European Patent Specification C08K 5/3492, C08K 5/3445,: C07D 251/64, C07D 251/18, C07D 487/04

Europäisches Patentamt
(19) European Patent Office *EP000851893B1*

Office européen des brevets (11) EP 0 851 893 B1
(12) EUROPEAN PATENT SPECIFICATION
(45) Date of publication and mention (51) Int Cl.7: C08K 5/3492, C08K 5/3445,
of the grant of the patent: C07D 251/64, C07D 251/18,
05.07.2000 Bulletin 2000/27
C07D 487/04
(21) Application number: 96931620.7
(86) International application number:
PCT/US96/14918
(22) Date of filing: 17.09.1996
(87) International publication number:
WO 97/11119 (27.03.1997 Gazette 1997/14)
(54) FORMALDEHYDE-FREE CROSSLINKERS

FORMALDEHYDFREIE VERNETZER
AGENTS RETICULANTS EXEMPTS DE FORMALDEHYDE
(84) Designated Contracting States: • LAWLESS, Barry, A.

AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL Milford, CT 06460 (US)
PT SE • LEES, Robert, G.
Stamford, CT 06902 (US)
(30) Priority: 20.09.1995 US 4055
(74) Representative:
(43) Date of publication of application: Diehl, Hermann, Dr. Dipl.-Phys. et al
08.07.1998 Bulletin 1998/28 DIEHL, GLÄSER, HILTL & PARTNER
Patentanwälte
(73) Proprietor: Cytec Technology Corp. Augustenstrasse 46
Wilmington, Delaware 19801 (US) 80333 München (DE)
(72) Inventors: (56) References cited:

• ZHAO, Hong EP-A- 0 698 627 WO-A-96/17879
Stamford, CT 06902 (US)
EP 0 851 893 B1
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).
Printed by Jouve, 75001 PARIS (FR)

EP 0 851 893 B1
Description
BACKGROUND OF THE INVENTION
5 Field of the invention
[0001] This invention relates to the N-1,2,2-trihydrocarbyloxyethyl derivatives of certain amino compounds, methods
for preparing such derivatives, and compositions containing such derivatives. These derivatives and compositions are
particularly suitable for use as crosslinking agents in curable compositions such as coatings, and do not release for-
10 maldehyde as a volatile by-product when cured.
Description of Related Art
[0002] Various derivatives of amino compounds, such as amino-1,3,5-triazines and glycolurils, are described in the
15 literature for use in a wide variety of fields. Certain of these derivatives, such as the partially or fully alkoxymethylated
derivatives of melamine, guanamines and glycoluril, are useful as crosslinkers in curable compositions which contain
resins having active hydrogen groups. See, for example, US4064191, US4081426, US4101520, US4118437,
US4129681, US4243705, US4271277, US4276212, US4330458, US4374164, US4433143, US4425466, US4873298,
US5155201 and US5256713.
20 [0003] While these alkoxymethylated derivatives provide excellent results in a number of aspects, they also have
the disadvantage of releasing formaldehyde as a volatile by-product under curing conditions. Despite the excellent
films which can be achieved with these systems, the coatings industry is under pressure to reduce the environmentally
undesirable emission of formaldehyde. As a result, it has long been a desire of industry to find acceptable alternative
crosslinkers which do not emit formaldehyde upon cure.
25 [0004] One such non-formaldehyde emitting alternative is the class of isocyanate and carbamate functional 1,3,5-tri-
azine crosslinking agents disclosed in commonly owned US4939213, US5084541, US5288865, EP-A-0604922 (cor-
responding to United States Application Serial No. 07/998,313, filed December 29, 1992), EP-A-0624577 (correspond-
ing to United States Application Serial No. 08/061,905, filed May 14, 1993), EP-A-0649842 (corresponding to United
States Application Serial No. 08/138,581, filed October 15, 1993), W095/30663 (corresponding to United States Ap-
30 plication Serial No. 08/239,009, filed May 6, 1994), WO96/04258 (corresponding to United States Application Serial
No. 08/286,835, filed August 5,1994), WO96/11915 (corresponding to United States Application Serial No. 08/324,549,
filed October 18, 1994) and WO96/15185 (corresponding to United States Application Serial No. 08/340,950, filed
November 16, 1994). Other non-formaldehyde emitting alternatives include, for example, the class of lactam substituted
1,3,5-triazine crosslinking agents disclosed in commonly owned WO93/10117 (corresponding to United States Appli-
35 cation Serial No. 07/973,676, filed November 9, 1992), and the class of acetal and enamine functional 1,3,5-triazine
crosslinking agents disclosed in commonly owned WO96/XXXXX (corresponding to United States Application Serial
No. 08/408,323, filed March 21, 1995). WO 96/17879 discloses a resin composition useful as a binder comprising the
reaction product of an amine derivative chosen from melamine, glycolurile or their mixtures with a C1 to C8 dialkox-
yethanal. The reaction mixture is then mixed, preferably reacted with a polyol having 2 or more hydroxyl groups.
40 [0005] The aforementioned have been found to be particularly useful as crosslinkers in coating compositions based
on active hydrogen and/or epoxy groups containing resins, with the cured coatings possessing a wide range of desirable
properties.
[0006] While some of these alternatives have shown great promise, the search continues for replacements for tra-
ditional amino derivative crosslinkers, which replacements retain many of the desirable properties of the traditional
45 crosslinkers but which emit little or no formaldehyde on cure.
SUMMARY OF THE INVENTION
[0007] We have now discovered a new class of amino compound derivatives prepared without formaldehyde, which
50 is capable of functioning as a highly compatible crosslinking agent for the wide variety of functional materials useable
in traditional amine-formaldehyde crosslinked systems. Curable systems (such as coatings) can be formulated with
these new amino compound derivatives to have no formaldehyde release on cure, with the resulting crosslinked articles
(such as crosslinked films) possessing physical and appearance characteristics comparable to crosslinked articles
derived from curable systems based on traditional amine-formaldehyde crosslinkers.
55 [0008] In its overall concept, the present invention is an N-1,2,2-trihydrocarbyloxyethyl derivative of an amino com-
pound, comprising the reaction product of:
(i) an amino compound having at least two =NH groups, selected from the group consisting of amino-1,3,5-triazines,
2
EP 0 851 893 B1
glycolurils and oligomers thereof,

(ii) a 2,2-dihydrocarbyloxy ethanal, and
(iii) a hydrocarbylol, excluding polyols having two or more hydroxyl groups, the reaction product containing, on
average, at least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least
5 about 2.0 1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
[0009] The present invention also includes a process of preparing such N-1,2,2-trihydrocarbyloxyethyl derivative of
an amino compound, comprising the steps of reacting (i), (ii) and (iii) under conditions so as to result in a derivative
containing, on average, at least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound,
10 and at least about 2.0 1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
[0010] Depending on the types and proportions of starting components and other reaction conditions as described
in further detail below, the derivatives in accordance with the present invention may comprise substantially a single
species of monomeric compound, or may comprise a complex mixture of monomeric and oligomeric compounds. The
monomeric compounds also form a specific part of the present invention, and can generally be described as compounds
15 comprising an amino core having pendant therefrom at least two 1,2,2-trihydrocarbyloxyethyl groups, of the following
general formula (I) or (II):
20
25
30
35
40 wherein
R1 is selected from H, a hydrocarbyl and -N(R2)(R3);

each R2 is independently selected from H and a hydrocarbyl;
each R3 is independently selected from H, a hydrocarbyl and an R group;
45 each R4 is independently selected from H and a hydrocarbyl; and
each R group is independently a group of the general formula (III)
50
wherein
55
each R5 is independently selected from H and a hydrocarbyl, and
each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge;
3
EP 0 851 893 B1
with the proviso that, per molecule, at least two of the R3 groups are independently an R group, and at least two R5
groups are independently a hydrocarbyl.
[0011] In any event, the aforementioned compounds and derivatives must contain, on average, at least about 2.0
1,2,2-trihydrocarbyloxyethyl groups (e.g., a group of the formula (III), wherein R5 is a hydrocarbyl group) per molecule,
5 which makes these compositions particularly suitable for use as crosslinking agents in a variety of end applications.
The present invention, consequently, also relates to curable compositions comprising (a) a crosslinker component
comprising the compounds and/or compositions in accordance with the present invention, and (b) a resin component
comprising a compound containing at least two groups capable of reacting with the 1,2,2-trihydrocarbyloxyethyl groups
of (a).
10 [0012] Without wishing to be bound by any particular theory, it is believed that the derivatives in accordance with the
present invention are primarily reactive via the activated ether of the 1,2,2-trihydrocarbyloxyethyl group (e.g., the hy-
drocarbyloxy in the 1 position). It has been surprisingly found that, without the presence of sufficient such activated
ether functionality, good curing results cannot be obtained. Groups capable of reacting with 1,2,2-trihydrocarbyloxyethyl
groups are, therefore, groups capable of reacting with activated ether groups within the meaning of the present inven-
15 tion, which are the same types of groups that are reactive with the alkoxymethyl and methylol functionality of traditional
amine-formaldehyde crosslinkers.
[0013] A particularly advantageous such use of the curable compositions of the present invention is in the form of a
coating composition. The present invention, therefore, also relates to curable coating compositions, methods for coating
substrates as well as the substrates coated therewith, crosslinked films or objects derived from the curable composition,
20 and various other end uses thereof.
[0014] As indicated above, the compounds and compositions of the present invention are prepared without using
formaldehyde and therefore are formaldehyde-free. Curable compositions employing these compounds and compo-
sitions as crosslinkers can also be formulated as formaldehyde free systems. Other advantages include rapid cure,
adaptability to waterbome coatings systems, and ability to produce fully cured coatings which have excellent appear-
25 ance and film and resistance properties.
[0015] These and other features and advantages of the present invention shall be more readily understood by those
of ordinary skill in the art from a reading of the following detailed description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

30
N-1,2,2-Trihydrocarbyloxyethyl Derivatives
[0016] As indicated above, the present invention is broadly an N-1,2,2-trihydrocarbyloxyethyl derivative of an amino
compound, comprising the reaction product of:
35
(i) an amino compound having at least two =NH groups, selected from the group consisting of amino-1,3,5-triazines,
glycolurils and oligomers thereof,
(ii) a 2,2-dihydrocarbyloxy ethanal, and
(iii) a hydrocarbylol, excluding polyols having two or more hydroxyl groups the reaction product containing, on
40 average, at least about 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and
at least about 2.0 1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
[0017] It should be noted that the term "hydrocarbyl," within the context of the present invention, is a group which
contains carbon and hydrogen atoms and includes, for example, alkyl, aryl, aralkyl, alkenyl and substituted derivatives
45 thereof.
[0018] Preferred as amino compounds are amino-1,3,5-triazines and glycolurils of the general formulas (IV) and (V):
50
55
4
EP 0 851 893 B1
10
15
20
25
wherein
R1 is selected from H, a hydrocarbyl and -N(R7)2,

each R7 is independently selected from H and a hydrocarbyl, with the proviso that at least two groups R7 are H, and
30 preferably that all R7 groups are H, and
preferably that all R4 groups are H.
[0019] As specific examples of preferred amino compounds of the general formula (IV) (wherein all R7 groups are
35 H) may be mentioned the guanamines, wherein R1 is selected from H and a hydrocarbyl; more preferably H, an alkyl
of 1 to 20 carbons atoms, an aryl of 6 to 20 carbon atoms and an aralkyl of 7 to 20 carbon atoms; and particularly a
phenyl group (benzoguanamine), a methyl group (acetoguanamine) and a cyclohexyl group (cyclohexylcarboguan-
amine).
[0020] Another specific example of a preferred amino compound of the general formula (IV) (wherein all R7 groups
40 are H) is melamine, wherein R1 is -N(R7)2.
[0021] The preferred amino compound of the general formula (V) (wherein all R4 and R7 groups are H) is glycoluril.
[0022] Preferred for the 2,2-dihydrocarbyloxy ethanal are compounds of the general formula (VI):
45
50
wherein
each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge.
55 Such 2,2-dihydrocarbyloxy ethanals and methods for their preparation are disclosed in US4835320. Preferred are
those wherein each R6 is independently an alkyl of 1 to 8 carbon atoms or an alkenyl of 1 to 8 carbon atoms, as well
as those wherein both R6 groups together form an alkylene bridge of 1 to 8 carbon atoms. Particularly preferred are
those wherein each R6 is independently an alkyl of 1 to 8 carbon atoms, and those wherein both R6 groups together
5
EP 0 851 893 B1
form an alkylene bridge of 1 to 4 carbon atoms. Specifically preferred examples include 2,2-dimethoxy ethanal, 2,2-di-
ethoxy ethanal, 2-methoxy-2-ethoxy ethanal, 2,2-dipropoxy ethanal, 2,2-dibutoxy ethanal, 2,2-dipentoxy ethanal,
2,2-dihexoxy ethanal, 2,2-dicyclohexoxy ethanal, 2,2-ethylenedioxy ethanal and 2,2-propylenedioxy ethanal. Most pre-
ferred are 2,2-dimethoxy ethanal and 2,2-dibutoxy ethanal, and particularly 2,2-dimethoxy ethanal (DME).
5 [0023] Preferred for the hydrocarbylol are hydroxy group-containing compounds having from 1 to 20 carbon atoms
such as, for example, alkylols, alkenols, phenols and alkoxyalkylols and excluding polyols having two or more hydroxyl
groups.
[0024] As specific preferred examples thereof may be mentioned methanol, ethanol, propanols, butanols, ethylhex-
anols, allyl alcohol and phenol. Especially preferred are the alkylols of 1-8 carbon atoms, particularly methanol and
10 butanols.
[0025] As indicated above, the derivatives in accordance with the present invention contain, on average, at least
about 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least about 2.0
1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
[0026] The guanamine derivatives preferably contain on average from about 1.5 to about 2.0 moles of combined
15 2,2-dihydrocarbyloxy ethanal per mole of guanamine. A specific preferred embodiment is a substantially monomeric
guanamine derivative which contains about 2.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of guan-
amine. Such a substantially monomeric guanamine derivative is depicted by the general formula (I), wherein:
R1 is selected from H and a hydrocarbyl,

20 preferably selected from H, an alkyl of 1 to 20 carbons atoms, an aryl of 6 to 20 carbon atoms and an aralkyl of
7 to 20 carbon atoms, and
especially selected from a phenyl group, a methyl group and a cyclohexyl group;
each R2 is selected from H and a hydrocarbyl, and

25 preferably H;
each R3 is a group of the formula (III);
each R5 is independently a hydrocarbyl,
preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls
and alkoxyalkylyls, and
30 especially independently an alkyl of 1 to 8 carbon atoms; and
each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge,
preferably independently selected from an alkyl of 1 to 8 carbon atoms and an alkenyl of 1 to 8 carbon
atoms, or together form an alkylene bridge of 1 to 8 carbon atoms, and
especially independently an alkyl of 1 to 8 carbon atoms, or together form an alkylene bridge of 1 to
35 4 carbon atoms.
[0027] The melamine derivatives preferably contain on average from about 2.0 to about 3.0 moles and, more pref-
erably, from about 2.3 to about 3.0 moles, of combined 2,2-dihydrocarbyloxy ethanal per mole of melamine. A specific
preferred embodiment is a substantially monomeric melamine derivative which contains about 3.0 moles of combined
40 2,2-dihydrocarbyloxy ethanal per mole of melamine. Such a substantially monomeric melamine derivative is depicted
by the general formula (I), wherein:
R1 is -N(R2)(R3);
each R2 is selected from H and a hydrocarbyl, and
45 preferably H;
each R3 is a group of the formula (III);
at least two of the R5 groups, and preferably each of the R5 groups, are independently a hydrocarbyl,
preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls and
alkoxyalkylyls, and
50 especially independently an alkyl of 1 to 8 carbon atoms; and
atoms, or together form an alkylene bridge of 1 to 8 carbon atoms, and
especially independently an alkyl of 1 to 8 carbon atoms, or together form an alkylene bridge of 1 to 4 carbon
55 atoms.
[0028] The glycoluril derivatives preferably contain on average from about 2.0 to about 4.0 moles and, more prefer-
ably, from about 3.0 to about 4.0 moles, of combined 2,2-dihydrocarbyloxy ethanal per mole of glycoluril. A specific
6
EP 0 851 893 B1
preferred embodiment is a substantially monomeric glycoluril derivative which contains about 4.0 moles of combined
2,2-dihydrocarbyloxy ethanal per mole of glycoluril. Such a substantially monomeric glycoluril derivative is depicted by
the general formula (II), wherein:
5 each R3 is a group of the formula (III);

preferably H;
at least two of the R5 groups, preferably at least three of the R5 groups, and especially each of the R5 groups,
are independently a hydrocarbyl,
10 preferably independently a hydrocarbyl of 1 to 20 carbon atoms selected from alkyls, alkenyls, phenyls and
alkoxyalkylyls, and
especially independently an alkyl of 1 to 8 carbon atoms; and
15 atoms, or together form an alkylene bridge of 1 to 8 carbon atoms, and
especially independently an alkyl of 1 to 8 carbon atoms, or together form an alkylene bridge of 1 to 4 carbon
atoms.
Processes for Preparing the Derivatives

20
[0029] The N-1,2,2-trihydrocarbyloxyethyl derivatives described above may be prepared in accordance with the
present invention by reacting (i), (ii) and (iii) under conditions sufficient to produce a derivative having, on average, at
least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of amino compound, and at least about 2.0
1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
25 [0030] In one specific embodiment of the present process, (i) and (ii) are contacted in a first step in the presence of
a basic catalyst to produce a 1-hydroxy-2,2-dihydrocarbyloxyethyl derivative intermediate, which in a subsequent step
is reacted with (iii) (e.g., alkylated) under acidic conditions (preferably in the presence of an acid catalyst). The first
step is typically conducted in an aqueous medium, at temperatures generally ranging from ambient to about 120°C.
Upon completion of the first step, the intermediate is isolated and added to an organic solvent for the second step.
30 Advantageously, an excess of the hydrocarbylol (iii) may be used as the organic solvent. The reaction of the intermediate
from the first step and (iii) is typically carried out under conditions and with acid catalysts similar to those involved in
an alkylating step for traditional amine-formaldehyde resins, which conditions and catalysts are well-known to those
of ordinary skill in the art.
[0031] In a second specific embodiment of the present process, (i), (ii) and (iii) are concurrently contacted in the
35 presence of an acid catalyst to directly result in the 1,2,2-trihydrocarbyloxy derivative. As with the second step above,
this reaction is typically carried out under conditions and with acid catalysts similar to those involved in an alkylating
step for traditional amine-formaldehyde resins, which conditions and catalysts are well-known to those of ordinary skill
in the art.
40 Curable Compositions
[0032] As described generally above, the curable compositions in accordance with the present invention comprise:
(a) a crosslinker component comprising an N-1,2,2-trihydrocarbyloxyethyl derivative as described above, and

45 (b) a resin component comprising a compound containing at least two groups capable of reacting with the 1,2,2-tri-
hydrocarbyloxyethyl groups of (a).
[0033] In addition to the N-1,2,2-trihydrocarbyloxyethyl derivative crosslinker described in detail above, the crosslink-
er component may optionally comprise a variety of additional ingredients. For example, the crosslinker component
50 may optionally contain other crosslinking agents, referred to herein as "co-crosslinkers," which include, particularly,
active-hydrogen and epoxy reactive crosslinking agents such as, for example, traditional amine-formaldehyde resins,
blocked and/or unblocked polyfunctional isocyanates, and isocyanate and carbamate functional 1,3,5-triazine car-
bamate crosslinkers.
[0034] As suitable amine-formaldehyde resins may be mentioned the partially or substantially fully methylolated,
55 partially or substantially fully etherified amino compounds based on melamine, guanamines, glycolurils and urea. In
general, such amine-formaldehyde resins are well known to those of ordinary skill in the art (see, for example, the
numerous previously incorporated references) and are generally available commercially. Most commonly, they include
melamines, guanamines such as benzo-, aceto- and cyclohexylcarbo-guanamines, glycolurils and ureas, as well as
7
EP 0 851 893 B1
the at least partially N-alkylolated and N-alkoxyalkylated derivatives thereof, and oligomers thereof.
[0035] As specific examples of commercially available amino resins of the type described above may be mentioned
those sold under the trademarks CYMEL® and BEETLE® of Cytec Industries, Inc. (West Paterson, New Jersey).
[0036] Polyisocyanate crosslinking agents, including blocked forms thereof, are generally well known in the art and
5 have been extensively used in coating compositions in a monomeric, oligomeric and/or polymeric form, and preferably
contain at least two reactive isocyanate groups. As specific examples of such may be mentioned hexamethylene di-
isocyanate; 2,2,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; meta-a,a,a',a'-te-
tramethylxylylenediisocyanate (commercially available under the trade designation m-TMXDI® aliphatic isocyanate
from Cytec Industries Inc., West Paterson, New Jersey); para-α,α,α',α'-tetramethylxylylenediisocyanate (available un-
10 der the trade designation p-TMXDI® aliphatic isocyanate from Cytec Industries Inc., West Paterson, New Jersey);
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, abbreviated as IPDI); bis
(4-isocyanatocyclohexyl)methane (hydrogenated MDI): biuret derivatives of various diisocyanates including, for exam-
ple, hexamethylene diisocyanate (commercially available under the trade designation Desmodur® N of Miles Inc.,
Pittsburgh, Pennsylvania); uretdione derivatives of various diisocyanates including, for example, hexamethylene di-
15 isocyanate and IPDI; isocyanurate derivatives of various diisocyanates including, for example, hexamethylene diiso-
cyanate (commercially available under the trade designation Desmodur® N 3390 of Miles Inc., Pittsburgh, Pennsylva-
nia) and IPDI (commercially available under the trade designation IPDI® T 1890 polyisocyanate of Huls America, Inc.,
Piscataway, N.J.); and urethane adducts of diisocyanates with polyols such as, for example, ethylene glycol, propylene
glycol, neopentyl glycol, trimethylolpropane, pentaerythritol and the like, as well as oligomeric and polymeric polyols,
20 for example, the 3:1 meta-α,α,α',α'-tetramethylxylylenediisocyanate/trimethylolpropane adduct (commercially availa-
ble under the trade designation CYTHANE® 3160 aliphatic polyisocyanate of Cytec Industries Inc., West Paterson,
New Jersey), and the 3:1 IPDI/trimethylolpropane adduct (commercially available under the trade designation SPEN-
LITE® P 25-A4-60 aliphatic urethane prepolymer of Reichhold Chemicals, Research Triangle Park, North Carolina).
[0037] The polyisocyanates may be blocked in a well-known manner with, for example, lower alkyl alcohols and
25 oximes.
[0038] As suitable isocyanate and carbamate functional 1,3,5-triazine carbamate crosslinkers may be mentioned
those having on average at least two isocyanate and/or carbamate groups attached to one or more 1,3,5-triazine cores.
In general, these 1,3,5-triazine compounds are also well known to those of ordinary skill in the art, as exemplified by
the numerous references previously incorporated above.
30 [0039] Suitable for use as the resin component are compounds containing at least two groups capable of reacting
with the 1,2,2-trihydrocarbyloxyethyl groups of (a) such as, for example, active hydrogen and/or epoxy groups, which
are generally the same types of materials suitable for use in traditional amine-formaldehyde resin crosslinked systems.
[0040] Preferred are the polyfunctional active hydrogen group containing compound. Active hydrogen-containing
functionality, as utilized herein, refers to functional groups which contain active hydrogens as is generally well-known
35 to those of ordinary skill in the art and includes, most commonly, hydroxyl, carboxyl and amino groups. When utilized
herein, hydroxyl is preferred.
[0041] Suitable such polyfunctional hydroxy group containing materials are again generally well known to those
skilled in the art, and contain at least two and preferably more than two hydroxy groups. Reference may be had to
previously incorporated US4939213, US5084541, US5288865, EP-A-0604922 (corresponding to United States Appli-
40 cation Serial No. 07/998,313, filed December 29, 1992), EP-A-0624577 (corresponding to United States Application
Serial No. 08/061,905 filed May 14, 1993), EP-A-0649842 (corresponding to United States Application Serial No.
08/138,581, filed October15, 1993), W095/30663 (corresponding to United States Application Serial No. 08/239,009,
filed May 6, 1994), W096/04258 (corresponding to United States Application Serial No. 08/286,835, filed August 5,
1994), WO96/11915 (corresponding to United States Application Serial No. 08/324,549, filed October 18, 1994) and
45 WO96/15185 (corresponding to United States Application Serial No. 08/340,950, filed November 16, 1994) for further
details.
[0042] As examples of preferred polyfunctional hydroxy group containing materials may be mentioned acrylic or
polyester backbone resins. Illustrative examples include acrylic resins which may be obtained by the copolymerization
of acrylic or methacrylic esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or
50 methacrylate, optionally with simultaneous use of additional vinyl compounds such as, for example, styrene. Illustrative
examples of the polyfunctional hydroxy group containing materials also include polyester resins which may be obtained,
for example, by the reaction of polycarboxylic acids with excess quantities of polyhydric alcohols. Other suitable poly-
functional hydroxy group containing resins include polyurethane prepolymers, alkyds, as well as hydroxy group con-
taining epoxy prepolymers such as those resulting from the reaction of a polyfunctional epoxy group containing com-
55 pound with an amine or with a polyfunctional carboxylic acid derivative.
[0043] In general, such resins may have pendent or terminal hydroxyl functionalities and preferably have the following
characteristics: weight average molecular weights (Mw) of from about 750 to about 7000, and more preferably from
about 2000 to about 5000; and hydroxyl numbers of from about 20 to about 120 mg KOH/g resin.
8
EP 0 851 893 B1
[0044] For waterbome applications, polyfunctional hydroxy group containing materials having thereon aqueous dis-
persion promoting groups such as carboxylic or sulfonic functionalities and higher molecular weights are generally
usable, such as disclosed in (WO96/15185, as well as GB1530022, EP-A-0568134, EP-A-0663413, US5075370 and
US5342878. Solid polyfunctional hydroxy group containing materials are suitable for use in powder coatings. For sol-
5 vent borne coatings, liquid polyfunctional hydroxy group containing materials are preferred. However, solid polyfunc-
tional hydroxy group containing materials may be used in cases when the solids are soluble in the solvent used in a
particular formulation. Specific suitable hydroxyl functional resins will be readily recognized by those of ordinary skill
in the art depending upon the desired end use.
[0045] Commercially available examples of polyfunctional hydroxy group containing materials include JONCRYL®
10 500 acrylic resin, a product of S.C.Johnson & Sons, Racine, WI; ACRYLOID® AT-400 acrylic resin, a product of Rohm
& Haas, Philadelphia, PA; CYPLEX® 1531 polyester resin, a product of Cytec Industries, West Paterson, NJ; CARGILL
3000 and 5776 polyester resins, products of Cargill, Minneapolis, MN; TONE® polyester resin, a product of Union
Carbide, Danbury, CT; K-FLEX® XM-2302 and XM-2306 resins, products of King Industries, Norwalk, CT; CHEMPOL®
11-1369 resin, a product of Cook Composites and Polymers, Port Washington, WI; JONCRYL® 540 acrylic emulsion
15 polymer, a product of S.C.Johnson & Sons, Racine, WI; RHOPLEX® AC-1024 acrylic emulsion resin, a product of
Rohm & Haas, Philadelphia, PA; XC® 4005 water reducible acrylic resin, a product of Cytec Industries, West Paterson,
NJ; CRYLCOAT® 3494 solid hydroxy terminated polyester resin, a product of UCB CHEMICALS USA, Smyma, GA;
RUCOTE® 101 polyester resin, a product of Ruco Polymer, Hicksville, NY; JONCRYL® SCX-800-A and SCX-800-B
hydroxyfunctional solid acrylic resins, products of S.C.Johnson & Sons, Racine, WI); and ALFTALAT® AN 745 hydrox-
20 yfunctional polyester resin, a product of Hoechst Corporation.
Other Ingredients
[0046] In addition to the crosslinker and resin components described in detail above, the curable compositions of
25 the present invention may optionally comprise a variety of additional ingredients normal for any particularly chosen
end use.
[0047] One common such additional ingredient is a cure catalysts for increasing the cure rate and thereby reducing
the cure temperature and/or cure time of the systems described herein. Suitable cure catalysts include those typically
suited for use in traditional amine-formaldehyde crosslinked systems, such as protic acid catalysts and Lewis acid
30 catalysts. As examples of the protic acid catalysts may be mentioned sulfonic acids such as p-toluene sulfonic acid or
dodecyl benzene sulfonic acid. Other examples include aryl and alkyl acid-phosphates and pyrophosphates, carboxylic
acids, sulfonimides and mineral acids. Latent acidic catalysts, such as amine-blocked p-toluene sulfonic acid or amine-
blocked dodecyl benzene sulfonic acid, are included within the meaning of protic acid catalysts. As examples of the
Lewis acid catalysts may be mentioned compounds of aluminum, boron, magnesium, antimony and tin. The use of
35 cure catalysts are optional in the present systems and, when utilized, are generally added in amounts ranging from
about 0.001 wt % to about 6.0 wt %, and preferably up to about 2.0 wt %, based on the combined weight of the resin
and crosslinker components (total resin solids).
[0048] The present curable compositions may also contain a solvent of the type typically found in coatings applica-
tions including, for example, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons and halogenated
40 hydrocarbons. In waterbome coating applications, the curable compositions may contain, in addition to water, a co-
solvent and an aqueous dispersion promoting material such as ethylhexanol, Texanol® (a C8-hydroxyalkyl ester of
methylpropionic acid commercially available from Eastman Chemical Company), surfactants and other related mate-
rials.
[0049] Other optional ingredients may be additionally used depending on the particular application. For example,
45 well known auxiliaries and additives typically utilized in the coatings industry including, for example, foam inhibitors,
levelling aids, pigments, dispersants such as pigment dispersing aids, dyes, UV absorbers, heat stabilizers, other
stabilizing additives such as antioxidants. Other optional ingredients have been exemplified in the many previously
incorporated references, and reference may be had thereto for further details.
50 Preparation and Uses of the Curable Compositions
[0050] The curable compositions of the present invention are suitable for numerous uses including, for example, as
coatings and adhesives, in decorative laminated boards, in the formation of crosslinked molded articles such as engi-
neering composites, for textile and paper treatment, and in any other field in which traditional amine-formaldehyde
55 resins are suitable for use.
[0051] The curable compositions may be prepared by admixing the various components via methods and in relative
amounts which are recognizable by those of ordinary skill in the art in the relevant field depending upon the particular
end use chosen. As a general rule, the resin component and the crosslinker component should preferably be admixed
9
EP 0 851 893 B1
in an equivalents ratio (equivalents of reactive functionality) of from about 0.5:1 to about 2:1, and more preferably from
about 0.8:1 to about 1.2:1.
[0052] An especially preferred use of the curable compositions in accordance with the present invention is in the
coatings field. Any conventional type of coating may be prepared using the curable compositions described herein,
5 including organic solvent based liquid coatings, waterbome coatings, powder coatings and high temperature coil coat-
ings. In coatings applications, the weight amounts of the various reactive components will be dependent upon factors
including, for example, the particular materials chosen, the presence of other reactive species as well as the desired
end use. Based upon these variables and others, those of ordinary skill in the art should be able to adjust the composition
of the coatings (including the relative amounts of the components) to achieve the desired effect.
10 [0053] Organic solvent based liquid coatings in accordance with the present invention may be prepared via conven-
tional means by adding into a commonly used organic coatings solvent the components of the curable composition
and the optional ingredients, if present, in any convenient order. In organic solvent based coatings, the systems are
formulated to produce a solids content level suitable for convenient application with minimal material loss, preferably
at a solids content level in the range of from about 20 weight percent to about 85 weight percent, and more preferably
15 at a solids content level in the range of from about 45 weight percent to about 80 weight percent, depending on the
method of application chosen.
[0054] Waterborne coating compositions in accordance with the present invention may be prepared by combining
the components of the coating in any particular order, but it is preferred to do so by preparing a dispersible composition
by substantially homogeneously mixing the coating components with a surface active material (which may be an in-
20 herent property of the resin component), then dispersing the dispersible composition in an aqueous medium, which
may comprise solely water or may contain other components such as minor amounts of water-miscible co-solvents to
ease dispersion or adjust viscosity. The waterborne coating compositions may be formulated to various solids contents,
generally ranging from about 20% to about 75% by weight solids, but preferably in the range of from about 30% to
about 55% by weight solids, depending on the method of application chosen.
25 [0055] Powder coating compositions in accordance with the present invention may be prepared by any well-known
method, for example, by dry mixing the components in a mixer or blender followed by compounding in an extruder and
granulating, grinding and then screening to obtain a powder of suitable mesh size for powder coating. For powder
coatings applications, compositions containing solid crosslinker and backbone resin components are preferred. Alter-
natively, some or all of the components may be dissolved in a solvent such as methylene chloride and spray dried by
30 well known techniques. Moreover, it may be preferable to masterbatch the crosslinking agent and the hydroxyl functional
resin prior to mixing the optional components of the composition in a manner well known to a person skilled in the art.
[0056] The present coating compositions are utilized by applying the coating to a substrate then curing the so-applied
coating to form crosslinked films. Liquid coatings may be applied, for example, by dipping, spraying, padding, brushing,
flowcoating, electrocoating or electrostatic spraying. After application, the liquid carrier (e.g., organic solvent and/or
35 water) is generally allowed to partially evaporate to produce a uniform coating on the substrate. Powder coatings may
be applied, for example, by means such as a powder gun, electrostatic deposition or deposition from a fluidized bed.
After deposition, the powder is typically heated usually to a temperature sufficient to cause the particles to soften, melt,
flow and begin to cure.
[0057] Full curing of the present coating compositions (and curable compositions) requires elevated temperatures
40 generally in the range of from about 25°C to about 450°C depending on the components as well as the end use
application. In liquid coatings applications, the cure temperature is typically in the range of from about 80°C to about
160°C. In powder coatings applications, the cure temperature is typically in the range of from about 110°C to about
230°C, preferably from about 150°C to about 220°C, and most preferably from about 170°C to about 200°C. In coil
coatings applications, the cure temperature is typically in the range of from about 250°C to about 450°C. Cure time
45 preferably is in the range of from about 1 second to about 30 minutes but may vary depending on the temperature
chosen for cure. For example, a fully cured coil coating may be obtained by either curing at 260°C for 1 minute or by
curing at 417°C for 20 seconds. Typical cure times for liquid and powder coatings are in the in the range of from about
5 minutes to about 30 minutes.
[0058] The coating compositions of this invention may be formulated for use in numerous areas such as original
50 equipment manufacturing (OEM) including automotive coatings, general industrial coatings including industrial main-
tenance coatings, architectural coatings and can coatings. They are usable as coatings for wire, appliances, automotive
parts, furniture, pipes and machinery. The present systems can be used as 1 K coatings in applications such as auto-
motive finishes, powder coatings, coil coatings including base coats and top coats. Suitable surfaces include metals
such as steel and aluminum, plastics, wood, and glass.
55 [0059] The examples which follow are intended to be illustrative of certain preferred embodiments of the invention
and are not to be construed to limit the invention in any manner. NMR spectra were obtained on a Varian Unity 300
Plus. IR spectra were obtained on a Digilab FTS 60A. LC/MS (Thermospray) was conducted on a Finnigen Mat TSQ-
700 spectrometer. Melting points were measured on a Electrothermal Melting Point Apparatus. 2,2-Dimethoxy ethanal
10
EP 0 851 893 B1
(DME) was obtained from Societe Francaise Hoechst as a 43 % solution in methyl tertiary butyl ether (MTBE) or as a
60 % solution in water. Melamine was obtained from Cytec Industries, West Paterson, N.J. Sodium bicarbonate and
n-butanol (HPLC grade, 99.8 %) were obtained from Aldrich Chemical Company. Xylenes (ACS reagent), p-toluenesul-
fonic acid (practical), methanol (100 %, ACS reagent) and methylene chloride (ACS reagent) were obtained from J. T.
5 Baker Chem. Co, Phillipsburg, N.J. Buffer solutions (Baxter calibrating buffer, pH 4, 7 and 10) were obtained from
Baxter Diagnostics, Inc., Deerfield, IL. Water used was deionized water. All amounts are expressed as parts by weight,
unless otherwise stated.
[0060] In some of the below examples, the DME utilized was purified by distilling a 43 % solution of DME in methyl
tertiary butyl ether (MTBE) (552 g total) under reduced pressure (72 mm/Hg). The fraction boiling at 50-60°C was
10 collected as a colorless liquid (174 g, yield 73%).
EXAMPLE 1
[0061] DME (210 g total, 60 % in water, 1.2 moles DME) was placed in a one liter reaction flask and the pH was
15 adjusted to 8.5 (buffer pH 10) with 20 % NaOH solution. Melamine (25.2 g, 0.2 moles) was then added and the mixture
was stirred (mechanical stirring) at 50-60°C until it turned into a clear solution (about 30 min). The reaction was con-
tinued for an additional 10 min at 50-60°C. The resulting mixture was distilled under vacuum (6 mm/Hg, 50°C) for 1 hr
to give a viscous liquid. After cooling the liquid to about 30°C, methanol (128 g, 4.0 moles) was added. The solution
was then adjusted to pH 3.5 (buffer pH 4) with concentrated nitric acid and allowed to react at 40°C for 1 hr with vigorous
20 stirring. The reaction was then stopped by adjusting the pH to 8.2 (buffer pH 7) with 50% NaOH solution. The solvent
was removed under reduced pressure using a rotary evaporator (6 mm/Hg, 50°C, about 1 hr). The residue was dis-
solved in methanol (128 g, 4.0 moles) and the pH was adjusted to 4.5 (buffer pH 4) with concentrated nitric acid. The
resulting solution was stirred at 60-65°C for 1 hr and the reaction was stopped by adjusting the pH to 7.2 (buffer pH
7) with 50% NaOH solution. The solvent was then removed under reduced pressure using a rotary evaporator (6 mm/
25 Hg, 50°C). Water (200 ml) was then added to dissolve the residue and the solution was extracted with methylene
chloride (3 x 150 ml). The organic layers were combined, washed with water (3 x 100 ml), and dried with anhydrous
MgSO4. Removal of the solvent under reduced pressure followed by crystallization in methanol gave substantially
monomeric N,N',N"-tris-(1,2,2-trimethoxyeth-1-yl)melamine as white crystals (36 g, 38 % yield), m.p. 111-114°C (un-
corrected). LC/MS (Thermospray, MH+): m/z calculated for C18H36O9N6+H 481. found 481. IR (KBr): 3332, 2943, 2833,
30 1583, 1565, 1450, 1373, 1189, 1078, 969, 944, 814 cm-1. 1H NMR (300 MHz, DMSO-d6): δ 7.20 (m, NH), 5.25 (m,
CH), 4.37 (m, CH), 3.30 (m, OCH3). 13C NMR (75 MHz, D2O): δ 166.5, 103.4, 81.0, 55.6, 55.3.
[0062] The spectral data were consistent with the composition represented by the formula (Melamine)(DME)3(Me)3.
EXAMPLE 2
35
[0063] Melamine (16.5 g, 0.13 moles), DME (freshly purified, 55 g, 0.53 moles), methanol (62 g, 1.95 moles) and p-
toluenesulfonic acid (0.33 g, 0.002 moles) were placed in a 500 ml reaction flask under a nitrogen atmosphere. The
mixture was stirred at reflux for 16 hr. Solvent was removed under reduced pressure using a rotary evaporator (6 mm/
Hg, 40°C). The residue was dissolved in methylene chloride (200 ml) and washed with water (2 x 80 ml), sodium
40 bicarbonate (2%, 80 ml) and water (2 x 80 ml). The organic layer was dried with anhydrous MgSO4 and evaporated
to dryness (6 mm/Hg, 40°C). Addition of xylenes gave a colorless solution of substantially monomeric N,N',N"-tris-
(1,2,2-trimethoxyeth-1-yl)melamine (84 g) having a solids level of 51 % as determined by the pan solids method (heating
at 105°C for 2 hr).
[0064] As in Example 1, the 13C NMR was consistent with the composition represented by the formula (Melamine)
45 (DME)3(Me)3.
EXAMPLE 3
[0065] Melamine (50 g, 0.4 moles), methanol (192 g, 6.0 moles), DME (freshly purified, 125 g, 1.2 moles) and p-
50 toluenesulfonic acid (1 g, 0.006 moles) were placed in a 500 ml reaction flask under a nitrogen atmosphere and stirred
at reflux for 24 hr. The reaction mixture was then cooled to room temperature and neutralized to pH 7 by 50% NaOH
(approximately 1.5 ml). The solvent was removed under reduced pressure (50°C/6 mm/Hg) and the residue was dis-
solved in 1,2-propylene glycol monomethyl ether (PGME). The solution was filtered to give a colorless solution. 13C
NMR of the product indicated an average composition of (Melamine)(DME)2.4(Me)2.0. A broad signal at 60 ppm, char-
55 acteristic of an NH-CH-NH linkage, indicated that the product contained oligomeric forms at about 50 weight % level.
11
EP 0 851 893 B1
EXAMPLE 4
[0066] Melamine (20 g, 0.16 moles), methanol (77 g, 2.4 moles), DME (freshly purified, 50 g, 0.48 moles) and con-
centrated nitric acid (2 g, 0.032 moles) were placed in a 500 ml reaction flask under a nitrogen atmosphere and stirred
5 at reflux for 24 hr. The reaction mixture was then cooled to room temperature and neutralized to pH 7 (buffer pH 7) by
50 % NaOH. The solution was filtered to give a colorless solution. 13C NMR of the product indicated an average com-
position of (Melamine)(DME)2.3(Me)1.6. The broad signal at 60 ppm, characteristic of an NH-CH-NH linkage, indicated
that the product contained oligomeric forms at about 66 weight % level.
10 EXAMPLE 5
[0067] DME (113 g, 60% in water, 0.65 moles) and melamine (16.5 g, 0.13 moles) were placed in a 500 ml reaction
flask and stirred at 70-80°C until the mixture became dear (about 30 min). The water was removed under reduced
pressure using a rotary evaporator (6 mm/Hg, 40°C, about 30 min). Methanol (83 g, 2.6 moles) and p-toluenesufonic
15 acid (0.34 g, 0.002 moles) were then added and the mixture was allowed to react at 70°C for 16 hr to give a yellow
solution. The methanol was removed under vacuum (6 mm/Hg,40°C), methylene chloride (200 ml) was added, the
solution was washed with water (4 x 60 ml) and thereafter dried with anhydrous MgSO4. Removal of the methylene
chloride under reduced pressure a viscous yellow liquid. 13C NMR spectrum indicated that the product was substantially
monomeric, having a composition consistent with the formula (Melamine)(DME)3(Me)3.
20
EXAMPLE 6
[0068] Melamine (45.4 g, 0.36 moles), n-butanol (400 g, 5.41 moles), DME (freshly purified, 150 g, 1.44 moles) and
p-toluenesulfonic acid (0.93 g, 0.005 moles) were placed in an one litter reaction flask under a nitrogen atmosphere
25 and stirred at 70-80°C for 24 hr. The solvent was removed under reduced pressure using a rotary evaporator (6 mm/
Hg, 50°C). The residue was dissolved in methylene chloride (400 ml) and washed with water (2 x 300 ml), NaHCO3
(2 x 200 ml) and water (2 x 300 ml). The organic layer was dried with anhydrous MgSO4 and the solvent was removed
under reduced pressure using a rotary evaporator. The residue was dissolved in 1,2-propylene glycol monomethyl
ether (PGME) to give a viscous solution (204 g, 65 % solids by pan solids method). 13C NMR (300 MHz, in PGME)
30 showed signals at 166.3 ppm for triazine carbons, 103.9 ppm for CH(OCH3)2, 80.5 ppm for CH(OBu)NH, 67.5 ppm for
OCH2, 54.4 ppm for OCH3, 31.9 ppm for CH2, 19.3 ppm for CH2 and 14.1 ppm for CH3, indicating an average com-
position of (Melamine)(DME)2.6(Bu)2.6.
COMPARATIVE EXAMPLE
35
[0069] In a 500 ml reaction flask, DME (freshly purified, 79 g, 0.76 moles) was dissolved in xylenes (80 ml) under a
nitrogen atmosphere. NaHCO3 (2.4 g) and melamine (24 g, 0.19 moies) were then added and the resulting mixture
was stirred at 50-55°C for 16 hr using a mechanical stirrer. Upon cooling to room temperature, the mixture had separated
into two distinct layers. The xylenes layer was discarded. The residue was further extracted with xylenes (2 x 80 ml)
40 and the xylenes layer was discarded. The residue was then dissolved in methylene chloride (100 ml) and filtered. The
methylene chloride was then removed under reduced pressure using a rotary evaporator to give a colorless, viscous
liquid (98 g). The crude product was soluble in ethyl acetate, methylene chloride and methyl ethyl ketone. IR (KBr)
showed the formation of a trisubstituted triazine, H-bonded OH groups and secondary amines. As expected, the com-
pound was unstable under the LC/MS (thermospray) analysis conditions and hence, a molecular ion peak was not
45 observed. 13C NMR (300 MHz, CDCl3) exhibited signals at 165.2 ppm for triazine carbons, 104.2 ppm for CH(OCH3)2,
74.2 ppm for NHCH(OH) and 55.6 ppm for OCH3, indicating that the product was substantially monomeric, having a
composition consistent with the formula (Melamine)(DME)3.
EXAMPLE 7
50
[0070] Coatings A-J were prepared by admixing the components with enough additional solvent to adjust the solids
level to the percentage, as listed in Tables I-X below. Films derived from Coatings A-J were compared to films derived
from comparative coatings (Comparative Coatings A-J) using a conventional-type methylated melamine-formaldehyde
resin as crosslinker. The physical and resistance properties of the coatings and the comparatives are also provided in
55 Tables I-X. These results show that curable systems based on the present compounds and compositions can be for-
mulated to produce results comparable to those obtained from more conventional systems crosslinked with traditional
amino-formaldehyde crosslinkers.
12
EP 0 851 893 B1
TABLE I
COATING A COMPARATIVE A
5 Polyfunctional Material Acryloid®AT400(1) Acryloid®AT400

Crosslinker EXAMPLE 2 Cymel®327 Resin(2)
Polyfunctional Material/Crosslinker 70/30 70/30
Solids (on TRS)(3) 65 Weight % 65 Weight %
Wire Cater Applicator # 34 # 34
10 Flash Time 15 minutes 15 minutes
Cure Time 30 minutes 30 minutes
Solvent Xylene Xylene
Butanol 10 Wt % on TRS 10 Wt % on TRS
15
Substrate B1000 CRS(4) B1000 CRS
Catalyst None None
150°C Cure
20 Mils (µm) 0.91 (23.1) 0.85 (21.6)

KHN25 13.7 14.0
MEK 200+/200+ 200+/200+
Appearance Good Good
(1) a hydroxy functional acrylic resin of Rohm & Haas Co., Philadelphia, PA
25 (2) a high imino methylated melamine-formaldehyde resin of Cytec Industries, West Paterson, NJ
(3) Total Resin Solids
(4) Bonderite cold rolled steel panels
30 TABLE II
COATING B COMPARATIVE B
Polyfunctional Material Acryloid®AT400 Acryloid®AT400
Crosslinker EXAMPLE 2 Cymel®327 Resin
35 Polyfunctional Material/Crosslinker 70/30 70/30
Solids (on TRS) 65 Weight % 65 Weight %
Flash Time 15 minutes 15 minutes
40
Substrate B1000 CRS B1000 CRS
Catalyst (PTSA)(5) 0.8 Wt % 0.8 Wt %
45
100°C Cure
Mils (µm) 0.91 (23.1) 0.85 (21.6)
KHN25 8.7 12.0
50 MEK 5/63 200+/200+
125°C Cure
55 Mils (µm) 0.93 (23.6) 0.88 (22.4)
KHN25 13.0 15.3
(5) p-Toluenesulfonic Acid, Weight % based on Total Resin Solids (TRS)
13
EP 0 851 893 B1
TABLE II (continued)
COATING B COMPARATIVE B
125°C Cure
5 MEK 200+/200+ 200+/200+
150°C Cure
10
Mils (µm) 0.81 (20.6) 0.87 (22.1)
KHN25 13.7 15.3
MEK 200+/200+ 200+/200+
15
TABLE III
COATING C COMPARATIVE C
20
Solids (on TRS) 62.3 Weight % 62.3 Weight %
30
Catalyst None None
125°C Cure
35
Mils (µm) 1.08 (27.4) 1.09 (27.7)
KHN25 5.7 12.1
MEK 25/200 100/200+
150°C Cure
40
Mils (µm) 1.18 (30.0) 1.03 (26.2)
KHN25 11.1 13.2
MEK 200+/200+ 200+/200+
45
TABLE IV
COATING D COMPARATIVE D
50 Crosslinker EXAMPLE 3 Cymel®327 Resin
55
14
EP 0 851 893 B1
TABLE IV (continued)
COATING D COMPARATIVE D
5 Catalyst (PTSA) 0.2 Wt % 0.2 Wt %
125°C Cure
Mils (µm) 1.11 (28.2) 1.09 (27.7)
10 KHN25 9.8 12.4
MEK 25/200+ 200+/200+
150°C Cure
15 Mils (µm) 1.16(29.5) 0.98 (24.9)
KHN25 10.6 15.3
MEK 200+/200+ 200+/200+
20
TABLE V
COATING E COMPARATIVE E
25
30 Cure Time 30 minutes 30 minutes
Catalyst (PTSA) 0.4 Wt % 0.4 Wt %
35
125°C Cure
Mils (µm) 1.18 (30.0) 1.18 (30.0)
KHN25 10.1 13.7
40
MEK 25/200+ 25/200+
150°C Cure
Mils (µm) 1.11 (28.2) 1.21 (30.7)
45
KHN25 10.8 14.2
MEK 200+/200+ 200+/200+
50 TABLE VI
COATING F COMPARATIVE F
15
EP 0 851 893 B1
TABLE VI (continued)
COATING F COMPARATIVE F
Catalyst (Cycat®296-9)(6) 1.0 Wt % 1.0 Wt %
10
125°C Cure
Mils (µm) 1.12 (28.4) 1.15 (29.2)
KHN25 8.4 13.7
15
MEK 25/60 200+/200+
150°C Cure
Mils (µm) 1.1 (27.9) 1.2 (30.5)
20
KHN25 11.7 14.0
MEK 200+/200+ 200+/200+
(6) a phosphoric acid derivative catalyst of Cytec Industries, West Paterson, NJ
25
TABLE VII
COATING G COMPARATIVE G
35
40 Catalyst None None
125°C Cure
Mils (µm) 1.15 (29.2) 1.09 (27.7)
45 KHN25 1.1 12.1
MEK 1/22 100/200+
150°C Cure
50 Mils (µm) 1.18 (30.0) 1.03 (26.2)
KHN25 9.8 13.2
MEK 200+/200+ 200+/200+
55
16
EP 0 851 893 B1
TABLE VIII
COATING H COMPARATIVE H
5 Polyfunctional Material Acryloid®AT400 Acryloid®AT400

15
125°C Cure
20 Mils (µm) 1.13 (28.7) 1.09 (27.7)

KHN25 8.2 12.4
MEK 25/150 200+/200+
150°C Cure
25
Mils (µm) 1.09 (27.7) 0.98 (24.9)
KHN25 10.5 15.3
MEK 200+/200+ 200+/200+
30
TABLE IX
COATING I COMPARATIVE I
40
45 Catalyst (PTSA) 0.4 Wt % 0.4 Wt %
125°C Cure
Mils (µm) 1.10 (27.9) 1.18 (30.0)
50 KHN25 10.0 13.7
MEK 25/200+ 100/200+
150°C Cure
55 Mils (µm) 0.98 (24.9) 1.21 (30.7)
KHN25 10.3 14.2
MEK 200+/200+ 200+/200+
17
EP 0 851 893 B1
TABLE X
COATING J COMPARATIVE J
5 Polyfunctional Material Acryloid®AT400 Acryloid®AT400

15
Catalyst (CYCAT®296-9) 1.0 Wt % 1.0 Wt %
125°C Cure
20 Mils (µm) 1.05 (26.7) 1.15 (29.2)

KHN25 10.3 13.7
MEK 25/200+ 200+/200+
150°C Cure
25
Mils (µm) 1.0 (25.4) 1.2 (30.5)
KHN25 10.3 14.0
MEK 200+/200+ 200+/200+
30
EXAMPLE 8
[0071] Coating K was prepared by admixing the components with enough additional solvent to adjust the solids level
to the percentage, as listed in Table XI below. A film derived from Coating K was compared to a film derived from a
comparative coating (Comparative Coatings K) using the crosslinker from the Comparative Example - which is a mela-
35
mine/DME condensate similar to the compounds of the present invention but containing no activated ether groups
(none of the 1-hydroxy groups have been alkylated). The physical and resistance properties of the coating and the
comparative, provided below in Table XI, clearly show the necessity of these activated ether groups as required by the
present invention.
40 TABLE XI
COATING K COMPARATIVE K
Crosslinker EXAMPLE 2 COMPARATIVE EXAMPLE
50
55
18
EP 0 851 893 B1
TABLE XI (continued)
COATING K COMPARATIVE K
100°C Cure
5
Mils (µm) 0.91 (23.1) 0.83 (21.1)
KHN25 8.7 1.8
MEK 5/63 1/5
Appearance Good Poor
10
125°C Cure
Mils (µm) 0.93 (23.6) 0.80 (20.3)
KHN25 13.0 1.8
15 MEK 200+/200+ 1/5
150°C Cure
20 Mils (µm) 0.81 (20.6) 0.75 (19.1)
KHN25 13.7 1.3
MEK 200+/200+ 1/ 5
25
EXAMPLES 9 AND 10
[0072] Waterbome Coatings L and M were prepared by admixing the components as listed in Tables XII-XIII below.
Films derived from Waterbome Coatings L and M were compared to films derived from comparative coatings (Com-
30 parative Coatings L and M) using a conventional-type methylated melamine-formaldehyde resin as crosslinker. The
physical and resistance properties of the coatings and the comparatives are also provided in Tables XII-XIII. These
results show that curable waterbome systems based on the present compounds and compositions can be formulated
to produce results comparable to those obtained from more conventional systems crosslinked with traditional amino-
formaldehyde crosslinkers.
35
40
45
50
55
19
EP 0 851 893 B1
TABLE XII
WATERBORNE COATINGS COATING L COMPARATIVE L
Polyfunctional Material Rhoplex®AC1024(7) Rhoplex®AC 1024
5 Crosslinker Example 2 Cymel®327 Resin
10
15
100°C Cure
Mils (µm) 1.12(28.4) 1.31 (33.3)
KHN25 10.9 11.0
MEK 150/200+ 150/200+
20
125°C Cure
Mils (µm) 1.07 (27.2) 1.13 (28.7)
KHN25 15.8 8.0
25 MEK 200+/200+ 200+/200+
150°C Cure
Mils (µm) 1.03 (26.2) 1.16 (29.5)
30
KHN25 18.2 18.2
MEK 200+/200+ 200+/200+
(7) a hydroxy functional acrylic emulsion resin of Rohm & Haas Company, Philadelphia, PA
35
TABLE XIII
YELLOWING ON OVERBAKE WATERBORNE COATINGS COATING M COMPARATIVE M
Polyfunctional Material Rhoplex®AC1024 Rhoplex®AC1024
40 Crosslinker Example 2 Cymel®327 Resin
Prime White Basecoat White Basecoat
50
150°C Cure
Mils (µm) 1.03 (26.2) 1.16 (29.5)
KHN25 18.2 18.2
55 MEK 200+/200+ 200+/200+
Initial Yellow Index -1.7 -1.6
Change in Yellow Index on Overbake:
20
EP 0 851 893 B1
TABLE XIII (continued)

YELLOWING ON OVERBAKE WATERBORNE COATINGS COATING M COMPARATIVE M
150°C Cure
5 1.8 hrs at 150°C 1.5 1.2
3.8 hrs at 150°C 3.9 4.4
8.0 hrs at 150°C 8.2 9.6
10 [0073] Although the present invention is described with reference to certain preferred embodiments, it is apparent
that modifications and variations thereof may be made by those skilled in the art without departing from the scope of
this invention as defined by the appended claims.
15 Claims
1. An N-1,2,2-trihydrocarbyloxyethyl derivative of an amino compound, comprising the reaction product of:
(i) an amino compound having at least two =NH groups, selected from the group consisting of amino-1,3,5-tri-
20 azines, glycolurils and oligomers thereof,
(ii) a 2,2-dihydrocarbyloxy ethanal and
(iii) a hydrocarbylol, excluding polyols having 2 or more hydroxyl groups
the reaction product containing, on average, at least 1.25 moles of combined 2,2-dihydrocarbyloxy ethanal per
25 mole of amino compound, and at least about 2.0 1,2,2-trihydrocarbyloxyethyl groups per molecule of derivative.
2. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 1, characterized in that the amino compound is selected
from the group consisting of amino-1,3,5-triazines and glycolurils of the general formulas (IV) and (V):
30
35
40
45
50
55 wherein
R1 is selected from H, a hydrocarbyl and -N(R7)2,

each R7 is independently selected from H and a hydrocarbyl, with the proviso that at least two groups R7 are H,
21
EP 0 851 893 B1
and preferably that all R7 groups are H, and

each R4 is independently selected from H and a hydrocarbyl, and preferably that all R4 groups are H.
3. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 2, characterized in that the amino compound is of the general
5 formula (IV) and all R7 groups are H.
4. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 3, characterized in that the derivative is a guanamine deriv-
ative containing on average from about 1.5 to about 2.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole
of guanamine.
10
5. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 3, characterized in that the derivative is a melamine deriv-
ative containing on average from about 2.0 to about 3.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole
of melamine.
15 6. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 2, characterized in that the amino compound is of the general
formula (V), all R4 groups are H and all R7 groups are H.
7. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 6, characterized in that the derivative is a glycoluril derivative
containing on average from about 2.0 to about 4.0 moles of combined 2,2-dihydrocarbyloxy ethanal per mole of
20 glycoluril.
8. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 1, characterized in that the 2,2-dihydrocarbyloxy ethanal

has the general formula (VI):
25
30
wherein

35
9. The N-1,2,2-trihydrocarbyioxyethyl derivative of claim 8, characterized in that each R6 is independently an alkyl
of 1 to 8 carbon atoms or an alkenyl of 1 to 8 carbon atoms, or both R6 groups together form an alkylene bridge
of 1 to 8 carbon atoms.
40 10. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 2, characterized in that the 2,2-dihydrocarbyloxy ethanal
has the general formula (VI):
45
50 wherein
11. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 1, characterized in that the hydrocarbylol is a hydroxy group-
55 containing compound having 1 to 20 carbon atoms.
12. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 2, characterized in that the hydrocarbylol is a hydroxy group-
containing compound having 1 to 20 carbon atoms.
22
EP 0 851 893 B1
13. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 10, characterized in that the hydrocarbylol is a hydroxy
group-containing compound having 1 to 20 carbon atoms.
14. A compound comprising an amino core having pendant therefrom at least two 1,2,2-trihydrocarbyloxyethyl groups,
5 of the following general formula (I) or (II):
10
15
20
25
wherein
30
R1 is selected from H, a hydrocarbyl and -N(R2)(R3);
each R2 is independently selected from H and a hydrocarbyl;
each R3 is independently selected from H, a hydrocarbyl and an R group;
each R4 is independently selected from H and a hydrocarbyl; and
35 each R group is independently a group of the general formula (III)
40
wherein
45 each R5 is independently selected from H and a hydrocarbyl, and each R6 is independently a hydrocarbyl, or
together form a hydrocarbylene bridge;
with the proviso that, per molecule, at least two of the R3 groups are independently an R group, and at least two
R5 groups are independently a hydrocarbyl.
50
15. The compound of claim 14, characterized in that the compound is of the general formula (I); each R2 is H; each
R3 is an R group; each R5 is independently selected from H and an alkyl of 1 to 8 carbon atoms, with the proviso
that at least two R5 groups are an alkyl of 1 to 8 carbon atoms; and each R6 is independently an alkyl of 1 to 8
carbon atoms or an alkenyl of 1 to 8 carbon atoms, or both R6 groups on each group of the formula (III) together
55 form an alkylene bridge of 1 to 8 carbon atoms.
16. The compound of claim 14, characterized in that the compound is of the general formula (II); each R4 is H; each
R3 is selected from H and an R group, with the proviso that at least two of the R3 groups are an R group; each R5
23
EP 0 851 893 B1
is selected from H and an alkyl of 1 to 8 carbon atoms, with the proviso that at least two R5 groups are an alkyl of
1 to 8 carbon atoms; and each R6 is independently an alkyl of 1 to 8 carbon atoms or an alkenyl of 1 to 8 carbon
atoms, or both R6 groups on each group of the formula (III) together form an alkylene bridge of 1 to 8 carbon atoms.
5 17. A process of preparing an N-1,2,2-trihydrocarbyloxyethyl derivative of an amino compound as set forth in any one
of claims 1-13, characterized in that the process comprises the step of contacting:
(i) an amino compound having at least two =NH groups, selected from the group consisting of amino-1,3,5-tri-
azines, glycolurils and oligomers thereof,
10 (ii) a 2,2-dihydrocarbyloxy ethanal and
(iii) a hydrocarbylol, excluding polyols having 2 or more hydroxyl groups
under conditions so as to result in a derivative containing, on average, at least 1.25 moles of combined 2,2-dihy-
drocarbyloxy ethanal per mole of amino compound, and at least about 2.0 1,2,2-trihydrocarbyloxyethyl groups per
15 molecule of derivative.
18. The process of claim 17, characterized in that in a first step (i) and (ii) are contacted in the presence of a basic
catalyst to produce a 1-hydroxy-2,2-dihydrocarbyloxyethyl derivative intermediate which, in a second step, is con-
tact with (iii) under acidic conditions to produce the N-1,2,2-trihydrocarbyloxyethyl derivative of the amino com-
20 pound.
19. The process of claim 17, characterized in that (i), (ii) and (iii) are concurrently contacted in the presence of an acid
catalyst to directly produce the N-1,2,2-trihydrocarbyloxyethyl derivative of the amino compound.
25 20. A curable composition comprising:
(a) a crosslinker component comprising an N-1,2,2-trihydrocarbyloxyethyl derivative of an amino compound

as set forth in any one of claims 1-16; and
(b) a resin component comprising a compound containing at least two groups capable of reacting with the
30 1,2,2-trihydrocarbyloxyethyl groups of (a).
21. A substrate coated with a crosslinked film derived from the curable composition according to claim 20.
35 Patentansprüche
1. N-1,2,2-Trihydrocarbyloxyethylderivat einer Aminoverbindung, umfassend das Reaktionsprodukt aus:
(i) einer Aminoverbindung mit mindestens zwei =NH-Gruppen, ausgewählt aus der Gruppe, die aus Amino-
40 1,3,5-Triazinen, Glykolurilen und Oligomeren davon besteht,
(ii) einem 2,2-Dihydrocarbyloxyethanal und
(iii) einem Hydrocarbylol, ausgenommen Polyole mit 2 oder mehr Hydroxylgruppen,

45
wobei das Reaktionsprodukt im Durchschnitt mindestens 1,25 Mol gebundenes 2,2-Dihydrocarbyloxyethanal pro
Mol Aminoverbindung und mindestens etwa 2,0 1,2,2-Trihydrocarbyloxyethylgruppen pro Molekül des Derivats
enthält.
50 2. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 1, dadurch gekennzeichnet, daß die Aminoverbindung aus

der Gruppe ausgewählt ist, die aus Amino-1,3,5-Triazinen und Glykolurilen der allgemeinen Formeln (IV) und (V)
besteht:
55
24
EP 0 851 893 B1
10
15
20
25
wobei
R1 aus einem H, einem Hydrocarbyl und -N(R7)2 ausgewählt ist,
30 jedes R7 unabhängig aus H und einem Hydrocarbyl ausgewählt ist, unter der Bedingung, daß mindestens zwei
R7-Gruppen H sind und vorzugsweise, daß alle R7-Gruppen H sind, und
jedes R4 unabhängig aus H und einem Hydrocarbyl ausgewählt ist, und vorzugsweise, daß alle R4-Gruppen
H sind.
35
3. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß die Aminoverbindung die
allgemeine Formel (IV) aufweist und daß alle R7-Gruppen H sind.
4. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 3, dadurch gekennzeichnet, daß das Derivat ein Guanamin-
40 derivat ist, das im Durchschnitt etwa 1,5 bis etwa 2,0 Mol gebundenes 2,2-Dihydrocarbyloxyethanal pro Mol Gua-
namin enthält.
5. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 3, dadurch gekennzeichnet, daß das Derivat ein Melamin-
derivat ist, das im Durchschnitt etwa 2,0 bis etwa 3,0 Mol gebundenes 2,2-Dihydrocarbyloxyethanal pro Mol Me-
45 lamin enthält.
6. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß die Aminoverbindung die

allgemeine Formel (V) aufweist, sämtliche R4-Gruppen H sind und sämtliche R7-Gruppen H sind.
50 7. N-l,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 6, dadurch gekennzeichnet, daß das Derivat ein Glykoluril-
derivat ist, das im Durchschnitt etwa 2,0 bis etwa 4,0 Mol gebundenes 2,2-Dihydrocarbyloxyethanal pro Mol Gly-
koluril enthält.
8. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 1, dadurch gekennzeichnet, daß das 2,2-Dihydrocarbylo-

55 xyethanal die allgemeine Formel (VI) aufweist:
25
EP 0 851 893 B1
wobei
10
wobei wobei jedes R6 unabhängig ein Hydrocarbyl ist oder sie zusammen eine Hydrocarbylenbrücke bilden.
9. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 8, dadurch gekennzeichnet, daß jedes R6 unabhängig ein

Alkyl mit 1 bis 8 Kohlenstoffatomen oder ein Alkenyl mit 1 bis 8 Kohlenstoffatomen ist oder daß beide R6-Gruppen
15 zusammen eine Alkylenbrücke mit 1 bis 8 Kohlenstoffatomen bilden.
10. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß das 2,2-Dihydrocarbylo-

xyethanal die allgemeine Formel (VI) aufweist:
20
25
wobei
30 jedes R6 unabhängig ein Hydrocarbyl ist oder sie zusammen eine Hydrocarbylenbrücke bilden.
11. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 1, dadurch gekennzeichnet, daß das Hydrocarbylol eine
Verbindung mit 1 bis 20 Kohlenstoffatomen ist, die eine Hydroxygruppe enthält.
35 12. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß das Hydrocarbylol eine
13. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 10, dadurch gekennzeichnet, daß das Hydrocarbylol eine
40
14. Verbindung, die einen Aminokern umfaßt, der als Seitengruppe davon mindestens zwei 1,2,2-Trihydrocarbyloxye-
thylgruppen der folgenden allgemeinen Formel (I) oder (II) aufweist:
45
50
55
26
EP 0 851 893 B1
10
wobei
R1 aus einem H, einem Hydrocarbyl und -N(R2)(R3) ausgewählt ist;

15
jedes R2 unabhängig aus H und einem Hydrocarbyl ausgewählt ist;
jedes R3 unabhängig aus H, einem Hydrocarbyl und einer R-Gruppe ausgewählt ist;
20 jedes R4 unabhängig aus H und einem Hydrocarbyl ausgewählt ist; und
jede R-Gruppe unabhängig eine Gruppe der allgemeinen Formel (III) ist
25
30
wobei
jedes R5 unabhängig aus H und einem Hydrocarbyl ausgewählt ist und jedes R6 unabhängig ein Hydrocarbyl
ist oder sie zusammen eine Hydrocarbylenbrücke bilden;
35
unter der Bedingung, daß pro Molekül mindestens zwei der R3-Gruppen unabhängig eine R-Gruppe sind und
mindestens zwei R5-Gruppen unabhängig ein Hydrocarbyl sind.
15. Verbindung nach Anspruch 14, dadurch gekennzeichnet, daß die Verbindung die allgemeine Formel (I) aufweist;
40 jedes R2 H ist; jedes R3 eine R-Gruppe ist; jedes R5 unabhängig aus H und einem Alkyl mit 1 bis 8 Kohlenstoff-
atomen ausgewählt ist, unter der Bedingung, daß mindestens zwei R5-Gruppen ein Alkyl mit 1 bis 8 Kohlenstoff-
atomen sind; und daß jedes R6 unabhängig ein Alkyl mit 1 bis 8 Kohlenstoffatomen oder ein Alkenyl mit 1 bis 8
Kohlenstoffatomen ist oder daß beide R6-Gruppen in jeder Gruppe der Formel (III) zusammen eine Alkylenbrücke
mit 1 bis 8 Kohlenstoffatomen bilden.
45
16. Verbindung nach Anspruch 14, dadurch gekennzeichnet, daß die Verbindung die allgemeine Formel (II) aufweist;
jedes R4 H ist; jedes R3 aus H und einer R-Gruppe ausgewählt ist unter der Bedingung, daß mindestens zwei der
R3-Gruppen eine R-Gruppe sind; jedes R5 aus H und einem Alkyl mit 1 bis 8 Kohlenstoffatomen ausgewählt ist
unter der Bedingung, daß mindestens zwei R5-Gruppen ein Alkyl mit 1 bis 8 Kohlenstoffatomen sind; und jedes
50 R6 unabhängig ein Alkyl mit 1 bis 8 Kohlenstoffatomen oder ein Alkenyl mit 1 bis 8 Kohlenstoffatomen ist oder
beide R6-Gruppen in jeder Gruppe der Formel (III) zusammen eine Alkylenbrücke mit 1 bis 8 Kohlenstoffatomen
bilden.
17. Verfahren zur Herstellung eines N-1,2,2-Trihydrocarbyloxyethylderivats einer Aminoverbindung nach einem der
55 Ansprüche 1 - 13, dadurch gekennzeichnet, daß das Verfahren den Schritt umfaßt, miteinander in Kontakt zu
bringen:
(i) eine Aminoverbindung, die mindestens zwei =NH-Gruppen aufweist, ausgewählt aus der Gruppe, die aus
27
EP 0 851 893 B1
Amino-1,3,5-Triazinen, Glykolurilen und Oligomeren davon besteht,
(ii) ein 2,2-Dihydrocarbyloxyethanal und
5 (iii) ein Hydrocarbylol, ausgenommen Polyole, die 2 oder mehr Hydroxylgruppen aufweisen,
unter solchen Bedingungen, daß sich ein Derivat ergibt, das im Durchschnitt mindestens 1,25 Mol gebundenes
2,2-Dihydrocarbyloxyethanal pro Mol Aminoverbindung und mindestens etwa 2,0 1,2,2-Trihydrocarbyloxyethyl-
gruppen pro Molekül Derivat enthält.
10
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß in einem ersten Schritt (i) und (ii) unter Anwesenheit
eines Basenkatalysators in Kontakt gebracht werden, um ein 1-Hydroxy-2,2-Dihydrocarbyloxyethylderivatz-
wischenprodukt zu erzeugen, das in einem zweiten Schritt unter aziden Bedingungen in Kontakt mit (iii) gebracht
wird, um das N-1,2,2-Trihydrocarbyloxyethylderivat der Aminoverbindung zu erzeugen.
15
19. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß (i), (ii) und (iii) gleichzeitig in Kontakt gebracht werden
unter Anwesenheit eines Säurekatalysators, um direkt das N-1,2,2-Trihydrocarbyloxyethylderivat der Aminover-
bindung zu erzeugen.
20 20. Vernetzbare Zusammensetzung, umfassend:
(a) eine Vernetzerkomponente, umfassend ein N-1,2,2-Trihydrocarbyloxyethylderivat einer Aminoverbindung

nach einem der Ansprüche 1 - 16; und
25 (b) eine Harzkomponente, umfassend eine Verbindung, die mindestens zwei Gruppen enthält, die in der Lage
sind, mit den 1,2,2-Trihydrocarbyloxyethylgruppen aus (a) zu reagieren.
21. Substrat, das mit einem vernetzten Film beschichtet ist, der aus der vernetzbaren Zusammensetzung nach An-
spruch 20 abgeleitet ist.
30
Revendications
1. Dérivé N-1,2,2-trihydrocarbyloxyéthylé d'un composé aminé, comprenant le produit de réaction :

35
(i) d'un composé aminé comportant au moins deux groupes =NH, choisi parmi les amino-1,3,5-triazines, les
glycoluriles et leurs oligomères,
(ii) d'un 2,2-dihydrocarboxyloxy éthanal, et
(iii) d'un hydrocarbylol, à l'exclusion des polyols comportant deux groupes hydroxyle ou plus ;
40
le produit de réaction contenant, en moyenne, au moins 1,25 mole de 2,2-dihydrocarbyloxy éthanal combiné par
mole de composé aminé, et au moins environ 2,0 groupes 1,2,2-trihydrocarbyloxyéthyle par molécule de dérivé.
2. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 1, caractérisé en ce que le composé aminé est choisi
45 parmi les amino-1,3,5-triazines et les glycoluriles correspondants aux formules générales (IV) et (V) :
50
55
28
EP 0 851 893 B1
10
dans lesquelles R1 est choisi parmi H, un groupe hydrocarbyle et -N(R7)2,

chaque groupe R7 est indépendamment choisi parmi H et un groupe hydrocarbyle, à condition qu'au moins
15 deux groupes R7 représentent H, et de préférence, que la totalité des groupes R7 représente H, et
chaque groupe R4 est indépendamment choisi parmi H et un groupe hydrocarbyle, de préférence, la totalité
des groupes R4 représente H.
3. Dérivé de N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 2, caractérisé en ce que le composé aminé cor-

20 respond à la formule générale (IV), et tous les groupes R7 représentent H.
4. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 3, caractérisé en ce que le dérivé est un dérivé de

guanamine contenant, en moyenne, d'environ 1,5 à environ 2,0 moles de 2,2-dihydrocarbyloxy éthanal combiné
par mole de guanamine.
25
mélamine contenant, en moyenne, d'environ 2,0 à environ 3,0 moles de 2,2-dihydrocarbyloxy éthanal combiné
par mole de mélamine.
30 6. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 2, caractérisé en ce que le composé aminé corres-

pond à la formule générale (V), tous les groupes R4 représentent H, et tous les groupes R7 représentent H.

glycolurile contenant, en moyenne, d'environ 2,0 à environ 4,0 moles de 2,2-dihydrocarbyloxy éthanal combiné
35 par mole de glycolurile.
8. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 1, caractérisé en ce que le 2,2-dihydrocarbyloxy

éthanal correspond à la formule générale (VI) :
40
45
dans laquelle chaque groupe R6 représente indépendamment un groupe hydrocarbyle, ou ils forment ensemble
un pont hydrocarbylène.
50 9. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 8, caractérisé en ce que chaque groupe R6 repré-

sente indépendamment un groupe alkyle de 1 à 8 atomes de carbone ou un groupe alcényle de 1 à 8 atomes de
carbone, ou les deux groupes R6 forment ensemble un pont alkylène de 1 à 8 atomes de carbone.
10. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 2, caractérisé en ce que le 2,2-dihydrocarbyloxy

55 éthanal correspond à la formule générale (VI) :
29
EP 0 851 893 B1
dans laquelle chaque groupe R6 représente indépendamment un groupe hydrocarbyle, ou ils forment ensemble
un pont hydrocarbylène.
10
11. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 1, caractérisé en ce que l'hydrocarbylol est un com-
posé à groupe hydroxy comportant de 1 à 20 atomes de carbone.
15 posé à groupe hydroxy comportant de 1 à 20 atomes de carbone.
posé à groupe hydroxy comportant de 1 à 20 atomes de carbone.
20 14. Composé comprenant un noyau aminé comportant au moins deux groupes 1,2,2-trihydrocarbyloxyéthylé latéraux
correspondants à la formule générale (I) ou (II) suivante :
25
30
35
40
45 dans lesquelles
R1 est choisi parmi H, un groupe hydrocarbyle et -N(R2)(R3) ;

chaque groupe R2 est indépendamment choisi parmi H et un groupe hydrocarbyle ;
chaque groupe R3 est indépendamment choisi parmi H, un groupe hydrocarbyle et un groupe R ;
50 chaque groupe R4 est indépendamment choisi parmi H et un groupe hydrocarbyle ; et
chaque groupe R représente indépendamment un groupe de formule générale (III) :
55
30
EP 0 851 893 B1
dans laquelle chaque groupe R5 est indépendamment choisi parmi H et un groupe hydrocarbyle, et
chaque groupe R6 représente indépendamment un groupe hydrocarbyle, ou ils forment ensemble un pont
hydrocarbylène ;
à condition que, par molécule, au moins deux des groupes R3 représentent indépendamment un groupe R,
5 et au moins deux groupes R5 représentent indépendamment un groupe hydrocarbyle.
15. Composé selon la revendication 14, caractérisé en ce que le composé correspond à la formule générale (I) ;
chaque groupe R2 représente H ; chaque groupe R3 représente un groupe R ; chaque groupe R5 est indépen-
damment choisi parmi H et un groupe alkyle comportant de 1 à 8 atomes de carbone, à condition qu'au moins
10 deux des groupes R5 représentent un groupe alkyle comportant de 1 à 8 atomes de carbone ; et chaque groupe
R6 représente indépendamment un groupe alkyle comportant de 1 à 8 atomes de carbone ou un groupe alcényle
comportant de 1 à 8 atomes de carbone, ou les deux groupes R6 présents sur chaque groupe de formule (III)
forment ensemble un pont alkylène comportant de 1 à 8 atomes de carbone.
15 16. Composé selon la revendication 14, caractérisé en ce que le composé correspond à la formule générale (II) ;
chaque groupe R4 représente H ; chaque groupe R3 est choisi parmi H et un groupe R, à condition qu'au moins
deux des groupes R3 représentent un groupe R ; chaque groupe R5 est choisi parmi H et un groupe alkyle com-
portant de 1 à 8 atomes de carbone, à condition qu'au moins deux des groupes R5 représentent un groupe alkyle
comportant de 1 à 8 atomes de carbone ; et chaque groupe R6 représente indépendamment un groupe alkyle
20 comportant de 1 à 8 atomes de carbone ou un groupe alcényle comportant de 1 à 8 atomes de carbone, ou les
deux groupes R6 présents sur chaque groupe de formule (III) forment ensemble un pont alkylène comportant de
1 à 8 atomes de carbone.
17. Procédé de préparation d'un dérivé N-1,2,2-trihydrocarbyloxyéthylé d'un composé aminé selon l'une quelconque
25 des revendications 1 à 13, caractérisé en ce que le procédé comprend l'étape de mise en contact :
(i) d'un composé aminé comportant au moins deux groupes =NH, choisi parmi les amino-1,3,5-triazines, les
glycoluriles et leurs oligomères,
(ii) d'un 2,2-dihydrocarboxyloxy éthanal, et
30 (iii) d'un hydrocarbylol, à l'exclusion des polyols comportant deux groupes hydroxyle ou plus ;
dans des conditions appropriées pour former un dérivé contenant, en moyenne, au moins 1,25 mole de 2,2-dihy-
drocarbyloxy éthanal combiné par mole de composé aminé, et au moins environ 2,0 groupes 1,2,2-trihydrocarby-
loxyéthyle par molécule de dérivé.
35
18. Procédé selon la revendication 17, caractérisé en ce que dans une première étape, les composants (i) et (ii) sont
mis en contact en présente d'un catalyseur basique pour produire un dérivé 1-hydroxy-2,2-dihydrocarbyloxyéthylé
intermédiaire qui, dans une deuxième étape, est mis en contact avec le composant (iii) dans des conditions acides
pour produire le dérivé N-1,2,2-trihydrocarbyloxyéthylé du composé aminé.
40
19. Procédé selon la revendication 17, caractérisé en ce que les composants (i), (ii) et (iii), sont simultanément mis
en contact en présence d'un catalyseur acide afin de produire directement le dérivé N-1,2,2-trihydrocarbyloxyéthylé
du composé aminé.
45 20. Composition durcissable, comprenant :
(a) un composant réticulant contenant un dérivé N-1,2,2-trihydrocarbyloxyéthylé d'un composé aminé selon
l'une quelconque des revendications 1 à 16 ; et
(b) un composant résineux comprenant un composé contenant au moins deux groupes capables de réagir
50 avec les groupes 1,2,2-trihydrocarbyloxyéthyle du composant (a).
21. Substrat revêtu d'un film réticulé dérivé de la composition durcissable de la revendication 20.
55
31

European Patent Specification C08K 5/3492, C08K 5/3445,: C07D 251/64, C07D 251/18, C07D 487/04

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European Patent Specification C08K 5/3492, C08K 5/3445,: C07D 251/64, C07D 251/18, C07D 487/04

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Europäisches Patentamt

(19) European Patent Ofﬁce *EP000851893B1*

(54) FORMALDEHYDE-FREE CROSSLINKERS

(84) Designated Contracting States: • LAWLESS, Barry, A.

(72) Inventors: (56) References cited:

Printed by Jouve, 75001 PARIS (FR)

BACKGROUND OF THE INVENTION

5 Field of the invention

Description of Related Art

SUMMARY OF THE INVENTION

glycolurils and oligomers thereof,

R1 is selected from H, a hydrocarbyl and -N(R2)(R3);

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

R1 is selected from H, a hydrocarbyl and -N(R7)2,

each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge.

R1 is selected from H and a hydrocarbyl,

each R2 is selected from H and a hydrocarbyl, and

5 each R3 is a group of the formula (III);

Processes for Preparing the Derivatives

(a) a crosslinker component comprising an N-1,2,2-trihydrocarbyloxyethyl derivative as described above, and

50 Preparation and Uses of the Curable Compositions

5 Polyfunctional Material Acryloid®AT400(1) Acryloid®AT400

20 Mils (µm) 0.91 (23.1) 0.85 (21.6)

5 Polyfunctional Material Acryloid®AT400 Acryloid®AT400

20 Mils (µm) 1.13 (28.7) 1.09 (27.7)

5 Polyfunctional Material Acryloid®AT400 Acryloid®AT400

20 Mils (µm) 1.05 (26.7) 1.15 (29.2)

TABLE XIII (continued)

1. An N-1,2,2-trihydrocarbyloxyethyl derivative of an amino compound, comprising the reaction product of:

R1 is selected from H, a hydrocarbyl and -N(R7)2,

and preferably that all R7 groups are H, and

8. The N-1,2,2-trihydrocarbyloxyethyl derivative of claim 1, characterized in that the 2,2-dihydrocarbyloxy ethanal

each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge.

each R6 is independently a hydrocarbyl, or together form a hydrocarbylene bridge.

25 20. A curable composition comprising:

(a) a crosslinker component comprising an N-1,2,2-trihydrocarbyloxyethyl derivative of an amino compound

1. N-1,2,2-Trihydrocarbyloxyethylderivat einer Aminoverbindung, umfassend das Reaktionsprodukt aus:

(ii) einem 2,2-Dihydrocarbyloxyethanal und

(iii) einem Hydrocarbylol, ausgenommen Polyole mit 2 oder mehr Hydroxylgruppen,

50 2. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 1, dadurch gekennzeichnet, daß die Aminoverbindung aus

R1 aus einem H, einem Hydrocarbyl und -N(R7)2 ausgewählt ist,

6. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß die Aminoverbindung die

8. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 1, dadurch gekennzeichnet, daß das 2,2-Dihydrocarbylo-

9. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 8, dadurch gekennzeichnet, daß jedes R6 unabhängig ein

10. N-1,2,2-Trihydrocarbyloxyethylderivat nach Anspruch 2, dadurch gekennzeichnet, daß das 2,2-Dihydrocarbylo-

R1 aus einem H, einem Hydrocarbyl und -N(R2)(R3) ausgewählt ist;

20 jedes R4 unabhängig aus H und einem Hydrocarbyl ausgewählt ist; und

Amino-1,3,5-Triazinen, Glykolurilen und Oligomeren davon besteht,

(ii) ein 2,2-Dihydrocarbyloxyethanal und

20 20. Vernetzbare Zusammensetzung, umfassend:

(a) eine Vernetzerkomponente, umfassend ein N-1,2,2-Trihydrocarbyloxyethylderivat einer Aminoverbindung

1. Dérivé N-1,2,2-trihydrocarbyloxyéthylé d'un composé aminé, comprenant le produit de réaction :

dans lesquelles R1 est choisi parmi H, un groupe hydrocarbyle et -N(R7)2,

3. Dérivé de N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 2, caractérisé en ce que le composé aminé cor-

4. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 3, caractérisé en ce que le dérivé est un dérivé de

30 6. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 2, caractérisé en ce que le composé aminé corres-

7. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 6, caractérisé en ce que le dérivé est un dérivé de

8. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 1, caractérisé en ce que le 2,2-dihydrocarbyloxy

50 9. Dérivé N-1,2,2-trihydrocarbyloxyéthylé selon la revendication 8, caractérisé en ce que chaque groupe R6 repré-

(19) European Patent Ofﬁce EP000851893B1