin ; et
al. |
July 1, 2010 |
FUNCTIONALIZED NANOPARTICLES
Abstract
Functionalized nanoparticles, which are obtainable by combining
in a first step a functionalized dyestuff, a silicon-based spacer
and a catalyst, and in a second step reacting the product obtained
in the first step with a co-reactive organic silicon, aluminum,
zirconium or titanium compound. Optionally, the thus obtained
functionalized nanoparticles can be combined or encapsulated with a
polymer. The functionalized nanoparticles are useful as colorants
and fluorescents in plastics, paints, inks, electronic materials,
cosmetic articles, and the like.
Inventors: |
Muller; Martin; (Lorrach,
DE) ; Bauer; Didier; (Neuenburg am Rhein, FR)
; Ruch; Thomas; (Delemont, CH) ; Feiler;
Leonhard; (Binzen, DE) ; Schlenker; Wolfgang;
(Aesch, CH) ; Cremer; Christian; (Lorrach,
DE) |
Correspondence
Address: |
BASF Performance Products LLC;Patent Department
540 White Plains Road, P.O. Box 2005
Tarrytown
NY
10591
US
|
Assignee: |
CIBA CORPORATION
Tarrytown
NY
|
Family ID: |
39705848 |
Appl. No.: |
12/598767 |
Filed: |
April 25, 2008 |
PCT Filed: |
April 25, 2008 |
PCT NO: |
PCT/EP08/55040 |
371 Date: |
March 5, 2010 |
Current U.S.
Class: |
8/636 ; 544/198;
546/14; 556/419; 556/421; 977/773 |
Current CPC
Class: |
Y10S 977/773 20130101;
B82Y 30/00 20130101; C08K 5/5455 20130101; Y10T 428/31663 20150401;
Y10T 428/2991 20150115; Y10T 428/2998 20150115; C09B 69/008
20130101; C07F 7/1804 20130101; C07B 2200/11 20130101 |
Class at
Publication: |
8/636 ; 546/14;
556/419; 556/421; 544/198; 977/773 |
International
Class: |
C09B 69/00 20060101
C09B069/00; C07F 7/18 20060101 C07F007/18 |
Foreign Application Data
Date |
Code |
Application Number |
May 11, 2007 |
EP |
07108002.2 |
Oct 19, 2007 |
EP |
07118846.0 |
Claims
1. Functionalized nanoparticles obtained by a) combining a
functionalized dyestuff of the formula (1a) ##STR00025## wherein
R.sub.1 stands for C.sub.1-C.sub.18alkoxy or --OH; R.sub.2, R.sub.3
independently from each other stand for C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18alkyl or --OH, E stands for a direct bond or a
bridging member, D is the residue of a chromophore, and a spacer of
the formula (1 b) R.sub.4(4-m)SiX.sub.m (1b) wherein each R.sub.4
represents a monovalent organic radical of from 1 to 24 carbon
atoms, optionally substituted by a monovalent organic radical, X
represents a group capable of undergoing hydrolysis and m is 0, 1,
2, 3 or 4; a catalyst, and optionally a solvent, at time T.sub.SB,
and treating the obtained mixture until time T.sub.SE, wherein
(T.sub.SE-T.sub.SB) is chosen in the range of from 1 and 48 hours,
at a temperature in the range of from 0 to 80.degree. C., b) adding
a co-reactive compound (1c) selected from the group consisting of
an organic silane, an organic alumina, an organic zirconia and an
organic titania, at time T.sub.CC, wherein T.sub.CC fulfils either
condition (a) T.sub.SB<T.sub.CC<T.sub.SE, condition (b)
T.sub.CC.gtoreq.T.sub.SE or condiition (c) wherein T.sub.CC fulfils
both (a) and (b) in case part of co-reactive compound (1c) is added
before T.sub.SE, and the other part after T.sub.SE, and treating
the obtained respective reaction mixture for a period of time
between 12 and 36 hours at a temperature between 0 and 80.degree.
C., and, optionally, after isolating the thus obtained
nanoparticles with well-known methods, c) combining the
nanoparticles with a polymer or, d) polymerizing a monomer or
monomer mixture in the presence of the nanoparticles.
2. Functionalized nanoparticles according to claim 1, wherein the
co-reactive compound (1c) is added at time T.sub.CC.gtoreq.T.sub.SE
(condition (a)).
3. Functionalized nanoparticles according to claim 1, wherein the
co-reactive compound (1c) is added at T.sub.CC, wherein
T.sub.SB<T.sub.CC<T.sub.SE (condition (b)).
4. Functionalized nanoparticles according to claim 3, wherein
between 10 to 90% by weight of the co-reactive organic compound
(1c) is added before T.sub.SE, but after T.sub.SB, and the residual
after or at time T.sub.SE (condition (c)).
5. Functionalized nanoparticles according to claim 1, wherein, in
the compound of formula (1b), R.sub.4 is a monovalent radical of
from 1 to 12 carbon atoms, which is unsubstituted or substituted by
a functional organic group selected from the group consisting of a
mercapto, an epoxy, an acrylyl, a methacrylyl, an allyl, a vinyl, a
halogeno and an amino group.
6. Functionalized nanoparticles according to claim 1, wherein, in
the compound of formula (1b), X stands for C.sub.1-C.sub.18alkoxy,
whereby the alkyl chain may be interrupted by one or more oxygen or
sulphur atoms.
7. Process for the manufacture of functionalized nanoparticles
comprising the steps of: a) combining a functionalized dyestuff of
the formula (1a) ##STR00026## wherein R.sub.1 stands for
C.sub.1-C.sub.18alkoxy or --OH; R.sub.2, R.sub.3 independently from
each other stand for C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkyl
or --OH, E stands for a direct bond or a bridging member, D is the
residue of a chromophore, and a spacer of the formula (1b)
R.sub.4(4-m)SiX.sub.m (1b) wherein each R.sub.4 represents a
monovalent organic radical of from 1 to 24 carbon atoms, optionally
substituted by a monovalent organic radical, X represents a group
capable of undergoing hydrolysis and m is 0, 1, 2, 3 or 4; a
catalyst, and optionally a solvent, at time T.sub.SB, and treating
the obtained mixture until time T.sub.SE, wherein
(T.sub.SE-T.sub.SB) is chosen in the range of from 1 and 48 hours,
at a temperature in the range of from 0 to 80.degree. C., b) adding
a co-reactive compound (1c) selected from the group consisting of
an organic silane, an organic alumina, an organic zirconia and an
organic titania, at time T.sub.CC, wherein T.sub.CC fulfils either
condition (a) T.sub.SB<T.sub.CC<T.sub.SE, condition (b)
T.sub.CC.gtoreq.T.sub.SE or condiition (c) wherein T.sub.CC fulfils
both (a) and (b) in case part of co-reactive compound (1c) is added
before T.sub.SE, and the other part after T.sub.SE, and treating
the obtained respective reaction mixture for a period of time
between 12 and 36 hours at a temperature between 0 and 80.degree.
C., and, optionally, after isolating the thus obtained
nanoparticles with well-known methods, c) combining the
nanoparticles with a polymer or, d) polymerizing a monomer or
monomer mixture in the presence of the nanoparticles.
8. (canceled)
9. A composition comprising the functionalized nanoparticles
according to claims 1 and an organic material.
10. Functionalized nanoparticles according to claim 5, wherein, in
the compound of formula (1b), X stands for C.sub.1-C.sub.18alkoxy,
whereby the alkyl chain may be interrupted by one or more oxygen or
sulphur atoms.
Description
[0001] The invention relates to functionalized nanoparticles, its
preparation and use.
[0002] Colorant and fluorescent nanoparticles are highly
recommended in decorative, electronic, industrial, security and
home and personal care markets delivering effects to the customers.
These applications require stabilized, migration free and heat
resistant fluorescents and colorants that can be specifically
modified like pigments to adapt on desired applications.
[0003] However, the fluorescent signal from a solid dyestuff is
weak, and the dye molecules in solid, in solvent or polymer matrix
are susceptible to migration, decomposition by heat and
irreversible photodegradation. It is a known fact that almost all
fluorescent dyes in application (solution, polymer, paint, ink or
matrix) are self-quenching if the concentration of dye gets high
enough. This means, that the dye itself decreases the fluorescence
intensity by promoting decay from the excited state without
emitting a photon.
[0004] Different approaches have emerged in recent years for
synthesizing fluorescent materials for use in a range of demanding
applications. In the first approach, the fluorescent dye is linked
to a polymer matrix. In the second, the fluorescent dye is
encapsulated in a polymer matrix ba at least on kind of polymer
prior to the end application to prevent dye molecules as good as
possible from migration and self quenching. In addition, in order
to avoid e.g. swelling or porosity change with pH changes,
agglomeration in aqueous medium etc. that are associated with the
above two approaches, silica nanoparticles had been manufactured
with an embedded dye. In all reports, water/alcohol soluble dyes
such as fluoresceine or rhodamine were used and the dye load was
low in order to avoid fluorescence self-quenching.
[0005] E.g. WO 2004/063387 A2 discloses fluorescent silica-based
nanoparticles comprising a core with a fluorescent silane compound
and a silica shell on this core. In particular, a reactive
fluorescent compound such as a dye is reacted with a co-reactive
organo-silane to form a fluorescent core particle. This fluorescent
core particle is further treated with a silica forming compound to
form a silica shell on the core. A disadvantage of the thus
produced particles is that the absorption is not high enough for
some applications, and that migration leads to bleeding if applied
in e.g. plastics or paper.
[0006] It was therefore an objective of present invention to
increase the quantum yield of fluorescent nanosized particles and
to decrease the effect of bleeding.
[0007] Accordingly functionalized nanoparticles were found, which
are obtainable by
[0008] a) combining a functionalized dyestuff of the formula (1
a)
##STR00001##
[0009] wherein
[0010] R.sub.1 stands for C.sub.1-C.sub.18alkoxy, --OH;
[0011] R.sub.2, R.sub.3 independently from each other stand for
C.sub.1-C.sub.18alkoxy or C.sub.1-C.sub.18alkyl, --OH,
[0012] E stands for a direct bond or a bridging member, preferably
for C.sub.1-C.sub.24alkylen, C.sub.6-- or C.sub.12aryl, or
(C.sub.6--)ar(C.sub.1-.sub.4)alkylene,
[0013] D is the residue of a chromophore, and a spacer of the
formula (1 b)
R.sub.4(4-m)SiX.sub.m (1b)
[0014] wherein each
[0015] R.sub.4 represents a monovalent organic radical of from 1 to
24 carbon atoms, optionally substituted by a monovalent organic
radical,
[0016] X represents a group capable of undergoing hydrolysis and m
is 0, 1, 2, 3 or 4;
[0017] a catalyst, and optionally a solvent, at time T.sub.SB,
[0018] and treating the obtained mixture until time T.sub.SE,
wherein (T.sub.SE-T.sub.SB) is chosen in the range of from 1 and 48
hours, at a temperature in the range of from 0 to 80.degree.
C.,
[0019] b) adding a co-reactive compound (1c) selected from the
group consisting of an organic silane, an organic alumina, an
organic zirconia and an organic titania, at time T.sub.CC, wherein
T.sub.CC fulfils condition (a) T.sub.CC.gtoreq.T.sub.SE, (b)
T.sub.SB<T.sub.CC<T.sub.SE, or (c)
T.sub.SB<T.sub.CC1<T.sub.SE.ltoreq.T.sub.CC2 in case part of
co-reactive compound (1c) is added before T.sub.SE, and the other
part after T.sub.SE,
[0020] and treating the obtained respective reaction mixture for a
period of time between 12 and 36 hours at a temperature between 0
and 80.degree. C.,
[0021] and, optionally, after isolating the thus obtained
nanoparticles with well-known methods,
[0022] c) combining the nanoparticles with a polymer or,
[0023] d) polymerizing a monomer or monomer mixture in the presence
of the nanoparticles.
[0024] The functionalized dyestuffs (1a) can be prepared in analogy
to known processes, in which a reactive chromophore is reacted with
a co-reactive organo-silane compound to form the functionalized
dyestuff (1a).
[0025] The chromophore thus can be linked by any known chemical
coupling methods using e.g. carboxylates, anhydrides, esters,
alcohols, thiols, carbamides, aldehydes, amines, sulfur oxides,
nitrogen oxides, halides or carbodiimide coupling as well as e.g.
addition reaction and ring-opening reactions.
[0026] As will be clear to one skilled in the art, suitable
protecting groups can be used during the ligation reaction. For
example, other functional groups present in the reactive organic
compound or co-reactive organo-silane can be partially or
completely be removed to provide the ligated-compounds, ie
preferably a organo-silane dyestuff. Suitable protecting groups and
methods for their incorporation and removal are well known in the
art (see for example Green, T. W.; Wutz, P. G. M. "Protecting
Groups In Organic Synthesis" 2.sup.nd edition, 1991, New York, John
Wiley & Sons, Inc.).
[0027] Additionally, when a carboxylic acid is reacted with a
hydroxyl group, a mercapto group, or an amine group to provide an
ester linkage, thioester linkage, or an amide linkage, the
carboxylic acid can be activated prior to the reaction, for
example, by formation of the corresponding acid chloride. Numerous
methods for activating carboxylic acids, and for preparing ester
linkages, thioester linkages, and amide linkages, are known in the
field (see for example, "Advanced Organic Chemistry: Reaction
Mechanisms and Structure, 4.sup.th ed., Jerry March, John Wiley
& Sons, pages 419 to 437, and 1281).
[0028] Reactive chromophores are well-known for example from
"Molecular Probes Handbook of Fluorescent Probes and Research
Chemicals", 6th ed., R. P. Haugland, ed. (1996). A typical
chromophore is e.g. a aromatic or heteroaromatic compound such as
is a pyrene, an anthracene, a naphthalene, an acridine, a stilbene,
an indole or benzindole, an oxazole or benzoxazole, a thiazole or
benzothiazole, a 4-amino-7-nitrobenz-2-oxa-1,3-diazole (NBD), a
cyanine, a carbocyanine, a carbostyryl, a porphyrin, a porphycene,
a salicylate, an anthranilate, an azulene, a perylene, a pyridine,
a quinoline, a coumarin (including hydroxycoumarins and
aminocoumarins and fluorinated derivatives thereof), naphthalimide,
rhodamine, fluoresceine, stilbene, xanthene, and benzoxanthenes and
like compounds, see for example U.S. Pat. No. 5,830,912; 4,774,339;
5,187,288; 5,248,782; 5,274,113; 5,433,896; 4,810,636; and
4,812,409.
[0029] As co-reactive organo-silane silanes of the general
formula
##STR00002##
[0030] can be used, where
[0031] R.sub.1 stands for C.sub.1-C.sub.18alkoxy, --OH;
[0032] R.sub.2, R.sub.3 independently from each other stand for
C.sub.1-C.sub.18alkoxy or C.sub.1-C.sub.18alkyl, --OH,
[0033] E stands for C.sub.1-C.sub.24alkylen, C.sub.6-- or
C.sub.12aryl, or (C.sub.6--)ar(C.sub.1-4)alkylene,
[0034] Y is a leaving group, e.g. a hydrolyzable group such as
C.sub.1-C.sub.4alkoxy, which can be substituted by
C.sub.1-C.sub.4alkoxy;
[0035] --NCO, NCS, --SH, halogen, --NH.sub.2, NHR.sub.5,
NR.sub.6R.sub.7, wherein R.sub.5, R.sub.6, R.sub.7 independently
from each other stand for C.sub.1-C.sub.18alkyl, or
amino-C.sub.1-C.sub.18alkyl.
[0036] C.sub.1-C.sub.18alkoxy stands for methoxy, ethoxy, n-,
i-propoxy, n-, i-, sec.-, tert.-butoxy, n-pentoxy, n-hexoxy,
n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy,
n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexydecoxy,
n-heptydecoxy, n-octadecoxy, preferably for C.sub.1-C.sub.4alkoxy
such as for methoxy, ethoxy, n-propoxy, n-butoxy.
[0037] C.sub.1-C.sub.4alkoxy group, which is substituted by
C.sub.1-C.sub.4alkoxy can be e.g. 2-methoxy-ethoxy,
2-methoxy-ethoxy-2-ethoxy.
[0038] C.sub.1-C.sub.18alkyl stands for methyl, ethyl, n-,
i-propyl, n-, i-, sec.-, tert.-butyl, n-pentyl, n-hexyl, n-heptyl,
n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexydecyl, n-heptydecyl, n-octadecyl,
preferably for C.sub.1-C.sub.4alkyl such as for methyl, ethyl,
n-propyl, n-butyl.
[0039] C.sub.1-C.sub.24alkylene stands for methylene, ethylene, n-,
i-propylene, n-, i-, sec.-, tert.-butylene, n-pentylene,
n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene,
n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene,
n-pentadecylene, n-hexydecylene, n-heptydecylene, n-octadecylene,
n-nonadecylene, n-eicosylene, n-uneicosylene, n-doeicosylene,
preferably C.sub.1-C.sub.8alkylene such as methylene, ethylene, n-,
i-propylene, n-, i-, sec.-, tert.-butylene, n-pentylene,
n-hexylene, n-heptylene, n-octylene, particularly preferred
C.sub.1-C.sub.4alkylene such as methylene, ethylene, n-,
i-propylene, n-, i-, sec.-, tert.-butylene.
[0040] C.sub.6-- or C.sub.12aryl stands for phenylene or
naphthylene, e.g. o-phenylene, m-phenylene, p-phenylene,
[0041] C.sub.6ar-C.sub.1-4alkylene stands for
--(CH.sub.2).sub.1-4-phenyl--, preferably for
--CH.sub.2-phenyl--,
[0042] Halogen stands for F, Cl, Br, or I.
[0043] Further definitions which will be used below are:
[0044] C.sub.2-C.sub.20alkenyl such as ethenyl (=vinyl), n--
(=allyl), i-propenyl, n-but-(1-, 2-, or 3-)enyl, i-but(1- or
2-)enyl, sec.-but(1-, 2- or 3-)enyl, tert.-butenyl, n-pentenyl,
n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl,
n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl,
n-pentadecenyl, n-hexydecenyl (=palmityl), n-heptydecenyl,
n-octadecenyl (=oleyl), preferably vinyl, oleyl, palmityl,
[0045] halogen-C.sub.1-C.sub.18alkyl such as chloro-, bromo- or
iodo-C.sub.1-C.sub.18alkyl, wherein C.sub.1-C.sub.18alkyl has the
above meaning, in particular preferred is iodo-n-propyl,
[0046] amino-C.sub.1-C.sub.18alkyl such as aminomethyl,
2-aminoethyl, 3-amino-n-propyl, 4-amino-n-butyl, 5-amino-n-pentyl,
6-amino-n-hexyl, 7-amino-n-heptyl, 8-amino-n-octyl,
9-amino-n-nonyl, 10-amino-n-decyl, 11-amino-n-undecyl,
12-amino-n-dodecyl, 13-amino-n-tridecyl, 14-amino-n-tetradecyl,
15-amino-n-pentadecyl, 16-amino-n-hexydecyl, 17-amino-n-heptydecyl,
18-amino-n-octadecyl, preferably for amino-C.sub.1-C.sub.4alkyl
such as for aminomethyl, 2-aminoethyl, 3-amino-n-propyl,
4-amino-n-butyl, more preferably for 3-amino-n-propyl,
[0047] amino-C.sub.6-- or C.sub.12aryl, such as aminophenyl,
preferably o-, m-, or p-aminophenyl, more preferred
p-aminophenyl,
[0048] mercapto-C.sub.1-C.sub.18alkyl, mercaptomethyl,
2-mercaptoethyl, 3-mercapto-n-propyl, 4-mercapto-n-butyl,
5-mercapto-n-pentyl, 6-mercapto-n-hexyl, 7-mercapto-n-heptyl,
8-mercapto-n-octyl, 9-mercapto-n-nonyl, 10-mercapto-n-decyl,
11-mercapto-n-undecyl, 12-mercapto-n-dodecyl,
13-mercapto-n-tridecyl, 14-mercapto-n-tetradecyl,
15-mercapto-n-pentadecyl, 16-mercapto-n-hexydecyl,
17-mercapto-n-heptydecyl, 18-mercapto-n-octadecyl, preferably for
mercapto-C.sub.1-C.sub.4alkyl such as for mercaptomethyl,
2-mercaptoethyl, 3-mercapto-n-propyl, 4-mercapto-n-butyl, more
preferably 3-mercapto-n-propyl.
[0049] Compounds (1 a') are known or can be prepared in analogy to
known methods. E.g. the use of functional mono-, bis- and
tris-alkoxysilanes for coupling and modification of co-reactive
functional groups is described in Kirk-Othmer, Encyclopedia of
Chemical Technology, Vol. 20, 3rd Ed., J. Wiley, N.Y.
[0050] In a preferred embodiment of this invention the co-reactive
organo-silanes (1a') are aminosilanes (1a''),
R.sub.1R.sub.2R.sub.3Si--E--NH.sub.2, in which E for stands for
C.sub.1-C.sub.24alkylen, preferably C.sub.1-C.sub.18alkylen, more
preferably C.sub.1-C.sub.8alkylen, or o-, m-, p-phenylene, and
R.sub.1.dbd.R.sub.2.dbd.R.sub.3 are --OH, C.sub.1-C.sub.18alkoxy or
C.sub.1-C.sub.4alkoxy, which is substituted by
C.sub.1-C.sub.4alkoxy. Particularly preferred are
aminoalkyltrialkoxysilanes, i.e. in which E stands for
C.sub.1-C.sub.8alkylen and R.sub.1.dbd.R.sub.2.dbd.R.sub.3 are
C.sub.1-C.sub.4alkoxy such as 3-amino-n-propyltrimethoxyilane and
3-amino-n-propyltriethoxysilane, most preferred is
3-amino-n-propyltriethoxysilane ("APTES").
[0051] Also preferred are amino-phenyl-tri-alkoxysilanes, in which
E stands for o-, m-, p-phenylene, and
R.sub.1.dbd.R.sub.2.dbd.R.sub.3 are C.sub.1-C.sub.8alkoxy or with
C.sub.1-C.sub.4alkoxy substituted C.sub.1-C.sub.4alkoxy, such as
o-aminophenyl--, m-aminophenyl--, p-aminophenyl-trialkoxysilanes,
preferably p-aminophenyl-trialkoxysilanes. In particular preferred
are p-aminophenyl-trialkoxysilanes.
[0052] Also mixtures of aminoalkyltrialkoxysilanes and
aminoaryltrialkoxysilanes can be used.
[0053] In case of compound (1a') is an isocyanoto-silane,
3-isocyanato-propyltriethoxysilane is most preferred.
[0054] In case of compounds (1a') is an isothiocyanoto-silane,
3-isothiocyanato-n-propyltriethoxysilane is most preferred.
[0055] In case of compound (1a') is a mercapto-silane,
mercapto-methyl(methyl)diethoxysilane,
3-mercapto-n-propyltriethoxysilane,
3-mercapto-n-propyl(methyl)diethoxysilane,
3-mercapto-propyl-di-methyl-ethoxysilane are preferred, most
preferred is 3-mercapto-n-propyltriethoxysilane.
[0056] In case compound (1a') is a halogenated organo-silanes,
3-iodo-n-propyl-triethoxysilane and
3-bromo-n-propyl-triethoxysilane are most preferred.
[0057] Although not desired to be limited by theory, the coupling
usually arises as a result of hydrolysis of the alkoxysilane groups
to silanol groups, see e.g. E. Pluedemann, Silane Coupling Agents,
Plenum Press, N.Y. 1982.
[0058] In a preferred embodiment of this invention the
functionalized dyestuff is prepared by the reaction of a
co-reactive aminosilane (1a'') with a reactive dyestuff
(D-hal):
R.sub.1R.sub.2R.sub.3Si--E--NH.sub.2+D-hal.fwdarw.R.sub.1R.sub.2R.sub.3S-
i--E--NHD+H-hal
[0059] As reactive dyestuff D-hal the known dyestuffs can be used,
preferably chemically reactive dyes as mentioned above are used. In
particular preferred are naphthalimides, porphycenes, rhodamines,
fluoresceines, stilbenes, xanthenes, and benzoxanthenes.
[0060] As co-reactive aminosilane
R.sub.1R.sub.2R.sub.3Si--E--NH.sub.2 (1a'') those are preferred,
where R.sub.1, R.sub.2, R.sub.3 stand for --OH,
C.sub.1-C.sub.8alkoxy, and E stands for C.sub.1-C.sub.8alkylen,
C.sub.6-- or C.sub.12aryl, or (C.sub.6--)ar(C.sub.1-4)alkylene.
[0061] Most preferred co-reactive aminosilanes
R.sub.1R.sub.2R.sub.3Si--E--NH.sub.2 (1a'') such as
4-amino-n-butyltriethoxysilane, 3-amino-n-propyltriethoxysilane,
3-amino-n-propyltrimethoxysilane, 3-amino-n-propylsilanetriol,
(3-amino-n-propyl)-methyl-di-methoxysilane,
(3-amino-n-propyl)-di-methyl-methoxysilane,
N-(2-aminoethyl)-3-amino-n-propyltrimethoxysilane,
N-(2-aminoethyl)-3-amino-n-propylmethyldimethoxysilane,
N-(6-aminohexyl)-3-amino-n-propyltrimethoxy-silane, and amino-o-,
-m-, -p-phenyltrimethoxysilanes as well as its isomer mixtures.
[0062] Generally, the reactive dyestuff D-hal is dissolved in a
solvent and the co-reactive aminosilane (1a'') is added. After the
addition, preferably the reaction is allowed to proceed to
completion. Of course, the reaction also can be carried out using
suspensions and the like.
[0063] Preferably, the molar ratio of aminosilane (1a'') to
dyestuff D-hal is chosen in the range of 1:1 to 100:1, preferably
from 2:1 to 15:1.
[0064] Preferred solvents are organic solvents, in particular polar
solvents such as acetonitrile, alcohols like ethanol, methanol,
1-propanol, 2-propanol, 1-methoxy-2-propanol, tetrahydrofurane
("THF"), dioxane, pyridine, N-methylpyrrolidone ("NMP"),
dimethylformamide ("DMF"), dimethylacetamide ("DMAA"), ketones like
tert.-butylmethylketone, preferably ethanol, dimethylacetamide,
dimethylformamide and acetonitrile. Of course, also mixtures of
solvents can be used, too. Naturally, other solvents can be used as
long as they do not interfere negatively with the reaction.
Generally, the reaction is carried out in a temperature range from
-10.degree. C. to the boiling point of the reaction mixture, which
as a rule is in the range of the boiling point of the used solvent
or solvent mixture.
[0065] For example, when carrying out the reaction in
dimethylacetamide or pyridine the preferred temperature is in the
range of 50 to 100.degree. C., preferably in the range of 70 to
90.degree. C. Or when, for example, the reaction is carried out in
acetonitrile, the preferred temperature range is chosen between 40
to 80.degree. C., more preferably from 50 to 75.degree. C.
[0066] The duration of the addition of the aminosilane (1a'') as
well as of the whole reaction depends on the reactivity of e.g. the
chosen educts, amounts and temperature. Usually a person skilled in
the art will know what to do and when the reaction is completed. A
typical time range for the addition of the aminosilane (1a'') would
be from 10 min to 2 hours, preferably from 10 to 60 min. A typical
time range for completion of the reaction would be from 1 to 12
hours, preferably from 1 to 6 hours.
[0067] If desired the obtained product can be isolated by known
methods such a filtration, centrifugation, crystallization,
decantation, chromatography, evaporation/distillation of residual
solvents and reactants and the like.
[0068] In another preferred embodiment of this invention the
functionalized dyestuff is prepared by the reaction of the
co-reactive aminosilane (1a'') with a reactive dyestuff comprising
a lactone group
##STR00003##
wherein R.sub.9 and R.sub.10 together with --C(.dbd.O)--O-- form a
lactone group within the dyestuff molecule.
[0069] In principle, all lactone group containing dyestuffs can be
used, preferred are rhodamine and fluoresceine based compounds such
as rhodamine B, fluoresceine and the like.
[0070] As co-reactive aminosilane (1a') the abovementioned
aminosilanes (1a'') are preferred.
[0071] Usually, this ring-opening reaction is carried out in the
presence of an acid such as a mineral acid, e.g. HCl, and HBr, or
dicyclohexylcarbodiimde ("DCC").
[0072] Generally, the reactive lactone dyestuff is dissolved in a
solvent and the co-reactive aminosilane (1a''), is added. After the
addition, preferably the reaction is allowed to proceed to
completion. Of course, the reaction also can be carried out using
suspensions and the like.
[0073] Preferably, the molar ratio of aminosilane (1a'') to
dyestuff is chosen in the range of 1:1 to 100:1, preferably from
2:1 to 15:1.
[0074] Usually this reaction is carried out in the presence of a
solvent. Preferred solvents are organic solvents such as polar
solvents like acetonitrile, alcohols like ethanol, methanol,
1-propanol, 2-propanol, 1-methoxy-2-propanol, tetrahydrofurane
("THF"), dioxane, pyridine, N-methylpyrrolidone ("NMP"),
dimethylformamide ("DMF"), dimethylacetamide ("DMAA"), ketones like
tert.-butylmethylketone, preferably ethanol, 1-methoxy-2-propanol,
dimethylacetamide, dimethylformamide and acetonitrile. Of course
also mixtures of solvents can be used, too. Naturally, other
solvents can be used as long as they do not interfere negatively
with the reaction.
[0075] Generally, the reaction is carried out in a temperature
range from 0.degree. C. to the boiling point of the reaction
mixture, which usually is in the range of the boiling point of the
used solvent or solvent mixture.
[0076] For example when carrying out the reaction in
dimethylacetamide or pyridine the preferred temperature is in the
range of 0 to 100.degree. C., preferably in the range of 0 to
60.degree. C.
[0077] The duration of the addition of the aminosilane (1a'') as
well as of the whole reaction depends on the reactivity of e.g. the
chosen educts, amounts and temperature. Usually a person skilled in
the art will know what to do and when the reaction is completed. A
typical time range for the addition of the aminosilane (1a'') would
be from 10 min to 2 hours, preferably from 10 to 60 min. A typical
time range for completion of the reaction would be from 1 to 12
hours, preferably from 1 to 6 hours.
[0078] If desired the obtained product can be isolated by known
methods such a filtration, centrifugation, crystallization,
decantation, chromatography, evaporation/distillation of residual
solvents and reactants etc.
[0079] In another preferred embiment of this invention the
functionalized dyestuff is prepared by the reaction of the
co-reactive aminosilane (1a'') with a reactive dyestuff comprising
a isothiocyanate group D--N.dbd.C.dbd.S or an active ester like
succinimidyl-ester:
D--N.dbd.C.dbd.S+R.sub.1R.sub.2R.sub.3Si--E--NH.sub.2.fwdarw.D--NH--C(.d-
bd.S)--NH--E--SiR.sub.1R.sub.2R.sub.3
[0080] Such reactions are well-known in the art and e.g. a similar
reaction is described in Langmuir, Vol. 8, No. 12, 1992, p.
2924).
[0081] Of course, it is also possible to use educts where the amino
group comes with the dye and the isothiocyanato group comes with
the silane.
[0082] As reactive dyestuff succinimidylesters and all
isothiocyanato group containg dyestuffs can be used such as
rhodamine derivatives, preferably
tetraethylrhodamine-5/6-isothiocyanate (TRITC),
fluoresceine-5-isothiocyanate (FITC),
7-dimethylamino-4-methylcoumarin-3-isothiocyanate (DACITC),
eosin-5-isothiocyanate, erythrosin-5-isothiocyanate, malachite
green isothiocyanate and the like.
[0083] Generally, the reactive dyestuff D--N.dbd.C.dbd.S or a
corresponding succinimidylester is dissolved in a solvent and the
co-reactive aminosilane (1a'') is added. After the addition,
preferably the reaction is allowed to proceed to completion. Of
course, the reaction also can be carried out using suspensions and
the like.
[0084] Preferably, the molar ratio of aminosilane (1a'') to
dyestuff is chosen in the range of 1:1 to 100:1, preferably from
2:1 to 15:1.
[0085] Usually this reaction is carried out in the presence of a
solvent. Preferred solvents are organic solvents, in particular
polar solvents such as acetonitrile, alcohols like ethanol,
methanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol,
tetrahydrofurane ("THF"), dioxane, pyridine, N-methylpyrrolidone
("NMP"), dimethylformamide ("DMF"), dimethylacetamide ("DMAA"),
ketones like tert.-butylmethylketone, preferably ethanol,
1-methoxy-2-propanol, dimethylacetamide, dimethylformamide and
acetonitrile. Of course also mixtures of solvents can be used, too.
Of course, other solvents can be used as long as they do not
interfere negatively with the reaction. A person skilled in the art
would know what to choose in such a case.
[0086] Generally, the reaction is carried out in a temperature
range from 0.degree. C. to the boiling point of the reaction
mixture, which usually is in the range of the boiling point of the
used solvent or solvent mixture.
[0087] For example, when carrying out the reaction in
dimethylacetamide or pyridine the preferred temperature is in the
range of 0 to 100.degree. C., preferably in the range of 0 to
60.degree. C.
[0088] The duration of the addition of the aminosilane (1a'') as
well as of the whole reaction depends on the reactivity of e.g. the
chosen educts, amounts and temperature. Usually a person skilled in
the art will know what to do and when the reaction is completed. A
typical time range for the addition of the aminosilane (1a'') would
be from 10 min to 2 hours, preferably from 10 to 60 min. A typical
time range for completion of the reaction would be from 1 to 48
hours, preferably from 1 to 24 hours.
[0089] If desired the obtained product can be isolated by known
methods such a filtration, centrifugation, crystallization,
decantation, chromatography, evaporation/distillation of residual
solvents and reactants etc.
[0090] In another preferred embodiment of this invention the
functionalized dyestuff can be prepared by the reaction of a
co-reactive isocyanatosilane R.sub.1R.sub.2R.sub.3Si--E--NCO with a
reactive hydroxy- or amino-dyestuff D-Z.sub.1, wherein Z.sub.1 can
be --OH or --NH.sub.2:
D--OH+R.sub.1R.sub.2R.sub.3Si--E--NCO.fwdarw.D--O--C(.dbd.O)--NH--E--SiR-
.sub.1R.sub.2R.sub.3
D--NH.sub.2+R.sub.1R.sub.2R.sub.3Si--E--NCO.fwdarw.D--NH--C(.dbd.O)--NH--
-E--SiR.sub.1R.sub.2R.sub.3
[0091] In cases where the hydroxyl group of the dyestuff is not
stable, it is more appropriate to use a corresponding protective
group, e.g. an ester like acetoxy. The hydroxyl group is usually
then generated in situ or before the reaction with the
isocyanatosilane for example by reaction of the ester with a common
base such as a alkali metal alcoholate like sodium methylate.
[0092] As reactive ester-dyestuff, which is a precursor of the
corresponding hydroxy-dyestuff D--OH, porphycenes such as
9-hydroxy-substituted 2,7,12,17-tetraalkyl--, --aryl--,
--alkoxyalkyl-- or --alkylaryl--, --alkoxyaryl-porphycenes and
mixtures thereof like mono-, di-, tri-2,7,12,17-substituted
porphycenes,
2,7,12,17-alkylarylsubstituted-3,6,13,16-tetraazaporphycenes,
preferably 9-hydroxy-2,7,12,17-tetrakis(methoxyethyl)-porphycene,
9-hydroxy-2,7,12,17-tetra-n-propylporphycene can be used.
[0093] As reactive amino-dyestuff D--NH.sub.2 porphycenes like
9-amino-substituted 2,7,12,17-tetraalkyl--, --aryl--,
--alkoxyalkyl-- or --alkylaryl--, --alkoxyaryl-porphycenes and
mixed substituted porhycenes like mono-, di-,
tri-2,7,12,17-substituted porphycenes,
2,7,12,17-alkylarylsubstituted-3,6,13,16-tetraazaporphycenes,
preferably 9-amino-2,7,12,17-tetrakis(methoxyethyl)-porphycene,
9-amino-2,7,12,17-tetra-n-propylporphycene can be used.
[0094] As co-reactive isocyanatosilane
R.sub.1R.sub.2R.sub.3Si--E--NCO those silanes are preferred in
which R.sub.1.dbd.R.sub.2.dbd.R.sub.3 stand for
C.sub.1-C.sub.4alkoxy such as methoxy, ethoxy, n-, i-propoxy, n-,
i-, sek.-, tert.-butoxy, preferably methoxy and ethoxy, and E
stands for C.sub.1-C.sub.8alkylene such as methylene, ethylene, n-,
i-propylene, n-, i-, sec.-, tert.-butylene, n-pentylene,
n-hexylene, n-heptylene, n-octylene, particularly preferred
C.sub.1-C.sub.4alkylene such as methylene, ethylene, n-,
i-propylene, n-, i-, sec.-, tert.-butylene, most preferred for
n-propylene. In particular preferred is
3-isocyanato-n-propyl-triethoxysilane.
[0095] Similar reactions are known, for example described in Chem.
Phys. Letters 245 (1995) 36-40). Generally, the reactive dyestuff
D-Z.sub.1 is dissolved in a solvent and the co-reactive
isocyanatosilane is added. After the addition, preferably the
reaction is allowed to proceed to completion. Of course, the
reaction also can be carried out using suspensions and the
like.
[0096] Preferably, the molar ratio of isocyanatosilane
R.sub.1R.sub.2R.sub.3Si--E--NCO to dyestuff is chosen in the range
of 1:1 to 100:1, preferably from 2:1 to 15:1.
[0097] Usually this reaction is carried out in the presence of a
solvent. Preferred solvents are organic solvents such as polar
solvents like acetonitrile, alcohols like ethanol, methanol,
1-propanol, 2-propanol, tetrahydrofurane ("THF"), dioxane,
pyridine, N-methylpyrrolidone ("NMP"), dimethylformamide ("DMF"),
dimethylacetamide ("DMAA"), ketones such as
tert.-butylmethylketone, preferably ethanol, dimethylacetamide,
dimethylformamide and acetonitrile. Of course, also mixtures of
solvents can be used, too. Naturally, other solvents can be used as
long as they do not interfere negatively with the reaction.
[0098] As a rule, the reaction can be carried out in a temperature
range from 0.degree. C. to the boiling point of the reaction
mixture, which usually is in the range of the boiling point of the
used solvent or solvent mixture.
[0099] For example, when carrying out the reaction in dioxane or
THF the preferred temperature is in the range of 0 to 50.degree.
C., preferably in the range of 5 to 30.degree. C.
[0100] The duration of the addition of the isocyanatosilane
R.sub.1R.sub.2R.sub.3Si--E--NCO as well as of the whole reaction
depends on the reactivity of e.g. the chosen educts, amounts and
temperature. Usually a person skilled in the art will know what to
do and when the reaction is completed. A typical time range for the
addition of the isocyanatosilane R.sub.1R.sub.2R.sub.3Si--E--NCO
would be from 10 min to 2 hours, preferably from 10 to 60 min. A
typical time range for completion of the reaction would be from 1
to 48 hours, preferably from 1 to 24 hours.
[0101] If desired the obtained product can be isolated by known
methods such a filtration, centrifugation, crystallization,
decantation, chromatography, evaporation/distillation of residual
solvents and reactants and the like.
[0102] The spacer of the formula (1b)
R.sub.4(4-m)SiX.sub.m (1b)
[0103] wherein each
[0104] R.sub.4 represents a monovalent organic radical of from 1 to
24 carbon atoms, optionally substituted by a monovalent organic
radical,
[0105] X represents a group capable of undergoing hydrolysis and m
is 0, 1, 2, 3 or 4, preferably 3;
[0106] are either well-known and commercially available (e.g. from
Fluka, Aldrich or ABCR Gelest) or can be synthesized by well-known
methods. In case more than one group R.sub.4 is in the spacer
molecule, then it can be the same or different, the same applies
for the group X.
[0107] Examples of a monovalent organic radical of from 1 to 24
carbon atoms, optionally substituted by a monovalent organic
radical, are C.sub.1-C.sub.24alkyl as defined above,
C.sub.5-C.sub.8cycloalkyl such as cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, preferably cyclohexyl,
C.sub.2-C.sub.20alkenyl as defined above, preferably vinyl, oleyl,
palmityl,
[0108] halogen-C.sub.1-C.sub.18alkyl, amino-C.sub.1-C.sub.18alkyl,
amino-C.sub.6-C.sub.12aryl, mercapto-C.sub.1-C.sub.18alkyl all as
defined above.
[0109] Examples of a group capable of undergoing hydrolysis, X, are
C.sub.1-C.sub.8alkoxy and C.sub.1-C.sub.6acyloxy (as in
tri-acetoxy-methylsilane)
[0110] such as methoxy, ethoxy, n-, i-propoxy, n-, i-, sec.-,
tert.-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, preferably
for C.sub.ra.sub.talkoxy such as for methoxy, ethoxy, n-propoxy,
n-butoxy, formyloxy, acetoxy, n-, i-propoyloxy, n-, i-, sec.-,
tert.-butoyloxy, n-pentoyloxy, n-hexoyloxy, preferably acetoxy.
[0111] In particular preferred spacers (1b) are
n-C.sub.1--C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silanes such as
methyl-trimethoxysilane, methyltriethoxysilane,
ethyl-trimethoxysilane, ethyl-triethoxysilane,
n-propyl-trimethoxysilan, n-propyl-triethoxysilan,
n-butyl-trimethoxysilane, n-octyl-trimethoxysilane,
n-octadecyl-trimethoxysilane, n-butyl-triethoxysilane,
n-octyl-triethoxysilane, n-octadecyl-triethoxysilane.
[0112] Of course, also mixtures of spacers (1a) can be used. E.g. a
preferred mixture can be chosen from methyltrimethoxysilane and
n-propyltrimethoxysilane, wherein a preferred mixing range would be
from 1:10 to 10:1, more preferably in the range of from 0.9:1 to
1.1:1.
[0113] Generally, the functionalized dyestuff (1a) is reacted with
the silane spacer (1b), wherein the molar ratio of silane spacer
(1b) to functionalized dyestuff (1a) is chosen in the range of from
1:10 to 100:1, preferably from1:1 to 50:1.
[0114] The catalyst, which usually is an acid or a base, is added
in order to start and maintain the reaction between the
functionalized dyestuff (1a) and the spacer (1b).
[0115] As acid the usual mineral acids or simple organic acids can
be used such as HCl, HF, CF.sub.3COOH, ClH.sub.2COOH, p-toluene
sulfonic acid and the like. As base the usual bases can be used
such as alkali metal hydroxides like lithium hydroxide, sodium
hydroxide or potassium hydroxide, earth alkali metal hydroxides
such as magnesium hydroxide, calcium hydroxide, ammonium hydroxide,
or alkali metal carbonates or earth alkali metal carbonates like
sodium carbonate, potassium carbonate, magnesium carbonate, calcium
carbonate or earth alkali metal hydrogen carbonates like calcium
hydrogen carbonate.
[0116] Generally, the catalyst is added in aqueous form, e.g. in a
preferred embodiment a 25% by weight aqueous ammonia solution is
used.
[0117] The amount of catalyst to functionalized dyestuff (1a)
usually is chosen in the range of from 10:1 to 1:20 mol.-%.
[0118] It can be advantageous to carry out this reaction in the
presence of an appropriate solvent. Such solvents can easily be
chosen by a person skilled in the art. As examples the following
solvents can be used: water, alcohols such as methanol, ethanol,
1-propanol, 2-propanol, methoxyethanol, 1-methoxy-2-propanol,
tetrahydrofurane, acetone, N,N-di-methyl acetamide,
N-methylpyrrolidone ("NMP"), dioxane, tert.-butylmethylketone, or
mixtures thereof. Usually the amount of solvent is chosen in the
range of from 5 to 99.9% by weight, preferably from 30 to 99% by
weight, based on the amount of functionalized dyestuff.
[0119] As a rule, the sequence of addition is not important for the
success of the invention. Usually, a mixture of the functionalized
dyestuff (1a), the spacer (1b) and a solvent is added to a mixture
of the catalyst and a solvent or solvent mixture.
[0120] The time, when all three main components are combined is
called T.sub.SB.
[0121] The obtained reaction mixture is then treated until time
T.sub.SE, wherein the difference (T.sub.SE-T.sub.SB) usually is
chosen in the range of from 1 and 48 hours.
[0122] Generally, the treatment is carried out at a temperature in
the range of from 0 to 80, preferably 10 to 50.degree. C.
[0123] After this first stage, it is possible to isolate the
desired product, e.g. by known methods such as centrifugation,
decantation, filtration or chromatography and the like. The
obtained particles will be called silsesquioxanes below.
[0124] Preferably, though, the process is carried on by adding a
co-reactive compound (1c), which is selected from the group
consisting of an organic silane, an organic alumina, an organic
zirconia and an organic titania.
[0125] Co-reactive compounds (1c) are known and commercially
available or can be synthesized by known methods.
[0126] Preferred organic silanes are e.g. unsubstituted or
substituted tetra-C.sub.1-C.sub.8alkoxysilanes such as
tetramethoxysilane, tetraethoxysilane ("TEOS"),
tetra-n-propoxysilane, tetra-n-butoxysilane;
tetrakis(methoxyethoxy)silane, tetrakis(ethoxyethoxy)silane,
tetrakis(methoxyethoxyethoxy)silane,
tetrakis(methoxypropoxy)silane, tetrakis(2-methyl-hexoxy)silane,
di-C.sub.1-C.sub.4alkyl-tetra-C.sub.1-C.sub.8alkoxydisilanes such
as dimethyltetraethoxydisiloxane;
tetra-C.sub.1-C.sub.4acyloxysilanes such as tetraacetoxysilane;
tetra-C.sub.2-C.sub.4alkenyloxysilanes such as tetraallyloxysilane,
as well as mixtures thereof, preferably tetraethoxysilane (TEOS)
and tetra-n-propoxysilane.
[0127] As co-reactive organic alumina such as
tri-C.sub.1-C.sub.4alkoxy aluminate like tri-n-, -i-propoxy
aluminate, tri-n-butoxy aluminate, but also alkoxy alumina-silica
compounds like di-C.sub.1-C.sub.4alkoxy aluminoxy
tri-C.sub.1-C.sub.4alkoxy silanes such as
di-butoxy-aluminoxy-triethoxy-silane, can be used.
[0128] As co-reactive organic zirconia such as
tetra-C.sub.1-C.sub.4alkoxy zirconate like tetra-n-butoxy
zirconate, tetraethoxy zirconate, tetra-n-, -i-propoxy zirconate,
can be used.
[0129] As co-reactive organic titania such as
tetra-C.sub.1-C.sub.4alkoxy titanate like tetra-n-butyl titanate,
tetraethoxy titanate, tetramethoxy titanate, tetra-n-, -i-propoxy
titanate, can be used.
[0130] The amount of silsesquioxane to the co-reactive compound
(1c) is usually chosen in the range of from 0.1 to 99% by weight to
2 to 90% by weight.
[0131] The time of adding the co-reactive compound (1c) is called
T.sub.CC, wherein T.sub.CC fulfils condition
[0132] (a) T.sub.CC.gtoreq.T.sub.SE,
[0133] (b) T.sub.SB<T.sub.CC<T.sub.SE, or
[0134] (c) T.sub.SB<T.sub.CC1<T.sub.SE.ltoreq.T.sub.CC2 in
case part of co-reactive compound (1c) is added before T.sub.SE,
and the other part after T.sub.SE.
[0135] After the addition of the co-reactive organic compound (1c)
the obtained reaction mixture is treated for a period of time
between 1 and 48, preferably between 12 and 36 hours.
[0136] Usually the temperature is chosen in the range of 0 to 80,
preferably from 10 to 50.degree. C.
[0137] Preferably, the reaction is carried out in the presence of a
solvent. In addition, it is preferred to add the co-reactive
organic compound (1c) as a mixture with an appropriate solvent.
[0138] Such solvents can be e.g. polar solvents such as water,
alcohols such as methanol, ethanol, 1-propanol, 2-propanol,
methoxyethanol, methoxypropanol, ethers like dioxane,
tetrahydrofurane, or N-containing solvents such as acetonitrile,
N,N-di-methyl formamide, N,N-di-methyl acetamide,
N-methylpyrrolidone or mixtures thereof. Usually the amount of
solvent is chosen in the range of from 5 to 99.9% by weight,
preferably from 30 to 99% by weight, based on the amount of
functionalized dyestuff.
[0139] Furthermore, advantageously the reaction mixture is stirred,
in particular vigorously during the addition of the co-reactive
compound (1c).
[0140] The obtained reaction product can be separated from the
reaction mixture by known methods such as centrifugation,
decantation, filtration, or chromatography and the like.
[0141] As a rule, the separated product can be further treated and
worked-up. A preferred method is to disperse the separated product
in a solvent such as alcohol like ethanol, n-, i-propanol,
methoxypropanol, or N,N-di-methyl formamide, N,N-di-methyl
acetamide, tetrahydrofurane, dioxane, acetonitrile,
N-methylpyrrolidone, preferably in ethanol or di-methyl acetamide,
and then to precipitate the desired prouct by addition of another
solvent such as ethyl acetate, butyl acetate, hexane, cylohexane,
toluene, preferably ethyl acetate.
[0142] After precipitation the desired product can be further
washed in order to remove undesired starting material or
by-products if required. E.g. it can be washed in a solvent such as
ethyl acetate, butyl acetate, propanol, methoxypropanol,
dichloromethane, cyclohexane, toluene or hexane, and separated from
the solvent by known methods such as centrifugation, filtration,
decantation, and chromatography. Remaining solvent can be removed
by known methods such as drying preferably in an atmosphere of
reduced pressure.
[0143] For further use, generally, the desired product can be
dispersed in a solvent such as an alcohol like methanol, ethanol,
propanol, methoxypropanol, or such as an ether like diethyl ether,
tetrahydrofurane, dioxane, or an ester such as ethyl acetate, or
N,N-di-methyl acetamide, acetonitrile, preferably ethanol or ethyl
acetate, and stored.
[0144] Optionally, after isolating the thus obtained nanoparticles
with well-known methods, the nanoparticles can be combined with a
polymer or, a monomer or monomer mixture is polymerized in the
presence of the nanoparticles.
[0145] In a preferred embodiment of this invention the whole amount
of co-reactive compound (1c) is added once or in small portions
within a short period of time, e.g. from 1 to 15 minutes, at time
T.sub.CC, such that condition (a) T.sub.CC.gtoreq.T.sub.SE is
fulfilled.
[0146] Naturally, the times T.sub.CC and T.sub.SE depend on the
nature of the reaction conditions and the reactivity of the educts.
E.g. in case of using a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane as spacer
(1b) and tetra-C.sub.1-C.sub.8alkoxysilanes as co-reactive compound
(1c) T.sub.SE is in the range of 1 to 24 h after T.sub.SB, which
means T.sub.CC can be chosen in the range of 24 h and upwards like
24 to 48 h. In other cases a person skilled in the art would know
what to do, because the reaction conditions and reactivities of the
desired educts are known or can be easily figured out.
[0147] Therefore, in a particular preferred embodiment, spacer (1b)
is a n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane such
as n-propyltrimethoxysilane or a mixture of different a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silanes such as
n-propyltrimethoxysilane and methyltrimethoxysilane, and the
co-reactive organic compound (1c) is a
tetra-C.sub.1-C.sub.8alkoxysilane such as TEOS, and T.sub.SE is
chosen such that the difference (T.sub.SE-T.sub.SB) is in the range
of 1 to 24 h, and T.sub.CC in the range of from 24 to 48 h, or 0 to
24 h after T.sub.SE.
[0148] The inventive compounds obtained by such a process will be
called silica-(or alumina-, zirconia- or titania-) core-shell
nanoparticles.
[0149] In another preferred embodiment of this invention the
addition of co-reactive compound (1c) is chosen such that the
condition (b) T.sub.SB<T.sub.CC<T.sub.SE is fulfilled.
[0150] The difference to the manufacture of silica (or alumina-,
zirconia- or titania-) core-shell nanoparticles described above is
the point in time of the addition of the co-reactive organic
compound (1c), which is added before all spacer has reacted:
##STR00004##
[0151] As stated above, the times T.sub.CC and T.sub.SE depend on
the nature of the reaction conditions and the reactivity of the
educts. E.g. in case of using a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane as spacer
(1b) and tetra-C.sub.1-C.sub.8alkoxysilanes as co-reactive compound
(1c) T.sub.SE is in the range of 1 to 24 h after T.sub.SB, which
means T.sub.CC can be chosen in the range of 1 to 24 h after
T.sub.SB. In other cases a person skilled in the art would know
what to do, because the reaction conditions and reactivities of the
desired educts are known or can be easily figured out. Generally,
after the addition of the co-reactive organic compound (1c) the
reaction time is chosen in the range of from 1 to 48 hours,
preferably from 12 to 36 h.
[0152] Therefore, in a particular preferred embodiment, spacer (1b)
is a n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane such
as n-propyltrimethoxysilane or a mixture of different a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silanes such as
n-propyltrimethoxysilane and methyltrimethoxysilane, and the
co-reactive organic compound (1c) is a
tetra-C.sub.1-C.sub.8alkoxysilane such as TEOS, and T.sub.SE is
chosen such that the difference (T.sub.SE-T.sub.SB) is in the range
of 1 to 24 h, and T.sub.CC in the range of from 1 to 24 h, or 1 to
24 h after T.sub.SE, preferably from 1 to 8 h after T.sub.SE.
Preferably, the reaction time is chosen between 12 and 36 h.
[0153] The inventive compounds obtained by such a process will be
called extended silica-(or alumina-, zirconia- or titania-) core
nanoparticles.
[0154] In another preferred embodiment of this invention the
addition of co-reactive compound (1c) is split: part of the
co-reactive compound (1c) is added before and the other part(s)
after T.sub.SE:
##STR00005##
[0155] In analogy to the above, the times T.sub.CC1, T.sub.CC2 and
T.sub.SE depend on the nature of the reaction conditions and the
reactivity of the educts. E.g. in case of using a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane as spacer
(1b) and tetra-C.sub.1-C.sub.8alkoxysilanes as co-reactive compound
(1c) T.sub.SE is in the range of 1 to 24 h after T.sub.SB, which
means T.sub.CC1 can be chosen in the range of 1 to 24 h after
T.sub.SB. In other cases a person skilled in the art would know
what to do, because the reaction conditions and reactivities of the
desired educts are known or can be easily figured out. Generally,
after the first addition of a part or parts of the co-reactive
organic compound (1c), i.e. before T.sub.SE, i.e. at time
T.sub.CC1, the reaction is allowed to proceed in range of from 1 to
48 hours, preferably from 12 to 36 h, before the second or further
addition(s) at time T.sub.CC2 are made. In other words, the
difference (T.sub.CC2-T.sub.CC1) preferably is chosen in the range
of from 1 to 48, more preferably from 12 to 36 h. Usually, after
each addition the reaction time is chosen in the range of from 1 to
48 hours, preferably from 12 to 36 h.
[0156] Therefore, in a particular preferred embodiment, spacer (1b)
is a n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silane such
as n-propyltrimethoxysilane or a mixture of different a
n-C.sub.1-C.sub.18alkyl-tri(C.sub.1-C.sub.18alkoxy)silanes such as
n-propyltrimethoxysilane and methyltrimethoxysilane, and the
co-reactive organic compound (1c) is a
tetra-C.sub.1-C.sub.8alkoxysilane such as TEOS, and T.sub.SE is
chosen such that the difference (T.sub.SE-T.sub.SB) is in the range
of 1 to 24 h. The first addition of the co-reactive organic
compound (1c), preferably half of the required amount, is added at
time T.sub.CC1 in the range of from 1 to 24 h, or 1 to 24 h after
T.sub.SE, preferably from 1 to 8 h after T.sub.SE. Then,
preferably, the reaction time is chosen between 12 and 36 h. After
that time the second portion is added and the reaction is allowed
to proceed for another 12 to 36 h.
[0157] It is also possible to use different co-reactive compounds
(1c) at different times T.sub.CC1 and T.sub.CC2, preferably the
same co-reactive compound (1c) is used.
[0158] The inventive compounds obtained by such a process will be
called extended silica-(or alumina-, zirconia- or titania-)
core-shell nanoparticles.
[0159] In a further embodiment of the present invention the
inventive nano-sized particles can be encapsulated by a polymer.
This can be done by combining the nanoparticles with a polymer or
by polymerizing a monomer or monomer mixture in the presence of the
nanoparticles.
[0160] According to present results, the polymer can improve
stability against oxygen and enhance fluorescence and light
fastness. In addition, the polymer can act as a dispersant.
[0161] As polymer the following can be used: polyacrylonitril,
polyacrylate, polymethacrylate, polymethylmethacrylate,
polymethylacrylate, polyethylene, polystyrene, polypropylene and
the like, or mixtures thereof, preferably polyacrylonitril,
polyethylene, polymethylmethacrylate, or mixtures thereof.
[0162] Preferably, the polymers are transparent and/or
crystalline.
[0163] Usually, the polymers have a low to medium ranged molecular
weight, i.e. from e.g. 10,000 to 500,000 g/mol, e.g. a
polyacrylonitril having a T.sub.g of 85.degree. C. and a molecular
weight of 150,000 g/mol, or a HDPE wax having a T.sub.g of
90.degree. C.
[0164] Such polymers are well-known and usually commercially
available. Usually the polymers or of course including copolymers
are manufactured from monomers like acrylic acid, methacrylic acid,
and its esters like e.g. methyl methacylate, styrene,
divinyl-benzene, acrylonitrile and the like as well as its
mixtures.
[0165] As one embodiment of the invention related to polymers which
are manufactured in the presence of the nanoparticles, of course
the corresponding desired monomers are used. The preferred
polymerization would be an emulsion polymerization, which is
described below.
[0166] Usually, the ratio of polymer to nanoparticles is chosen in
the range of from 1 to 99% by weight, preferably from 20 to 70% by
weight, based on the weight of the nanoparticles
[0167] Generally, a dispersion of the inventive nanoparticles and
the desired polymer in a solvent, preferably a polar organic
solvent such as dimethylsulfoxid, dimethylformamid (DMF),
dimethylacetamide (DMA), N-methyl-pyrrolidone (NMP), acetonitril,
ethanol, n-propanol, dimethylsulfoxid (DMSO) and the like, is
treated under elevated temperature, typically in the range of from
20 to 120.degree. C., preferably from 50 to 90.degree. C. for a
period of time preferably in the range of from 0.1 to 6 h. Then an
additional solvent, also preferably a polar solvent such as water
or an organic solvent or mixtures thereof like alcohols like
methanol, ethanol, n-, i-propanol is added in order to precipitate
the polymer.
[0168] The precipitation of the polymer is typically carried out in
the range of from 20 to 120.degree. C., preferably from 50 to
90.degree. C. for a period of time in the range of usually from 0.1
to 3 h. Generally, the treatment is continued thereafter at
preferably a temperature in the range of e.g. from 30 to 80.degree.
C. for preferably 1 to 10 hours. Afterwards the obtained solid
product is separated by known methods such as filtration preferably
at room temperature, and as a rule washed and dried, e.g. for 3 to
12 hours at a temperature of from 50 to 90.degree. C. under an
atmosphere of reduced pressure such as from 50 to 80 hPa.
[0169] Of course, there are other possibilities to initiate the
precipitation of the polymer, e.g. by omitting the second solvent,
but decreasing the temperature of the mixture accordingly or by
evaporation of the solvent or parts thereof in such a way, that a
precipitation occurs. Such methods are well known to the person
skilled in the art, therefore no further explanations are
necessary.
[0170] Another embodiment of this invention concerns a process of
encapsulation of the nanoparticles by in-situ polymerization of
monomers like acrylate, methacrylate, styrene, etc., and mixtures
thereof, usually catalysed by known compounds in the art as AlBN,
acids, bases, etc. or by the use of temperature induced
polymerization techniques. The polymerization, preferably emulsion
polymerization, as such is well-known for the person skilled in the
art, e.g. from Handbook of Polymer Synthesis 1992, Hans Rytger
Kricheldorf (ISBN 0824785150).
[0171] In a preferred embodiment of this invention, silica
core-shell nanoparticles or the silsesquioxane compounds are
encapsulated by the polymerization of methyl methacrylate in the
presence of said silica core-shell nanoparticles.
[0172] Typically, a mixture of methyl methacrylate,
azo-bisisobutyronitrile (AlBN) and a solvent is added to a
dispersion or suspension of silica core-shell nanoparticles or
silsesquioxanes in an aqueous solvent mixture and heated to start
and maintain the polymerization reaction. After the end of
polymerization, the reaction mixture is worked up in a usual way,
such as separation of the desired product, washing and drying it.
In some cases it is preferred to carry out the reaction under an
inert atmosphere.
[0173] As an example, the solvent used for the silica core-shell
nanoparticles suspension can be an alcohol, preferably a
water-soluble alcohol such as methanol or ethanol, preferably a
water-ethanol mixture.
[0174] The weight ratio of silica core-shell nanoparticles to
solvent can be chosen in the range of from 1:10 to 1:200,
preferably from 1:50 to 1:100. In can be advantageous to homogenize
this mixture with known methods such as stirring or treating with
ultrasonic waves.
[0175] Furthermore, the suspension obtained preferably is saturated
with an inert gas like nitrogen or argon.
[0176] The solvent used in the methyl methacrylate mixture can be
an alcohol, preferably a water-soluble alcohol such as methanol or
ethanol.
[0177] The weight ratio of methyl methacrylate to solvent can be
chosen in the range of from 1:1 to 100:1, preferably from 1:1 to
1:10. Furthermore, the solution obtained preferably is saturated
with an inert gas like nitrogen or argon.
[0178] The weight ratio of methyl methacrylate to AlBN usually is
chosen in the range of from 10:1 to 1000:1, and the weight ratio of
methyl methacrylate to solvent preferably is chosen in the range of
from 1:1 to 100:1, preferably 1:1 to 10:1.
[0179] The reaction temperature as a rule is chosen in the range of
from 20 to 100.degree., preferably from 40 to 70.degree. C.
[0180] The reaction time can be chosen in the range of from 12 h to
48 h, preferably from 18 to 36 h.
[0181] Another embodiment of this invention concerns a process for
the manufacture of functionalized nanoparticles comprising the
steps of:
[0182] a) combining a functionalized dyestuff of the formula
(1a)
##STR00006##
[0183] wherein
[0184] R.sub.1 stands for C.sub.1-C.sub.18alkoxy, --OH;
[0185] R.sub.2, R.sub.3 independently from each other stand for
C.sub.1-C.sub.18alkoxy or C.sub.1-C.sub.18alkyl, --OH,
[0186] E stands for a direct bond or a bridging member,
[0187] D is the residue of a chromophore, and a spacer of the
formula (1b)
R.sub.4(4-m)SiX.sub.m (1b)
[0188] wherein each
[0189] R.sub.4 represents a monovalent organic radical of from 1 to
24 carbon atoms, optionally substituted by a monovalent organic
radical,
[0190] X represents a group capable of undergoing hydrolysis and m
is 0, 1, 2, 3 or 4;
[0191] a catalyst,
[0192] and optionally a solvent, at time T.sub.SB,
[0193] and treating the obtained mixture until time T.sub.SE,
wherein (T.sub.SE-T.sub.SB) is chosen in the range of from 1 and 48
hours, at a temperature in the range of from 0 to 80.degree.
C.,
[0194] b) adding a co-reactive compound (1c) selected from the
group consisting of an organic silane, an organic alumina, an
organic zirconia and an organic titania, at time T.sub.CC, wherein
T.sub.CC fulfils condition (a) T.sub.SB<T.sub.CC<T.sub.SE,
(b) T.sub.CC.gtoreq.T.sub.SE or (c) both (a) and (b) in case part
of co-reactive compound (1c) is added before T.sub.SE, and the
other part after T.sub.SE,
[0195] and treating the obtained respective reaction mixture for a
period of time between 12 and 36 hours at a temperature between 0
and 80.degree. C.,
[0196] and, optionally, after isolating the thus obtained
nanoparticles with well-known methods,
[0197] c) combining the nanoparticles with a polymer or,
[0198] d) polymerizing a monomer or monomer mixture in the presence
of the nanoparticles.
[0199] The details for carrying out this process are already
described above.
[0200] If desired the obtained treated silica core-shell
nanoparticles and silsesquioxanes can be powdered by known methods
such as milling, e.g. milling of the product, which has been cooled
down well below the freezing point of water, e.g. with liquid
nitrogen.
[0201] A further embodiment of this invention concerns the use of
the inventive functionalized nanoparticles for coloring an organic
material.
[0202] Still another embodiment of this invention concerns a
composition comprising the inventive functionalized nanoparticles
and an organic material.
[0203] The inventive nanoparticles can be used in all areas, where
colored particles, in particular fluorescent particles can be
applied such as in the fields of decoration, security, packaging,
light managing enery collector systems (solar technology) and
electronic materials, where colored polymer are applied, preferably
with the additional condition, that the dyestuff does not exhibit
any migration, for inks for ink jet, offset printing ink, for
fluorescent coating paints, for medicinal diagnostic applications,
for cosmetics (hair-dyeing, make-up, and the like), for color
filters (polymer/paint formulation for displays, electronic
applications), for electrophoretic color filter (e-paper), or for
optical brighteners (for textile, paper, coatings, cosmetics).
[0204] The inventive nanoparticles exhibit improved quantum
efficiency, an excellent migration stability, and an excellent
thermostability.
EXAMPLES
Example 1
(a) Preparation of the Dyestuff
[0205] 10.0 g of a commercial grade 4-chloronaphthalic anhydride
(0.04 mol, tech. dried, from ACROS) is suspended in 50 ml of
methanol at room temperature. A solution of 5.3 ml of
isopentylamine (0.045 mol, Fluka purum 98%) in 10 ml methanol is
added dropwise. The reaction mixture is heated to 65.degree. C. and
stirred overnight. The beige suspension is then filtered, washed
with methanol and dried in a vacuum oven at 80.degree. C.
overnight.
(b) Functionalizing the Dyestuff
[0206] 4.5 g (0.015 mol) of the above obtained dyestuff is
dissolved in 10 ml of dimethylacetamide ("DMA"; Fluka purum) at
80.degree. C. Then 33.2 g of 3-aminopropyltriethoxysilane (0.15 mol
Aldrich) is added over a period of 30 min. After 2 h, the obtained
orange solution is cooled to room temperature. Part of the product
is isolated from the reaction mixture by chromatography with silica
gel (X 60, Merck) and a solvent mixture of 10% of water, 40% of
ethanol, 20% of pyridine and 30% ethyl acetate. The product is then
isolated by evaporating the solvent as a brown paste.
##STR00007##
Example 1a
Reaction of Functionalized Dye with a Spacer; Silica Core-Shell
Particles
[0207] A mixture of 0.25 g of the modified compound of example 1 as
described above, 100 ml of 2-propanol and 2.5 g of
n-propyltrimethoxysilane is added to a mixture of 150 ml of
2-propanol, 100 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution (Fluka). The combined mixtures are stirred
vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged. The
residue is dispersed in ethyl acetate, washed and centrifuged
thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
Example 1aa
Synthesis of Extended Silica-Core-Particles
[0208] A mixture of 0.25 g of the modified dyestuff of example 1 as
described above, 100 ml of 2-propanol and 2.5 g of
n-propyltrimethoxysilane is added to a mixture of 150 ml of
2-propanol, 100 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution (Fluka). The combined mixtures are stirred
vigorously for 4 h at room temperature. Then, 5 g of
tetraethoxysilane in 30 ml of ethanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged. The
residue is dispersed in ethanol, precipitated by addition of ethyl
acetate, washed and centrifuged thrice, thereafter no starting
material is found in the supernatant. The thus obtained residue is
dried 24 h under an atmosphere of reduced pressure (70 hPa) at a
temperature of 60.degree. C.
Example 1aaa
Extended Silica-Core-Shell Particles
[0209] A mixture of 0.25 g of the modified dyestuff of example 1 as
described above, 100 ml of 2-propanol and 2.5 g of
n-propyltrimethoxysilane is added to a mixture of 150 ml of
2-propanol, 100 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution (Fluke). The combined mixtures are stirred
vigorously for 4 h at room temperature. Then, 2.5 g of
tetraethoxysilane dissolved in 20 ml of ethanol is added to the
vigorously stirred solution. The mixture is stirred for additional
24 h at room temperature, then another 2.5 g of tetraethoxysilane
dissolved in 20 ml of ethanol is added to the vigorously stirred
solution. The mixture is stirred for additional 24 h at room
temperature. Thereafter, the thus obtained silica extended
core-shell particles are separated from the reaction mixture by
centrifugation. The separated extended core-shell particles are
dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material is found
in the supernatant. The thus obtained residue is dried 24 h under
an atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. For storage, parts of the obtained residue are
re-dispersed in ethanol.
[0210] The thus obtained residue is dried 24 h under an atmosphere
of reduced pressure (70 hPa) at a temperature of 60.degree. C.
Example 1b
Reaction of Functionalized Dye with a Mixture of Spacers;
Silica-Core-Shell Particles
[0211] A mixture of 0.25 g of the modified compound of example 1 as
described above, 100 ml of 2-propanol, 1.25 g of
n-propyltrimethoxysilane and 1.25 g of methyltrimethoxysilane is
added to a mixture of 150 ml of 2-propanol, 100 ml of deionized
water and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 24 h at room
temperature. Then, 5 g of tetraethoxysilane in 50 ml of 2-propanol
are added. Afterwards this reaction mixture is stirred for 24 h and
then centrifuged. The residue is dispersed in ethyl acetate, washed
and centrifuged thrice, thereafter no starting material is found in
the supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
Example 1bb
Extended Silica-Core-Particles
[0212] A mixture of 0.25 g of the modified dyestuff of example 1 as
described above, 100 ml of 2-propanol, 1.25 g of
n-propyltrimethoxysilane and 1.25 g of methyltrimethoxysilane is
added to a mixture of 150 ml of 2-propanol, 100 ml of deionized
water and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 4 h at room
temperature. Then, 5 g of tetraethoxysilane (Aldrich, 99.99%) in 30
ml of ethanol are added. Afterwards this reaction mixture is
stirred for 24 h and then centrifuged. The residue is dispersed in
ethanol, precipitated by addition of ethyl acetate, washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Part of the obtained residue is stored as dispersion
in ethanol.
Example 1bbb
Extended Silica-Core-Shell Particles
[0213] A mixture of 0.25 g of the modified dyestuff of example 1 as
described above, 100 ml of 2-propanol, 1.25 g of
n-propyltrimethoxysilane and 1.25 g of methyltrimethoxysilane is
added to a mixture of 150 ml of 2-propanol, 100 ml of deionized
water and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 4 h at room
temperature. Then, 2.5 g of tetraethoxysilane dissolved in 20 ml of
ethanol is added to the vigorously stirred solution. The mixture is
stirred for additional 24 h at room temperature, then another 2.5 g
of tetraethoxysilane dissolved in 20 ml of ethanol is added to the
vigorously stirred solution. The mixture is stirred for additional
24 h at room temperature. Thereafter, the thus obtained silica
extended core-shell particles are separated from the reaction
mixture by centrifugation. The separated extended core-shell
particles are dispersed in ethanol, precipitated by addition of
ethyl acetate, washed and centrifuged thrice until no starting
material is found in the supernatant. The thus obtained residue is
dried 24 h under an atmosphere of reduced pressure (70 hPa) at a
temperature of 60.degree. C. For storage, parts of the obtained
residue are re-dispersed in ethanol.
[0214] The thus obtained residue is dried 24 h under an atmosphere
of reduced pressure (70 hPa) at a temperature of 60.degree. C.
Example 1c
Polymer (PAN) Encapsulated Silica Core-Shell Particles
[0215] A dispersion of 1 g of silica core-shell nano-particles of
example 1a (see above) and 1.5 g of polyacrylonitrile (PAN, powder,
Tg. 85.degree. C., Tm. 317.degree. C., Sigma-Aldrich) in 40 ml of
DMSO is heated to 80.degree. C. under vigorously stirring. After 2
h, 100 ml of 70% ethanol are added dropwise to the reaction mixture
followed by an additional stirring for 8 h at a temperature of
50.degree. C. Afterwards, the reaction mixture is filtered off,
washed with 50 vol.-% of a ethanol/water mixture and dried for 24 h
under an atmosphere under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C.
Example 1d
Polymer (PMMA) Encapsulated Silica Core-Shell Particles
[0216] A dispersion of 1.5 g of silica core-shell nano-particles of
example 1a in 60 ml of ethanol and 5 g of water is saturated with
nitrogen gas, and then treated with ultra sonic for 20 min for
homogenization. The suspension is further treated with nitrogen gas
under vigorously stirring at room temperature. 2 g of methyl
metacrylate (MMA, Fluke) and 60 mg of azo-isobutyronitrile (AlBN,
Aldrich) are dissolved in 1 g of ethanol and added to the
suspension. After stirring the suspension under nitrogen for 24 h
at a temperature of 50.degree. C., the reaction mixture is cooled
to room temperature, treated with ultra sonic for 20 min and
centrifuged. The residue is washed two times with ethanol and dried
in a vacuum oven under an atmosphere of reduced pressure (70 hPa)
at a temperature of 60.degree. C. (yield: 0.88 g). The polymer
coated particles are treated with liquid nitrogen and milled in a
mortar to obtain a fine powder.
[0217] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a
stabilizing mixture consisting of 92.21% of a softening agent
(diisodecyl phthalate, DIDP, Vestinol, Huls Chemie), 4.19% of a
rheology stabilizer (Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn
stabilizer (Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil
having a thickness of 0.5 mm and a content of 1% by weight of the
used product. A migration test (according to DIN 53775 part 3:
measured during 24 h at 80.degree. C. and a pressure of 1
kg/cm.sup.2, with heat stress during 30 min at 180.degree. C.) is
carried out: no migration could be observed, but a high
fluorescence.
Comparative Example 1
Silica-Core-Shell Particles without Spacer
[0218] A mixture of 0.25 g of the modified compound of example 1 as
described above and 100 ml of 2-propanol (Merck, 98%) is added to a
mixture of 150 ml of 2-propanol, 100 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged. The
residue is dispersed in ethyl acetate, washed and centrifuged
thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
Comparative example 2
Comparative Example "Surface Modification"
##STR00008##
[0220] 0.25 g of the fluorescent naphthalimide derivative as
described above in example 1 are added to a suspension of 3 g
nano-sized silica particles (34% SiO.sub.2 in aqueous suspension,
Ludox.RTM.TMA, RTM Aldrich) in 96% ethanol and heated 24 h at a
temperature of 50.degree. C. under vigorously stirring. After
completion of the reaction and cooling down to room temperature, 50
ml of ethyl acetate are added to precipitate the fluorescent silica
nanoparticles. The obtained suspension is centrifuged at 2000 rpm
and washed with ethyl acetate until the supernatant is completely
discoloured. The solid residue is then dried for 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
Application Examples
[0221] The nanoparticles of the above examples are checked in a
PVC-foil application to compare fluorescence intensities and
coloration abilities. The absorption of the samples are corrected
to obtain the relative fluorescence quantum yield.
(A) Comparison of Photophysical Properties
[0222] The standard (comparative example 2) consists of surface
modified silica nanoparticles, linked with fluorescence dye
naphthalimide as described above. Comparative example 1, a
core-shell nanoparticle without any spacer, is used as closest
prior art example. All inventive examples 1a and 1b exhibit a
higher relative fluorescence quantum yield ("FQY") compared to the
comparative examples:
TABLE-US-00001 Sample in PVC foil (0.5 mm) FQY surface modified
sample (comp. ex. 2) 1.00 comparative example 1 0.38 example 1a
1.08 example 1b 1.29
[0223] Measurement of fluorescence quantum yield in PVC relative to
reference Instrument: Cary Eclipse
TABLE-US-00002 (Reference) Sample Description comp. ex. 1 ex. 1a
Ex. 1b comp. ex. 2 Matrix PVC PVC PVC PVC Excitation wavelength
[nm] 440.0 440.0 440.0 440.0 Excitation slit [nm] 2.5 2.5 2.5 2.5
Emission slit [nm] 2.5 2.5 2.5 2.5 Scan rate [nm/min] 600.0 600.0
600.0 600.0 Data interval [nm] 1.0 1.0 1.0 1.0 Averaging time [s]
0.1 0.1 0.1 0.1 Excitation filter Auto Auto Auto Auto Emission
filter 360-1100 nm 360-1100 nm 360-1100 nm 360-1100 nm PMT voltage
[V] 810 810 810 810 Relative Quantum Yield 0.38 1.08 1.29 1.00
(B) Migration Resistance
[0224] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration:
TABLE-US-00003 Sample 1% in PVC foil (0.5 mm) Migration (Grey
Scale) Example 1a 5 Example 1aa 5 Example 1b 5 Example 1bb 5
Migration scale from 1 to 5: wherein 5 = very good, no migration; 1
= bad
(C) Heat Resistance
[0225] Polyethylene (HDPE SABIC.RTM.M 80063S Powder) and 0.25% by
weight, based on the total amount of polyethylene and sample, of a
sample of the inventive product are extruded at a temperature of
300.degree. C. So obtained chips with thickness of 2 mm are
measured in a colorimeter in order to obtain the coloristic changes
influenced by high temperature extrusion in HDPE:
TABLE-US-00004 Sample HDPE (2 mm) 0.25% DE Example 1a 0.8 Example
1aa 1.8 Example 1b 1.6 Example 1bb 1.2
[0226] Wherein DE expresses the deviation from hue, chroma and
lightness. DE=0 means no color deviation at all. DE values below 2
are very good values and expected in industry.
Example 2
(a) Preparation of a Fluorescent Perinone (Step 1)
##STR00009##
[0228] A mixture of 12.2 g of a commercial grade
4-chloronaphthalanhydride (0.05 mol, Acros tech. dried), 50 ml of
acetic acid and 5.4 g of o-phenylendiamine (0.05 mol, Fluke purum
99%) is heated to 85.degree. C. After 2 h the reaction mixture is
cooled to room temperature followed by the addition of 200 ml of
acetic acid. The obtained yellow suspension is then filtered,
washed with acetic acid and water and dried in a vacuum oven at
80.degree. C. overnight.
(b) Functionalizing the Dyestuff (Step 2)
[0229] 4.6 g (0.015 mol) of the above perinone are suspended in 30
ml of dimethylacetamide at 80.degree. C. Subsequently 33.2 g of
3-aminopropyltriethoxysilane ("APTES") (0.15 mol) are added over 15
min yielding a color change from yellow to orange after the end of
addition. After 6 h the reaction mixture is cooled to room
temperature. The desired product is obtained by chromatography
(silica gel, eluent: ethyl acetate/toluene/pyridine 3:9:1), and
subsequent work-up by evaporation of the solvent mixture.
Example 2a
Silica-Core-Shell Particles
[0230] A mixture of 0.25 g of the modified perinone of example 2 as
described above, 100 ml of 2-propanol and 5 g of
n-propyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for an additional 24 h and then
centrifuged. The residue is dispersed in ethyl acetate, washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0231] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2aa
Extended Silica-Core-Particles
[0232] A mixture of 0.25 g of the modified perinone of example 2 as
described above, 100 ml of 2-propanol and 5 g of
n-propyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 4 h at room temperature. Then, 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C.
[0233] For storage, parts of the above obtained product are
re-dispersed in ethanol.
[0234] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
4.8).
Example 2b
Reaction of Functionalized Perinone with a Mixture of Spacers;
Silica-Core-Shell Particles
[0235] A mixture of 0.25 g of the modified perinone of example 2 as
described above, 100 ml of 2-propanol, 2.5 g of
n-propyltrimethoxysilane and 2.5 g of methyltrimethoxysilane is
added to a mixture of 200 ml of 2-propanol, 150 ml of deionized
water and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 24 h at room
temperature. Then, 5 g of tetraethoxysilane in 50 ml of 2-propanol
are added. Afterwards this reaction mixture is stirred for 24 h and
then centrifuged. The residue is dispersed in ethyl acetate, washed
and centrifuged thrice, thereafter no starting material is found in
the supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0236] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2bb
Extended Silica-Core-Particles
[0237] A mixture of 0.25 g of the modified perinone of example 2 as
described above, 100 ml of 2-propanol, 2.5 g of
n-propyltrimethoxysilane and 2.5 g of methyltrimethoxysilane is
added to a mixture of 200 ml of 2-propanol, 150 ml of deionized
water and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 4 h at room
temperature. Then, 5 g of tetraethoxysilane (Aldrich, 99.99%) in 30
ml of ethanol are added. Afterwards this reaction mixture is
stirred for 24 h and then centrifuged. The residue is dispersed in
ethanol, precipitated by addition of ethyl acetate, washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Parts of the obtained residue are stored as
dispersion in ethanol.
[0238] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2c
Silica-Core-Shell Particles; Perylene-Bis-Imide-Silane
Silica-Nanoparticles
##STR00010##
[0240] (a) Functionalizing a perylene derivative (see: Chem. Mater.
2000, 12, 352-362 M.Schneider, K. Muellen)
[0241] A mixture of 0.785 g (2 mmol) of
3,4:9,10-perylenetetracarboxylic bisanhydride and 70 ml of dry
ethanol is stirred for 1/2 h under an argon atmosphere, then it is
heated to 110.degree. C. Thereafter, 3.542 g (16 mmol) of
(3-aminopropyl)triethoxysilane (APTES) are added dropwise. The
reaction mixture is stirred for 12 h at reflux conditions and under
an inert atmosphere. After the mixture is cooled to room
temperature, the precipitate is collected by suction filtration and
washed thoroughly with cold ethanol. A dark red product is obtained
in 82% yield.
[0242] (b) A mixture of 0.25 g of the modified perylene derivative
obtained above, 80 ml of dimethylacetamide ("DMA"), 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 200 ml of 2-propanol, 150 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 24 h at room temperature. Then 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for additional 24 h and then
centrifuged. The residue is dispersed in ethyl acetate, washed and
centrifuged thrice until no starting material is found in the
supernatant. The thus obtained residue is dried during 24 h in an
atmosphere under an atmosphere of reduced pressure (70 hPa) at a
temperature of 60.degree. C.
[0243] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2cc
Extended Silica-Core-Particles
[0244] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 80 ml of DMA, 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 200 ml of 2-propanol, 150 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 4 h at room temperature. Then 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C.
[0245] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2d
Silica-Core-Shell Particles
[0246] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 80 ml of DMA, 100 ml of
2-propanol, 2.5 g of n-propyltrimethoxysilane and 2.5 g of
methyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% weight-%
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged.
[0247] The residue is dispersed in ethyl acetate, washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0248] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2dd
Extended Silica-Core-Particles
[0249] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 80 ml of DMA, 100 ml of
2-propanol, 2.5 g of n-propyltrimethoxysilane and 2.5 g of
methyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 4 h at room temperature. Then, 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C. Parts of the
obtained residue are stored as dispersion in ethanol.
[0250] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2e
[0251] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 50 ml of DMA, 80 ml of
2-propanol, 2.5 g of n-propyltrimethoxysilane and 2.5 g of
methyltrimethoxysilane is added to a mixture of 100 ml of
2-propanol and 30 g of 25% by weight aqueous ammonia solution. The
combined mixtures are stirred vigorously for 24 h at room
temperature. Then, 300 ml of water is added and this reaction
mixture is stirred for 24 h and then centrifuged. The residue is
washed with ethanol, water and dried 24 h under an atmosphere of
reduced pressure (70 hPa) at a temperature of 60.degree. C.
[0252] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 4.8).
Example 2f
[0253] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 50 ml of DMA, 80 ml of
2-propanol, 2.5 g of octadecyltriethoxysilane (Aldrich) is added to
a mixture of 100 ml of 2-propanol and 30 g of 25% by weight aqueous
ammonia solution. The combined mixtures are stirred vigorously for
24 h at room temperature. Then, 300 ml of water is added dropwise
during 2 h and this reaction mixture is stirred for 24 h and then
centrifuged. The residue is washed with ethanol, water and dried 24
h under an atmosphere of reduced pressure (70 hPa) at a temperature
of 60.degree. C.
[0254] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 4.7).
Example 2q
Silica-Core-Shell Particles; Perylene-Bis-Imide-Silane
Silica-Nanoparticles
##STR00011##
[0256] (a) Functionalizing a perylene derivative (see e.g.:
US2008029739; Chem. Mater. 2000, 12, 352-362 M. Schneider, K.
Muellen)
[0257] A mixture of
1,6,7,12-tetra(4'-t-butylphenoxy)-3,4,9,10-perylene tetracarboxylic
dianhydride (1.7 g, 2 mmol) and 150 ml of dry ethanol is stirred
for 1/2 h under an argon atmosphere, then it is heated to reflux
(79.degree. C.). Thereafter, 3.542 g (16 mmol) of
(3-aminopropyl)-triethoxysilane (APTES) are added dropwise. The
reaction mixture is stirred for 36 h at reflux conditions and under
an inert atmosphere. After the mixture is cooled to room
temperature, the precipitate is collected by suction filtration,
washed with methanol and recristallized from
dichlormethane/methanol and dried in vacuum. A dark violet product
is obtained in 79% yield.
[0258] (b) A mixture of 0.25 g of the modified perylene derivative
obtained above, 100 ml of dimethylacetamide ("DMA"), 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 200 ml of 2-propanol, 150 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 24 h at room temperature. Then 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for additional 24 h and then
centrifuged. The residue is dispersed in ethyl acetate, washed and
centrifuged thrice until no starting material is found in the
supernatant. The thus obtained residue is dried during 24 h in an
atmosphere under an atmosphere of reduced pressure (70 hPa) at a
temperature of 60.degree. C.
[0259] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2gg
Extended Silica-Core-Particles
[0260] A mixture of 0.25 g of the modified perylene of example 2 g
as described above, combined first with 100 ml of DMA, 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 200 ml of 2-propanol, 150 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 4 h at room temperature. Then 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C.
[0261] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2ggg
Extended Silica-Core-Particles with Reduced Dye Loading
[0262] A mixture of 50 mg of the modified perylene of example 2 g
as described above, combined first with 80 ml of DMA, 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 200 ml of 2-propanol, 150 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 4 h at room temperature. Then 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are
added.
[0263] Afterwards this reaction mixture is stirred for 24 h and
then centrifuged. The residue is dispersed in ethanol, precipitated
by addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C.
[0264] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2h
Silica-Core-Shell Particles
[0265] A mixture of 0.25 g of the modified perylene of example 2 g
as described above, combined first with 100 ml of DMA, 100 ml of
2-propanol, 2.5 g of n-propyltrimethoxysilane and 2.5 g of
methyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% weight-%
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged. The
residue is dispersed in ethyl acetate, washed and centrifuged
thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0266] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2hh
Extended Silica-Core-Particles
[0267] A mixture of 0.25 g of the modified perylene of example 2c
as described above, combined first with 100 ml of DMA, 100 ml of
2-propanol, 2.5 g of n-propyltrimethoxysilane and 2.5 g of
methyltrimethoxysilane is added to a mixture of 200 ml of
2-propanol, 150 ml of deionized water and 30 g of 25% by weight
aqueous ammonia solution. The combined mixtures are stirred
vigorously for 4 h at room temperature. Then, 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C. Parts of the
obtained residue are stored as dispersion in ethanol.
[0268] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 2i
[0269] A mixture of 0.1 g of the modified perylene of example 2 g
as described above, combined first with 50 ml of DMA, 80 ml of
2-propanol, 2.5 g of octadecyltriethoxysilane (Aldrich) is added to
a mixture of 100 ml of 2-propanol and 30 g of 25% by weight aqueous
ammonia solution. The combined mixtures are stirred vigorously for
24 h at room temperature. Then, 300 ml of water is added dropwise
during 2 h and this reaction mixture is stirred for 24 h and then
centrifuged. The residue is washed with ethanol, water and dried 24
h under an atmosphere of reduced pressure (70 hPa) at a temperature
of 60.degree. C.
[0270] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 4.0).
Example 3
Preparation of the Following Functionalized Dyestuff
##STR00012##
[0272] 150 .mu.l of concentrated HCl (37%, Merck) are added to 100
mg of Rhodamine B Base in 3 ml of deionized water. Then the mixture
is evaporated to dryness. To the obtained dried residue 5 ml of
dimethylformamide (Aldrich, 99.9%) are added. Thereafter, 100 mg of
dicyclohexylcarbodiimide ("DCC") and 2 g of
(3-aminopropyl)triethoxysilane are added. The reaction mixture is
then stirred until termination of the reaction at room temperature
and finally centrifuged. The obtained red solution is kept in the
dark at a temperature below 7.degree. C. Part of the product is
isolated by chromatography with ethyl acetate/methanol/pyridine
2:5:1. For further use, the reacton mixture is useful for reactions
without any workup.
Example 3a
Preparation of Alumina Core-Shell Particles
[0273] To 10 mg of the fluorescent dye compound of example 3 as
described above are added 200 ml of ethanol and 30 g of 25% by
weight aqueous ammonia solution under vigorously stirring. After 24
h at room temperature under exclusion from light, 10 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 150 ml of 2-propanol
(Aldrich, 99.9%) are added. The mixture is then stirred for
additional 24 h, after which time the obtained core-shell particles
are centrifuged. The residue is dispersed in ethanol, precipitated
by addition of ethyl acetate, washed and centrifuged thrice until
no starting material is found in the supernatant. The thus obtained
residue is dried 24 h under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C. Parts of the obtained
residue are stored as dispersion in ethanol.
[0274] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 5).
Example 3aa
Extended Alumina-Core Particles
[0275] To 10 mg of the fluorescent dye compound of example 3 as
described above are added 200 ml of ethanol and 30 g of 25% by
weight aqueous ammonia solution under vigorously stirring. After 4
h at room temperature under exclusion from light, 10 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 150 ml of 2-propanol
(Aldrich, 99.9%) are added under vigorously stirring. The mixture
is stirred for additional 24 h and the extended alumina-core
particles are centrifuged. The residue is dispersed in ethanol,
precipitated by addition of ethyl acetate, washed and centrifuged
thrice until no starting material or unreacted compounds are found
in the supernatant. The thus obtained residue is dried 24 h under
an atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Parts of the obtained residue are stored as
dispersion in ethanol.
[0276] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 5).
Example 3aaa
Extended Alumina-Core-Shell Particles
[0277] To 10 mg of the fluorescent dye compound of example 3 as
described above are added 200 ml of ethanol and 30 g of 25% by
weight aqueous ammonia solution under vigorously stirring. After 4
h at room temperature under exclusion from light, 5 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of 2-propanol
(Aldrich, 99.9%) are added. The mixture is stirred for additional
24 h at room temperature, then another 5 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of 2-propanol
(Aldrich, 99.9%) are added to the vigorously stirred solution. The
mixture is stirred for additional 24 h at room temperature and the
extended Alumina-core-shell particles are centrifuged. The residue
is dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material or
unreacted compounds are found in the supernatant. The thus obtained
residue is dried 24 h under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C. Parts of the obtained
residue are stored as dispersion in ethanol.
[0278] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 3b
Alumina Core-Shell Particles
[0279] (a) Functionalizing the Dyestuff
##STR00013##
[0280] 100 mg of tetraethylrhodamine isothiocyanate (Rhodamine B
isothiocyanate, mixture of isomers obtained from Aldrich) are
stirred in 40 ml of ethanol (99.9% Aldrich) with 2 g of
3-aminopropyltriethoxysilane for 48 h at room temperature under
protection of light. Part of the reaction mixture is isolated by
chromatography with ethyl acetate/methanol/pyridine 2:5:1. For
further use, the reacton mixture is useful for reactions without
any workup.
[0281] (b) Preparation of the Al-Core-Shell Particles
[0282] To 10 mg of the functionalized compound as described above
under (a) are added 200 ml of ethanol and 30 g of 25% by weight
aqueous ammonia solution under vigorously stirring. After 24 h at
room temperature under exclusion from light, 15 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 200 ml of 2-propanol
(Aldrich, 99.9%) are added. The mixture is then stirred for
additional 24 h, after which time the obtained silica
core-alumina-shell particles are centrifuged. The residue is
dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material is found
in the supernatant.
[0283] The thus obtained residue is dried 24 h under an atmosphere
of reduced pressure (70 hPa) at a temperature of 60.degree. C.
Parts of the obtained residue are stored as dispersion in
ethanol.
[0284] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 3bb
Extended Alumina-Core Particles
[0285] To 10 mg of the functionalized compound as described above
under example 3b (a) are added 200 ml of ethanol and 30 g of 25% by
weight aqueous ammonia solution under vigorously stirring. After 4
h at room temperature under exclusion from light, 10 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 150 ml of 2-propanol
(Aldrich, 99.9%) are added under vigorously stirring. The mixture
is stirred for additional 24 h and the extended alumina-core
particles are centrifuged. The residue is dispersed in ethanol,
precipitated by addition of ethyl acetate, washed and centrifuged
thrice until no starting material are found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C. Part of the
obtained residue is stored as dispersion in ethanol.
[0286] 0.4 g g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
consisting of 92.21% of a softening agent (Diisodecyl phthalate,
DIDP, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed improved migration (grey
scale 5).
Example 3bbb
Extended Alumina-Core-Shell Particles
[0287] To 10 mg of the functionalized compound as described above
under example 3b (a) are added 200 ml of ethanol and 30 g of 25% by
weight aqueous ammonia solution under vigorously stirring. After 4
h at room temperature under exclusion from light, 5 g of aluminium
tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of 2-propanol
(Aldrich, 99.9%) are added under vigorously stirring. The mixture
is stirred for additional 24 h at room temperature, then 5 g of
aluminium tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of
2-propanol (Aldrich, 99.9%) are added under vigorously stirring.
The mixture is stirred for additional 24 h at room temperature;
thereafter the extended Alumina-core-shell particles are
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice until no
starting material is found in the supernatant. The thus obtained
residue is dried 24 h under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C. Parts of the obtained
residue are stored as dispersion in ethanol.
[0288] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 3c
Triple-Dye-Doped Alumina Core-Shell Particles
[0289] (a) Functionalizing of the Fluoresceine 5(6)-Isothiocyanate
Dyestuff
[0290] A mixture of 5 mg of fluoresceine 5- and 6-isothiocyanate
(90%, obtained from Aldrich) 4 ml of ethanol (Aldrich, 99.9%) and
100 mg of 3-aminopropyltriethoxysilane are stirred for 48 h at room
temperature under protection against light. Part of the product is
isolated by evaporation of the solvent; the rest is left in the
reaction mixture for further reaction.
##STR00014##
[0291] (b) Functionalizing of 5- and-6-Carboxy-X-Rhodamine
Succinimidyl Ester Dyestuff
[0292] A mixture of 5 mg of a 5- and 6-carboxy-X-rhodamine
succinimidyl ester (available from Invitrogen/Molecular Probes), 4
ml of anhydrous DMF (Aldrich, 99.9%) and 100 mg of
3-aminopropyltriethoxysilane are stirred for 48 h at room
temperature under protection against light. Part of the product is
isolated by evaporation of the solvent; the rest is left in the
reaction mixture for further reaction.
##STR00015##
[0293] (c) Functionalizing of the 5- and 6-Carboxyrhodamine 6G
Succinimidyl Ester Dyestuff
[0294] A mixture of 5 mg of 5- and 6-carboxyrhodamine 6G
succinimidyl ester,
##STR00016##
[0295] 4 ml of anhydrous DMF (Aldrich, 99.9%) and 100 mg of
3-aminopropyltriethoxysilane are stirred for 48 h at room
temperature under protection against light yielding
##STR00017##
[0296] Part of the product is isolated by evaporation of the
solvent, the rest is left in the reaction mixture for further
reaction.
[0297] (d) Preparation of the Triple-Dye-Doped Alumina Core-Shell
Particles
[0298] A mixture of 5 mg of each of the above under (a) to (c)
prepared functionalized dyes in 150 ml of ethanol (96% Merck) is
added to a mixture of 150 ml of ethanol, 30 g of 25% by weight of
ammonia (from FLUKA) and 100 ml of water under vigorously stirring.
After 24 h at room temperature under protection against light, 15 g
of aluminium tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml
of 2-propanol (Aldrich, 99.9%) are added. The mixture is then
stirred for additional 24 h, after which time the obtained alumina
core-shell particles are centrifuged. The residue is dispersed in
ethanol, precipitated by addition of ethyl acetate, washed and
centrifuged thrice until no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Parts of the obtained residue are stored as
dispersion in ethanol.
[0299] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 3cc
Extended Alumina-Core-Particles
[0300] A mixture of 5 mg of each of the above under example 3c (a)
to (c) prepared functionalized dyes in 150 ml of ethanol (96%
Merck) is added to a mixture of 150 ml of ethanol, 30 g of 25% by
weight of ammonia and 100 ml of water under vigorously stirring.
After 4 h at room temperature under exclusion from light, 15 g of
aluminium tri-isopropoxid (Aldrich, 99.99%) dissolved in 200 ml of
2-propanol (Aldrich, 99.9%) are added under vigorously stirring.
The mixture is stirred for additional 24 h and the extended
alumina-core particles are centrifuged. The residue is dispersed in
ethanol, precipitated by addition of ethyl acetate, washed and
centrifuged thrice until no starting material are found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Parts of the obtained residue are stored as
dispersion in ethanol.
[0301] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 3ccc
Extended Alumina-Core-Shell Particles
[0302] A mixture of 5 mg of each of the above under example 3c (a)
to (c) prepared functionalized dyes in 150 ml of ethanol (96%
Merck) is added to a mixture of 150 ml of ethanol, 30 g of 25% by
weight of ammonia and 100 ml of water under vigorously stirring.
After 4 h at room temperature under exclusion from light, 7.5 g of
aluminium tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of
2-propanol (Aldrich, 99.9%) are added under vigorously stirring.
The mixture is stirred for additional 24 h. Then another 7.5 g of
aluminium tri-isopropoxid (Aldrich, 99.99%) dissolved in 100 ml of
2-propanol (Aldrich, 99.9%) are added under vigorously stirring.
The mixture is stirred for additional 24 h and the extended
alumina-core-shell particles are centrifuged. The residue is
dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material are found
in the supernatant. The thus obtained residue is dried 24 h under
an atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Parts of the obtained residue are stored as
dispersion in ethanol.
[0303] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 4
Silica Core-Shell Particles
[0304] A mixture of 10 mg of each fluorescent dye compound obtained
as described above in examples 3c(a) (mixture of fluoresceine
isothiocyanate dyestuff), example 3c(c) (mixture of 5- and
6-carboxyrhodamine 6 G succinimidyl ester derivative) and example 3
(Rhodamine B-derivative) in 150 ml of ethanol (96% Merck) is added
to a mixture of 200 ml of ethanol (96%, Merck), 30 g of 25% by
weight of ammonia (from FLUKA) and 100 ml of water under vigorously
stirring. After 24 h at room temperature under protection against
light, 25 g of tetraethoxysilane (TEOS) dissolved in 100 ml of
ethanol are added. This mixture is then stirred for additional 24 h
and the obtained core-shell particles are centrifuged. The residue
is dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material or
unreacted compounds are found in the supernatant. The thus obtained
residue is dried 24 h under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C. Parts of the obtained
residue are stored as dispersion in ethanol.
[0305] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 4a
Extended Silica-Core-Particles
[0306] A mixture of 10 mg of each fluorescent dye compound obtained
as described above in examples 3c(a) (mixture of fluoresceine
isothiocyanate dyestuff), example 3c(c) (mixture of 5- and
6-carboxyrhodamine 6 G succinimidyl ester derivative) and example 3
(Rhodamine B-derivative) in 150 ml of ethanol (96% Merck) is added
to a mixture of 200 ml of ethanol (96%, Merck), 30 g of 25% by
weight of ammonia (from FLUKA) and 100 ml of water under vigorously
stirring. After 4 h at room temperature under exclusion against
light, 25 g of tetraethoxysilane dissolved in 150 ml of ethanol is
added to the vigorously stirred solution. This mixture is then
stirred for additional 24 h at room temperature, and the extended
silica-core particles are centrifuged. The residue is dispersed in
ethanol, precipitated by addition of ethyl acetate, washed and
centrifuged thrice until no starting material or unreacted
compounds are found in the supernatant. The thus obtained residue
is dried 24 h under an atmosphere of reduced pressure (70 hPa) at a
temperature of 60.degree. C. Parts of the obtained residue are
stored as dispersion in ethanol.
[0307] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 5
A Hybridized Fluorescent Whitening Agent (FWA)
[0308] (a) Functionalizing of a reactive FWA according to the
following reaction scheme:
##STR00018##
[0309] (a1) Preparation of the Reactive Fluorescent Whitening
Agent
[0310] A solution of 64 g of
4-amino-4'-nitrostilbene-2,2'-disulfonic acid in 900 ml water is
added to a mixture of 150 g methylethylketone, 173 g of ice and 30
g of cyanuric chloride. During the addition, the reaction
temperature is kept below 10.degree. C. by external cooling and the
pH is kept between 4.5 and 5 by the addition of 53 ml of a 15%
sodium carbonate solution in water. After the addition is complete,
a solution of 18 g diethanolamine in 30 ml of water is added and
the pH is adjusted to between 7 and 7.5 by the addition of 81 ml of
15% aqueous sodium carbonate solution. The reaction solution is
then stirred for 1 h at 40.degree. C. followed by 1 h at 60.degree.
C. 22 g diethanolamine are then added and the reaction solution is
heated to 98.degree. C. Simultaneously, the pH is adjusted to
between 9 and 9.3 by the addition of 49 ml 4N aqueous sodium
hydroxide solution, and 200 ml of the methylethylketone/water
mixture is distilled off. The reaction solution is then stirred for
2 h at 98.degree. C. The solution is cooled to room temperature,
200 g sodium chloride is added and the suspension stirred for 30
minutes, after which the formed precipitate is filtered off.
[0311] The product obtained in this manner (300 g) is then
suspended in 400 ml of water and added portionwise to a mixture of
600 ml water, 40 g of iron and 10 ml of glacial acetic acid at
100.degree. C. The mixture is stirred for 1.5 hours, rendered
alkaline by 32% aqueous sodium hydroxide and filtered. The filtrate
is treated with sodium dithionite, acidified with 125 ml
concentrated hydrochloric acid and cooled to room temperature. The
precipitate is filtered off, washed with 100 ml of water and dried
in vacuum. Thus 94 g of yellow crystals are obtained. 36 g of this
material is dissolved in water up to 360 ml. During 1 hour this
solution is added to a mixture of 110 ml methylethylketone, 9.9 g
cyanuric chloride, 130 ml water and 200 g ice. Simultaneously the
pH is adjusted to between 4 and 4.5 by the addition of 12 ml of a
15% sodium carbonate solution.
[0312] After the addition of 6 g of diethanolamine in 25 ml water
during 5 minutes, the mixture is heated to 40.degree. C. for 40
minutes and to 60.degree. C. for 30 minutes while the pH is
adjusted to a value between 7 and 7.7 by addition of 15% sodium
carbonate solution. Stirring is continued at 60.degree. C. for
another 30 minutes before heating further to 98.degree. C. when 125
ml of the methylethylketone/water mixture is distilled off. After
cooling to room temperature 100 g of sodium chloride is added and
the mixture is stirred for 30 min. The formed precipitate is
filtered off and dried in vacuum. Thus 66.1 g of yellow crystals
are obtained (product contains 26.7% sodium chloride).
[0313] (a2) Functionalization of the Reactive FWA obtained in Step
(a1)
[0314] To 1 g of the above obtained reactive FWA (73.3% content,
rest=NaCl) in 25 ml of dimethylacetamide at 60.degree. C. 3.32 g of
3-aminopropyltriethoxysilane (15 mmol) are added over 30 min. After
2 h, the solution is cooled to room temperature. Part of the
product is isolated by evaporation of the solvent.
[0315] (b) Silica Core-Shell Particles
[0316] A mixture of 1 g of the above functionalized FWA, 100 ml of
2-propanol, and 5 g of n-propyltrimethoxysilane is added to a
mixture of 150 ml of 2-propanol, 100 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 24 h at room temperature. Then, 5 g of
tetraethoxysilane in 50 ml of 2-propanol are added. Afterwards this
reaction mixture is stirred for 24 h and then centrifuged. The
residue is dispersed in ethanol (80%), washed and centrifuged
thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0317] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 5aa
Extended Silica-Core-Particles
[0318] A mixture of 1 g of the above functionalized FWA, 100 ml of
2-propanol and 5 g of n-propyltrimethoxysilane is added to a
mixture of 150 ml of 2-propanol, 100 ml of deionized water and 30 g
of 25% by weight aqueous ammonia solution. The combined mixtures
are stirred vigorously for 4 h at room temperature. Then 5 g of
tetraethoxysilane (Aldrich, 99.99%) in 30 ml of ethanol are added.
Afterwards this reaction mixture is stirred for 24 h and then
centrifuged. The residue is dispersed in ethanol, precipitated by
addition of ethyl acetate, washed and centrifuged thrice,
thereafter no starting material is found in the supernatant. The
thus obtained residue is dried 24 h under an atmosphere of reduced
pressure (70 hPa) at a temperature of 60.degree. C. Part of the
residue is re-dispersed in ethanol for storage.
[0319] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 6.a
Seed Particles from Reactive Red 218
##STR00019## ##STR00020##
[0321] (a) Functionalizing Reactive Red 218
[0322] 1 g of Reactive Red 218 (obtained as Cibacron.RTM.Red P-6B
from Ciba) is dissolved in 25 ml of dimethylacetamide (DMA) at
60.degree. C. 1.42 g of 3-aminopropyltriethoxy silane (5 eq.) are
added over 30 min. After 4 h stirring at 80.degree. C., the violet
solution is cooled to room temperature. Part of the product is
isolated by evaporation of the solvent.
[0323] (b) Preparation of Seed Particles
[0324] A mixture of 1 g of the above obtained functionalized
Reactive Red 218 and 100 ml of 2-propanol is added to a mixture of
150 ml of 2-propanol, 50 ml of deionized water and 20 g of 25% by
weight aqueous ammonia solution. The combined mixtures are stirred
vigorously for 24 h at room temperature and then centrifuged. The
residue is dispersed in ethanol (80%), washed and centrifuged
thrice, thereafter no starting material is found in the
supernatant.
[0325] The thus obtained residue is dried 24 h under an atmosphere
of reduced pressure (70 hPa) at a temperature of 60.degree. C.
[0326] (c) Surface Modification (Michael Addition) of the
3-Aminopropyl-Group with an Acrylate Derivative
[0327] The above (b) obtained dark red residue is re-dispersed in
50 ml of dimethylacetamide, combined with 15 g of dodecylacrylate
(Aldrich, techn. 90%) and stirred for 16 h at a temperature of
45.degree. C. Then the mixture is diluted with 100 ml of ethyl
acetate, washed and centrifuged thrice until no starting material
is found in the supernatant. The desired product is obtained by
evaporation of the solvent.
[0328] Part of the product is dispersed in dodecane (1% particle
content w/w) for analyzing electrophoretic properties and particle
size by DLS (Dynamic Light Scattering) with a MALVERN
Zeta-Sizer:
TABLE-US-00005 Example 6a Data (20.degree. C. in dodecane)
Zeta-Potential: +53.9 mV Mobility: 0.0462 m.sup.2/Vs .times.
10.sup.-8 Particle size (DLS): 13 nm
Example 6aa
Extended Silica-Seed-Particles
[0329] A mixture of 1 g of the above obtained functionalized
Reactive Red 218 and 100 ml of 2-propanol is added to a mixture of
150 ml of 2-propanol, 50 ml of deionized water and 20 g of 25% by
weight aqueous ammonia solution (from FLUKA). The combined mixtures
are stirred vigorously for 4 h at room temperature. Then 0.4 g of
tetraethoxysilane (Aldrich, 99.99%) dissolved in 20 ml of
2-propanol are added to the vigorously stirred solution. The
mixture is stirred for additional 24 h at room temperature, and the
extended silica-seed particles are centrifuged. The residue is
dispersed in ethanol, precipitated by addition of ethyl acetate,
washed and centrifuged thrice until no starting material or
unreacted compounds are found in the supernatant. The thus obtained
residue is dried 24 h under an atmosphere of reduced pressure (70
hPa) at a temperature of 60.degree. C. Part of the residue is
re-dispersed in ethanol for storage.
[0330] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
5).
Example 6b
Acid Yellow 95 Seed-Particles
[0331] (a) Functionalizing the Dyestuff according to the Following
Scheme:
##STR00021##
[0332] To 1 g of Acid Yellow 95 (obtained as Cibacron.RTM.Yellow
D-6GS from Ciba Specialty Chemicals) in 25 ml of dimethylacetamide
at a temperature of 60.degree. C. 1.42 g of
3-aminopropyltriethoxysilane (5 eq.) are added over 30 min. After 4
h stirring at 80.degree. C., the dark brown solution is cooled to
room temperature. Part of the product is isolated by evaporation of
the solvent.
[0333] (b) Preparation of Seed Particles
[0334] A mixture of 1 g of the above obtained functionalized Acid
Yellow 95 and 100 ml of 2-propanol is added to a mixture of 150 ml
of 2-propanol, 50 ml of deionized water and 20 g of 25% by weight
aqueous ammonia solution (from FLUKA). The combined mixtures are
stirred vigorously for 24 h at room temperature and then
centrifuged. The residue is dispersed in ethanol (80%), washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0335] (c) Surface Modification (Michael Addition) of the
3-Aminopropyl-Group with an Acrylate Derivative
[0336] The above (b) obtained residue is re-dispersed in 50 ml of
dimethylacetamide, combined with 15 g of dodecylacrylate (Aldrich,
techn. 90%) and stirred for 16 h at a temperature of 45.degree. C.
Then the mixture is diluted with 100 ml of ethyl acetate, washed
and centrifuged thrice until no starting material is found in the
supernatant. The desired product is obtained by evaporation of the
solvent.
Example 6c
Reactive Blue Seed-Particles
[0337] (a1) Functionalizing the Dye According to the Following
Reaction Scheme:
##STR00022##
[0338] 1 g of the above phthalocyanine dye (obtained as Reactive
Dye Cibacron.RTM.Blue P-GR from Ciba Specialty Chemicals) is
dissolved at 60.degree. C. in 25 ml of dimethylacetamide. Then 1.42
g of 3-aminopropyltriethoxysilane (5 eq.) are added at 80.degree.
C. Parts of the obtained product are isolated by distillation of
residual solvent.
[0339] (a2) Preparation of Seed Particles
[0340] A mixture of 1 g of the above obtained functionalized
phthalocyanine and 100 ml of 2-propanol is added to a mixture of
150 ml of 2-propanol, 50 ml of deionized water and 20 g of 25% by
weight aqueous ammonia solution (from FLUKA). The combined mixtures
are stirred vigorously for 24 h at room temperature and then
centrifuged. The residue is dispersed in ethanol (80%), washed and
centrifuged thrice, thereafter no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C.
[0341] (a3) Surface Modification (Michael Addition) of the
3-Aminopropyl-Group with an Acrylate Derivative
[0342] The above (b) obtained residue is re-dispersed in 50 ml of
dimethylacetamide, combined with 15 g of dodecylacrylate (Aldrich,
techn. 90%) and stirred for 16 h at a temperature of 45.degree. C.
Then the mixture is diluted with 100 ml of ethyl acetate, washed
and centrifuged thrice until no starting material is found in the
supernatant. The desired product is obtained by evaporation of the
solvent.
Example 6d
Hair Dye Red Seed-Particles
[0343] (a1) Functionalizing the Dyestuff According to the Following
Reaction Scheme:
##STR00023##
[0344] To a mixture of 0.75 g of the above diazo dye (CAS Registry
Number 161328-92-3) and 70 ml of anhydrous ethanol a mixture of 2.9
g of 3-aminopropyltriethoxysilane and 20 ml of ethanol is added and
the combined mixtures are heated to a temperature of 78.degree. C.
After 4 h, the dark red solution is cooled to room temperature.
Parts of the product are isolated by evaporation of the
solvent.
[0345] (a2) Preparation of the Desired Seed Particles According to
the Following Reaction Scheme:
##STR00024##
[0346] To 1 g of the above obtained functionalized dyestuff are
added 150 ml of ethanol, 50 ml of water and 30 g of 25% by weight
aqueous ammonia solution (from FLUKA) and the reaction mixture is
then stirred vigorously for 24 h at room temperature. Thereafter,
50% of the solvent is evaporated in a rotary evaporator under an
atmosphere of reduced pressure. The residue is mixed with 200 ml of
ethyl acetate, centrifuged and the obtained residue washed and
centrifuged thrice with ethyl acetate until no starting material is
found in the supernatant. The thus obtained residue is dried 24 h
under an atmosphere of reduced pressure (70 hPa) at a temperature
of 60.degree. C.
[0347] (a3) Surface Modification (Michael Addition) of the
3-Aminopropyl-Group with an Acrylate Derivative
[0348] The above (a2) obtained dark red colored residue is
dispersed in 50 ml of dimethylacetamide, combined with 15 g of
dodecylacrylate (Aldrich, techn. 90%) and stirred for 16 h at a
temperature of 45.degree. C. Then the mixture is diluted with 100
ml of ethyl acetate, washed and centrifuged thrice until no
starting material is found in the supernatant. The desired product
is obtained by evaporation of the solvent.
[0349] The product is analyzed with a MALVERN Zeta-Sizer:
TABLE-US-00006 Example 6d Data (20.degree. C. in dodecane)
Zeta-Potential: -42.1 mV Mobility: 0.0362 m.sup.2/Vs .times.
10.sup.-8 Particle size (DLS): 7 nm
Example 6dd
Extended Silica-Seed-Particles
[0350] To 1 g of the above obtained functionalized dyestuff
according to example 6d(a2) are added 150 ml of ethanol, 50 ml of
water and 30 g of 25% by weight aqueous ammonia solution (from
FLUKA) and the reaction mixture is then stirred vigorously for 4 h
at room temperature. Then 0.3 g of tetraethoxysilane (Aldrich,
99.99%) dissolved in 20 ml of 2-propanol are added to the
vigorously stirred solution. The mixture is stirred for additional
24 h at room temperature, and the extended silica-seed particles
are centrifuged. The residue is dispersed in ethyl acetate, washed
and centrifuged thrice until no starting material is found in the
supernatant. The thus obtained residue is dried 24 h under an
atmosphere of reduced pressure (70 hPa) at a temperature of
60.degree. C. Part of the residue is re-dispersed in ethyl acetate
for storage.
[0351] 0.4 g of the obtained product and 26.6 g of PVC
(EVIPOL.RTM.SH 7020, EVC GmbH, Frankfurt/Main), 14.6 g of a mixture
of stabilizer consisting of 92.21% of a softening agent (diisodecyl
phthalate, Vestinol, Huls Chemie), 4.19% of a rheology stabilizer
(Rheoplast.RTM.39, Ciba) and 3.60% of a Ba/Zn stabilizer
(Irgastab.RTM.BZ 561, Ciba) are calandered to a PVC-foil having a
thickness of 0.5 mm and a content of 1% by weight of the
corresponding sample. A migration test (measured during 24 h at
80.degree. C. and a pressure of 1 kg/cm.sup.2, with heat stress
during 30 min at 180.degree. C.) showed no migration (grey scale
4.8)
* * * * *