Title: Aqueous, effect-producing coating material, method for the production thereof and use of the same
Abstract: An aqueous effect coating material comprising at least one water soluble or dispersible binder,
- at least one effect pigment, and
- a neutralized mixture of at least two fatty acids;
process for its preparation, and its use in automotive OEM finishing, automotive refinish, the interior and exterior coating of constructions, the coating of doors, windows and furniture, and also industrial coating, including coil coating, container coating, and the coating of electrical components.
Patent Number: 6,997,980 Issued on 02/14/2006 to Wegner, et al.
| Inventors:
|
Wegner; Egon (Veitshöchheim, DE);
Jansing; Frank (Tauberbischofsheim, DE)
|
| Assignee:
|
BASF Coatings AG (Munster, DE)
|
| Appl. No.:
|
433764 |
| Filed:
|
December 20, 2001 |
| PCT Filed:
|
December 20, 2001
|
| PCT NO:
|
PCT/EP01/15174
|
| 371 Date:
|
June 5, 2003
|
| 102(e) Date:
|
June 5, 2003
|
| PCT PUB.NO.:
|
WO02/053658 |
| PCT PUB. Date:
|
July 11, 2002 |
Foreign Application Priority Data
| Jan 04, 2001[DE] | 101 00 195 |
| Current U.S. Class: |
106/403; 106/404; 106/413; 106/415; 106/417; 523/171; 524/186; 524/236; 524/300; 524/322 |
| Current Intern'l Class: |
C09C 1/66 (20060101); C09C 1/62 (20060101); C09C 1/64 (20060101); C09D 5/29 (20060101) |
| Field of Search: |
523/171
524/186,236,300,322
106/403,404,413,415,417
|
References Cited [Referenced By]
U.S. Patent Documents
| 2522538 | Sep., 1950 | Rethwisch et al.
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| 4236934 | Dec., 1980 | Bell.
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| 4484951 | Nov., 1984 | Uchimura et al.
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| 4489135 | Dec., 1984 | Drexler et al.
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| 4522655 | Jun., 1985 | Claassen et al.
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| 4725317 | Feb., 1988 | Wheeler.
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| 4851460 | Jul., 1989 | Stranghöner et al.
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| 4880867 | Nov., 1989 | Göbel et al.
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| 4914148 | Apr., 1990 | Hille et al.
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| 4945128 | Jul., 1990 | Hille et al.
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| 5075372 | Dec., 1991 | Hille et al.
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| 5236995 | Aug., 1993 | Salatin et al.
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| 5334420 | Aug., 1994 | Hartung et al.
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| 5342882 | Aug., 1994 | Göbel et al.
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| 5368944 | Nov., 1994 | Hartung et al.
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| 5370910 | Dec., 1994 | Hille et al.
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| 5416136 | May., 1995 | Konzmann et al.
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| 5418264 | May., 1995 | Obloh et al.
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| 5552496 | Sep., 1996 | Vogt-Birnbrich et al.
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| 5569705 | Oct., 1996 | Vogt-Birnbrich et al.
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| 5571861 | Nov., 1996 | Klein et al.
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| 5654391 | Aug., 1997 | Göbel et al.
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| 5658617 | Aug., 1997 | Gobel et al.
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| 5691425 | Nov., 1997 | Klein et al.
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| 5760128 | Jun., 1998 | Baltus et al.
| |
| 5869198 | Feb., 1999 | Erne et al.
| |
| 5905132 | May., 1999 | Wegner et al.
| |
| 6001424 | Dec., 1999 | Lettmann et al.
| |
| 6001915 | Dec., 1999 | Schwarte et al.
| |
| 6221949 | Apr., 2001 | Gross et al.
| |
| 6372875 | Apr., 2002 | Mayer et al.
| |
| 6448326 | Sep., 2002 | Mayer et al.
| |
| Foreign Patent Documents |
| 2073115 | Jan., 1993 | CA.
| |
| 2102169 | May., 1994 | CA.
| |
| 2102170 | May., 1994 | CA.
| |
| 4110520 | Oct., 1992 | DE.
| |
| 0394737 | Sep., 1990 | EP.
| |
| 63234072 | Sep., 1988 | JP.
| |
Other References
JPO abstract for JP 63-234072 (Ishijima et al.).
Translation of JP 63-234072-A, Ishijima et al. (Sep. 29, 1988).
English Language Abstract for DE4328092.
English Language Abstract for EP0593454.
English Language Abstract for JP10-120936 (Dec. 5, 1998).
English Language Abstract for EP0297576.
English Language Abstract for DE 4005961.
|
Primary Examiner: Thexton; Matthew A.
Claims
What is claimed is:
1. An aqueous effect coating material comprising at least one water soluble or
dispersible binder,
at least one effect pigment, and
a neutralized mixture of at least two fatty acids selected from the group consisting
of fatty acids having 6 to 30 carbon atoms in the molecule, comprising from 1 to
6 percent by weight of the neutralized mixture of at least two fatty acids, based
on the weight of the effect pigment, wherein an excess of neutralizing agent is
employed for the neutralized mixture of at least two fatty acids and wherein the
neutralizing agent is selected from the group consisting of ammonia, trimethylamine,
triethylamine, tributylamine, amino alcohols, dibutylamine, dimethylaniline, diethylaniline,
triphenylamine, dimethylethanolamine, diethylethyanolamine, methyldiethanolamine,
2-aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine, triethanolamine,
and combinations thereof.
2. The coating material as claimed in claim 1, wherein the at least one effect
pigment comprises at least one metallic effect pigment.
3. The coating material as claimed in claim 1, wherein the at least one effect
pigment comprises at least one aluminum effect pigment.
4. The coating material as claimed in claim 3, wherein the at least one aluminum
effect pigment is selected from the group consisting of nonleafing pigments.
5. The coating material as claimed in claim 3, wherein the aluminum effect pigment
or pigments are selected from the group consisting of aluminum effect pigments
having a substantially circular form and aluminum effect pigments having a substantially
elongate form.
6. The coating material as claimed in claim 3, wherein the at least one aluminum
effect pigment is selected from the group consisting of leafing pigments.
7. The coating material as claimed in claim 1, wherein at least two fatty acids
selected from the group consisting of caproic acid, enanthic acid, caprylic acid,
pelargonic acid, capric acid, undecylic acid, lauric acid, myristic acid, palmitic
acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid, lignoceric
acid, cerotic acid, and melissic acid are used.
8. The coating material as claimed in claim 1, wherein the water soluble or dispersible
binder or binders are selected from the group consisting of polyurethanes, polyesters,
and polyurethane modified (meth)acrylate copolymers.
9. A process for preparing a coaxing material as claimed in claim 1, which comprises
(I) dispersing the effect pigment or pigments in a mixture comprising
at least one water miscible organic solvent,
at least one water soluble or dispersible binder, and
the neutralized mixture of at least two fatty acids;
(II) combining the resulting dispersion (I) with an aqueous solution or dispersion
of at least one water soluble or dispersible binder.
10. A method of coating with a coating material as claimed in claim 1 to a substrate
selected from the group consisting of automotive substrates, interior and exterior
constructions, doors, windows, furniture, industrial substrates, coil, containers,
and electrical components.
11. The coating material as claimed in claim 1, wherein the neutralized mixture
of at least two fatty acids comprises neutralized palmitic, stearic, and oleic acids.
Description
The present invention relates to a novel, aqueous, effect coating material, especially
a metallic aqueous basecoat material. The present invention further relates to
a process for preparing the novel aqueous effect coating material. The present
invention additionally relates to the use of the novel aqueous effect coating material
to produce single-coat or multicoat effect coating systems.
Aqueous effect coating materials, in particular metallic aqueous basecoat
materials, especially polyurethane-based metallic aqueous basecoat materials, are
known, for example, from the patent applications EP 0 089 497 A1, EP 0 256 540
A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003
A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708
788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP
0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP
0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1,
EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431
A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747,
EP 0 401 565 A1 and EP 0 817 684 column 5, lines 31 to 45. They are used in particular
to produce multicoat effect coating systems by the wet-on-wet technique, in which
the metallic aqueous basecoat material is applied to a substrate and the resulting
wet film is dried but not cured. The resulting basecoat film is then overcoated
with a clearcoat material, after which basecoat film and clearcoat film are cured
together. Alternatively, they may be used to produce solid-color topcoats.
The application and the curing of the aqueous effect coating materials may be
accompanied by the formation of what are known as clouds, i.e., areas of light/dark
shading. These are an indicator of deficiencies in dispersing and/or orienting
the effect pigments, especially metal effect pigments, in the finish. However,
it is precisely in the case of particularly high-value products having extensive
finishes, such as automobiles, for example, that cloudy finishes are fundamentally
unacceptable, since paint defects of this kind suggest low quality in the entire
product (e.g., the automobile).
Although it is known that the cloudiness may be reduced to a certain extent
by adding Aerosil pastes, talc pastes, white pastes or flatting pastes to the aqueous
effect coating materials, the addition of such pastes frequently has a deleterious
effect on the shade (shade shift) and on the metallic effect (reduction).
It is an object of the present invention to provide a novel aqueous effect coating
material from which the disadvantages of the prior art are now absent and which
instead gives single-coat and multicoat effect coating systems which exhibit light/dark
shading (clouds) either not at all or to a considerably reduced extent relative
to the prior art coating systems, and, moreover, leads to an improved metallic
effect and improves the gassing stability of the effect pigments. The novel aqueous
effect coating materials and the novel single-coat and multicoat effect coating
systems produced from them should otherwise continue to have the advantageous properties
profile of the known aqueous effect coating materials and of the single-coat and
multicoat effect coating systems produced from them, if not indeed exceeding said
profile. Moreover, the novel aqueous effect coating materials should be available
simply using customary and known starting materials with minimal material modification
to the known coating materials, so that they can be prepared, handled, applied
and cured in existing equipment.
A further object of the present invention was to find a novel process for preparing
aqueous effect coating materials which, with minimal modification of the known
processes for preparing such coating materials, provides novel aqueous effect coating
materials which are suitable for producing single-coat and multicoat effect coating
systems which are entirely or substantially cloud-free.
Accordingly, we have found the novel aqueous effect coating material,
comprising at least one water soluble or dispersible binder,
- at least one effect pigment, and
- a neutralized mixture of at least two fatty acids.
In the text below, the novel aqueous effect coating material is referred to as
the "coating material of the invention".
Additionally, we have found the novel process for preparing the coating
material of the invention, which involves
(I) dispersing the effect pigment or pigments in a mixture comprising
- at least one water miscible organic solvent,
- at least one water soluble or dispersible binder, and
- a neutralized mixture of at least two fatty acids; and then
(II) combining the resulting dispersion (I) with the aqueous solution or
dispersion of at least one water soluble or dispersible binder.
In the text below, the novel process for preparing the coating material of the
invention is referred to as the "process of the invention".
Further subject matter of the invention will emerge from the description.
The optical effects brought forth by the coating material of the invention are
preferably metallic effects and/or dichroic optical effects, but especially metallic
effects (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998,
page 176, "Effect pigments" and pages 380 and 381, "Metal oxide-mica pigments"
to "Metal pigments").
The coating material of the invention comprises at least one water soluble or
dispersible binder.
The binders may be curable physically, thermally, or thermally and with actinic
radiation. The latter is referred to by those in the art as dual cure.
In the context of the present invention, the term "physical curing" denotes the
curing of a layer of a coating material by film formation through loss of solvent
from the coating material, with linking within the coating taking place via looping
of the polymer molecules of the binders (regarding the term, cf. Römpp, op.
cit., pages 73 and 74, "Binders"). Alternatively, filming takes place by way of
the coalescence of binder particles (cf. Römpp, op. cit., pages 274 and 275,
"Curing"). Normally, no crosslinking agents are required for this purpose. If desired,
the physical curing may be assisted by atmospheric oxygen, by heat, or by exposure
to actinic radiation.
Where the binders are thermally curable, they may be thermally externally crosslinking
or self-crosslinking, especially externally crosslinking. In the context of the
present invention, the term "self-crosslinking" refers to the property of a binder
whereby it enters into crosslinking reactions with itself. A prerequisite for this
is that the binders already include both kinds of complementary reactive functional
groups that are necessary for thermal crosslinking, or reactive functional groups
which are able to react "with themselves". Externally crosslinking, on the other
hand, is the term used to refer to those binders in which one kind of complementary
reactive functional groups is present in the binder and the other kind in a curing
or crosslinking agent. For further details, reference is made to Römpp, op.
cit., "Curing", pages 274 to 276, especially page 275, bottom.
In the context of the present invention, actinic radiation is electromagnetic
radiation, such as near infrared (NIR), visible light, UV radiation or X-rays,
especially UV radiation, and corpuscular radiation such as electron beams.
The binders are oligomeric and polymeric resins. By oligomers are meant resins
containing at least 2 to 15 monomer units in the molecule. In the context of the
present invention, polymers are resins which contain at least 10 repeating monomer
units in the molecule. For further details of these terms, reference is made to
Römpp, op. cit., page 425, "Oligomers".
Examples of suitable binders are random, alternating and/or block, linear
and/or branched and/or comb addition (co)polymers of ethylenically unsaturated
monomers, or polyaddition resins and/or polycondensation resins. Regarding these
terms, reference is made for further details to Römpp, op. cit., page 457,
"Polyaddition" and "Polyaddition resins (polyadducts)", and also pages 463 and
464, "Polycondensates", "Polycondensation" and "Polycondensation resins", and also
pages 73 and 74, "Binders".
Examples of suitable addition (co)polymers are (meth)acrylate (co)polymers
or partially saponified polyvinyl esters, in particular (meth)acrylate copolymers,
especially polyurethane modified (meth)acrylate copolymers.
Examples of suitable polyaddition resins and/or polycondensation resins
are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers,
epoxy resins, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes,
polyether-polyurethanes or polyester-polyether-polyurethanes, especially polyesters
and polyurethanes.
The self-crosslinking thermally curable or dual-cure binders comprise reactive
functional groups which are able to enter into crosslinking reactions with groups
of their kind or with complementary reactive functional groups. The externally
crosslinking thermally curable or dual-curable binders comprise reactive functional
groups which are able to enter into crosslinking reactions with complementary reactive
functional groups which are present in crosslinking agents. Examples of suitable
complementary reactive functional groups for use in accordance with the invention
are compiled in the following overview. In the overview, the variable R stands
for an acyclic or cyclic aliphatic, an aromatic and/or an aromatic-aliphatic (araliphatic)
radical; the variables R′ and R" stand for identical or different aliphatic
radicals or are linked with one another to form an aliphatic or heteroaliphatic ring.
|
| Overview: Examples of complementary functional groups |
| Binder |
and crosslinking agent |
| |
or |
| Crosslinking agent |
and binder |
|
| —SH |
—C(O)—OH |
| —NH2 |
—C(O)—O—C(O) |
| —OH |
—NCO |
| —O—(CO)—NH—(CO)—NH2 |
—NH—C(O)—OR |
| —O—(CO)—NH2 |
—CH2—OH |
| >NH |
—CH2—O—R |
| |
—NH—CH2—O—R |
| |
—NH—CH2—OH |
| |
—N(—CH2—O—R)2 |
| |
—NH—C(O)—CH(—C(O)OR)2 |
| |
—NH—C(O)—CH(—C(O)OR)(—C(O)—R) |
| |
—NH—C(O)—NR′R′′ |
| |
>Si(OR)2 |
| |
| |
##STR1##
|
| |
| |
##STR2##
|
| |
| |
##STR3##
|
| |
| |
—C(O)—N(CH2—CH2—OH)2 |
|
The selection of the respective complementary groups is guided on the one hand
by the consideration that they must not enter into any unwanted reactions, in particular
no premature crosslinking, during the preparation, storage and application of the
coating materials of the invention, and/or, if appropriate, must not disrupt or
inhibit the curing with actinic radiation, and on the other by the temperature
range within which crosslinking is to take place.
In the case of the coating materials of the invention, it is preferred to employ
crosslinking temperatures from 60 to 180° C.
In this context, in the case of multicomponent systems, especially two-component
systems, in which the binders are stored separately from the crosslinking agents
until shortly before application, crosslinking temperatures of from 60 to 100°
C. are employed. It is preferred to employ binders containing thio, hydroxyl, primary
and secondary amino, and also imino groups, and crosslinking agents containing
free isocyanate groups.
In the case of the one-component systems, in which the binders are present with
the crosslinking agents, it is preferred to employ crosslinking temperatures above
100° C.
Use is therefore made preferably of binders containing thio, hydroxyl, N-methylolamino,
N-alkoxymethylamino, imino, carbamate, allophanate, epoxy or carboxyl groups, preferably
hydroxyl or epoxy groups, in particular epoxy groups, on the one hand and, preferably,
of crosslinking agents containing anhydride, carboxyl, epoxy, blocked isocyanate,
urethane, methylol, methylol ether, siloxane, carbonate, amino, hydroxyl and/or
beta-hydroxyalkylamide groups, preferably epoxy, hydroxyl, beta-hydroxyalkylamide,
unblocked isocyanate, urethane or alkoxymethylamino groups, on the other.
In the case of self-crosslinking binders, use is made in particular of methylol,
methylol ether and/or N-alkoxymethylamino groups.
The binders contain functional groups which render them dispersible in water
and/or soluble in water. These are alternatively
(f1) functional groups which can be converted into cations by neutralizing
agents and/or quaternizing agents, or
(f2) functional groups which can be converted into anions by neutralizing
agents, and/or anionic groups, and/or
(f3) nonionic hydrophilic groups, especially poly(alkylene ether) groups.
Examples of suitable functional groups (f1) which can be converted into
cations by neutralizing agents and/or quaternizing agents are primary, secondary
or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups,
especially tertiary amino groups or secondary sulfide groups.
Examples of suitable cationic groups (f1) are primary, secondary, tertiary
or quaternary ammonium groups, tertiary sulfonium groups or quaternary phosphonium
groups, preferably quaternary ammonium groups or tertiary sulfonium groups, but
especially tertiary sulfonium groups.
Examples of suitable functional groups (f2) which can be converted into
anions by neutralizing agents are carboxylic, sulfonic or phosphonic acid groups,
especially carboxylic acid groups.
Examples of suitable anionic groups (f2) are carboxylate, sulfonate or phosphonate
groups, especially carboxylate groups.
Examples of suitable neutralizing agents for functional groups (f1) convertible
into cations are inorganic and organic acids such as sulfuric acid, hydrochloric
acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic
acid or citric acid.
Examples of suitable neutralizing agents for functional groups (f2) convertible
into anions are ammonia, amines such as trimethylamine, triethylamine, tributylamine,
or amino alcohols, dibutylamine, dimethylaniline, diethylaniline, triphenylamine,
dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol,
dimethylisopropylamine, dimethylisopropanolamine or triethanolamine, for example.
Preferred neutralizing agents used are dimethylethanolamine, dibutylamine and/or triethylamine.
The complementary reactive functional groups described above may be incorporated
into the binders by the customary and known methods of polymer chemistry. This
can be done, for example, by incorporating monomers which carry the corresponding
reactive functional groups, and/or by means of polymer-analogous reactions.
Examples of suitable olefinically unsaturated monomers containing reactive
functional groups by means of which these groups may be introduced into the (meth)acrylate
copolymers are
(a1) monomers which carry per molecule at least one hydroxyl, amino, alkoxymethylamino,
carbamate, allophanate or imino group, such as
- hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha,beta-olefinically
unsaturated carboxylic acid which are derived from an alkylene glycol which is
esterified with the acid, or which are obtainable by reacting the alpha,beta-olefinically
unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene
oxide, especially hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic
acid, crotonic acid, maleic acid, fumaric acid or itaconic acid in which the hydroxyalkyl
group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate,
crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as
1,4-bis(hydroxymethyl)cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or
methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate,
monomaleate, monofumarate or monoitaconate; reaction products of cyclic esters,
such as epsilon-caprolactone, for example, and these hydroxyalkyl or hydroxycycloalkyl esters;
- olefinically unsaturated alcohols such as allyl alcohol;
- polyols such as trimethylolpropane monoallyl or diallyl ether or pentaerythritol
monoallyl, diallyl or triallyl ether;
- reaction products of acrylic acid and/or methacrylic acid with the glycidyl
ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per
molecule, especially a Versatic® acid, or, instead of the reaction product,
an equivalent amount of acrylic acid and/or methacrylic acid which subsequently,
during or after the polymerization reaction, is reacted with the glycidyl ester
of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule,
especially a Versatic® acid;
- aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate;
- N,N-di(methoxymethyl)aminoethyl acrylate or methacrylate or N,N-di(butoxymethyl)aminopropyl
acrylate or methacrylate;
- (meth)acrylamides such as (meth)acrylamide, N-methyl-, N-methylol-,
N,N-dimethylol-, N-methoxymethyl-, N,N-di(methoxymethyl)-, N-ethoxymethyl- and/or N,N-di(ethoxyethyl)-(meth)acrylamide;
- acryloyloxy- or methacryloyloxyethyl, -propyl or -butyl carbamate or
allophanate; further examples of suitable monomers containing carbamate groups
are described in the patents U.S. Pat. Nos. 3,479,328, 3,674,838, 4,126,747, 4,279,833
or 4,340,497;
(a2) monomers which carry per molecule at least one acid group, such as
- acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic
acid, fumaric acid or itaconic acid;
- olefinically unsaturated sulfonic or phosphonic acids or their partial esters;
- mono(meth)acryloyloxyethyl maleate, succinate or phthalate; or
- vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all
isomers) or vinylbenzenesulfonic acid (all isomers);
(a3) monomers containing epoxy groups, such as the glycidyl ester of acrylic
acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid
or itaconic acid, or allyl glycidyl ether.
Monomers of the type described above that are of relatively high functionality
are generally used in minor amounts. In the context of the present invention, minor
amounts of monomers of relatively high functionality are those amounts which do
not lead to crosslinking or gelling of the copolymers, especially the (meth)acrylate
copolymers, unless the specific intention is to prepare crosslinked polymeric microparticles.
Examples of suitable monomers for introducing reactive functional groups
into polyesters or polyester-polyurethanes are 2,2-dimethylolethyl- or -propylamine
blocked with a ketone, the resulting ketoxime group being hydrolyzed again after
the incorporation; or compounds containing two hydroxyl groups or two primary and/or
secondary amino groups and also at least one acid group, in particular at least
one carboxyl group and/or at least one sulfonic acid group, such as dihydroxypropionic
acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid,
2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic
acid, α,δ-diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic
acid or 2,4-diaminodiphenyl ether sulfonic acid.
One example of introducing reactive functional groups by way of polymer-analogous
reactions is the reaction of hydroxyl-containing resins with phosgene, resulting
in resins containing chloroformate groups, and the polymer-analogous reaction of
the chloroformate-functional resins with ammonia and/or primary and/or secondary
amines to give resins containing carbamate groups. Further examples of suitable
methods of this kind are known from the patents U.S. Pat. Nos. 4,758,632 A, 4,301,257
A or 2,979,514 A.
The dual-cure binders further comprise on average at least one, preferably at
least two, group(s) containing per molecule at least one bond which can be activated
with actinic radiation.
In the context of the present invention, a bond which can be activated with actinic
radiation is a bond which on exposure to actinic radiation becomes reactive and,
with other activated bonds of this kind, enters into polymerization reactions and/or
crosslinking reactions which proceed in accordance with free-radical and/or ionic
mechanisms. Examples of suitable bonds are carbon-hydrogen single bonds or carbon-carbon,
carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds
or double bonds. Of these, the carbon-carbon double bonds are particularly advantageous
and are therefore used with very particular preference in accordance with the invention.
For the sake of brevity, they are referred to below as "double bonds".
Accordingly, the group which is preferred in accordance with the invention
contains one double bond or two, three or four double bonds. If more than one double
bond is used, the double bonds may be conjugated. In accordance with the invention,
however, it is of advantage if the double bonds are present in isolation, in particular
each being present terminally, in the group in question. It is of particular advantage
in accordance with the invention to use two double bonds, or especially one double bond.
If on average per molecule more than one group which can be activated with actinic
radiation is employed, the groups are structurally different from one another or
are of the same structure.
If they are structurally different from one another, this means in the context
of the present invention that use is made of two, three, four or more, but especially
two, groups which can be activated with actinic radiation, which are derived from
two, three, four or more, but especially two, monomer classes.
Examples of suitable groups are (meth)acrylate, ethacrylate, crotonate,
cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl,
isopropenyl, allyl or butenyl groups; dicyclopentadienyl ether, norbornenyl ether,
isoprenyl ether, isopropenyl ether, allyl ether or butenyl ether groups; or dicyclopentadienyl
ester, norbornenyl ester, isoprenyl ester, isopropenyl ester, allyl ester or butenyl
ester groups, but especially acrylate groups.
Preferably, the groups are attached to the respective parent structures
of the binders via urethane, urea, allophanate, ester, ether and/or amide groups,
but in particular by ester groups. Normally, this occurs as a result of customary
and known polymer-analogous reactions such as, for instance, the reaction of lateral
glycidyl groups with the olefinically unsaturated monomers described above that
contain an acid group, of lateral hydroxyl groups with the halides of these monomers,
of hydroxyl groups with isocyanates containing double bonds such as vinyl isocyanate,
methacryloyl isocyanate and/or 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene
(TMI® from CYTEC), or of isocyanate groups with the hydroxyl-containing monomers
described above.
In the case of the polyurethanes and of the polyesters, the groups may be introduced
with the aid of compounds containing at least one, especially one, of the above-described
isocyanate-reactive or acid-reactive functional groups and at least one, especially
one, bond which can be activated with actinic radiation. Examples of suitable compounds
of this kind are
- 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl,
bis(hydroxy-methyl)cyclohexane, neopentyl glycol, diethylene glycol, dipropylene
glycol, dibutylene glycol or triethylene glycol acrylate, methacrylate, ethacrylate,
crotonate, cinnamate, vinyl ether, allyl ether, dicyclopentadienyl ether, norbornenyl
ether, isopropenyl ether, isopropenyl ether or butenyl ether;
- trimethylolpropane mono-, glycerol mono-,trimethylolethane mono-, pentaerythritol
mono-,homopentaerythritol mono-, pentaerythritol di-,homopentaerythritol di-, trimethylolpropane
di-, glycerol di-, trimethylolethane di-,pentaerythritol tri-, or homopentaerythritol
tri-acrylate, -methacrylate, -ethacrylate, -crotonate, -cinnamate, -vinyl ether,
-allyl ether, -dicyclopentadienyl ether, -norbornenyl ether, -isoprenyl ether,
-isopropenyl ether or -butenyl ether; or
- reaction products of cyclic esters, such as epsilon-caprolactone, for
example, and the hydroxyl-containing monomers described above; or
- 2-aminoethyl (meth)acrylate and/or 3-aminopropyl (meth)acrylate.
The binders described above are customary and known compounds and are described
in detail, for example, in the patent applications EP 0 089 497 A1, EP 0 256 540
A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003
A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708
788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP
0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP
0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1,
EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634 431
A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747,
EP 0 401 565 A1, EP 0 817 684 column 5 lines 31 to 45, DE 44 37 535 A1, page 7
line 8 to page 8 line 49, EP 0 787 195 A1, DE 40 05 961 A1, DE 41 10 520 A1, EP
0 752 455 B1, DE 198 55 455 B1, DE 199 488 121 A1, DE 198 469 171 A1, EP 0 788
523 B1 or WO 95/12626.
The amount of the binders described above and crosslinking agents described below
in the coating material of the invention may vary very widely. Based in each case
on the solids content of the coating material of the invention, the amount is preferably
from 10 to 90, more preferably from 15 to 80, with particular preference from 20
to 80, with very particular preference from 25 to 80, and in particular from 30
to 80% by weight.
Moreover, the coating material of the invention comprises at least one
effect pigment.
Examples of suitable effect pigments are metallic effect pigments such as
commercially customary aluminum bronzes, aluminum bronzes chromated in accordance
with DE 36 36 183 A1, and commercially customary stainless steel bronzes, and also
nonmetallic effect pigments, such as pearlescent pigments and interference pigments,
platelet-shaped effect pigments based on iron oxide with a shade from pink to brownish
red, liquid-crystalline effect pigments or fluorescent pigments (daylight fluorescent
pigments) such as bis(azomethine) pigments. For further details, reference is made
to Römpp, op. cit., page 176, "Effect pigments" and pages 380 and 381, "Metal
oxide-mica pigments" to "Metal pigments" and to the patent applications and patents
DE 36 36 156 A1, DE 37 18 446 A1, DE 37 19 804 A1, DE 39 30 601 A1, EP 0 068 311
A1, EP 0 264 843 A1, EP 0 265 820 A1, EP 0 283 852 A1, EP 0 293 746 A1, EP 0 417
567 A1, U.S. Pat. Nos. 4,828,826 A and 5,244,649 A.
Preference is given to the use of metallic effect pigments, especially
aluminum effect pigments (cf. Römpp, op. cit., pages 24 and 25, "Aluminum pigments").
The aluminum effect pigments are leafing pigments (cf. Römpp, op. cit.,
page 351, "Leafing pigments") or non-leafing pigments (cf. Römpp, op. cit.,
page 412, "Non-leafing pigments"). They are platelet-shaped and of substantially
circular form (silver dollar type) or of substantially elongate form (cornflake type).
The amount of effect pigment or effect pigments in the coating material of the
invention may vary very widely and is guided firstly by the hiding power of the
effect pigment and by the intensity of the target optical effect. Based on its
solids content, the coating material of the invention preferably contains from
0.1 to 50, more preferably from 0.5 to 40, with particular preference from 1 to
40, with very particular preference from 1.5 to 35, and in particular from 2 to
30% by weight of effect pigment or effect pigments.
The coating material of the invention further comprises a neutralized mixture
of at least two fatty acids. They are preferably selected from the group consisting
of fatty acids having 6 to 30 carbon atoms in the molecule. Examples of suitable
fatty acids are caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric
acid, undecylic acid, lauric acid, inyristic acid, palmitic acid, stearic acid,
oleic acid, elaidic acid, araclaidic acid, behenic acid, lignoceric acid, cerotic
acid, and melissic acid.
The neutralizing agent used comprises at least one base selected from the group
consisting of primary, secondary and tertiary, aromatic, aliphatic and cycloaliphatic
monoamines or polyamines, amino alcohols, and ammonia. Examples of suitable neutralizing
agents are those described above for functional groups (f2) which can be converted
into anions. They are preferably used in excess. It is preferred to use from 0.7
to 2, in particular from 1.1 to 1.5, equivalents of base per equivalent of acid.
The coating material of the invention preferably comprises the neutralized fatty
acid mixture in an amount, based on the effect pigment, of from 0.5 to 10, more
preferably from 0.8 to 8, with particular preference from 1 to 6, with very particular
preference from 1.2 to 5, and in particular from 1.4 to 4% by weight.
Moreover, the coating material of the invention may comprise customary
and known color pigments, electrically conductive or magnetically shielding pigments,
soluble dyes and/or fillers.
Examples of suitable inorganic color pigments are white pigments such as
titanium dioxide, zinc white, zinc sulfide or lithopones; black pigments such as
carbon black, iron manganese black or spinel black; chromatic pigments such as
chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green,
cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt violet
and manganese violet, red iron oxide, cadmium sulfoselenide, molybdate red or ultramarine
red; brown iron oxide, mixed brown, spinel phases and corundum phases or chrome
orange; or yellow iron oxide, nickel titanium yellow, chrome titanium yellow, cadmium
sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
Examples of suitable organic color pigments are monoazo pigments, disazo
pigments, anthraquinone pigments; benzimidazole pigments, quinacridone pigments,
quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone
pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo
pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine
pigments or aniline black.
For further details, reference is made to Römpp, op. cit., pages 180 and
181, "Iron blue pigments" to "Black iron oxide", pages 451 to 453, "Pigments" to
"Pigment volume concentration", page 563, "Thioindigo pigments", page 567, "Titanium
dioxide pigments", pages 400 and 467, "Naturally occurring pigments", page 459,
"Polycyclic pigments", page 52 "Azomethine pigments", "Azo pigments", and page
379, "Metal complex pigments".
Examples of suitable electrically conductive pigments are titanium dioxide/tin
oxide pigments.
Examples of suitable magnetically shielding pigments are pigments based
on iron oxides or chromium dioxide.
Suitable soluble organic dyes are lightfast organic dyes having little or
no tendency to migrate from the coating materials of the invention or from the
coatings produced from them. The migration tendency can be estimated by the skilled
worked on the basis of his or her general knowledge in the art and/or determined
with the aid of simple preliminary rangefinding experiments, as part of tinting
tests, for example.
Examples of suitable organic and inorganic fillers are chalk, calcium sulfates,
barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as
aluminum hydroxide or magnesium hydroxide, or organic fillers such as polymer powders,
especially those of polyamide or polyacrylonitrile. For further details, reference
is made to Römpp, op. cit., pages 250 ff, "Fillers".
It may be of advantage to use mixtures of platelet-shaped inorganic fillers such
as talc or mica and nonplatelet-shaped inorganic fillers such as chalk, dolomite,
calcium sulfates or barium sulfate, since by this means it is possible effectively
to set the viscosity and the rheology.
The pigments, dyes and fillers described above may be present in a finely divided,
nonhiding form.
The coating material of the invention may additionally comprise additives such
as water miscible organic solvents, water immiscible or sparingly miscible solvents,
nanoparticles, reactive diluents curable thermally or with actinic radiation, the
organic solvents described above which are miscible with water and/or only sparingly
miscible with water, UV absorbers, light stabilizers, free-radical scavengers,
thermolabile free-radical initiators, photoinitiators and photocoinitiators, crosslinking
agents, thermal crosslinking catalysts, devolatilizers, slip additives, polymerization
inhibitors, defoamers, emulsifiers, wetting agents, dispersants, adhesion promoters,
leveling agents, film forming auxiliaries, rheology control additives (thickeners),
flame retardants, siccatives, dryers, antiskinning agents, corrosion inhibitors,
waxes and/or flatting agents.
In the context of the present invention, water miscible organic solvents are
typical
paint solvents which are miscible in any proportion with water, such as ethylene
glycol, propylene glycol, butyl glycol and the methyl, ethyl or propyl ethers thereof,
ketones such as acetone or diacetone alcohol, cyclic ethers such as tetrahydrofuran
or dioxane, or amides such as N,N-dimethylformamide or N-methylpyrrolidone (cf.
Paints Coatings and Solvents, edited by Dieter Stoye and Werner Freitag, second
edition, Wiley-VCH, Weinheim and New York, 1998, pages 329 and 330).
The organic solvents which are immiscible with water or sparingly miscible with
water accommodate preferably less than 10, more preferably less than 9, and in
particular less than 8% by weight of water at 20° C., based on water and solvent.
Conversely, water accommodates preferably less than 6, more preferably less than
5, and in particular less than 4% by weight, at 20° C., based on water and
solvent. Examples of suitable organic solvents immiscible with water or sparingly
miscible with water are ketones such as methyl isobutyl ketone, diisobutyl ketone,
cyclohexanone or trimethylcyclohexanone, ethers as dibutyl ether, esters such as
isopropyl acetate, butyl acetate, ethyl glycol acetate or butyl glycol acetate,
or higher alcohols such as hexanol, cyclohexanol, trimethylcyclohexanol or 2-ethyl-1-hexanol
(isooctanol) (cf. Paints Coatings and Solvents, edited by Dieter Stoye and Werner
Freitag, second edition, Wiley-VCH, Weinheim and New York, 1998, pages 329 and 330).
Suitable nanoparticles are in particular those based on silicon dioxide,
aluminum oxide and zirconium oxide having a particle size <50 nm which have
no flatting effect. Examples of suitable nanoparticles based on silicon dioxide
are pyrogenic silicas, which are sold under the trade name Aerosil® VP8200,
VP721 or R972 by Degussa or under the trade name Cab 0 Sil® TS 610, CT 1110F.
or CT 1110G by CABOT. In general, these nanoparticles are sold in the form of dispersions
in monomers curable with actinic radiation, such as the reactive diluents described
below. Examples of suitable monomers which are especially suitable for the present
end use are alkoxylated pentaerythritol tetraacrylate or triacrylate, ditrimethylolpropane
tetraacrylate or triacrylate, dineopentyl glycol diacrylate, trimethylolpropane
triacrylate, trishydroxyethyl isocyanurate triacrylate, dipentaerythritol pentaacrylate
or hexaacrylate, or hexanediol diacrylate. In general, these dispersions contain
the nanoparticles in an amount, based in each case on the dispersions, of from
10 to 80% by weight, preferably from 15 to 70% by weight, with particular preference
from 20 to 60% by weight, and in particular from 25 to 50% by weight. An example
of an especially suitable dispersion of nanoparticles is the dispersion sold under
the trade name High Link® OG 103-31 by Clariant Hoechst.
Examples of suitable thermally curable reactive diluents are positionally
isomeric diethyloctanediols or hydroxyl-containing hyperbranched compounds or dendrimers,
as described for example in the German patent applications DE 198 05 421 A1, DE
198 09 643 A1 or DE 198 40 405 A1.
Examples of suitable reactive diluents curable with actinic radiation are
those described in Römpp, op. cit., on page 491 under the entry "Reactive
diluents" or in column 7 lines 1 to 26 of DE 198 18 715 A1, or reactive diluents
containing in the molecule at least 5, in particular 5, bonds which can be activated
with actinic radiation, such as dipentaerythritol pentaacrylate, for example.
Examples of suitable thermally labile free-radical initiators are organic
peroxides, organic azo compounds or C—C-cleaving initiators such as dialkyl
peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides,
ketone peroxides, azo dinitriles, or benzpinacol silyl ethers.
Examples of suitable crosslinking catalysts are dibutyltin dilaurate, dibutyltin
dioleate, lithium decanoate, zinc octoate or bismuth salts such as bismuth lactate
or bismuth dimethylolpropionate.
Examples of suitable photoinitiators and coinitiators are described in Römpp,
op. cit., pages 444 to 446.
Examples of suitable crosslinking agents, as are used in multicomponent
systems and are normally added subsequently to the coating material of the invention,
are polyisocyanates containing on average at least 2.0, preferably more than 2.0,
and in particular more than 3.0, isocyanate groups per molecule, such as
- diisocyanates such as isophorone diisocyanate (i.e., 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane),
5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane, 5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane,
5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethylcyclohexane, 1-isocyanato-2-(3-isocyanatoprop-1-yl)-cyclohexane,
1-isocyanato-2-(3-isocyanatoeth-1-yl)cyclohexane, 1-isocyanato-2-(4-isocyanatobut-1-yl)-cyclohexane,
1,2-di-isocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane,
1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,
1,4-diisocyanatocyclohexane, dicyclohexylmethane 2,4′-diisocyanate, trimethylene
diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene
diisocyanate (HDI), ethylethylene diisocyanate, trimethylhexane diisocyanate, heptamethylene
diisocyanate or diisocyanates derived from dimeric fatty acids, as sold under the
commercial designation DDI 1410 by the company Henkel and described in patents
WO 97/49745 and WO 97/49747, especially 2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentylcyclohexane,
or 1,2-, 1,4- or 1,3-bis(isocyanatomethyl)cyclohexane, 1,2-, 1,4- or 1,3-bis(2-isocyanatoeth-1-yl)cyclohexane,
1,3-bis(3-isocyanatoprop-1-yl)cyclohexane, 1,2-, 1,4- or 1,3-bis(4-isocyanatobut-1-yl)cyclohexane
or liquid bis(4-isocyanatocyclohexyl)methane with a trans/trans content of up to
30% by weight, preferably 25% by weight and in particular 20% by weight, as described
in patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 and DE 17
93 785 A1, preferably isophorone diisocyanate, 5-isocyanato-1-(2-isocyanatoeth-1-yl)-1,3,3-trimethylcyclohexane,
5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane, 5-isocyanato-(4-isocyanatobut-1-yl)-1,3,3-trimethylcyclohexane,
1-isocyanato-2-(3-isocyanatoprop-1-yl)cyclohexane, 1-isocyanato-2-(3-isocyanatoeth-1-yl)cyclohexane,
1-isocyanato-2-(4-isocyanatobut-1-yl)cyclohexane or HDI, especially HDI;
- polyisocyanates containing isocyanurate, biuret, allophanate, iminooxadiazinedione,
urethane, urea, carbodiimide and/or uretdione groups, which are prepared in a customary
and known manner from the diisocyanates described above; examples of suitable preparation
techniques and polyisocyanates are known, for example, from the patents CA 2,163,591
A, U.S. Pat. Nos. 4,419,513 A, 4,454,317 A, EP 0 646 608 A, U.S. Pat. No. 4,801,675
A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524
500 A1, EP 0 566 037 A1, U.S. Pat. Nos. 5,258,482 A, 5,290,902 A, EP 0 649 806
A1, DE 42 29 183 A1 and EP 0 531 820 A1; or
- dual-cure polyisocyanates, which are prepared from the above-described
polyisocyanates and the above-described compounds containing at least one, especially
one, of the above-described isocyanate-reactive or acid-reactive functional groups
and at least one, especially one, bond which can be activated with actinic radiation
(cf., e.g., the European patent application EP 0 928 800 A1).
Examples of suitable crosslinking agents as used in one-component systems
are amino resins, as described for example in Römpp, op. cit., page 29, "Amino
resins", in the textbook "Lackadditive" [Additives for Coatings] by Johan Bieleman,
Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., in the book "Paints, Coatings
and Solvents", second, completely revised edition, D. Stoye and W. Freitag (eds.),
Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., in the patents U.S. Pat. No.
4,710,542 A and EP 0 245 700 A1, and in the article by B. Singh and coworkers,
"Carbamylmethylate
