U.S. patent application number 09/970991 was filed with the patent office on 2002-07-25 for polymerizable organosilicon nanocapsules.
This patent application is currently assigned to DEGUSSA AG. Invention is credited to Edelmann, Roland, Monkiewicz, Jaroslaw.
Application Number | 20020098243 09/970991 |
Document ID | / |
Family ID | 26007286 |
Filed Date | 2002-07-25 |
United States Patent
Application |
20020098243 |
Kind Code |
A1 |
Edelmann, Roland ; et
al. |
July 25, 2002 |
Polymerizable organosilicon nanocapsules
Abstract
The present invention provides a polymerizable organosilicon
nanocapsule, which includes: a nanoscale core A, which includes: at
least one particle comprising at least one oxide or mixed oxide,
KA--O, of at least one metal or semimetal selected from the group
including main groups 2 to 6 of the Periodic Table, transition
groups 1 to 8 of the Periodic Table, lanthanides, and mixtures
thereof; and an organosilicon shell B, which includes: at least one
organosilicon compound having the formula (Ia): (Si'O--).sub.xSi--R
(Ia) wherein R is a vinyl or allyl group; wherein x is a number
from 0 to 20; wherein remaining free valences of Si are each
independently (KA--O)--, SiO-- or --Z; wherein remaining free
valences of Si' are each independently (KA--O)--, SiO--, --R, or
wherein the Z's are each independently hydroxyl or alkoxy radicals;
and wherein each Si and Si' in the shell B have not more than one R
group attatched thereto.
Inventors: |
Edelmann, Roland; (Wehr,
DE) ; Monkiewicz, Jaroslaw; (Rheinfelden,
DE) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
DEGUSSA AG
Duesseldorf
DE
|
Family ID: |
26007286 |
Appl. No.: |
09/970991 |
Filed: |
October 5, 2001 |
Current U.S.
Class: |
424/497 ;
264/4.7 |
Current CPC
Class: |
C09C 1/3081 20130101;
C09C 1/00 20130101; Y10T 428/2984 20150115; C01P 2004/64 20130101;
C08K 9/06 20130101; C01P 2006/12 20130101; C09C 1/407 20130101;
B01J 13/02 20130101; C09C 3/12 20130101; B82Y 30/00 20130101; C09C
1/3684 20130101 |
Class at
Publication: |
424/497 ;
264/4.7 |
International
Class: |
A61K 009/16; A61K
009/50 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 2000 |
DE |
100 49 632.6 |
Jan 9, 2001 |
DE |
101 00 633.0 |
Claims
1. A polymerizable organosilicon nanocapsule, comprising: a
nanoscale core A, which comprises: at least one particle comprising
at least one oxide or mixed oxide, KA--O, of at least one metal or
semimetal selected from the group consisting of main groups 2 to 6
of the Periodic Table, transition groups 1 to 8 of the Periodic
Table, lanthanides, and mixtures thereof; and an organosilicon
shell B, which comprises: at least one organosilicon compound
having the formula (Ia): (Si'O--).sub.xSi--R (Ia) wherein R is a
vinyl or allyl group; wherein x is a number from 0 to 20; wherein
remaining free valences of Si are each independently (KA--O)--,
SiO-- or --Z; wherein remaining free valences of Si' are each
independently (KA--O)--, SiO--, --R, or wherein the Z's are each
independently hydroxyl or alkoxy radicals; and wherein each Si and
Si' in the shell B have not more than one R group attatched
thereto.
2. The nanocapsule according to claim 1, wherein said nanocapsule
has the following formula (Ib): (KA--O)--{(Si'O--).sub.x(Si--R}
(Ib) wherein R is a vinyl or allyl group; wherein x is a number
from 0 to 20; wherein the remaining free valences of Si are each
independently KA--O, SiO-- or --Z; wherein the remaining free
valences of Si' are each independently KA--O, SiO--, --R, or --Z;
wherein the Z's are each independently hydroxyl or alkoxy radicals;
and wherein each Si and Si' in the shell B have not more than one R
group attatched directly thereto.
3. The nanocapsule according to claim 1, wherein said organosilicon
compound of the shell B is attached to said KA--O core A (KA--O) by
one or more covalent linkages.
4. The nanocapsule according to claim 1, wherein the core A is an
oxide and/or mixed oxide (KA--O) of an element selected from the
group consisting of Si, Al, Ti and Zr.
5. The nanocapsule according to claim 1, wherein said nanocapsule
has an average diameter of from 10 to 400 nm.
6. The nanocapsule according to claim 1, wherein the core A has an
average particle diameter of from 1 to 100 nm.
7. The nanocapsule according to claim 1, wherein at least one of
the free valencies of Si or Si' or both in said shell is
(KA--O).
8. The nanocapsule according to claim 1, wherein said shell is not
covalently bonded to said core KA--O.
9. A composition, comprising the nanocapsule according to claim 1
and at least one selected from the group consisting of a liquid, a
curable synthetic resin, a precursor of a synthetic resin, and a
mixture thereof.
10. The composition according to claim 9, which is a coating
composition or coating material.
11. The composition according to claim 9, wherein the curable
synthetic resin or precursor of a curable synthetic resin comprises
at least one selected from the group consisting of acrylate,
methacrylate, epoxide, epoxy resin, polyurethane, polyurethane
resin, unsaturated polyester, unsaturated polyester resin, epoxy
acrylate, polyester acrylate, urethane acrylate, silicone acrylate,
and mixtures thereof.
12. A process, which comprises applying the composition according
to claim 9 to a substrate.
13. The process according to claim 12, further comprising
subjecting the coated substrate to photochemical curing.
14. The process according to claim 12, which is a process for
producing a scratch-resistant coating.
15. The process according to claim 13, wherein said photochemical
curing comprises curing with UV radiation or electron beams at a
temperature ranging from 10 to 60.degree. C.
16. A composition, comprising the nanocapsule according to claim 1
and a cured resin, wherein said cured resin comprises at least one
selected from the group consisting of acrylate, methacrylate,
epoxide, epoxy resin, polyurethane, polyurethane resin, unsaturated
polyester, unsaturated polyester resin, epoxy acrylate, polyester
acrylate, urethane acrylate, silicone acrylate, and mixtures
thereof.
17. The composition according to claim 16, wherein the core A has
an SiO.sub.2 content of up to 60% by weight, based on the
composition.
18. The composition according to claim 16, which is a
scratch-resistant coating.
19. A coated article, comprising the composition according to claim
16 in contact with a substrate.
20. The coated article according to claim 19, wherein said
substrate is selected from the group consisting of sheetlike
substrate, paper, metal foil, polymer film, metal, aluminum, iron,
steel, brass, copper, silver, magnesium, nonferrous metal alloy,
wood, board, textile, stone, plastic, thermoplastic, polycarbonate,
glass, ceramic and combinations thereof.
21. The coated article according to claim 19, which is selected
from the group consisting of decorative paper, aluminum foil,
polycarbonate auto glazing, PVC window frame, door, furniture, and
worktop.
22. A polymerizable organosilicon nanocapsule prepared by a
process, comprising reacting: (i) at least one nanoscale oxide
and/or mixed oxide (KA--O) particle of at least one metal or
semimetal selected from the group consisting of main groups two to
six of the Periodic Table of the Elements, transition groups one to
eight of the Periodic Table of the Elements, lanthanides, and
combinations thereof, with (ii) at least one vinyltrialkoxysilane
and/or allyltrialkoxysilane, alkoxy being a methoxy, ethoxy,
n-propoxy or i-propoxy group, and (iii) optionally, at least one
monomeric and/or oligomeric silicic ester which carries at least
one selected from the group consisting of methoxy, ethoxy,
n-propoxy, i-propoxy group, and combinations thereof and has an
average degree of oligomerization of from 1 to 50, and (iv)
optionally, at least one organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom independently carries at least one functionality
selected from the group consisting of alkyl, fluoroalkyl,
cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl,
glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
mercaptoalkyl, ureidoalkyl, aryl, alkoxy, and combinations thereof,
and remaining free valences of the silicon atoms in the siloxane
are satisfied by methoxy or ethoxy or hydroxyl groups, and (v)
optionally, a further organofunctional silane having the formula
II: R'.sub.sR".sub.rSiY.sub.(4-s-r) (II), in which the groups R'
and R" are identical or different and are each independently
selected from the group consisting of a linear, branched or cyclic
alkyl group having 1 to 20 carbon atoms, chloroalkyl, bromoalkyl,
iodoalkyl, isocyanoalkyl, cyanoalkyl, fluoroalkyl, perfluoroalkyl,
alkenyl, aryl, acylalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
sulfane, mercaptoalkyl, thiacyamidoalkyl, glycidyloxyalkyl,
aminoalkyl, diaminoalkyl, triaminoalkyl, carbonatoalkyl or
ureidoalkyl group, the respective alkylene groups containing 1 to 6
carbon atoms, Y is a methoxy, ethoxy, i-propoxy, n-propoxy or
2-methoxyethoxy group, s is 1 or 2 or 3, and r is 0 or 1 or 2,
subject to the proviso that (s+r).ltoreq.3, wherein said reacting
is carried out in situ in a liquid, a curable synthetic resin or a
precursor of a synthetic resin.
23. The nanocapsule according to claim 22, wherein the nanoscale
oxide and/or mixed oxide (KA--O) is an oxide and/or mixed oxide of
an element selected from the group consisting of Si, Al, Ti and
Zr.
24. The nanocapsule according to claim 22, which has an average
diameter of from 110 to 400 nm.
25. The nanocapsule according to claim 22, wherein the curable
synthetic resin or precursor of a curable synthetic resin comprises
at least one selected from the group consisting of acrylate,
methacrylate, epoxide, epoxy resin, polyurethane, polyurethane
resin, unsaturated polyester, unsaturated polyester resin, epoxy
acrylate, polyester acrylate, urethane acrylate, silicone acrylate,
and mixtures thereof.
26. A process for preparing a polymerizable organosilicon
nanocapsule, comprising reacting: (i) at least one nanoscale oxide
and/or mixed oxide (KA--O) particle of at least one metal or
semimetal selected from the group consisting of main groups two to
six of the Periodic Table of the Elements, transition groups one to
eight of the Periodic Table of the Elements, lanthanides, and
combinations thereof, with (ii) at least one vinyltrialkoxysilane
and/or allyltrialkoxysilane, alkoxy being a methoxy, ethoxy,
n-propoxy or i-propoxy group, and (iii) optionally, at least one
monomeric and/or oligomeric silicic ester which carries at least
one selected from the group consisting of methoxy, ethoxy,
n-propoxy, i-propoxy group, and combinations thereof and has an
average degree of oligomerization of from 1 to 50, and (iv)
optionally, at least one organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom independently carries at least one functionality
selected from the group consisting of alkyl, fluoroalkyl,
cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl,
glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
mercaptoalkyl, ureidoalkyl, aryl, alkoxy, and combinations thereof,
and remaining free valences of the silicon atoms in the siloxane
are satisfied by methoxy or ethoxy or hydroxyl groups, and (v)
optionally, a further organofunctional silane having the formula
II: R'.sub.sR".sub.rSiY.sub.(4-s-r) (II), in which the groups R'
and R" are identical or different and are each independently
selected from the group consisting of a linear, branched or cyclic
alkyl group having 1 to 20 carbon atoms, chloroalkyl, bromoalkyl,
iodoalkyl, isocyanoalkyl, cyanoalkyl, fluoroalkyl, perfluoroalkyl,
alkenyl, aryl, acylalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
sulfane, mercaptoalkyl, thiacyamidoalkyl, glycidyloxyalkyl,
aminoalkyl, diaminoalkyl, triaminoalkyl, carbonatoalkyl or
ureidoalkyl group, the respective alkylene groups containing 1 to 6
carbon atoms, Y is a methoxy, ethoxy, i-propoxy, n-propoxy or
2-methoxyethoxy group, s is 1 or 2 or 3, and r is 0 or 1 or 2,
subject to the proviso that (s+r).ltoreq.3, wherein said reacting
is carried out in situ in a liquid, a curable synthetic resin or a
precursor of a synthetic resin.
27. The process as claimed in claim 26, wherein the nanoscale oxide
and/or mixed oxide (KA--O) has an average particle diameter of from
1 to 100 nm.
28. The process as claimed in claim 26, wherein the curable
synthetic resin or precursor of a curable synthetic resin comprises
at least one selected from the group consisting of acrylate,
methacrylate, epoxide, epoxy resin, polyurethane, polyurethane
resin, unsaturated polyester, unsaturated polyester resin, epoxy
acrylate, polyester acrylate, urethane acrylate, silicone acrylate,
and mixtures thereof.
29. The process as claimed in claim 26, wherein from 0.1 to 60% by
weight of nanoscale oxide and/or mixed oxide (KA--O) is present,
based on the weight of the synthetic resin.
30. The process as claimed in claim 26, wherein (i) and at least
one selected from the group consisting of (ii), (iii), (iv) and (v)
are employed in a weight ratio ranging from 4:1 to 1:1.
31. The process as claimed in claim 26, wherein the reaction is
conducted in the presence of a catalyst.
32. The process as claimed in claim 26, wherein the reaction is
conducted in the presence of water.
33. The process as claimed in claim 26, wherein the reaction is
conducted in the presence of a wetting agent.
34. The process as claimed in claim 26, wherein the reaction is
conducted at a temperature ranging from 30 to 100.degree. C.
35. The process as claimed in claim 26, wherein the curable
synthetic resin or a precursor of a curable synthetic resin is
introduced heated, catalyst, optionally, a wetting agent and water
are added, components (ii) to (v) are introduced, and then
component (i) is added with mixing.
36. The process as claimed in claim 26, further comprising removing
alcohol from the reaction system during the reaction, after the
reaction, or both.
37. A process for preparing a composition based on a curable
synthetic resin and comprising polymerizable organosilicon
nanocapsules, the process comprising: heating the curable synthetic
resin or a precursor of the curable synthetic resin, adding
catalyst, optionally, a wetting agent and water, adding at least
one organosilicon component of the formula III:
R.sup.1R.sup.2.sub.nSiX.sub.3-n (III) where the groups R.sup.1 and
R.sup.2 are identical or different, R.sup.1 is an alkenyl group
having 2 to 18 carbon atoms, an aryl, alkylaryl, an arylalkyl, an
acylalkyl, an aminoalkyl, a diaminoalkyl, a triaminoalkyl, an
alkyloxyalkyl, an acylalkyl, a cyanoalkyl, an isocyanoalkyl, a
glycidyloxyalkyl, an acyloxyalky, an acryloyloxyalkyl, a
mercaptoalkyl, a polysulfide-alkyl or a methacryloyloxyalkyl group,
and R.sup.2 possesses the same definition as R.sup.1 or is a
linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
which is unsubstituted or substituted, and optionally, a monomeric
and/or oligomeric silicic ester which carries at least one selected
from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy
group and combinations thereof and has an average degree of
oligomerization of from 1 to 50, and optionally, an
organofunctional siloxane whose functionalities are identical or
different and in which each silicon atom in the siloxane carries at
least one functionality selected from the group consisting of
alkyl, fluoroalkyl, cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl,
diaminoalkyl, triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl,
glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
mercaptoalkyl, ureidoalkyl, aryl, alkoxy, methoxy, ethoxy, and
combinations thereof, and remaining free valences of the silicon
atoms in the siloxane are satisfied by methoxy or ethoxy or
hydroxyl groups, mixing and then adding at least one nanoscale
oxide and/or mixed oxide (KA--O) particle of at least one metal or
semimetal selected from the group consisting of main groups 2 to 6,
of the Periodic Table of the Elements, transition groups 1 to 8 of
the Periodic Table of the Elements, lanthanides, and mixtures
thereof with thorough mixing, and removing alcohol formed by
hydrolysis and/or condensation.
38. The process as claimed in claim 37, wherein the organosilicon
component of the formula III is selected from the group consisting
of 3-methacryloyloxypropyltrimethoxysilane,
3-methacryloyloxypropyltriethoxy- silane,
3-methacryloyloxypropylmethyldimethoxysilane,
3-methacryloyloxypropylmethyldiethoxysilane,
3-methacryloyloxy-2-methylpr- opyltrimethoxysilane,
3-methacryloyloxy-2-methylpropyltriethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane,
vinylmethyldimethoxysilane, and vinylmethyl diethoxysilane.
39. The process as claimed in claim 37, wherein a nanoscale silica
is used as oxide component (KA--O).
40. The process as claimed in claim 37, wherein from 0.5 to 6 mol
of water are used per mole of Si of the organosilicon component of
the formula III.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to polymerizable organosilicon
nanocapsules having a core and an organosilicon shell, processes
for preparing, and uses of same. Such compounds are particularly
suited for use in scratch-resistant coatings.
[0003] 2. Discussion of the Background
[0004] It is known that the surface properties of sol or gel
particles or of metal or semimetal oxides can be modified by
treatment with a hydrolyzable organosilane or organosiloxane, which
generally involves the attachment of just a single-ply silane layer
to the oxide or sol gel particle. Oxides or sol or gel particles
treated in this way, examples being inorganic pigments or fillers,
may be incorporated into a polymer matrix, films, coating
compositions and coatings producible therewith. In general,
however, the scratch resistance of such polymer systems is low.
[0005] DE 198 46 660 discloses nanoscale, surface-modified oxide or
mixed-oxide particles enveloped by organosilicon groups bonded
covalently to the oxide particle, the organofunctional groups being
described as reactive groups and normally being oriented outward,
so that by means of polymerization they are bound into the polymer
matrix with the polymer material when the prepolymer is cured. The
process of preparing such coating compositions is complicated,
since the organosilane and the oxide component are incorporated
separately into the prepolymer.
[0006] DE 198 46 659 possesses the same priority as DE 198 46 660
and relates to a laminate provided with a scratch-resistant
synthetic-resin layer which likewise contains nanoscale,
surface-modified oxide particles. DE 198 46 659 teaches
specifically the use of acryloyloxyalkylsilanes to produce a shell
around nanoscale oxide particles that possess reactive,
radiation-crosslinkable groups. The preparation of the coating
composition in this case is likewise via a time-consuming reaction
of a nanoscale silica with 3-methacryloyloxypropyltrimethoxysilane
(DYNASYLAN.RTM. MEMO) in an acrylate formulation in the presence of
water, an acid, and a wetting agent. Again, the components must be
brought together separately and in a specific sequence.
[0007] Hydrolyzable silane components having ethylenically
unsaturated organic groups are usually high-priced starting
materials, however. In addition, DYNASYLAN.RTM. MEMO tends to react
in the presence of even slight traces of a polymerization initiator
or radiation with the undesirable result that the viscosity of a
corresponding formulation may rise drastically. To avoid the
unwanted polymerization, stabilizers must be added. It is therefore
often difficult to master the handling of the starting materials
and the preparation of such coating systems.
[0008] The coating compositions described above are frequently of
high viscosity, and usually contain only a small fraction of oxide
particles, which impacts the scratch resistance of the subsequent
coating. It is difficult to apply such highly viscous coating
compositions to a substrate, especially when the substrate in
question is thin and can be destroyed by tearing. The scratch
resistance of coatings obtainable in this way is in need of
improvement, and with such highly viscous systems, a specific,
complex application apparatus is required. In many cases, solvents
are added to coating compositions of such high viscosity, but this
undesirably leads to an increase in the organic emissions (VOC
problem; VOC=volatile organic compounds).
SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide
polymerizable organosilicon-modified nanoparticles and a process
for their production.
[0010] Another object is to provide a process for preparing coating
compositions for scratch-resistant coatings in as simple and
economic a manner as possible.
[0011] Another object of the invention is to provide articles with
a corresponding scratch-resistant synthetic-resin coating.
[0012] These and other objects have now been achieved by the
present invention, the first embodiment of which provides a
polymerizable organosilicon nanocapsule, which includes:
[0013] a nanoscale core A, which includes:
[0014] at least one particle including at least one oxide or mixed
oxide, KA--O, of at least one metal or semimetal selected from the
group including main groups 2 to 6 of the Periodic Table,
transition groups 1 to 8 of the Periodic Table, lanthanides, and
mixtures thereof; and
[0015] an organosilicon shell B, which includes:
[0016] at least one organosilicon compound having the formula
(Ia):
(Si'O--).sub.xSi--R (Ia)
[0017] wherein R is a vinyl or allyl group;
[0018] wherein x is a number from 0 to 20;
[0019] wherein remaining free valences of Si are each independently
(KA--O)--, SiO-- or --Z;
[0020] wherein remaining free valences of Si' are each
independently (KA--O)--, SiO--, --R, or --Z;
[0021] wherein the Z's are each independently hydroxyl or alkoxy
radicals; and
[0022] wherein each Si and Si' in the shell B have not more than
one R group attatched thereto.
[0023] Another embodiment of the present invention provides a
composition, which includes the above nanocapsule and at least one
selected from the group including a liquid, curable synthetic
resin, a precursor of a synthetic resin, and a mixture thereof.
[0024] Another embodiment of the present invention provides a
process, which includes applying the above composition to a
substrate.
[0025] Another embodiment of the present invention provides a
composition, which includes the above nanocapsule and a cured
resin, wherein said cured resin includes at least one selected from
the group including acrylate, methacrylate, epoxide, epoxy resin,
polyurethane, polyurethane resin, unsaturated polyester,
unsaturated polyester resin, epoxy acrylate, polyester acrylate,
urethane acrylate, silicone acrylate, and mixtures thereof.
[0026] Another embodiment of the present invention provides a
coated article, which includes the above composition in contact
with a substrate.
[0027] Another embodiment of the present invention provides a
polymerizable organosilicon nanocapsule prepared by a process,
which includes reacting:
[0028] (i) at least one nanoscale oxide and/or mixed oxide (KA--O)
particle of at least one metal or semimetal selected from the group
including main groups two to six of the Periodic Table of the
Elements, transition groups one to eight of the Periodic Table of
the Elements, lanthanides, and combinations thereof, with
[0029] (ii) at least one vinyltrialkoxysilane and/or
allyltrialkoxysilane, alkoxy being a methoxy, ethoxy, n-propoxy or
i-propoxy group, and
[0030] (iii) optionally, at least one monomeric and/or oligomeric
silicic ester which carries at least one selected from the group
including methoxy, ethoxy, n-propoxy, i-propoxy group, and
combinations thereof and has an average degree of oligomerization
of from 1 to 50, and
[0031] (iv) optionally, at least one organofunctional siloxane
whose functionalities are identical or different and in which each
silicon atom independently carries at least one functionality
selected from the group including alkyl, fluoroalkyl, cyanoalkyl,
isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl,
alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl,
acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl,
aryl, alkoxy, and combinations thereof, and remaining free valences
of the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, and
[0032] (v) optionally, a further organofunctional silane having the
formula II:
R'.sub.SR".sub.RSiY.sub.(4-s-r) (II),
[0033] in which the groups R' and R" are identical or different and
are each independently selected from the group including a linear,
branched or cyclic alkyl group having 1 to 20 carbon atoms,
chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl, cyanoalkyl,
fluoroalkyl, perfluoroalkyl, alkenyl, aryl, acylalkyl,
acryloyloxyalkyl, methacryloyloxyalkyl, sulfane, mercaptoalkyl,
thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, carbonatoalkyl or ureidoalkyl group, the respective
alkylene groups containing 1 to 6 carbon atoms, Y is a methoxy,
ethoxy, i-propoxy, n-propoxy or 2-methoxyethoxy group, s is 1 or 2
or 3, and r is 0 or 1 or 2, subject to the proviso that
(s+r).ltoreq.3,
[0034] wherein the reacting is carried out in situ in a liquid, a
curable synthetic resin or a precursor of a synthetic resin.
[0035] Another embodiment of the present invention provides a
process for preparing a polymerizable organosilicon nanocapsule,
which includes reacting:
[0036] (i) at least one nanoscale oxide and/or mixed oxide (KA--O)
particle of at least one metal or semimetal selected from the group
including main groups two to six of the Periodic Table of the
Elements, transition groups one to eight of the Periodic Table of
the Elements, lanthanides, and combinations thereof, with
[0037] (ii) at least one vinyltrialkoxysilane and/or
allyltrialkoxysilane, alkoxy being a methoxy, ethoxy, n-propoxy or
i-propoxy group, and
[0038] (iii) optionally, at least one monomeric and/or oligomeric
silicic ester which carries at least one selected from the group
including methoxy, ethoxy, n-propoxy, i-propoxy group, and
combinations thereof and has an average degree of oligomerization
of from 1 to 50, and
[0039] (iv) optionally, at least one organofunctional siloxane
whose functionalities are identical or different and in which each
silicon atom independently carries at least one functionality
selected from the group including alkyl, fluoroalkyl, cyanoalkyl,
isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl,
alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl,
acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl,
aryl, alkoxy, and combinations thereof, and remaining free valences
of the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, and
[0040] (v) optionally, a further organofunctional silane having the
formula II:
R'.sub.sR".sub.rSiY.sub.(4-s-r) (II),
[0041] in which the groups R' and R" are identical or different and
are each independently selected from the group including a linear,
branched or cyclic alkyl group having 1 to 20 carbon atoms,
chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl, cyanoalkyl,
fluoroalkyl, perfluoroalkyl, alkenyl, aryl, acylalkyl,
acryloyloxyalkyl, methacryloyloxyalkyl, sulfane, mercaptoalkyl,
thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, carbonatoalkyl or ureidoalkyl group, the respective
alkylene groups containing 1 to 6 carbon atoms, Y is a methoxy,
ethoxy, i-propoxy, n-propoxy or 2-methoxyethoxy group, s is 1 or 2
or 3, and r is 0 or 1 or 2, subject to the proviso that
(s+r).ltoreq.3,
[0042] wherein the reacting is carried out in situ in a liquid, a
curable synthetic resin or a precursor of a synthetic resin.
[0043] Another embodiment of the present invention provides a
process for preparing a composition based on a curable synthetic
resin and including polymerizable organosilicon nanocapsules, the
process including:
[0044] heating the curable synthetic resin or a precursor of the
curable synthetic resin,
[0045] adding catalyst, optionally, a wetting agent and water,
[0046] adding at least one organosilicon component of the formula
III:
R.sup.1R.sup.2.sub.nSiX.sub.3-n (III),
[0047] where the groups R.sup.1 and R.sup.2 are identical or
different, R.sup.1 is an alkenyl group having 2 to 18 carbon atoms,
an aryl, alkylaryl, an arylalkyl, an acylalkyl, an aminoalkyl, a
diaminoalkyl, a triaminoalkyl, an alkyloxyalkyl, an acylalkyl, a
cyanoalkyl, an isocyanoalkyl, a glycidyloxyalkyl, an acyloxyalky,
an acryloyloxyalkyl, a mercaptoalkyl, a polysulfide-alkyl or a
methacryloyloxyalkyl group, and R.sup.2 possesses the same
definition as R.sup.1 or is a linear, branched or cyclic alkyl
group having 1 to 20 carbon atoms, which is unsubstituted or
substituted, and
[0048] optionally, a monomeric and/or oligomeric silicic ester
which carries at least one selected from the group including
methoxy, ethoxy, n-propoxy, i-propoxy group and combinations
thereof and has an average degree of oligomerization of from 1 to
50, and
[0049] optionally, an organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom in the siloxane carries at least one functionality
selected from the group including alkyl, fluoroalkyl, cyanoalkyl,
isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl,
alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl,
acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl,
aryl, alkoxy, methoxy, ethoxy, and combinations thereof, and
remaining free valences of the silicon atoms in the siloxane are
satisfied by
[0050] methoxy or ethoxy or hydroxyl groups, mixing and then adding
at least one nanoscale oxide and/or mixed oxide (KA--O) particle of
at least one metal or semimetal selected from the group including
main groups 2 to 6, of the Periodic Table of the Elements,
transition groups 1 to 8 of the Periodic Table of the Elements,
lanthanides, and mixtures thereof with thorough mixing, and
[0051] removing alcohol formed by hydrolysis and/or
condensation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0052] Various other objects, features and attendant advantages of
the present invention will be more fully appreciated as the same
becomes better understood from the following detailed description
of the preferred embodiments of the invention.
[0053] It has surprisingly now been found that polymerizable
organosilicon nanocapsules may be obtained in a simple and economic
way by reacting:
[0054] (i) at least one nanoscale oxide and/or mixed oxide (KA--O)
of at least one metal or semimetal of main groups two to six or
transition groups one to eight of the Periodic Table of the
Elements, or of the lanthanides, with
[0055] (ii) vinyltrialkoxysilane and/or allyltrialkoxysilane,
alkoxy preferably being a methoxy, ethoxy, n-propoxy or i-propoxy
group, and
[0056] (iii) if desired, a monomeric and/or oligomeric silicic
ester which carries methoxy, ethoxy, or i- and/or n-propoxy groups
and has an average degree of oligomerization of from 1 to 50,
preferably from 2 to 10, with particular preference from 3 to 5,
and
[0057] (iv) if desired, an organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom in the siloxane carries a functionality selected from
the group including alkyl, which is linear, branched or cyclic with
1 to 20 carbon atoms, preferably 1 to 16 carbon atoms, fluoroalkyl,
cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, alkoxy alkyl, hydroxyalkyl, acylalkyl,
glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl,
mercaptoalkyl, ureidoalkyl, aryl and alkoxy, preferably methoxy,
ethoxy, n-propoxy or i-propoxy, and the remaining free valences of
the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, and
[0058] (v) if desired, a further organofunctional silane of the
general formula II
R'.sub.sR".sub.rSiY.sub.(4-s-r) (II),
[0059] in which the groups R' and R" are identical or different and
are each a linear, branched or cyclic alkyl group having 1 to 20
carbon atoms, preferably 1 to 16 carbon atoms, a chloroalkyl,
bromoalkyl, iodoalkyl, isocyanoalkyl, cyanoalkyl, fluoroalkyl or
perfluoroalkyl, alkenyl, aryl, acylalkyl, acryloyloxyalkyl,
methacryl-oyloxyalkyl, sulfane, mercaptoalkyl, thiacyamidoalkyl,
glycidyloxyalkyl, aminoalkyl, diaminoalkyl, triaminoalkyl,
carbonatoalkyl or ureidoalkyl group, the respective alkylene groups
containing 1 to 6 carbon atoms, R" is preferably a methyl, Y is a
methoxy, ethoxy, i-propoxy, n-propoxy or 2-methoxyethoxy group, and
s is 1 or 2 or 3 and r is 0 or 1 or 2, subject to the proviso that
(s+r).ltoreq.3,
[0060] in situ in a curable synthetic resin or a precursor of a
curable synthetic resin, i.e., a liquid prepolymer or a mixture of
corresponding prepolymers, for example, an acrylate, methacrylate,
epoxide, polyurethane and/or unsaturated polyester. In accordance
with this procedure, the polymerizable organosilicon nanocapsules
are obtained, advantageously, simultaneously incorporated
homogeneously into the prepolymer.
[0061] Further, it has surprisingly been found that the following
reaction for the preparation in situ of a polymerizable coating
composition that contains organosilicon nanocapsules may be
conducted in a particularly advantageous way if an organosilane
containing a reactive, polymerizable organofunctional group, such
as a vinyl group or allyl group or a group as may be inferred from
DE 198 46 660 and DE 198 46 659 (the entire contents of each of
which being hereby incorporated by reference), and at least one
hydrolyzable group, preferably methoxy, ethoxy, i- or n-propoxy or
2-methoxyethoxy, or at least one hydroxyl group, together if
desired with abovementioned components (iii) to (v), is first
introduced into a liquid, curable synthetic resin or a precursor of
a synthetic resin, together with a catalyst, wetting agents if
desired, and water the system is mixed and only then is the
component (i) added, with thorough mixing, and hydrolysis alcohol
formed is stripped from the system, i.e., in such a way that in the
present process, in contrast to the teaching of DE 198 46 659 and
DE 198 46 660, the organosilicon components and the oxide component
are not incorporated alternately or separately into the
prepolymer.
[0062] The present process is surprising and advantageous in that
it is thereby possible, simply and economically, to obtain a
coating composition for scratch-resistant coatings which includes
polymerizable organosilicon nanocapsules, possesses a comparatively
low viscosity, and is homogeneous, it being possible for the
coating composition to contain a particularly high proportion of
polymerizable organosilicon nanoparticles.
[0063] In general, in this process, hydrolyzable groups of the
organosilicon components hydrolyze and/or condense with one another
and envelop the oxide nanoparticles (KA--O). If appropriate, the
hydrolyzable groups or hydroxyl groups may condense with hydroxyl
groups present on the surface of the oxide nanoparticles (KA--O),
or with free valences of organosilicon components of the shell B,
to form a covalent linkage. It should be highlighted that, in
particular, vinyl trimethoxysilane (DYNASYLAN.RTM. VTMO) exhibits a
hydrolysis behavior, i.e., preparation behavior, which is again
significantly improved over that of vinyl triethoxysilane
(DYNASYLAN.RTM. VTEO).
[0064] In the case of the present process, the reaction takes place
suitably in the presence of defined amounts of water. It is
preferred to use from 0.5 to 6 mol of water, with particular
preference from 0.5 to 4 mol of water, with very particular
preference from 1 to 1.5 mol of water, per mole of a hydrolyzable,
Si-bonded group of the organosilicon components. These ranges
include 0.75, 1.1, 1.8, 2, 2.5, 3, 4.5 and 5 mol of water. The use
of a catalyst and of a wetting agent is preferred.
[0065] In particular it is possible in the case of the present
process, through the use of vinyl trimethoxysilane or
vinyltriethoxysilane, to obtain coating compositions having high
solids contents, high transparency, and good processing
properties.
[0066] In general in the case of dilatant coating systems of this
kind, the target viscosity is up to 2500 mPa s. Preferably,
solvent-free coating compositions of the invention possess a
viscosity of >500 to 2000 mPa s, with particular preference from
800 to 1000 mPa s. These ranges include 600, 700, 900, 1100, 1500,
1800, 2000, and 2300 mPa s. In this case the amounts of
polymerizable nanoscale capsules in coating compositions of the
invention are suitably between 5 and 60% by weight, which range
includes 10, 20, 30, 40 and 50% by weight.
[0067] Preferably, in the case of the present process, the product
substantially includes nanoscale oxide or mixed-oxide particles,
with a complete and multilayer organosilicon shell, referred to as
polymerizable organosilicon nanocapsules, which are obtained
directly, advantageously, in fine dispersion in a curable synthetic
resin or a precursor of a curable synthetic resin, and the
comparatively low-viscosity product mixture may be used as it is or
as a basis for coating materials for the scratch-resistant coating
of surfaces.
[0068] The organosilicon shell in the nanocapsule of the present
invention may be covalently bonded to the core, or it may be in
contact with the core but not covalently bonded to the core.
Preferably, at least one covalent bond is present between the shell
and the core. The nanocapsules may be present in compositions as
either a bonded type or a non-bonded type or may be present as a
mixture of bonded and non-bonded types.
[0069] The organosilicon shell may completely or partially cover
the core, independently of the bonding or non-bonding nature of the
nanocapsule. Preferably, the organosilicon shell completely or
substantially completely covers the core. The nanocapsule may be
present in compositions as only the completely covered or as only
the partially covered or mixtures of completely covered and
partially covered. Preferably, the nanocapsules are present as
mixtures of both completely and partially covered types.
[0070] Coating materials or coating compositions of the invention
may optionally contain as further components initiators for the
photochemical curing and/or UV curing, such as Darocur.RTM. 1173,
Lucirin.RTM. TPO-L, stabilizers, such as HALS compounds, Tinuvins,
and also antioxidants, such as Irganox.RTM..
[0071] By means of the present preparation method, a solvent-free,
comparatively low-viscosity coating material or a composition
containing polymerizable organosilicon nanocapsules of the
invention is accessible simply, directly, and economically.
[0072] The coating of a substrate with the present composition is
generally comparatively easy owing to the low viscosity of the
composition.
[0073] Preferably, the present, comparatively low-viscosity
composition, or the coating material, may be provided with an
unexpectedly high proportion of organosilicon nanocapsules, it
being possible to incorporate up to 60% by weight oxide or
mixed-oxide content, based on the coating composition, into the
system. This range includes 10, 20, 30, 40 and 50% by weight.
[0074] The coating is preferably cured photochemically by UV
irradiation or by irradiation with electron beams. The irradiation
is normally conducted at a temperature of from 10 to 60.degree. C.,
advantageously at ambient temperature. This range includes 15, 20,
25, 30, 40 and 50.degree. C.
[0075] Articles or substrates coated in accordance with the
invention are generally notable for outstanding scratch resistance
in accordance with DIN 53 799 (hard metal balls) and for good
abrasion resistance (DIN 52 347), the entire contents of each of
which being incorporated by reference.
[0076] Accordingly it is possible, especially with coating
compositions of the invention that include vinyl- or
allyl-functional organosilicon nanocapsules, to achieve excellent
scratch resistance.
[0077] Preferably, the present invention accordingly provides a
process for preparing a composition based on a curable synthetic
resin or precursor of a curable synthetic resin and containing
polymerizable organosilicon nanocapsules by introducing and heating
the curable synthetic resin or its precursor, adding catalyst,
wetting agent if desired, and defined amounts of water, adding at
least one organosilicon component of the general formula III
R.sup.1R.sup.2.sub.nSiX.sub.3-n (III),
[0078] where the groups R.sup.1 and R.sup.2 are identical or
different, R.sup.1 is an alkenyl group having 2 to 18 carbon atoms,
an aryl, alkylaryl, an arylalkyl, an acylalkyl, an aminoalkyl, a
diaminoalkyl, a triaminoalkyl, an alkyloxyalkyl, an acylalkyl, a
cyanoalkyl, an isocyanoalkyl, a glycidyloxyalkyl, an acyloxyalky,
an acryloyloxyalkyl, a mercaptoalkyl, a polysulfide-alkyl or a
methacryloyloxyalkyl group, and R.sup.2 possesses the same
definition as listed for R.sup.1 or is a linear, branched or cyclic
alkyl group having 1 to 20 carbon atoms, preferably 1 to 16 carbon
atoms, which is unsubstituted or substituted, and
[0079] if desired, a monomeric and/or oligomeric silicic ester
which carries methoxy, ethoxy, n-propoxy or i-propoxy groups and
has an average degree of oligomerization of from 1 to 50, and
[0080] if desired, an organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom in the siloxane carries a functionality from the group
including alkyl, which is linear, branched or cyclic with 1 to 16
carbon atoms, fluoroalkyl, cyanoalkyl, isocyanoalkyl, alkenyl,
aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl, hydroxyalkyl,
acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl,
methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl and alkoxy,
preferably methoxy or ethoxy, and the remaining free valences of
the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, mixing the system and then adding at
least one nanoscale oxide and/or mixed oxide (KA--O) of at least
one metal or semimetal from main groups 2 to 6 or transition groups
1 to 8 of the Periodic Table of the Elements, or of the
lanthanides, with thorough mixing, in the course of which process
the alcohol formed by hydrolysis and/or condensation is removed
from the system.
[0081] Another preferred embodiment of the present invention
provides polymerizable organosilicon nanocapsules including a
nanoscale core A, which includes at least one oxide and/or. mixed
oxide (KA--O) of at least one metal or semimetal from main groups 2
to 6 or transition groups 1 to 8 of the Periodic Table of the
Elements, or of the lanthanides, and an organosilicon shell B,
wherein the organosilicon shell B includes at least one
organosilicon constituent of the general formula Ia
(Si'O--).sub.xSi--R (Ia),
[0082] in which R is a vinyl or allyl group and x is a number from
0 to 20, the remaining free valences of Si being satisfied by
SiO--, and/or --Z and the free valences of Si' being satisfied by
SiO--, --R and/or --Z, the groups Z being identical or different
and being hydroxyl and/or alkoxy radicals, and each Si and Si' of
the shell B carrying not more than one group R,
[0083] and/or wherein the organosilicon shell B is bonded to the
core A (KA--O) via one or more covalent linkages to give the
general formula Ib
(KA--O)--{(Si'O--).sub.xSi--R} (Ib)
[0084] in which R is a vinyl or allyl group and x is a number from
0 to 20, preferably from 1 to 15, with particular preference from 2
to 10, the remaining free valences of Si being satisfied by
(KA--O)--, SiO--, and/or --Z and the free valences of Si' being
satisfied by (KA--O)--, SiO--, --R and/or --Z, the groups Z being
identical or different and being hydroxyl and/or alkoxy radicals,
and each Si and Si' of the shell B carrying not more than one group
R.
[0085] In the compounds having the formula (Ia) and/or (Ib), the
range of 0 to 20 for x includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,
12, 13, 14, 15, 16, 17, 18, and 19.
[0086] Preferably, in the compounds of formulas (Ia) and/or (Ib),
the Si and Si' are tetravalent silicons.
[0087] Preferred alkoxy radicals of the groups Z are those with a
linear, cyclic or branched alkyl radical having 1 to 18 carbon
atoms, and particular preference is given to methoxy, ethoxy, i- or
n-propoxy groups.
[0088] Referring to the Periodic Table, of which the version
disclosed in The Merck Index, 11.sup.th ed., Merck & Co. 1989
is hereby incorporated in its entirety by reference, the term,
"main groups 2 to 6" refers to groups IIa, IIIa, IVa, Va and VIa,
respectively; and the term, "transition groups 1 to 8" refers to
groups Ib, IIb, IIIb, IVb, Vb, VIb, VIb and VIII, respectively; and
lanthanides refer to any of elements 57-71.
[0089] Thus, in the case of organosilicon nanocapsules of the
invention, the weight ratio between core A and shell B is
preferably from 1:1 to 4:1. This range includes all values and
subranges therebetween, including 1.5:1, 2:1, 2.5:1, 3:1, and
3.5:1.
[0090] The core A of the polymerizable organosilicon nanocapsules
of the invention preferably includes at least one oxide and/or
mixed oxide (KA--O), including oxide hydroxides, selected from the
group the elements Si, Al, Ti and/or Zr, for example, SiO.sub.2,
such as pyrogenically prepared silica, silicates, Al.sub.2O.sub.3,
aluminum hydroxide, alumosilicates, TiO.sub.2, titanates, ZrO.sub.2
or zirconates. Mixtures are possible.
[0091] Including the shell B, polymerizable organosilicon
nanocapsules of the invention preferably have an average diameter
of from 10 to 400 nm, with particular preference from 20 to 100 nm.
These ranges include 30, 40, 50, 60, 70, 80, 90, 200 and 300
nm.
[0092] Another preferred embodiment of the present invention
provides polymerizable organosilicon nanocapsules obtainable by
reacting
[0093] (i) at least one nanoscale oxide and/or mixed oxide (KA--O)
of at least one metal or semimetal from main groups two to six or
transition groups one to eight of the Periodic Table of the
Elements, or of the lanthanides, with
[0094] (ii) vinyltrialkoxysilane and/or allyltrialkoxysilane,
alkoxy being a methoxy, ethoxy, n-propoxy or i-propoxy group,
and
[0095] (iii) if desired, a monomeric and/or oligomeric silicic
ester which carries methoxy, ethoxy, or n- and/or i-propoxy groups
and has an average degree of oligomerization of from 1 to 50, for
example, tetramethoxysilane, tetraethoxysilane, such as
DYNASIL.RTM.A, tetrapropoxysilane, such as DYNASIL.RTM.P, or an
oligomeric ethyl silicate, such as DYNASIL.RTM.40, and
[0096] (iv) if desired, an organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom in the siloxane carries a functionality selected from
the group including alkyl, which is linear, branched or cyclic with
1 to 20 carbon atoms, fluoroalkyl, cyanoalkyl, iso-cyanoalkyl,
alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl,
hydroxyalkyl, acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl,
methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl and alkoxy,
preferably methoxy or ethoxy, and the remaining free valences of
the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, preference being given to those
siloxanes having an average degree of oligomerization of from 1 to
20, preferably having an average degree of oligomerization of from
2 to 10, as may be preferably found in the German patent
applications 199 55 047.6,
1 199 61 972.7, EP 0 518 057, EP 0 590 270, EP 0 716 127, EP 0 716
128, EP 0 760 372, EP 0 814 110, EP 0 832 911, EP 0 846 717, EP 0
846 716, EP 0 846 715, EP 0 953 591, EP 0 955 344, EP 0 960 921, EP
0 978 525, EP 0 930 342, EP 0 997 469, EP 1 031 593, and EP 0 075
697, (the entire contents of each of which being hereby
incorporated by reference)
[0097] and
[0098] (v) if desired, a further organofunctional silane of the
general formula II
R'.sub.sR".sub.rSiY.sub.(4-s-r) (II),
[0099] in which the groups R' and R" are identical or different and
are each a linear, branched or cyclic alkyl group having 1 to 20
carbon atoms, a chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl,
cyanoalkyl, fluoroalkyl or perfluoroalkyl, alkenyl, aryl,
acylalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, sulfane,
mercaptoalkyl, thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl,
diaminoalkyl, triaminoalkyl, carbonatoalkyl or ureidoalkyl group,
the respective alkylene groups containing 1 to 6 carbon atoms, R"
is preferably a methyl, Y is a methoxy, ethoxy, i-propoxy,
n-propoxy or 2-methoxyethoxy group, and s is 1 or 2 or 3 and r is 0
or 1 or 2, subject to the proviso (s+r).ltoreq.3,
[0100] in situ in a substantially liquid, curable synthetic resin
or a precursor of a synthetic resin.
[0101] Furthermore, an object of the present invention is a process
for the production of polymerizable silicon-organic nanocapsules as
well as for the production of a composition containing
polymerizable silicon-organic nanocapsules. The polymerizable
silicon-organic nanocapsules are particularly suitable in the
production, in situ, of a fluid, curable synthetic resin, or in a
precursor stage of a synthetic resin. The synthetic resin
composition which contains the polymerizable silicon-organic
nanocapsules can be used as a coating agent or as a paint or paint
base for the production of scratch-resistant coatings on a
substrate. The present invention also contemplates a substrate
coated with the synthetic resin.
[0102] Another preferred embodiment of the present invention
provides a process for preparing polymerizable organosilicon
nanocapsules, which includes reacting
[0103] (i) at least one nanoscale oxide and/or mixed oxide (KA--O)
and at least one metal or semimetal from main groups two to six or
transition groups one to eight of the Periodic Table of the
Elements, or of the lanthanides, with
[0104] (ii) vinyltrialkoxysilane and/or allyltrialkoxysilane,
alkoxy being a methoxy, ethoxy, n-propoxy or i-propoxy group,
and
[0105] (iii) if desired, a monomeric and/or oligomeric silicic
ester which carries methoxy, ethoxy, or n- and/or i-propoxy groups
and has an average degree of oligomerization of from 1 to 50,
preferably from 2 to 10, with particular preference from 3 to 5,
and
[0106] (iv) if desired, an organofunctional siloxane whose
functionalities are identical or different and in which each
silicon atom in the siloxane carries a functionality selected from
the group including alkyl, which is linear, branched or cyclic with
1 to 20 carbon atoms, fluoroalkyl, cyanoalkyl, isocyanoalkyl,
alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl,
hydroxyalkyl, acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl,
methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl and alkoxy,
preferably methoxy or ethoxy, and the remaining free valences of
the silicon atoms in the siloxane are satisfied by methoxy or
ethoxy or hydroxyl groups, and
[0107] (v) if desired, a further organofunctional silane of the
general formula II
R'.sub.sR".sub.rSiY.sub.(4-s-r) (II),
[0108] in which the groups R' and R" are identical or different and
are each a linear, branched or cyclic alkyl group having 1 to 20
carbon atoms, a chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl,
cyanoalkyl, fluoroalkyl or perfluoroalkyl, alkenyl, aryl,
acryloyloxyalkyl, methacryloyloxyalkyl, sulfane, mercaptoalkyl,
thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl, diaminoalkyl,
triaminoalkyl, carbonatoalkyl or ureidoalkyl group, the respective
alkylene groups containing 1 to 6 carbon atoms, R" is preferably a
methyl, Y is a methoxy, ethoxy, i-propoxy, n-propoxy or
2-methoxyethoxy group, and s is 1 or 2 or 3 and r is 0 or 1 or 2,
subject to the proviso (s+r).ltoreq.3,
[0109] in situ in a substantially liquid, curable synthetic resin
or a precursor of a synthetic resin.
[0110] The following compounds may be employed in particular, but
not exclusively, as organofunctional silanes as per (v):
methyltrimethoxysilane (DYNASYLAN.RTM. MTMS), methyl
triethoxysilane (DYNASYLAN.RTM. MTES), propyltrimethoxysilane
(DYNASYLAN.RTM. PTMO), propyltriethoxysilane (DYNASYLAN.RTM. PTEO),
i-butyltrimethoxysilane (DYNASYLAN.RTM. IBTMO),
i-butyltriethoxysilane (DYNASYLAN.RTM. IBTEO),
octyltrimethoxysilane (DYNASYLAN.RTM. OCTMO), octyltriethoxysilane
(DYNASYLAN.RTM. OCTEO), hexadecyltrimethoxysilane (DYNASYLAN.RTM.
9116), hexadecyltriethoxysilane (DYNASYLAN(.RTM. 9216),
3-chloropropyltrialkoxys- ilanes, 3-bromopropylalkoxysilanes,
3-iodopropylalkoxysilanes, 3-chloropropyltrichlorosilanes,
3-chloropropylmethyldialkoxy-silanes,
3-chloropropylmethyldichlorosilanes,
3-chloropropyldimethylalkoxysilanes,
3-chloropropyldimethylchlorosilanes,
3-aminopropylmethyldialkoxysilanes, 3-aminopropyltrialkoxysilane,
including 3-aminopropyltrimethoxysilane (DYNASYLAN.RTM. AMMO),
3-aminopropyltriethoxysilane (DYNASYLAN.RTM. AMEO),
N-(n-butyl)-3-aminopropyltrimethoxysilane (DYNASYLAN.RTM. 1189),
n-aminoethyl-3-aminopropylmethyldimethoxysilane (DYNASYLAN.RTM.
1411), 3-aminopropylmethyldiethoxysilane (DYNASYLAN.RTM. 1505),
N-aminoethyl-3-aminopropylmethyldialkoxysilane,
N-aminoethyl-3-aminopropy- ltrimethoxysilane (DYNASYLAN.RTM. DAMO),
triamino-functional propyltrimethoxysilane (DYNASYLAN.RTM. TRIAMO),
including
{N-aminoethyl-N'-(3-tri-alkoxysilylpropyl)}ethylenediamines and
also {N-aminoethyl-N-(3-trialkoxysilylpropyl)}ethylenediamines,
triamino-functional propylmethyldialkoxysilanes,
3-(4,5-dihydroimidazolyl- )propyltriethoxysilane (DYNASYLAN.RTM.
IMEO), 3-methacryloyloxypropylalkox- ysilanes,
3-methacryloyloxypropyltrimethoxysilane (DYNASYLAN.RTM. MEMO),
3-methacryloyloxyisobutyltrialkoxysilanes,
3-glycidyloxypropyltrialkoxysi- lanes,
3-glycidyloxypropyltrimethoxysilane (DYNASYLAN.RTM. GLYMO), 3
glycidyloxypropyltriethoxysilane (DYNASYLAN.RTM. GLYEO),
3-mercaptopropylalkoxysilanes, 3-mercaptopropyltrimethoxysilane
(DYNASYLAN.RTM. MTMO), vinyltrialkoxysilanes, including
vinyltrimethoxysilane (DYNASYLAN.RTM. VTMO), vinyltriethoxysilane
(DYNASIL.RTM.VTEO), vinyltris(2-methoxyethoxy)silane
(DYNASYLAN.RTM. VTMOEO), perfluoroalkyltrialkoxysilanes,
fluoroalkyltrialkoxysilanes, including
tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxy-
silane (DYNASYLAN.RTM. F 8261),
tridecafluorooctylmethyldialkoxysilanes, trimethylchlorosilane,
triethylchlorosilane, (H.sub.5CO).sub.3Si(CH.sub.2-
).sub.3--S.sub.4--(CH.sub.2).sub.3Si(OC.sub.2H.sub.5).sub.3 1,4-bis
(3-triethoxysilylpropyl) tetrasulfane (Si-69),
(H.sub.5C.sub.2O).sub.3Si (CH.sub.2).sub.3--NCS
3-thiacyamidopropyltriethoxysilane (Si-264),
(H.sub.5C.sub.2O).sub.3Si(CH.sub.2).sub.3--S.sub.2--(CH.sub.2).sub.3Si(OC-
.sub.2H.sub.5).sub.3 1,2-bis (3-triethoxysilylpropyl) disulfane
(Si-266), 3-cyanopropyltrialkoxysilanes, including
3-cyanopropyltrimethoxysilane, N,N',N"-tris(trimethoxysilylpropyl)
triisocyanurate,
3-{methoxy(polyethyleneglycidyl)}propyltrialkoxysilanes,
allyltrialkoxysilanes, allymethyldialkoxysilane,
allyldimethylakoxysilane- ,
3-methacryloyloxy-2-methylpropyltrialkoxysilanes,
3-amino-2-methylpropyltrialkoxysilanes,
(cyclohex-3-enyl)-ethyltrialkoxys- ilanes,
N-(3-trialkoxysilylpropyl)alkyl carbamates,
3-azidopropyltrialkoxysilanes,
4-(2-trialkoxysilylethyl)-1,2-epoxycyclohe- xanes,
bis(3-alkoxysilylpropyl)amines, tris(3-alkoxysilylpropyl)amines,
3-acryloyloxypropyl-trialkoxysilanes, including
3-acryloyloxymethyl-dialk- oxysilane,
3-acryloyloxydimethylalkoxysilane, with methoxy, ethoxy,
2-methoxyethoxy, propoxy or acetoxy advantageously standing for one
of the abovementioned alkoxy groups.
[0111] In the process of the invention, a preferable procedure
involves introducing the generally liquid components of the
prepolymer and heating them, adding a defined amount of water,
catalyst if desired, wetting agent if desired, and the
organosilicon components (ii) to (v), and subsequently introducing
the oxide component (i) with thorough mixing. Preferably, the
synthetic resin components, catalyst, wetting aids, water and the
organosilicon components, and further auxiliaries if desired, are
suitably first of all combined and mixed and only then is the oxide
component (KA--O) added, a component mixture obtained by this
preparation procedure being notable, inter alia and in particular,
for good processing properties.
[0112] In the process of the invention it is preferred to employ
from 0.1 to 60% by weight, more preferably from 15 to 50% by
weight, with particular preference from 20 to 45% by weight, with
very particular preference from 25 to 40% by weight, in particular
from 30 to 35% by weight, of nanoscale oxide and/or mixed oxide
(KA--O), based on the composition. These ranges include 1, 5, 10,
12, 22, 32, 42, 52 and 55% by weight.
[0113] In the process of the invention it is preferred to employ a
nanoscale oxide and/or mixed oxide (KA--O) having an average
particle diameter of from 1 to 100 nm, with particular preference
from 5 to 50 nm, and with very particular preference from 10 to 40
nm. These ranges include 2, 5, 15, 20, 25, 30, 45, 50, 60, 70, 80
and 90 nm. The oxides and/or mixed oxides may possess a BET surface
area of from 40 to 400 m.sup.2/g, preferably from 60 to 250
m.sup.2/g, with particular preference from 80 to 250 m.sup.2/g.
These ranges include 50, 70, 90, 100, 150, 175, 200, 300 and 350
m.sup.2/g. As nanoscale oxides or mixed oxides it is possible for
example--but not exclusively--to employ pyrogenic silica, which may
have been modified by further fractions of metal or semimetal, such
as aluminum, titanium, iron or zirconium.
[0114] It is further preferred to employ the oxide component (i)
and at least one silane-based component, especially (ii), (iii),
(iv) and/or (v), in a weight ratio of from 4:1 to 1: 1, with
particular preference from 3.5:1 to 1.5: 1, with very particular
preference from 3:1 to 2:1. These ranges include 3.25:1, 2.25:1,
and 1.25:1.
[0115] The preferable liquid and/or curable synthetic resin or
precursor of a liquid, curable synthetic resin, i.e., a prepolymer
or a mixture of prepolymers, used in the process of the invention
includes, for example, acrylates, methacrylates, epoxides, epoxy
resins, polyurethanes, polyurethane resins, unsaturated polyesters,
unsaturated polyester resins, epoxy acrylates, polyester acrylates,
urethane acrylates, silicone acrylates, polyfunctional monomeric
acrylates, such as trimethylolpropane triacrylate,
trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane
triacrylate, propoxylated trimethylolpropane triacrylate,
pentaerythritol triacrylate, ethoxylated pentaerythritol
tetraacrylate, alkoxylated tetraacrylates, ditrimethylolpropane
tetraacrylates, 3,4-epoxycyclohexyl-1-methyl
3,4-epoxycyclohexane-1'-carboxylate, 1,6-hexanediol diacrylate--to
name but a few examples--or mixtures of two or more of the
aforementioned synthetic resins and/or prepolymers, examples being
mixtures of monofunctional and/or bifunctional and/or
polyfunctional monomeric, optionally low-viscosity acrylates.
Mixtures are possible.
[0116] The reaction of the invention takes place in general in the
presence of a well-defined amount of water. For this purpose it is
preferred to employ from 1 to 6 mol of water per mole of Si of the
organosilicon components. This range includes 1.1, 1.5, 2, 2.5, 3,
3.5, 4, 4.5, 5 and 5.5 mol water.
[0117] The reaction of the invention is preferably conducted in the
presence of a catalyst. A particularly suitable catalyst is an
acid, preferably malefic anhydride, malefic acid, acidic acid,
acidic anhydride, glycolic acid, citric acid, methanesulfonic acid
or phosphoric acid. Mixtures are possible.
[0118] The use of a wetting agent may be helpful for the
implementation of the reaction of the invention. Accordingly, the
reaction is preferably conducted in the presence of sodium dodecyl
sulfate.
[0119] In the process of the invention, the reaction is preferably
conducted at a temperature in the range from 30 to 100.degree. C.,
more preferably at a temperature in the range from 50 to 80.degree.
C. This range includes 40, 45, 55, 60, 70, 75 and 90.degree. C.
[0120] Hydrolysis and condensation in the reaction of the invention
generally produces an alcohol, which is preferably removed from the
reaction system during the reaction and/or afterward. The removal
of the alcohol formed during the reaction may be carried out by
distillation, appropriately under reduced pressure. In general, the
amount of alcohol in the product mixture, i.e., in the composition
obtained by the reaction of the invention, is reduced to <2% by
weight, preferably to from 0.01 to 1% by weight, with particular
preference to from 0.1 to by weight, so as to give, advantageously,
a solvent-free composition, i.e., a solvent-free coating material
base or a solvent-free coating material.
[0121] Such compositions of the invention, directly or following
the addition of further coating components, may be used to
outstanding effect for the scratch-resistant coating of
substrates.
[0122] The present invention accordingly also provides a
composition based on a curable synthetic resin and including
polymerizable organosilicon nanocapsules of the invention or
prepared in accordance with the invention.
[0123] The present invention further provides a composition or a
coating material based on a curable synthetic resin and obtainable
as described herein.
[0124] Further components may appropriately be added to the
composition of the invention or to the coating material of the
invention, examples being initiators for the photochemical curing,
Darocur.RTM. 1173, Lucirin.RTM. TPO-L, coatings stabilizers, such
as HALS compounds, Tinuvins, and also antioxidants, such as
Irganox.RTM.. Additives of this kind are generally employed in
amounts of from 0.1 to 5% by weight, preferably from 2 to 3% by
weight, based on the formulation or coating material. The
introduction of further components into the coating system is
suitably accompanied by thorough mixing. Advantageously, despite a
large amount of polymerizable organosilicon nanocapsules, the
formulations and coating materials of the invention are preferably
notable for a comparatively low viscosity of from 500 to 1000 mPa
s. This range includes 600, 700, 800 and 900 mPa s. The behavior of
the systems is generally dilatent.
[0125] The liquid used in the process of the invention preferably
includes one or more selected from the group including alcohol,
methanol, ethanol, propanol, and/or the further components
discussed above and below.
[0126] Accordingly, the invention also provides for the use of a
composition of the invention as a coating material or as the basis
for the preparation of a coating composition or coating material,
especially for systems for scratch-resistant coating.
[0127] The application of the composition of the invention or of a
coating material of the invention generally takes place by
application to a substrate. For the coating of substrates it is
possible to use the customary coating techniques, such as roller
application, knifecoating, dipping, flow coating, pouring, spraying
or brushing, for example.
[0128] By way of example, the formulation of the invention or the
coating material may be applied uniformly to sheetlike substrates,
such as paper, metal foils or polymer films, using a roll
applicator, and then cured. The coating may suitably be cured at
ambient temperature, i.e., coating temperature, by means of a W or
electron beam process (EBC), which is environment-friendly since
there is no solvent.
[0129] For electron beam curing, it is preferred to generate
electrons having an energy of around 140 keV, the dose being from
30 to 60 kGy, preferably from 40 to 50 kGy. The residual .degree. 2
content is preferably <200 ppm. Photochemical curing is suitably
performed under inert gas: under nitrogen or argon, for
example.
[0130] Alternatively, the coating may be cured by means of W
irradiation, using monochromatic or polychromatic UV lamps with a
wavelength of from 150 to 400 nm. In the case of UV curing, as
well, it is possible to operate at ambient temperature, between 10
and 60.degree. C., for example. Here again, the O.sub.2 content is
suitably <200 ppm.
[0131] Accordingly, through the use of compositions and coating
materials of the invention, it is possible in a particularly
advantageous manner to produce coatings of outstanding scratch
resistance. Moreover, coatings of the invention also possess good
abrasion resistance. The determination of scratch hardness or
scratch resistance is carried out here, in general, in accordance
with DIN 53 799 using a hard metal ball. The abrasion can be
effected, for example, in accordance with DIN 52 347 using coated
faceplates.
[0132] The present invention accordingly likewise provides a
process for producing a scratch-resistant coating, which includes
applying a composition of the invention or a coating material of
the invention to a ground or substrate and subjecting it to
preferably photochemical curing. Alternatively, curing may be
effected by chemical means, oxidatively, for example, using, for
example, peroxide and an elevated temperature.
[0133] The present invention further provides scratch-resistant
coatings obtainable by applying a composition of the invention or a
coating material of the invention as described herein.
[0134] Coatings of the invention preferably have a thickness of
from 1 to 100 .mu.m, with particular preference from 2 to 40 .mu.m,
and with very particular preference from 5 to 15 .mu.m. These
ranges include 10, 20, 30, 50, 60, 70, 80 and 90 .mu.m.
[0135] Accordingly it is possible in a particularly simple and
economic way to furnish, for example, metals, such as aluminum,
iron, steel, brass, copper, silver, magnesium, nonferrous metal
alloys, wood, paper, board, textiles, stone products, plastics,
thermoplastics, polycarbonate, glass, and ceramic, with a
particularly scratch-resistant coating. The selection of the
substantially solid substrate materials for coating is
unrestricted. Such substrates may be furnished, for example, with a
protective coating, known as top coating, as is employed, for
example, as a clearcoat system in the automobile industry.
[0136] In particular it is possible by the present coating process
to obtain, simply and economically, articles endowed with scratch
resistance, such as decorative paper, aluminum foils, polycarbonate
auto glazing, PVC window frames, doors, worktops, to name but a
few.
[0137] Decorative paper of the invention, for example, is used for
a simultaneously cost-effective, scratch-resistant and optically
advantageous surface design of furniture.
[0138] Also provided by the present invention are articles having a
coating of the invention, obtainable as described herein. In
particular, the present invention provides a decorative paper
obtainable as described herein.
[0139] An especially preferred embodiment of the present invention
provides a polymerizable organosilicon nanocapsule, which
includes:
[0140] a nanoscale core A, which includes:
[0141] at least one oxide or mixed oxide, KA--O, of at least one
metal or semimetal selected selected from the group including an
element from main groups 2 to 6 of the Periodic Table, an element
from transition groups 1 to 8 of the Periodic Table, a lanthanide,
and mixtures thereof; and
[0142] an organosilicon shell B, which includes:
[0143] at least one organosilicon compound having the formula
(Ia):
(Si'O--).sub.xSi--R (Ia)
[0144] wherein R is a vinyl or allyl group;
[0145] wherein x is a number from 0 to 20;
[0146] wherein Si and Si' are each tetravalent silicons;
[0147] wherein remaining free valences of Si are each independently
SiO-- or --Z;
[0148] wherein remaining free valences of Si' are each
independently SiO--, --R, or --Z;
[0149] wherein the Z's are each independently hydroxyl or alkoxy
radicals;
[0150] and wherein each Si and Si' in the shell B have not more
than one R group attatched thereto;
[0151] and wherein said organosilicon compound of the shell B is
attached to said KA--O core A (KA--O) by one or more covalent
linkages having the formula Ib
(KA--O)--{(Si'O--).sub.xSi--R} (Ib)
[0152] wherein R is a vinyl or allyl group;
[0153] wherein x is a number from 0 to 20;
[0154] wherein the remaining free valences of Si are each
independently KA--O, SiO-- or --Z;
[0155] wherein the remaining free valences of Si' are each
independently KA--O, SiO--, --R, or --Z;
[0156] wherein the Z's are each independently hydroxyl or alkoxy
radicals;
[0157] and wherein each Si and Si' in the shell B have not more
than one R group attatched directly thereto.
EXAMPLES
[0158] Having generally described this invention, a further
understanding can be obtained by reference to certain specific
examples which are provided herein for purposes of illustration
only and are not intended to be limiting unless otherwise
specified.
[0159] Starting Materials:
2 Particle core A BET surface area Average (DIN 66 131; in Raw
Material particle size m.sup.2/g) Pyrogenic silica AEROSIL .RTM.
200 14 nm 200 .+-. 20 Shell B Raw material Vinyltrimethoxysilane
DYNASYLAN .RTM. VTMO Vinyltriethoxysilane DYNASYLAN .RTM. VTEO
3-Methacryloyloxypropyltrimethoxysilane DYNASYLAN .RTM. MEMO
Organic substrate/synthetic-resin component Ethoxylated
pentaerythritol tetraacrylate Sartomer .RTM. 494 Auxiliaries
Catalyst Maleic anhydride Wetting agent Sodium dodecyl sulfate
Reactant Water
Example 1
[0160] 18.0 parts by weight of AEROSIL 200/9.0 parts by weight of
DYNASYLAN VTMO/73.0 parts by weight of Sartomer 494:
[0161] 29.2 kg of Sartomer 494 (from Cray Valley) and 16 g of
4-hydroxyanisole are charged to a stirred vessel and heated to 65
to 70.degree. C. To the heated acrylate there are added a solution
of 0.15 kg of malefic anhydride and 0.072 kg of sodium dodecyl
sulfate in 1.44 kg of water, and also over the course of 30 minutes
3.6 kg of DYNASYLAN VTMO. Subsequently, within the temperature
range indicated above and with intensive stirring, 7.2 kg of
AEROSIL 200 are metered in over the course of 1 to 2 hours.
Stirring is continued for one hour at from 65 to 70.degree. C. and
methanol is removed from the system under reduced pressure.
Finally, the batch is cooled to room temperature.
Example 2
[0162] 18.0 parts by weight of AEROSIL 200/11.6 parts by weight of
DYNASYLAN VTEO/70.4 parts by weight of Sartomer 494:
[0163] 29.2 kg of Sartomer 494 (from Cray Valley) and 48 g of
4-hydroxyanisole are charged to a stirred vessel and heated to 65
to 70.degree. C. To the heated acrylate there are added a solution
of 0.15 kg of malefic anhydride and 0.075 kg of sodium dodecyl
sulfate in 1.5 kg of water, and also over the course of 30 minutes
4.81 kg of DYNASYLAN VTEO. Subsequently, within the temperature
range indicated above and with intensive stirring, 7.466 kg of
AEROSIL 200 are metered in over the course of 1 hour. Stirring is
continued for 3 hours at from 65 to 70.degree. C. and ethanol is
removed from the system under reduced pressure. Finally, the batch
is cooled to room temperature.
Example 3
[0164] 18.0 parts by weight of AEROSIL 200/9.0 parts by weight of
DYNASYLAN MEMO/73.0 parts by weight of Sartomer 494:
[0165] 29.2 kg of Sartomer 494 (from Cray Valley) and 16 g of
4-hydroxyanisole are charged to a stirred vessel and heated to 65
to 70.degree. C. To the heated acrylate there are added a solution
of 0.15 kg of malefic anhydride and 0.0262 kg of sodium dodecyl
sulfate in 0.5246 kg of water, and also over the course of 30
minutes 3.6 kg of DYNASYLAN MEMO. Subsequently, within the
temperature range indicated above and with intensive stirring, 7.2
kg of AEROSIL 200 are metered in over the course of 1 to 2 hours.
Stirring is continued for 60 minutes at from 65 to 70.degree. C.
and methanol is removed from the system under reduced pressure.
Finally, the batch is cooled to room temperature.
[0166] Use Examples
[0167] The coating materials of examples 1 to 3 are applied by hand
to square PVC plates (edge length 10 cm, thickness 2 mm) using a
coating bar with a gap height of 50 .mu.m and are cured in a
low-energy electron accelerator (140 keV) with a dose of 50 kGy.
The residual oxygen content in the accelerator was <200 ppm. The
same procedure is carried out using Sartomer 494 (comparative
example). The specimens are tested for their scratch hardness in
accordance with DIN 53 799 using a hard metal ball (diameter 1 mm).
The specimens are also tested for abrasion resistance in accordance
with DIN 52 347 and ASTM D-1044. The abrasion resistance was
determined by measuring the light scattering (haze) after 100 and,
respectively, 500 Taber revolutions (2 CS-10 abrasive wheels,
covered with 5-42 emery paper, F=5.5.+-.0.2 M, 3 individual
measurements, arithmetic mean). The results of the tests are
collated in Table 1.
3TABLE 1 Properties of the coating Ratio of resin: (evaluation)
SiO.sub.2:silane A: Scratch {parts by hardness {N} Examples
Formulation weight} B: Haze {%} (DS VTMO) 29.2 kg Sartomer 494
73.0:18.0:9.0 A: 9.0 N (very Example 1 7.2 kg Aerosil 200 good) 3.6
kg DS VTMO B: 2.9/6.4 Maleic anhydride (good) (DS VTEO) 29.2 kg
Sartomer 494 70.4:18.0:11.6 A: 8.5 N Example 2 7.466 kg Aerosil 200
(good) 4.82 kg DS VTEO B: 3.5/7.9 Maleic anhydride (still good) (DS
MEMO) 29.2 kg Sartomer 494 73.0:18.0:9.0 A: 8.5 N Example 3 7.2 kg
Aerosil 200 (good) 3.6 kg DS MEMO B: 4.1/8.6 Maleic anhydride
(worse than Ex. 1 and 2) (Sartomer 494 100% Sartomer 494 100 A: 6.0
N (poor) on PVC) B: 20.3/61.4 Comparative (very poor) Example PVC
substrate -- -- A: 4.0 N (very poor) B: 101.2/127.5 (very poor)
[0168] Obviously, numerous modifications and variations of the
present invention are possible in light of the above teachings. It
is therefore to be understood that within the scope of the appended
claims, the invention may be practiced otherwise than as
specifically described herein.
[0169] This application is based on German patent applications
10049632.6, filed Oct. 5, 2000, and 10100633.0, filed Jan. 9, 2001,
the entire contents of each of which are hereby incorporated by
reference, the same as if set forth at length.
* * * * *