U.S. patent application number 09/933111 was filed with the patent office on 2001-12-27 for formulations.
Invention is credited to Hennenmann, Alfred, Kieser, Manfred.
Application Number | 20010056135 09/933111 |
Document ID | / |
Family ID | 6493005 |
Filed Date | 2001-12-27 |
United States Patent
Application |
20010056135 |
Kind Code |
A1 |
Kieser, Manfred ; et
al. |
December 27, 2001 |
Formulations
Abstract
The present invention relates to formulations which essentially
comprise a film-former or a casting resin and pearl luster pigments
which are coated with a silane of the formula I
SiR.sup.1R.sup.2R.sup.3R.sup.4 I.
Inventors: |
Kieser, Manfred; (Darmstadt,
DE) ; Hennenmann, Alfred; (Darmstadt, DE) |
Correspondence
Address: |
MILLEN, WHITE, ZELANO & BRANIGAN, P.C.
2200 CLARENDON BLVD.
SUITE 1400
ARLINGTON
VA
22201
US
|
Family ID: |
6493005 |
Appl. No.: |
09/933111 |
Filed: |
August 21, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09933111 |
Aug 21, 2001 |
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09597232 |
Jun 20, 2000 |
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09597232 |
Jun 20, 2000 |
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08275485 |
Jul 15, 1994 |
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Current U.S.
Class: |
523/171 ;
523/212; 524/449 |
Current CPC
Class: |
C09C 2200/408 20130101;
C09C 2200/407 20130101; C09C 3/12 20130101; C01P 2004/84 20130101;
C01P 2004/20 20130101; C09C 1/0015 20130101; C09D 5/36 20130101;
C01P 2004/82 20130101; C09C 1/0021 20130101; C01P 2006/22
20130101 |
Class at
Publication: |
523/171 ;
523/212; 524/449 |
International
Class: |
C09D 005/29; C08K
003/34; C08K 009/06 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 26, 1994 |
DE |
P 43 23 914 |
Claims
What is claimed is:
1. A formulation comprising a film-former or casting resin,
characterized in that it contains pearl lustre pigments which are
coated with one or more silanes of the formula I
SiR.sup.1R.sup.2R.sup.3R.sup.4 I in which R.sup.1 and/or R.sup.2
are alkyl having from 1-30 carbon atoms, in which one or two
non-adjacent CH.sub.2 groups may also be replaced by --CH.dbd.CH--,
--O--, --CO--, --COO-- or --OCO--, and the remaining radicals
R.sup.1-4 independently of one another are halogen or alkoxy having
from 1-20 carbon atoms, in which one or two non-adjacent CH.sub.2
groups may also be replaced by --CH.dbd.CH--, --O--, --CO--,
--COO-- or --OCO--.
2. A formulation according to claim 1, characterized in that the
silane is a compound of the formula IA
(C.sub.nH.sub.2n+1)Si(OC.sub.mH.sub.2m+1).su- b.3, IA in which m is
1-10 and n is 1-30.
3. A formulation according to claim 1, characterized in that the
content of pearl lustre pigment in the formulation is from 0.3-15%
by weight.
4. A formulation according to claim 1, characterized in that the
film-former is a powder coating.
5. A formulation according to claim 1, characterized in that the
film-former is a high-solids or a radiation-curing film-former.
6. A formulation according to claim 1, characterized in that the
pearl lustre pigment is a mica or silicate flake coated with one or
more metal oxides.
7. A formulation according to claim 6, characterized in that the
pearl lustre pigment is a mica flake coated with titanium
dioxide.
8. A substrate coated with a film-former or casting resin according
to claim 1.
9. A formulation according to claim 5, wherein the film-former is a
polyester-TGIC powder coating.
10. A formulation according to claim 1, wherein the film-former or
casting resin is a coating compound.
Description
FORMULATIONS
[0001] The present invention relates to formulations which
essentially comprise a film-former or casting resin and a silanized
pearl lustre pigment.
[0002] In the case of metal effect pigments, in terms of their
applications characteristics, there are various types of pigments,
namely the so-called leafing and non-leafing types.
[0003] Leafing refers to the floating or accumulation and the
orientation of pigments at the surface of a coating substance or of
a coating. Under the effect of the interfacial tension between
pigment and coating composition, the lamellar pigment particles
move to the surface of the coating composition where they come
together to form a continuous film. The visual impression given is
of a closed metallic surface of high reflectivity with a
silvery-bright metallic gleam. The phenomenon of leafing has
previously only been observed for metal effect pigments.
[0004] In the case of pearl lustre pigments based on mica, the only
pigments known so far are those with non-leafing properties; in
other words, pearl lustre pigments exhibit, in virtually all those
areas in which they are used, a non-leafing behaviour, i.e. a good
compatibility with the medium surrounding them: the individual
pigment particles are completely wetted and distributed in the
medium in which they are embedded.
[0005] However, in some areas of application, in particular those
in which the orientation of pearl lustre pigments is incomplete,
such as film-formers, powder coatings and casting resins, a leafing
behaviour is very often desirable.
[0006] The object was therefore to discover formulations which
contain pearl lustre pigment and in which a leafing effect is
observed.
[0007] It has now been found that, surprisingly, pearl lustre
pigments which have been coated with a silane, with the aim of
achieving improved compatibility, exhibit a pronounced leafing
behaviour in film-formers and casting resins. In the formulation,
leafing leads to a significantly improved orientation of the
pigments at the surface, resulting in an increased pearl
lustre.
[0008] The invention therefore relates to formulations essentially
comprising a film-former or casting resin, characterized in that
they contain pearl lustre pigments which are coated with one or
more silanes of the formula I
SiR.sup.1R.sup.2R.sup.3R.sup.4 I
[0009] in which
[0010] R.sup.1 and/or R.sup.2 are alkyl having from 1-30 carbon
atoms, in which one or two non-adjacent CH.sub.2 groups may also be
replaced by --CH.dbd.CH--, --O--, --CO--, --COO-- or --OCO--, and
the remaining radicals R.sup.1-4 independently of one another are
halogen or alkoxy having from 1-20 carbon atoms, in which one or
two non-adjacent CH.sub.2 groups may also be replaced by
--CH.dbd.CH--, --O--, --CO--, --COO-- or --OCO--.
[0011] Pigments coated with a silane of the formula I are already
known from EP 0,492,223. The pigments it describes are used for
inhibiting yellowing in plastics.
[0012] This document, however, does not describe the combination of
silanized pearl lustre pigment and film-former or casting resin for
achieving a leafing effect.
[0013] An essential constituent of the formulation according to the
invention is the silanized pearl lustre pigment. All conventional
pearl lustre pigments can be used as the base pigment, for example
mica or silicate flakes coated with coloured or colourless metal
oxides such as TiO.sub.2, Fe.sub.2O.sub.3, SnO.sub.2,
Cr.sub.2O.sub.3, ZnO and other metal oxides, alone or as a mixture
in a single layer or in successive layers. These pigments are known
from, for example, the German Patents and Patent Applications 14 57
468, 19 59 998, 20 09 566, 22 14 545, 22 15 191, 22 44 298, 23 13
331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51
355, 32 11 602 and 32 35 017 and are commercially available, for
example under the tradename Iriodin.RTM. from E. Merck,
Darmstadt.
[0014] The silanization of the pearl lustre pigments is carried out
as described in EP 0,492,223. The silanized pearl lustre pigments
preferably used are pigments, in particular TiO.sub.2-coated mica
pigments, which are coated with a silane or silane mixture of the
formula I SiR.sup.1R.sup.2R.sup.3R.sup.4, in which the radicals
R.sup.1-4 have the following meanings:
[0015] R.sup.1 and/or R.sup.2 are alkyl having from 1-30 carbon
atoms, and in particular 10-30 carbon atoms, in which one or two
non-adjacent CH.sub.2 groups may also be replaced by --CH.dbd.CH--
and/or --O--. Particular preference is given to decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, nonadecyl, eicosanyl, heneicosanyl, docosanyl,
tricosanyl, tetracosanyl, pentacosanyl, hexacosanyl, heptacosanyl,
octacosanyl, nonacosanyl, triacontanyl, 12,12-dimethyltetradecyl,
11-propyl-12-butylpentadecyl and
8,8-dimethyl-12-propyl-13-propylhexadecyl radicals.
[0016] the remaining radicals R.sup.1-4 are halogen or alkoxy
having from 1-20 carbon atoms, in particular 1-10 carbon atoms, in
which one or two non-adjacent CH.sub.2 groups may also be replaced
by --CH.dbd.CH--, --O--, --CO--, --COO-- or --OCO--. Particular
preference is given to fluoro, chloro, methoxy, ethoxy, propoxy,
butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy or
decyloxy radicals.
[0017] The pearl lustre pigments which are particularly preferably
used are coated with a silane or silane mixture of the formula
IA
(C.sub.nH.sub.2n+1)Si(OC.sub.mH.sub.2m+1).sub.3 IA
[0018] in which n is 1-30 and
[0019] m is 1-10. The silane mixture preferably consists of two or
three silanes of formula I or IA.
[0020] All conventional casting resins, for example gel coats, and
film-forming systems are suitable for the formulation according to
the invention. The term film-forming system should be understood
here as meaning all solvent-containing or else solvent-free binder
systems with which it is possible, by physical or chemical methods,
for example drying at room temperature or at elevated temperatures
of up to about 200.degree. C., polymerization and/or crosslinking
induced by chemical means or by radiation, for example UV
radiation, and other conventional treatment methods, to form smooth
and readily adhering films. It is preferred to use high-solids
film-formers, UV- and electron beam-curing film-formers and, in
particular, powder coatings.
[0021] The production of the formulation is simple and easy to
manage. The silanized pearl lustre pigment is stirred, with or
without the addition of solvent, into the film-former or into the
casting resin and mixed intensively (for example with a modified
dissolver). The formulation is then applied (for example by
brushing, dipping, spraying or electrostatically) to the substrate
material to be coated, so that the substrate surface is fully
covered with a homogeneous film. Finally the coating is fully cured
under the conventional conditions. Due to the leafing effect a
coating of pronounced pearl lustre is obtained in which the pearl
lustre pigment is accumulated at the surface.
[0022] The leafing effect, that is the floating of the pearl lustre
pigments at the surface of the film-former or the casting resin,
and the leafing stability--a leafing effect which is unchanged over
a prolonged period in the formulation--depend on the film-forming
system and on the casting resin used.
[0023] The degree of pigmentation, the viscosity and the curing
characteristics of the film-former or casting resin may also
influence the leafing effect.
[0024] For a good leafing effect, the pigmented formulation should
not contain more than 15% by weight of pearl lustre pigments. The
pigment content is preferably between 0.3-10% and is in particular
from 1-5%, based in each case on the binder or resin.
[0025] Over the silanized pigments it is also possible to apply, as
a top coat, one or more clearcoats, for example an aqueous coating
or powder coating, to improve the surface quality; the aim of this
as a rule is to achieve a further improvement in both the
appearance and the durability of the overall finish. The
transparent final coat, however, is not absolutely necessary.
[0026] The formulations according to the invention can be applied
to any desired substrate materials, for example metals such as
iron, steel, aluminium, copper, bronze, brass and metal foils, or
else metal-coated surfaces of glass, ceramic and concrete, and also
to wood, for example furniture, or clay, paper, packaging
materials, for example plastic containers, or films, boards or
other materials for decorative and/or protective purposes. The
finishes obtained in every case, due to the leafing effect, are
highly lustrous and of enhanced reflectivity. Furthermore, due to
the compact platelet structure of the individual pigment particles
at the surface, a good mechanical and chemical resistance is
achieved.
[0027] Without further elaboration, it is believed that one skilled
in the art can, using the preceding description, utilize the
present invention to its fullest extent. The following preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not limitative of the remainder of the disclosure
in any way whatsoever.
[0028] In the foregoing and in the following examples, all
temperatures are set forth uncorrected in degrees Celsius and
unless otherwise indicated, all parts and percentages are by
weight.
[0029] The entire disclosures of all applications, patents and
publications, cited above and below, and of corresponding
application(s) German P 43 23 914.5, filed Jul. 16, 1993, are
hereby incorporated by reference.
[0030] The following examples are intended to illustrate the
invention, but without limiting it.
EXAMPLE 1
[0031] I. Pigment Preparation
[0032] 1st step
[0033] 3 g of n-hexadecyltriethoxysilane (Si 116 from Degussa AG,
Frankfurt, FRG) are stirred with 3 g of H.sub.2O and 50 g of
ethanol for 0.5 h at room temperature
[0034] 2nd step
[0035] 150 g of Iriodin 103 (TiO.sub.2-coated mica flakes with a
particle size of 10-60 .mu.m from E. Merck, Darmstadt, FRG) are
placed in a suitable mixer (for example a modified dissolver). The
prehydrolysed silane solution (Si 116 solution) is added to the
pigment, which is being agitated. Over a period of 1 h, the wetted
pigment is heated with stirring to 100.degree. C.
[0036] Finally the coated pearl lustre pigment is dried for 3 h at
150.degree. C.
[0037] II. Comparison of Applications Properties of Leafing and
Non-leafing Pigments in a Powder Coating
[0038] a) Untreated Pearl Lustre Pigment (Non-leafing Type)
[0039] 5 g of Iriodin 103 are mixed intensively with 95 g of
polyester-TGIC powder coating (Teodur 00013 clear, Herberts,
Wuppertal, FRG) under dry conditions.
[0040] Application is carried out electrostatically onto an
aluminium panel. Curing is carried out under the conditions
conventional for a powder coating for 20 min at 200.degree. C. The
pearl lustre finish obtained does not exhibit leafing. The pigment
is uniformly distributed in the matrix.
[0041] b) Silanized Pearl Lustre Pigment (Leafing Type)
[0042] In analogy to IIa) 5 g of the TiO.sub.2 mica pigment
obtained under I. are mixed intensively with 95 g of a
polyester-TGIC powder coating under dry conditions.
[0043] Application is carried out electrostatically onto an
aluminium panel. Curing of the powder coating is carried out as for
the untreated pigment, for 20 min at 200.degree. C.
[0044] A highly lustrous finish is obtained in which the pigment
has floated to the surface. The pigment has accumulated at the
surface of the matrix (leafing behaviour).
EXAMPLE 2
[0045] I. Pigment Preparation
[0046] Pigment preparation is carried out in analogy to Example 1
but employing, instead of Iriodin 103, Iriodin 119
(TiO.sub.2-coated mica flakes with a particle size of 5-25
.mu.m).
[0047] II. Comparison of Applications Properties of Leafing and
Non-leafing Pigments in Unsaturated Polyester Resin
[0048] a) Untreated Pearl Lustre Pigment (Non-leafing Type)
[0049] 0.5 g of Iriodin 119 is stirred with 50 g of Palatal K 700
(BASF, Ludwigshafen, FRG) and with 0.2 g of Accelatator NL 49 S
(Akzo Chemicals, Duren, FRG) for 15 min. 1.0 g of Cyclonox 11 (Akzo
Chemicals, DUren, FRG) is then added and the mixture is stirred for
a further 1 min. The mixture is then divided. Using a doctor knife,
the first portion is applied to glass at a layer thickness of 1 mm.
The second portion is applied to glass using a brush.
[0050] Result:
[0051] Both samples exhibit a non-uniform distribution. In the case
of application by brush, the brush strokes are visible. In the case
of application with the doctor knife, "Bnard cells" are visible. A
faint pearl lustre can be observed.
[0052] b) Silanized Pearl Lustre Pigment (Leafing Type)
[0053] In analogy to the experiment carried out above, the pearl
lustre pigment silanized in I (Iriodin 119 with silane
aftertreatment) is used. The experimental conditions are otherwise
unchanged.
[0054] Result:
[0055] Both samples exhibit a uniform layer of pearl lustre
pigments at the surface. Neither brush strokes nor "Bnard cells"
are visible. The pearl lustre is very good.
EXAMPLE 3
[0056] I. Pigment Preparation
[0057] Analogous to Example 2, but methyltriethoxysilane (ABCR,
Karlsruhe) is employed instead of n-hexadecyltriethoxysilane.
[0058] II. Comparison of Applications Properties of Leafing and
Non-leafing Pigments in a UV-curing Clearcoat
[0059] a) Untreated Pearl Lustre Pigment (Non-leafing Type)
[0060] 0.5 g of Iriodin 119 is stirred with 50 g of UV clear coat
(Jger, Dusseldorf, FRG) for 15 min. The mixture is then divided.
Using a doctor knife, the first portion is applied to glass at a
layer thickness of 250 .mu.m. The second portion is applied to
glass using a brush. After a waiting time of one minute, both
samples are cured using a 300 watt UV lamp.
[0061] Result:
[0062] Both samples exhibit a non-uniform distribution. In the case
of application by brush, the brush strokes are visible. In the case
of application with the doctor knife, "Bnard cells" are visible.
Only a faint pearl lustre is evident.
[0063] b) Silanized Pearl Lustre Pigment (Leafing Type)
[0064] In analogy to the experiment carried out above, silanized
pearl lustre pigment (Iriodin 119 with silane aftertreatment) is
used. Prior to exposure (curing), a waiting time of 1 min is
allowed to achieve a leafing effect. The experimental conditions
are otherwise retained.
[0065] Result:
[0066] Both samples exhibit a uniform and highly lustrous layer of
pearl lustre pigments at the surface. Neither brush strokes nor
"Bnard cells" were visible. The pearl lustre is very good.
[0067] The preceding examples can be repeated with similar success
by substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in the
preceding examples.
[0068] From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this invention,
and without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *