Note: Descriptions are shown in the official language in which they were submitted.
1 328531
23189-6954
This invention relates to binders containing modlfied
copolymers which contain chemically lncorporated, oleflnically
unsaturated (meth)acrylate groups in addition to chemically
incorporated, intramolecular acid anhydride groups, and organic
polyamines containing blocked amino groups and to their use in
moisture-hardening coating compositions and sealing compounds.
BACKGROUND OF THE INVENTION
The use of combinations of organic compounds containing
at least two intramolecular carboxylic anhydride groups per
10 molecule, particularly copolymers containing succinic anhydride,
and polyhydroxyl compounds as binders for paints and coating
compositions is already known from EP-A-48 128.
However, the notion of applylng the principle of this
publication to the reaction of amines with anhydrides is
complicated by the fact that the reaction of amines with
anhydrldes ls a very fast reaction, even at room temperature,
which leads to crosslinked products with cleavage of the
anhydrlde. The resultlng, extremely short pot lives have hitherto
prevented polyanhydrides and polyamines from being used together
ln coatlng systems.
One possible solutlon to the problem is dlsclosed ln
DE-OS 2, 853 477 whlch descrlbes mixtures of blocked polyamlnes
and polyanhydrldes whlch have good pot llves, but harden on
addltlon of water to form crossllnked products. Ketlmlnes and
aldlmlnes obtalned by reactlon of polyamines wlth ketones and
aldehydes are descrlbed as suitable blocked polyamines.
Compounds containlng at least two cyclic carboxylic
:' ~
:, 1
'
:
., .
. '~
- 1 328531
anhydride groups in the molecule, more especially reaction
products of polyols with cyclic dianhydrides in a ratio of
hydroxyl to anhydride groups of 1:2, or copolymers of an
unsaturated cyclic anhydride with polyunsaturated compounds
or ~-olefins are mentioned as polyanhydrides.
The olefinically unsaturated compounds to be used in
the production of the copolymers are discussed in only very
broad terms in the general description of DE-OS 2 ~53 477;
in particular, there is no reference whatever to the guan-
titative ratios between the individual monomers to be used
in the production of the copolymers. The concrete dis-
closure of the Examples is confined to copolymers of buta-
diene oil and maleic anhydride in a ratio of 1:1 and to co-
polymers of wood oil with maleic anhydride. ~owever, these
copolymers are attended by disadvantages because their com-
bination with bis-ketimines or bis-aldimines ultimately
leads to heavily discolored products. In addition, coating
compositions containing unsaturated oils, such as butadiene
oil or wood oil, as binder component lead to coatings which
tend readily to turn brittle and are not weatherproof.
In addition, the Examples of DE-OS 2 853 477 show that
dimethylformamide i6 used as solvent~ in the processing of
the binders specifically described therein, in addition to
which unacceptable solids contents of only about 20% are
2~i used.
Another possibility of lengthening the pot lives is to
use oxazolanes instead of the amines.
Water-hardenable compositions of oxazolanes and poly-
anhydrides iare known in principle from DE-OS 2 610 406
where oxazolanes are combined with polyanhydrides to form
water-hardenable sealing compounds and adhesives. Reaction
products of polyunsaturated fatty acids with maleic anhy-
dride and polyanhydrides of C3_CB alkyl (meth)acrylate and
maleic anhydride, more especially of butyl acrylate and
maleic anhydride, are described as suitable polyanhydrides.
e A 26 158 2
. ~
: .
.
1 32853~ 23189-6954
The systems specifically described in DE-OS 2 610 406
are still greatly in need of improvement in regard to their
suitability for the production of high-quality, colourless paint
films combining hardness with high resistance to solvents and
chemicals. This applies both to the systems based on copolymers
of maleic anhydride and butyl acrylate which are described in the
Examples and to systems based on reaction products of maleic
anhydride with polyunsaturated fatty acid esters which lead to
yellowing end products.
The use of compounds containing unsaturated (meth)-
acrylate groups in combination with polyamines for lacquers and
coating systems is known, for example, from EP-A 34720, 40288, 165
580, 167 042 and 203 296.
However, the reactlvity of blnder combinations such as
these ls in need of improvement. Even where selected catalyst
systems are added, the degree of crossllnklng ls stlll not
sufflcient and requlres at least very long reactlon times,
partlcularly where hardening is carrled out at room temperature.
The ob~ect of the present invention is to provlde new
binder combinations which are suitable for the production of high-
quality C,ystems of adequate pot llfe optionally hardening under
the effect of atmo6pheric moisture. The coatings obtained are
intended to be clear, colourless, non-yellowing and ~olvent-
', resistant.
Thls ob~ect ls achleved by the provlsion of blndercomblnatlons contalnlng the modifled copolymers and blocked
polyamlnes descrlbed ln detall herelnafter.
.~
,. . . ' :: '
, ' :,: .
1 32853~
23189-6954
BRIEF DESCRIPTION OF THE INVENTION
In addition to (A) copolymers containing chemlcally
incorporated intramolecular carboxylic anhydride groups and
chemically incorporated (meth)acrylate groups, the binders or
binder combinations according to the invention described in detail
hereinafter contain (B) organic polyamines containing blocked
amino groups. In the hardening of the binders, which takes place
by a "double-cure" mechanism, there is an addition reactlon
between the unsaturated (meth)acrylate groups and the amino groups
(released under the effect of moisture) in addition to the very
fast reaction between the anhydride groups and the amino groups
treleased by the effect of moisture). Any hydroxyl groups addi-
tlonally present in the binders may be added onto the anhydride
groups so that there are numerous crosslinking possibilities,
enabling high crosslink densities to be obtained. It is thus
possible to satisfy even stringent requirements in regard to
resistance to solvents and chemicals.
DETAILED DESCRIPTION
The present invention relates to binders containing
(A) 30 to 99 parts by weight modifled copolymers havlng a
weight average molecular weight of from 1,500 to 75,000 of
~; olefinically unsaturated compounds containing chemically incor-
porated groups reactive to amlno groups ln an addition reaction,
characterized in that the modified copolymers contain both
(1) intramolecular carboxylic anhydrlde groups and
(11) olefinically unsaturated (meth)acrylate groups
ln chemlcally bound form as the groups reactlve to amlno groups,
.
'' ' ~
. .
,
,. : :, . ., . ~
1 32853 1
23189-6954
the anhydride equivalent weight being in the range from 392 to
9,800 and the (meth~acrylate equivalent weight in the range from
284 to 7,100,
(B) 1 to 70 parts by weight of a polyamine component
consisting of at least one organic polyamine contalning blocked
amino groups
and, optionally,
(C) auxiliaries and additives,
the nature of and quantitative ratios between components (A) and
(B) being selected so that, for every blocked amino group of
component (B), there are in all 0.2 to 8 anhydride and (meth)-
acrylate groups of component (A).
A process for the production of the modified copolymers
used as component (A) in the binders i8 characterized in that in a
flrst reaction step
(a) from 5 to 30 parts by welght copolymerizable, anhydride-
functional monomers and
(b) 70 to 95 parts by weight of other copolymerizable
monomers corresponding to general formulae (I), (II) and (III)
20 CH O R H O
I 3 11 12
CH ~C - C-OR CH2~C-R3 and/orCH2~C - COOR
(I) (II) ~III)
in which
i8 a linear or branched allphatlc hydrocarbon radical
containing from 1 to 18 carbon atoms,
R2 1~ hydrogen, a methyl group, an ethyl group, a chlorine or
fluorine atom,
~ 5
'' ' ' ; ~ ~ .' -
- , .
1 328531
23189-6954
R3 is an aromatic hydrocarbon radical containing 6 to 12
carbon atoms (by which are also meant aromatic radicals containing
aliphatic substituents), a nitrlle group, a carboxylate group
containing 2 to 9 carbon atoms, an alkoxy group containing 2 to 7
carbon atoms or an aminocarbonyl group optionally bearing C1-C6
alkyl substituents, optionally containing ether bridges, at the
nitrogen atom, and
R4 corresponds in its meaning to the definition given for R1,
but need not be identical with R1,
are converted by radlcal-initiated copolymerization into an
anhydride-functional copolymer and, in a second reaction step,
the copolymer thus obtained is modified by reaction with, based on
the copolymerized anhydride groups, a subequivalent quantity of
~ hydroxyl- or aminofunctional (meth)acrylates.
The present invention also relates to the use of these
binders as, or in, moisture-hardening coating compositions and
sealing compounds.
. The modified copolymers contain both intramolecular
carboxylic anhydride groups and also olefinically unsaturated
20 (meth)acrylate groups in chemically bound form and have a weight
average molecular weight, as determined by gel permeation
chromatography, of from 1,500 to 75,000, preferably from 3,000 to
50,000 and more preferably from 3,000 to 30,000. The anhydride
I equivalent weight (quantity in `'g" containing 1 mol of chemically
: incorporated, intramolecular carboxyllc anhydride groups) iB in
the range from 392 to 9,800 and preferably in the range from 784
to 4,900. The (meth)acrylate equivalent weight (quantity in "g"
~6
~- ,: , . :.
1 328531
23189-6954
containing a total of 1 mol of chemically incorporat~d acrylate
and/or methacrylate groups) is in the range from 284 to 7,100 and
preferably in the range from 568 to 3,900.
The process for the production of the modlfied copoly-
mers, is carried out in a two-step reaction in which a copolymer
(A') containing intramolecular carboxylic anhydride groups is
prepared in the first step and is then converted into the modified
copolymers (A) according to the invention in the second step by
reaction with hydroxyl- or aminofunctional (meth)acrylates.
: 10 The copolymers (A') are preferably prepared from a mon-
~,
6a
.,~
; ~ -
.:`, -
:~,. .
, :
'' ' : " ' :
.: :
,- '
. .
1 32853 1
omer mixture consisting of
a) from 5 to 30 parts by weight copolymerizable monomers
containing anhydride groups and
b) from 70 to 95 parts by weight of other copolymerizable
monomers corresponding to the general formulae
IH3 l2
CH2~C-COOR1 , CH2 C-R3 and/or CH2~C-COOR4
(I) tII) (III)
in which
R1 is a linear or branched aliphatic hydrocarbon
radical containing from 1 to 18 carbon atoms,
R2 is hydrogen, a methyl group, an ethyl group, a
. chlorine atom or fluorine atom,
R3 i6 an aromatic hydrocarbon radical containing 6
to 12 carbon atoms (by which are also meant
aromatic radical6 containing aliphatic substi-
tuents), a nitrile group, a carboxylate group
containing 2 to 9 carbon atoms, an al~oxy group
containing 2 to 7 carbon atoms or an amino car-
bonyl group optionally bearing C~-C0 alkyl sub-
stituents - optionally containing ether bridges
- at the nitrogen atom and
: 25 R~ corresponds in its meaning to the definition
given for Rl, but need not be identical with R~.
Typical examples o~ monomers a) are, for example, ita-
conic anhydride, maleic anhydride, maleic anhydride being
pre~erred.
Particularly pre~erred monomer~ b) are those corre-
sponding to the above general formulae ln which
R~ ie a linear or branched aliphatic hydrocarbon radical
containing 1 to 8 carbon atoms,
R2 i6 hydrogen or a methyl group,
R3 i6 an aromatic hydrocarbon radical containing 6 to 12
Le A 26 158 7
. .
.
--
: ' :
,
. .. . ~ . .
, .
1 32853 1
.
carbon atoms (by which are also meant aromatic radi-
; cals containing aliphatic substituents), a nitrile
group, a carboxylate group containing 2 to 9 carbon
atoms, an alkoxy group containing 2 to 7 carbon atoms
S or an aminocarbonyl group optionally bearing el-C6
alkyl substituents - optionally containing ether
.~ bridges - at the nitrogen and
: R~ corresponds in its meaning to the definition just
given for Rl.
Typical examples of suitable or preferred radicals R
and R~ are methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-
butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl or
n-dodecyl radicals.
Typical examples of suitable or preferred substituents
lS R2 are hydrogen, methyl groups, ethyl groups, chlorine or
fluorine atoms.
Typical examples of suitable or preferred radicals R3
are aliphatie radieals of the type ~ust mentioned by way of
example for Rl, exeept for methyl, and in addition phenyl,
. 20 eyclohexyl, 2-, 3- and 4-methylphenyl, propoxy, n-butoxy,
aeetyl, propionyl, n-butyryl or N-methoxymethyl aminoear-
bonyl radieals.
I Partieularly preferred eomponents for the produetion
of the eopolymers A') are those eopolymers eorre~ponding to
the above definitions in whieh
a) from 5 to 30 parts by weight and more espee~lly from
8 to 25 parts by welght maleie anhydride,
b) from 5 to 85 parts by weight and more espeelally from
25 to 73 part~ by weight monomers eorrespondlng to the
following formulae
CIH3 ~2
CH2~C-COOR1 and/or CH2~C-R3
:1 .
Le A 26 158 8
~ . .
'`
~..
1 328531
and
from 10 to 6s parts by weight and more especially from
19 to S0 parts by weight monomers corresponding to the
following formula
H
CH2=C-C00~4
are present in copolymerized form.
In a particularly preferred embodiment, component A'~
ia a copolymer corresponding to the above definition in
which - per 100 parts by weight maleic anhydride - from 40
to 140 parts by weight of other monomers selected from the
group consisting of styrene, vinyl toluene, ~-methyl sty-
rene, ~-ethyl styrene, nucleus-substituted diethyl sty-
; renes, isopropyl styrenes, butyl styrenes and methoxy
~tyrenes optionally representing isomer mixtures, ethyl
vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
n-butyl vinyl ether, isobutyl vinyl ether, vinyl acetate,
vinyl propionate, vinyl butyrate and mixtures of these
monomers are present in copolymerized form, optionally in
addition to other comonomers.
The copolymers A') may be prepared by copolymerization
of the monomers mentioned by way of example by standard
radical polymerization processes, such as for example bulk
or solution polymerization.
The monomer~ are copolymerized at temperatures in the
range ~rom 60 to 200-C and preferably at temperatures in
the range from 80 to 160-C in the pre~ence of radical
formers and, optionally, molecular weight regulators.
The copolymerization i~ preferably carried out in
inert solvents at solids contents o~ 30 to 95% by weight.
8uitable solvent~ are, for example, aromatic hydrocarbons,
~ such as benzene, toluene, xylene; esters, such as ethyl
; 35 acetate, butyl acetate, methyl glycol acetate, ethyl glycol
I Le A 26 15R 9
.
.. . . .
. .
~ . :
1 328531
acetate, methoxypropyl acetate; ethers, such as tetrahydro-
furan, dioxane, diethylene glycol dimethyl ether; ketones,
such as acetone, methyl ethyl ketone, methyl isobutyl
ketone.
The copolymerization may be carried out continuously
or discontinuously. Normally, the monomer mixture and the
initiator are introduced uniformly and continuously into a
polymerization reactor and the corresponding quantity of
polymer is continuously removed at the same time. It is
thus possible with advantage to produce chemically substan-
tially uniform copolymers. Chemically substantially uni-
form copolymers may also be produced by allowing the re-
action mixture to run at a constant rate into a stirred
vessel without removal of the polymer.
It is also possible, for example, initially to intro-
duce part of the monomers, for example in solvents of the
type mentioned, and to add the remaining monomers and auxi-
liaries either separately or together to the monomers ini-
tially introduced at the reaction temperature.
In general, the polymerization is carried out at an
excess pressure of 0 to 20 bar. The initiators are used in
quantities of from 0.05 to 15% by~weight, based on the
total quantity of monomers.
Suitable initiators are standard radical initiators
such as, for example, aliphatic azo compounds, such as azo-
diisobutyronitrile, azo-bis-2-methyl valeronitrile, 1,1'-
azo-bis-l-cyclohexane nitrile and 2,2'-azo-bis-isobutyric
; acid alkyl ester; symmetrical diacyl peroxides, for exampleacetyl, propionyl or butyryl peroxide, bromine-, nitro-,
methyl- or methoxy-substituted benzoyl peroxides,
symmetrical peroxydicarbonates, for example
diethyl, diisopropyl, dicyclohexyl and also dibenzoyl
peroxydicarbonate; tert.-butyl peroctoate, tert.-butyl
perbenzoate or tert.-butyl phenyl peracetate, and also
peroxycarbonates such as, for example, tert.-butyl-N-
!
ke A 26 158 10
1 3~531
(phenylperoxy)-carbonate or tert.-butyl-N-(2-, 3- or 4-
chlorophenylperoxy)-carbonate; hydroperoxides, such as for
example tert.-butyl hydroperoxide, cumene hydroperoxide;
dialkyl peroxides, such as dicumyl peroxide, tert.-butyl
cumyl peroxide or di-tert.-butyl peroxide.
~o regulate the molecular weight of the copolymers,
standard regulators may be used during their production,
including for example tert.-dodecyl mercaptan, n-dodecyl
mercaptan or diisopropyl xanthogene disulfide. The molec-
ular weight regulators may be added in quantities of from
0.1 to 10% by weight, based on the total quantity of
~onomers.
The solutions of the copolymers A') obtained during
the copolymerization reaction may then be used for the
modification reaction without further working up. However,
it is of course also possible to free the copolvmers from
any residues of unreacted monomers still present and from
solvent and to modify the copolymers A') present as
distillation residue.
To produce the modified copolymers A), the copolymers
A') containing carboxylic anhydride groups are reacted with
hydroxyl- or aminofunctional (meth)acrylates in such a way
that the cyclic anhydride groups are partially opened by an
addition reaction of the functional (meth)acrylates men-
tioned with formation of a semiester or semiamide struc-
ture. Modified copolymers A) are then present, containing
both unsaturated (meth)acrylate groups and also intramolec-
ular carboxylic anhydride groups in chemically bound ~orm.
The ring-opening reaction of the cyclic carboxylic
anhydride groups in the described copolymers A') by amino-
functional (meth)acrylates, such as for example N-tert.-
butyl aminoethyl methacrylate, takes place even at low
temperatures, such as room temperature for example. How-
ever, it is of advantage to accelerate the reaction by
heating to 120'C. To suppress unwanted secondary poly-
Le A 26 158 11
''' '
,, ~ ' ' ~ '
., , " ~
: :
:, .
1 328531
merization reactions, it is best to use polymerization
inhibitors such as, for example, hydroquinone or hydro-
quinone monomethyl ether.
The corresponding ring-opening reaction by hydroxyl-
functional (meth)acrylates, such as for example hydroxy-
ethyl (meth)acrylate, requires temperatures in the range
from 70 to 150C and preferably in the range from 80 to
130C. This reaction is also best carried out in the
presence of polymerization inhibitors of the type mentioned
by way of example above. The ring-opening reaction of the
cyclic carboxylic anhydride groups may be carried out, for
example, with any (meth)acrylates having a molecular weight
in the range from 116 to 1,500 or mixtures thereof which
contain one free hydroxy group or one primary or secondary
amino group. These products may also contain several
(meth)acrylate groups. For example, it is possible to use
hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydr-
oxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydr-
oxybutyl acrylate, glycerol diacrylate, glycerol dimeth-
acrylate, trimethylolpropane diacrylate, trimethylolpropane
dimethacrylate, pentaerythritol triacrylate, penterythritol
trimethacrylate, mono(meth)acrylates of polyethoxylated or
propoxylated ethylene or propylene glycol, dimethacrylates
of polyethoxylated or propoxylated trimethylolpropane, tri-
tmeth)acrylates of polyethoxylated or propoxylated penta-
erythritol, N-tert.-butylamino ethyl methacrylate.
Tertiary amines acting as cataly6ts, such as for
example triethylamine or tributylamine, may additionally be
added to accelerate the ring-opening reaction.
In the second step of the process according to the
invention, i.e. the modification of the copolymers A'), the
hydroxyl- or aminofunctional (meth)acrylates mentioned by
way of example are generally used in such quantities that,
for every carboxylic anhydride group in the copolymers A'),
there are from 0.01 to 0.99 hydroxyl groups and/or amino
Le A 26 158 12
' ~
.
- 1 328531
groups of the unsaturated modification component.
As already mentioned, the modification reaction may be
carried out both in the absence of organic solvents of the
type mentioned by way of example or even in the presence of
5the 801vents used in the production of the copolymers A').
In addition to the modified copolymers A), the binders
according to the invention contain organic polyamines con-
taining blocked amino groups as hardener 8). "Blocked
amino groups" are understood to be groups which react with
10water with release of primary and/or secondary amino
groups. Particularly preferred blocked polyamines B) are
compounds which contain aldimine, ketimine, oxazolane,
hexahydropyrimidine and/or tetrahydroimidazole groups and
which, at the 8ame time, may also contain several of these
groups.
The blocked polyamines B) have a weight average molec-
ular weight in the range from 86 to 10,000 and preferably
in the range from 250 to 4,000 and, on a statistical
average, contain from 1 to 50, preferably from 2 to 10 and
20more preferably from 2 to 4 structural units corresponding
to the following general formulae
I
R ~C ~ 7 ~ ,C~N,R7 and/or R ,C-N
~ IV ) ` ~ Vl )
in Which
R~ and ~ may be the 8ame or di~erent and repreaent
hydrogen, aliphatic hydrocarbon radical8 containing
from 1 to 18 carbon atoms, cycloaliphatic hydrocarbon
radical8 containing from 5 to 10 carbon atoms, arali-
phatic hydrocarbon radicals containing from 7 to 18
carbon atoms or phenyl radicals; the two substituents
Le A 26 158 13
.~, .
:
1 32853 1
R5 and R8 may also form a 5-membered or 6-membered
cycloaliphatic ring together with the adjacent carbon
atom and, preferably, at most one of these substitu-
ents is hydrogen, and
R~ is a difunctional aliphatic hydrocarbon radical con-
taining 2 to 6 carbon atoms, with the proviso that 2
or 3 carbon atoms are arranged between the two nitro-
gen atoms.
The molecular weights mentioned may be determined by
the method of gel permeation chromatography (molecular
weights above 1,000) or from the stoichiometry of the
starting materials used for the production of the compounds
(molecular weights up to 1,000).
Components B) preferably used are, for example, those
containing hexahydropyrimidine or tetrahydroimidazole
6tructures corresponding to general formula (IV), in which
Rs and F~ may be the same or different and represent ali-
phatic hydrocarbon radicals containing 2 to 10 carbon
atoms: one of these substituents may also be hydrogen and
R~ may be an optionally alkyl-substituted ethylene or tri-
methylene radical.
The blocked polyamines of the type mentioned are pro-
duced in known manner by reaction of corresponding alde-
hyde~ or ketones with the corresponding polyamines.
Aldehydes or ketones ~uitable for the production of
the compounds B) containing hexahydropyrimidine or tetra-
hydroimidazole groups are, for example, those corresponding
to the following general formula:
,C O
:, R6
which preferably have ~ molecular weight of from 72 to 200
~ketones) or from 58 to 250 (aldehydes).
Le A 26 1$8 14
~.
... .. .
, ' .
1 3~853 1
Examples of such aldehydes and ketones are acetone,
methyl ethyl ketone, methyl propyl ketone, methyl isopropyl
ketone, methyl-n-butyl ketone, methyl isobutyl ketone,
methyl-n-amyl ketone, methyl isoamyl ketone, methyl heptyl
ketone, diethyl ketone, ethyl butyl ketone, ethyl amyl ke-
tone, diisopropyl ketone, diisobutyl ketone, cyclohexanone,
isophorone, methyl-tert.-butyl ketone, 5-methyl-3-hepta-
none, 4-heptyl ketone, 1-phenyl-2-propanone, acetophenone,
methyl nonyl ~etone, 3,3,5-trimethyl cyclohexanone, formal-
dehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-
butyraldehyde, trimethyl acetaldehyde, 2,2-dimethyl propan-
al, 2-ethyl hexanal, 3-cyclohexene-1-carboxaldehyde, hexan-
al, heptanal, octanal, valeraldehyde, benzaldehyde, tetra-
hydrobenzaldehyde, hexahydrobenzaldehyde, acrolein, croton-
aldehyde, propargylaldehyde, p-tolylaldehyde, 2-methyl pen-
tanal, 3-methyl pentanal, phenyl ethanal, 4-methyl pen-
tanal.
Aldehydes and ketones preferably used for the produc-
tion of the compounds containing hexahydropyrimidine or
tetrahydroimidazole groups are butyraldehyde, isobutyral-
dehyde, trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-
ethyl hexanal, hexanal, 3-cyclohexane-1-carboxaldehyde,
heptanal, octanal, hexahydrobenzaldehyde, 2-methyl pentan-
al, cyclohexanone, cycloheptanone, methyl isopropyl ketone,
acetone, 3,3,5-trimethyl cyclohexanone and methyl cyclo-
; hexanone.
It is of course also possible to use mixtures of dif-
ferent ketones and aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
~he polyamines used for the production of the com-
pounds containing hexahydropyrimidine or tetrahydroimidaz-
ole groups are, in particular, organic compounds containing
at least two primary and/or secondary amino groups.
Suitable polyamines are, for example, those corre-
; 35 sponding to the following general formula
Le A 26 158 15
;
- .- ','
1 328531
Ra-NH-R7-NH-Rg
in which
R, is as defined above and
R8 and Rg may be the same or different and represent hydro-
qen, aliphatic hydrocarbon radicals containing from 1
to 10 and preferably from 1 to 4 carbon atoms, cyclo-
. aliphatic hydrocar~on radicals containing from 5 to lo~ and preferably 6 carbon atoms or aromatic hydrocarbon
: radicals containing from 7 to 15 and preferably 7 car-bon atoms, the hydrocarbon radicals mentioned, partic-
ularly the aliphatic hydrocarbon radicals mentioned,
optionally containing heteroatoms, such as oxygen,
nitrogen or sulfur in the form of ether, ester, amide,
urethane, oxirane, ketone, lactam, urea, thioether,
thioester or lactone groups; the radicals may also
contain reactive hydroxyl or amino groups.
Particularly preferred polyamines are those in which
. R8 and R~ may be the same or different and represent hydro-gen and/or C~-C6 alkyl radicals, such as methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, n-pentyl
or n-hexyl radical6, or in which at least one of the sub-
stituents Ra and R~ is a group of~the type obtained by
addition of an amine hydrogen atom onto an olefinically
unsaturated compound. Olefinically unsaturated compounds
suitable for the production of modified polyamines such as
these are, for example, derivatives Or ~meth)acrylic acid,
such as esters, amides, nitriles or, for example, aromatic
vinyl compounds, such as styrene, ~-methyl styrene, vinyl
toluene or, for example, vinyl esters, such as vinyl ace-
tate, vinyl propionate, vinyl butyrate or, for example,
vinyl ethers, such as ethyl vinyl ether~propylvinyl ether,
butyl vinyl ether, or monoesters and diesters of fumaric
acid, maleic acid or tetrahydrophthalic acid.
Re and/or R~ may also represent an aminoalkyl or hy-
droxyalkyl radical containing, for example, 2 to 4 carbon
i Le A 26 158 16
.1
, : -
: .
,
~, ,
. ."
;' , ~ '
,
1 32~531
atoms.
Especially preferred polyamines are ethylenediamine,
1,2-propylenediamine, 1,3-propylenediamine, 1,2- and 1,3-
butylenediamine, diethylenetriamine and derivatives of
these polyamines.
Compounds containing oxazolane groups of general
formula (V) suitable for use as component B) are preferably
those in which R5 and R~ may be the same or different and
represent hydrogen or aliphatic hydrocarbon radicals
containing 1 to 18 and more especially 1 to 8 car~on atoms,
or in which the substituents R5 and R~ together with the
carbon atom of the heterocyclic ring, form a cycloaliphatic
ring containing in all from 4 to 9 carbon atoms, more
especially a cyclohexane ring, with the proviso that at
most one of the substituents R5 and R6 is hydrogen, and R7
i~ an alkenyl radical containing 2 to 4 and preferably 2
to 3 carbon atoms, with the proviso that at least 2 carbon
atoms sre arranged between the oxygen atom and the nitrogen
atom.
The oxazolane-containing component B) is produced in
known manner by reaction of corresponding aldehydes or ke-
tones having the following formula
; R5~
C~O
R6~
. .
with 6ultable hydroxyamines of the type mentioned in more
detail hereinafter.
Ba~ically, suitable aldehydes or ketones are those of
the type already mentloned by way o~ example in the fore-
going. Preferred ~ldehydes or ketones in thi~ case are
butyraldehyde, isobutyraldehyde, trimethyl acetaldehyde,
2,2-dimethyl propanal, 2-ethyl hexanal, 3-cyclohexene-1-
carboxaldehyde, hexahydro~enzaldehyde, cyclopentanone, cy-
.
Le A 26 158 17
.
1 32~531
clohexanone, methyl cyclopentanoner methyl cyclohexanone,
3,3,s-trimethyl cyclohexanone, cyclobutane, methyl cyclo-
butane, acetone, methyl ethyl ketone and methyl isobutyl
ketone.
It is of course also possible to use mixtures of dif-
ferent ketones and aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
Hydroxyamines are, in particular, organic compounds
which contain at least one aliphatic group and at least one
aliphatically bound hydroxyl group. The hydroxyamines
generally have a molecular weight in the range from 61 to
500 and preferably in the range from 61 to 300.
Suitable hydroxyamines are, for example, bis-(2-
hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-
hydroxybutyl)-amine, bis-(3-hydroxypropyl)-amine, bis-~3-
hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(2-hydroxy-
ethyl)-amine, 2-(methylamino)-ethanol, 2-(ethylamino)-
ethanol, 2-(propylamino)-ethanol, 2-(butylamino)-ethanol,
2-amino-2-methyl-1-propanol,2-amino-2-ethyl-1-propanol,2-
amino-2-propyl-1-propanol, 2-amino-2-methylpropane-1,3-
diol, 2-amino-3-methyl-3-hydroxybutane, propanolamine,
ethanolamine.
Particularly preferred hydroxyamines are bis-(2-hy-
droxyethyl)-amine, bis-(2-hydroxypropyl)-Amine, bis-(2-hy-
droxybutyl)-amine, bis-(3-hydroxyhexyl)-amine, 2-(methyl-
amino)-ethanol, 2-(ethylamino)-ethanol, 2-amino-2-methyl-
~ l-propanol, 2-amino-2-ethyl-1-propanol, propanolamine and
; ethanolamine.
Preferred compounds containlng aldimlne or ketimine
; 30 groups are thoee which contain structural units havlng the
followlng general formula
R5~
C~N-
- Le A 26 ~58 18
.:
1 32~531
in which
Rs and R6 may be the same or different and represent hydro-
gen or aliphatic hydrocarbon radicals containing 1 to
8 carbon atoms which may also be attached together
with the carbon atom to form a cycloaliphatic ring,
more especially a cyclohexane ring.
In principle, the aldehydes or ketones already men-
tioned by way of example in the foregoing are suitable for
the production of these compounds. Preferred aldehydes or
ketones in this case are butyraldehyde, isobutyraldehyde,
trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-ethyl
hexanal, 3-cyclohexene-1-carboxaldehyde, hexahydrobenz-
aldehyde and, in particular, ketones which have a boiling
point below 170-C and which show high ~olatility at room
temperature, including for example methyl isobutyl ketone,
methyl isopropyl ketone, diethyl ketone, diisobutyl ketone,
methyl tert.-butyl ketone.
It is of course also possible to use mixtures of dif-
ferent ketones or aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
The polyamines used for the production of component B)
containing ketimine or aldimine groups are, in particular,
; organic compounds containing at least two aliphatically
and/or cycloaliphatically bound primary amino groups. How-
` 25 ever, the use of polyamines containing aromatic amino
groups is also possible, although less preferred. The
polyamines generally have a molecular weight of from 60 to
500 and preferably from 88 to 400, although it i5 also
pos~ible to use relatively high molecular weight, amino-
terminated prepolymers as the polyamine component in the
production of component B).
Particularly preferred polyamines are diprimary ali-
phatic or cycloaliphatic diamines such as, for example,
tetramethylenediamine, hexamethylenediamine, isophorone-
diamine, bis-(4-aminocyclohexyl)-methane, bis-aminomethyl
Le A 26 158 19
,
~ .,
~!,' . . ~, , '~
.
.. ' . : ,
'
1 32~531
hexahydro-4,7-methanoindane, 1,4-cyclohexanediamine, 1,3-
cyclohexandiamine, 2-methyl cyclohexanediamine, 4-methyl
cyclohexanediamine, 2,2,5-trimethyl hexanediamine, 2,2,4-
trimethyl hexanediamine, butane-1,4-diol bis-(3-aminopro-
S pyl)-ether, 2,5-diamino-2,5-dimethyl hexane, bis-amino-
methyl cyclohexane, bis-(4-amino-3,5-dimethylcyclohexyl)-
methane or mixtures thereof.
Tetramethylenediamine, hexamethylenediamine, isophor-
onediamine, bis-aminomethyl cyclohexane, 1,4-cyclohexane-
diamine, bis-aminomethyl hexahydro-4,7-methanoindane and
bis-(4-aminocyclohexyl)-methane are particularly preferred.
In addition to these preferred diamines, prepolymers
terminated by primary amino groups, i.e. compounds contain-
ing at least two terminal amino groups and having a molec-
ular weight of from 500 to 5,000 and preferably from 500 to
2,000, may also be used for the production of the aldimines
or ketimines. These compounds include, for example the
aminopolyethers known per se from polyurethane chemistry,
of the type described for example in EP-A 0 081 701, or re-
2Q action products - for example containing amide, urea, ure-
thane or secondary amino groups - of at least difunctional
carboxylic acids, isocyanates or epoxides with diamines of
the type mentioned by way of example above, these reaction
products also containing at least two primary amino groups.
Mixtures of such relatively high molecular weight poly-
amines with the low molecular weight polyamines mentioned
may also be used.
Aromatic polyamines which, in principle, are also
~uitable, but les8 pre~erred, for the production of the
3~ aldimines or ketimines include, for example, 2,4- and 2,6-
diaminotoluene, 1,4-diaminobenzene or 4,4'-diaminodiphenyl
methane.
Component B), which may contain aldimine, ketimine,
oxazolane, hexahydropyrimidine or tetrahydroimidazole
groups, is prepared by reaction of the starting components,
Le A 26 158 20
1 32~531
generally in such quantitative ratios that the amino com-
pounds are present in a 1 to 1.5-fold molar excess, based
on the carbonyl groups, according to the particular reac-
tion required. Catalytic quantities of acidic substances,
such as for example p-toluenesulfonic acid, hydrochloric
acid, sulfuric acid, aluminium(III) chloride, tin com-
pounds, may optionally be used to accelerate the reaction.
The reaction is generally carried out at a temperature
in the range from 60 to 180C, the reaction being carried
out in the presence of an entraining agent to remove the
water of reaction until the calculated quantity of water
has been eliminated or until no more water is eliminated.
The entraining agent and any unreacted starting mater-
ials present are then removed by distillation. Suitable
entraining agents are, for example, toluene, xylene, cy-
clohexane, octane. The crude products thus obtained may be
used without further purification as component B) for the
production of the binder combinations. Where the purity of
component B? has to meet particularly stringent require-
ments, it is also possible to obtain components B) in pure
form, for example by distillation.
The preferred, blocked polyamines of component B) also
include those which contain 2 to 10 structural units corre-
sponding to general formula (IV), (V) or (VI) and which are
obtained by linkage of different compounds containing such
structural units to form, for example, ester, ether, amide,
urea and/or urethane bonds.
The compounds containing structural units correspond-
ing to the above formulae, which are to be linked to one
another in this way, must contain at least one primary or
~econdary amino group or at least one hydroxyl group in
non-blocked form. Suitable modifying agents, which are
suitable for linking the compounds mentioned, are for
example, polyisocyanates, polyepoxides, polycarboxylic
acids and polyacryloyl compounds.
Le A 26 158 21
;. ,
. .
.
~\
,
1 32853 1
Polyisocyanates suitable for this modification reac-
tion are, for example, aliphatic, cycloaliphatic, arali-
phatic, aromatic and heterocyclic polyisocyanates of the
type described, for example, by W. Siefken in Justus
Liebigs Annalen der Chemie, 562, pages 75 to 1346, for
example 1,4-tetramethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-
diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-
1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyan-
atomethyl cyclohexane, 2,4- and 2,6-hexahydrotolylene di-
- isocyanate, hexahydro-1,3- and -1,4-phenylene diisocyanate,
perhydro-2,4'- and/or -4,4'-diphenyl methane diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, di-
phenyl methane-2,4'- and/or -4,4'-diisocyanate, naphthy-
lene-1,5-diisocyanate, mixtures of these and other polyiso-
cyanates, polyisocyanates containing carbodiimide groups
(for example DE-OS 10 92 007), polyisocyanates containing
allophanate groups (for example GB-P 944,890), polyiso-
cyanates containing isocyanurate groups (for example DE-PS
10 22 789, DE-PS 12 22 067), polyisocyanates containing
urethane groups (for example US-P 3,394,164) or polyi80-
; cyanates obtained by reaction of at least difunctional hy-
droxy compounds with excess, at least difunctional iso-
: 25 cyanates, polyisocyanates containing biuret groups (for
example DE-PS 11 01 394) and prepolymers or polymers con-
taining at lea6t two isocyanate groups.
Representatives of these compounds, which may be used
in accordance with the invention, are described, for ex-
ample, in High Polymers, Vol. XVI, "Polyurethanes, Chem-
lstry and Technology", Interscience Publishers, New York/
London, Vol. I, 1962, pages 32 to 42 and 45 to 54 and Vol.
. II, 1964, pages 5 - 6 and 198 - 199 and in Kunststoff Hand-
buch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag,
. 35 Munchen, 1966, pages 45 to 72.
Le A 26 15~ 22
, .
' ' :
1 32853 1
Polyepoxides suitable for the modification reaction
mentioned above are, for example, aliphatic, cycloalipha-
tic, araliphatic, aromatic and heterocyclic compounds con-
taining at least two epoxide groups, such as for example
epoxidized esters of aliphatic, polybasic acids with un-
saturated monohydric alcohols, glycidyl ethers of poly-
hydroxy compounds, glycidyl esters of polycarboxylic acids,
copolymers containing epoxide groups.
Polycarboxylic acids suitable for the modification
reaction are, for example, aliphatic, cycloaliphatic, aral-
iphatic, aromatic and heterocyclic compounds containing at
least two carboxyl groups, such as for example adipic acid,
dimeric fatty acid, phthalic acid, terephthalic acid, iso-
phthalic acid, fumaric acid, maleic acid, succinic acid,
trimellitic acid, pyromellitic acid, copolymers containing
(meth)acrylic acid, acidic polyesters or acidic polyamides.
Instead of the acids mentioned by way of example, it
is also possible to use the corresponding anhydrides (pro-
viding the acids in question form intramolecular anhy-
dride6) or the corresponding simple alkyl esters, particu-
larly methyl esters, for the modification reaction.
Compounds containing at least~ two olefinic double
bonds of the type mentioned above, which are suitable for
the modification reaction, are in particular derivatives of
acrylic acid or methacrylic acid, such as for example
hexanediol-bie-(meth)acrylate, trimethylolpropane tris-
(meth)acrylate, pentaerythritol tetra-(meth)acrylate, OH-
functional polyesters or polyacrylates esterified with
acrylic acid, diethylene glycol dimethacrylate, reaction
products o~ polyisocyanates with hydroxyalkyl ~meth)acry-
late.
In the modification reaction to produce components ~)
of relatively high functionality, it is also possible to
use mixtures of different blocked amines which contain at
least one free hydroxyl group or amino group reactive to
Le A 26 158 23
.. . . ... .
,. .
: . -
:. : -
,. .
1 32~53 1
the modifying agent.
Polyamines containing ketimine or aldimine groups,
which still contain at least one free primary or secondary
amino group or a free hydroxyl group, are obtained, for
example, by reaction of at least difunctional amines with
ketones and/or aldehydes in such equivalent ratios that at
least one amino group remains free.
Even where, for example, polyamines containing at
least one secondary amino group in addition to primary
amino groups are used, the reaction with aldehydes or
; ketones results in the formation of aldimines or ketimines
which contain at least one free secondary amino group
(where an equivalent ratio of primary amino groups to car-
bonyl groups of 1:1 has been used) or which contain free
primary amino groups in addition to at least one secondary
amino group (where the carbonyl compounds have been used in
less than the equivalent quantity, based on the primary
amino groups). Primary/secondary polyamines such as these
are, for example, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, dipropylenetriamine, tripropylene-
tetramine.
Compounds containing oxazolane groups, which also have
- at least one reactive primary or secondary amino group or
a hydroxy group, are obtained for example by reaction of
hydroxyamines containing at least one other hydroxy group
and/or primary or secondary amino qroup in addition to a
hydroxy group and a secondary amino group or by reaction of
suitable hydroxyamines containing a hydroxy group and a
primary amino group in suitable equivalent ratios with ke-
tones and/or aldehydes of the type described, for example,
in the foregoing. Suitable hydroxyamines are, for example,
bis-(2-hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine,
bis-~2-hydroxybutyl)-amine, bis-(3-hydroxypropyl)-amine,
bis-~3-hydroxyhexyl)-amine, N-~2-hydroxypropyl)-N-(6-hy-
droxyhexyl)-amine, 2-amino-2-methyl-1-propanol, 2-amino-2-
e A 26 158 24
.. r- . , :
'' ' :~ '
1 32~531
methylpropane-1,3-diol, 2-amino-3-methyl-3-hydroxybutane,
aminoethanol.
The hydroxyamines containing oxazolane groups, which
also have at least one free primary or secondary amino
group or a hydroxy group, are prepared by reaction of the
starting components mentioned in such an e~uivalent ratio
of amino or hydroxy groups to aldehyde or ketone groups
that at least one primary or secondary amino group or a hy-
droxy group is not blocked and is available for the subse-
quent reaction with the reactant used as modifying agent.
Compounds containing hexahydropyrimidine or tetrahy-
droimidazole groups, which also have at least one reactive
primary or secondary amino group or a hydroxy group, are
obtained for example by reaction of hydroxyamines contain-
ing two secondary amino groups in addition to at least one
hydroxy group, such as for example N-methyl-N'-4-hydroxy-
tetramethylenediamine, or by reaction of polyamines con-
taining at least one primary amino group or at least two
other secondary amino groups in addition to at least one
secondary amino group, such as for example N-methyl-1,3-
diaminoethane, N-methyl-1,3-diaminopropane, N-methyl-1,3-
diaminobutane, diethylenetriamine, N-methyl diethylenetri-
amine, N,N-bis-(3-aminopropyl)-amine, N,N'-dimethyl di-
ethylenetriamine.
The compounds containing hexahydropyrimidine or tetra-
hydroimidazole groups, which also have at least one free
primary or secondary amino group or a hydroxyl group, are
prepared by reaction of the starting compounds mentioned in
~uch an equivalent ratio of amino or hydroxy groups to al-
dehyde or keto groups that at least one primary or sec-
ondary amino group or a hydroxyl group is not blocked and
is available for the subsequent reaction with the reactant
used as modi~ying agent.
The following structural units, which are suitable for
the synthesis of relatively high molecular weight compon-
Le A 26 158 25
,, , - .
, ~ .
." ' ' .
1 328531
ents B) of the type in question containing ester, ether,
amide, urea, urethane bonds, are mentioned by way of
example for the purposes of further illustration:
- bisketimine of diethylenetriamine and acetone
H
CH3~ ¦ ,CH3
C~N-cH2-cH2-N-c~2-cH2-N~c~cH
- aldimine of isophoronediamine and isobutyraldehyde
,H
H3 ~ H2-N~C~ ~CH3
H~ ~ ~CH3
- oxazolane of diethanolamine and isobutyraldehyde
r~
Ho-cH2-cH2
H3C-CH-CH3
- hexahydropyrimidine ofN-methyl-1,3-diaminopropane and
cyclohexanone
~
H- ~ N-CH3
I~ the modl~ylng agents mentioned by way of example
above are reacted with hexahydropyrlmidines or tetrahydro-
lmidazole~ containlng free primary or secondary amino or
hydroxyl groups, hexahydropyrlmidines or tetrahydroimida-
35zoles of higher runctionality are formed. The same applies
Le A 26 158 26
.
. .
" . ., ~: ;
1 32~531
to the modification of aldimines or ketimines and to the
modification of oxazolanes.
However, if the modifying agents are reacted with mix-
tures of hexahydropyrimidines, tetrahydroimidazoles, ald-
imines, ketimines and/or oxazolanes containing free primary
or 6econdary amino or hydroxyl groups, crosslin~ing compon-
ents B) are formed in which hexahydropyrimidines, tetra-
hydroimidazoles, ~etimines, aldimines and/or oxazolanes are
chemically linked to one another.
Accordingly, various compounds suitable as component
B) may be obtained by these modification or crosslinking
reactions.
The modification reaction is normally carried out in
a solvent of the type mentioned by way of example above at
reaction temperatures of 30 to 180-C, optionally using a
water 6eparator.
In general, an equivalent ratio is selected between
reactive groups of the blocked polyamines and the reactive
groups of the "modifying agent". However, it is also
possible to use the "modifying agents" in less than
equivalent quantities, for example in 0.75 to 0.99 times
the equivalent quantity.
Polyamines suitable as component B), which may be ob-
tained by the modification reactions mentioned, are for ex-
ample compounds corresponding to the following formulae:
~ ~ ~ ~
CH3 1 C-NH-~CH2)6-NH-C ~ CH3
Le A 26 158 27
. , .
.,
~ t
..
.
1 328531
CH~C~ CH~ I n
X
1l 1l n
~O-C-NH- ~cH2)6-NH-c-o~cH2)2-NxD
lPlY~ 1l
,CH2CH2-N-C~
O-C-NH- ~ CH2 ) 6 -NH-C-tl
`CH2CH2-N'
1l n
~CIH2)6-NH-c-x-cH3
O o~
nN-C-~ CH2)6~ 1l n
o CH2)6-NH-C-- ~CH2)2;7~o
CH3-cH2-cH-cH2-cH2-cH2-cH3
CH3~ cH2-fH-cH2-~c~H2fH-cH2-NH-~cH2)6-N;~
OH OH
~e A.26~ i8 28
,
.
. .
1 32~53 ~
~ H2CH2-0-C-~c~2)6-c-ocH2cH2- ~
,~
~ 8 1I fH2CH2-N~
CH3 ~ CH2CH2-C-0-~CH2~6-0-C-CH2CH2-N
CH2CH2-NrC~
In addition to the essential components A) and B), the
binders accord~ng to the invention may contain auxiliaries
and additives of various kinds as further components e).
These various auxiliaries and additives include, for
example, Cl) monohydric and/or polyhydric alcohols which
may be present in the binders in quantities of up to 20
parts by weight, based on lO0 parts by weight of the com-
binations of A) and B).
Suitable monohydric alcohols are, for example,
ethanol, n-propanol, isopropanol, n-butanol, sec.-butanol,
tert.-butanol, n-pentanol, isopentanol, n-hexanol, iso-
~ hexanol, eyelopentanol, cyclohexanoi, heptanol, oetanol,
methyl glyeol, ethyl glycol, propyl glycol, isopropyl
glyeol, butyl glyeol, methyl diglycol, ethyl diglyeol,
propyl diglyeol, butyl diglyeol, methyl triglyeol, hexyl
glyeol, propylene glyeol monomethyl ether, tripropylene
glyeol monoethyl ether, dipropylene glyeol monomethyl
; ether, glyeolie aeid alkyl ester, laetie aeid alkyl e~ter,
2-ethyl butanol, 2-ethyl hexanol, 3-methoxybutanol, diaee-
tone aleohol, furfuryl aleohol, tetrahydro~ur~uryl aleohol,
eapryl aleohol, eaprie aleohol, laurie aleohol, myri~tie
aleohol, palmitie aleohol, ~tearie aleohol, arachic alco-
hol, behenie alcohol, lignoceric aleohol, lauroleic alco-
hol, myristoleie aleohol, palmitoleie alcohol, oleic alco-
Le A 26 158 29
::
.. - . ~ .
.. , : ~
.
;~ :
1 32~53 1
hol, gadoleic alcohol, erucic alcohol, linoleic alcohol,
linolenic alcohol, licanic alcohol, arachidonic alcohol,
synthetic fatty alcohols and mixtures of these and other
monoalcohols.
Suitable polyhydric alcohols are, for example, co-
polymers known Der se of acrylic acid derivatives, meth-
acrylic acid derivatives, aromatic vinyl compounds, vinyl
ethers and vinyl esters which contain hydroxyl-functional
monomers, such as hydroxyalkyl (meth)acrylates for example,
in copolymerized form. Copolymers such as these are des-
cribed, for example, in EP-A-64 338, EP-A-134 691, EP-A-103
199, EP-A-48 128.
Other polyhydric alcohols are hydroxyl-functional
polyester resins known ~ se, of the type described for
example in H. Wagner/H.F. Sarx, Lackkunstharze, Carl-
Hanser-Verlag Munchen 1971, pages 86 et sea.
Other polyhydric alcohols are, for example, hydroxyl-
functional polyether compounds such as, for example, the
alkoxylation products of low molecular weight, polyhydric
alcohols of the type mentioned by way of example in the
following.
Other suitable polyhydric alcohols are, for example,
6imple polyhydric alcohols, such as neopentyl glycol,
hexanediol, butanediol, 1,4-cyclo~exanediol, 1,4-cyclo-
hexane dimethanol, ethylene glycol, qlycerol, trimethylol-
propane, propane-1,2-diol, propane-1,3-triol, pentane-1,5-
diol, octadecane-1,12-diol, 2-butene-1,4-diol, 2-butyne-
1,4-diol, pentaerythritol, 4,4-~1-methylethylidene)-bis-
cyclohexanol, bis-hydroXymQthyl hexahydro-4,7-methano-
indane, 2,2-bis-n-(2-hydroxyethoxy)-phenyl propane.
Other suitable polyhydric alcohols are, for example,
reaction products o~ caprolactone with the alcohols
mentioned.
Finally, other suitable polyhydric alcohols are
hydroxyl-functional polyaddition compounds, of the type
Le A 26 158 30
, .
,
.
' ' '
- '' -
1 32~531
obtainable from excess quantities of polyhydroxyl compounds
of the type mentioned by way of example with organic
polyisocyanates of the type mentioned by way of example.
The binder combinations acc~rding to the invention may
also contain C2) catalysts as further auxiliaries. Suit-
able catalysts are, in particular, tertiary amines having
a molecular weight in the range from 89 to 1,000, such as
for example 1,4-diazabicyclo-(2,2,2)-octane, triethylamine,
triethanolamine, dimethyl ethanolamine, methyl diethanol-
amine, diethyl hexanolamine, N,N,N',N'-tetramethyl ethyl-
enediamine, N,N-dimethyl-1,3-propanediamine, 1,8-diazabi-
cyclo-(5,4,0)-undec-7-ene.
Finally, the binder combinations according to the
invention may contain, for example, solvents or diluents,
levelling aids, antioxidants, fillers, pigments and W
absorbers as further auxiliaries and additives C).
The binders or binder combinations according to the
invention are prepared by mixing the starting components A)
and B) and, optionally, the auxiliaries and additives C)
with one another. Where solvents or diluents are used as
component C), they may already have been added to one or
more of the individual components or, alternatively, may be
added to the mixture of components A) and B). In one pos-
sible embodiment in particular, the solvents or diluents
are actually present during the preparation of one or more
starting components, as described for example in the fore-
going with reference to the production o~ the copolymers.
The solvents or diluents should be substantially anhydrous
to ensure an adeguate pot life of the mixtures. Solvents
or d~luents are generally used in the quantities necessary
to establish suitable processing viscosities of the combin-
ations according to the invention. The solvent content of
the binders according to the invention to be used in ac-
cordance with the invention is generally between 10 and 80%
by weight. However, it is also possible in principle by
Le A 26 158 31
~ .
,
,:
1 328531
using suitable, comparatively low molecular weight copoly-
mers A) to reduce the solvent or diluent content even
further or to eliminate the need to use such auxiliaries
altogether.
In one preferred embodiment of the process according
to the invention, compounds B) which contain no groups
reactive to anhydride and unsaturated (meth)acrylate groups
in the absence of moisture and of which the blocked amino
groups consist solely of hexahydropyrimidine, tetrahydro-
imidazole, aldimine, ketimine andJor oxazolane groups of
the type mentioned are used as sole blocked polyamines.
The preferred combinations according to the invention
produced in this way contain 40 to 9o parts by weight of
copolymers A) and 10 to 60 parts by weight of compounds B)
containing hexahydropyrimidine, tetrahydroimidazole,
ketimine, aldimine or oxazolane groups.
The quantitative ratios in which components A) and B)
are used are generally selected in such a way that, for
; every blocked amino group of component B), there is a total
of 0.2 to 8 and preferably 0.5 to 4 unsaturated (meth)-
acrylate and anhydride groups of component A). In general,
a larger excess of the groups just mentioned within the
ranges mentioned will be selected when the other components
contain reactive groups which react with unsaturated
~meth)acrylate or acid anhydride groups in the absence of
moisture. Groups such as these include in particular
primary or Secondary amino groups which may be present in
component B), for example in addition to the blocked amino
group~, and also alcoholic hydroxyl groups which may be
present in component C) or even in component ~) in addition
to the blocked amino groups. In general, however,
alcoholic hydroxyl groups are substantially inert to
unsaturated (meth)acrylate and acid anhydride groups under
- the conditions of the process according to the invention
(room temperature), so that the hydroxyl groups only have
.~
Le A 26 158 32
,:
', ' .
: .
r ~
: .
.: , : .
~ 328531
to be considered when they are used in the form of
substantially involatile alcohols which do not evaporate
durin~ the use of the combinations according to the inven-
tion and may be considered as reactant for component A),
S for example at relatively high temperatures of the type
prevailing during the hardening of coatings.
Complex mixtures containing amide groups (through re-
action of the acid anhydride groups with amino groups) or
amino groups (through reaction of unsaturated (methlacry-
late groups with amino groups) are formed where the binders
according to the invention are produced by mixing of the
individual components, particularly when compounds con-
taining free primary or secondary amino groups in addition
to the blocked amino groups are used as component B). Ac-
lS cordingly, the expression "binders" in the context of the
invention encompasses not only pure mixtures of the indi-
vidual components A) and B) and, optionally, the other
components, in which no reaction products of the individual
components are present, but also systems in which reaction
products of this type are present in addition to the in-
dividual components or which essentially consist solely of
such reaction products. In all variants of the production
of the binders according to the invention by mixing of the
individual components, the type of individual components
and the quantitative ratios between them are preferably
~elected in such a way that the molar ratio of acid anhy-
dride and un6aturated (meth)acrylate groups to blocked
am~no groups on completion of the reaction, which may take
place spontaneously, between acid anhydride or unsaturated
~meth)acrylate groups on the one hand and primary or
. secondary amino groups on the other hand is ~rom 0.2:1 to
:~ 8:1 and more especially from 0.5:1 to 4:1, in which case an
excess of acid anhydride or unsaturated (meth)acrylate
. groups should again be considered where the individual
' 35 components used contain alcoholic hydroxyl groups which may
i Le A 26 158 33
;
;,~, .,......... . .. : i
. ~
.
` .
~ 328~3~
be considered in addition to the blocked amino groups as
reactant for the acid anhydride or unsaturated (meth)-
acrylate groups in the use according to the invention.
In addition, in the context of the invention, "blocked
polyamines B) containing hydrogen atoms reactive to acid
anhydride or unsaturated (meth)acrylate groups" are under-
stood to be not only blocked polyamines of the type men-
tioned which contain reactive hydrogen atoms in chemically
bound form, but also those which are present in admixture
with excess polyamine or hydroxylamine used for their
production.
So far as the suitability of the binder combinations
according to the invention is concerned, it is largely im-
material whether the possibly spontaneous reaction between
the copolymers A) and the groups reactive to acid anhydride
or unsaturated (meth)acrylate groups has already come com-
pletely to an end. If desired, however, it is also pos-
sible to terminate this reaction before the use according
to the invention by brief heating to 40 to lOO-C. For the
rest, the binders according to the invention are preferably
produced at room temperature.
The binders according to the invention are generally
liquid at room temperature (often because of the presence
of solvents), show adequate stability in storage in the
absence of water and, after application to a substrate,
generally harden rapidly in the presence of atmospheric
moisture.
In general, crosslinked films are obtained even at
room temperature. The basically very rapid hardening pro-
cess may be further accelerated by drying at higher tem-
peratures. Drying times of 10 to 30 minutes at temper-
atures of 80 to 130-C are advantageous.
Where blocked amino groups particularly stable to
hydrolysis are used or where involatile polyhydric alcohols
C) are co-used, this forced drying at elevated temperatures
Le A 26 158 34
~i .
.
-
,
-
t 32853 ~
may be necessary to obtain the optimal property spectrum.
The coating compositions and sealing compounds con-
taining the binders according to the invention may contain
the auxiliaries and additives normally used in lacquers, in-
cluding for example pigments, fillers, levelling aids, an-
tioxidants or W absorbers.
These auxiliaries and additives should be largely
anhydrous and are preferably incorporated in the starting
components, generally in component A), before the produc-
tion of the binders.
The laoquers and coating compositions containing the
products according to the invention as binders generally
have a pot life of 1 to 24 hours. However, the pot life
may be corrected upwards or downwards as required through
the choice of suitable reactants. The coating compositions
(la¢quers) an~ 6ealing compounds may be applied to any, op-
tionally pretreated, substrates, including for example
metals, wood, glass, ceramics, stone, concrete, plastics,
textiles, leather, cardboard or paper, by spray coating,
spread coating, dip coating, flood coating, casting, roll
coating, trowelling.
In the following Examples, all-parts and percentages
are by weight, unless otherwise stated.
, .
EXAMPLES
l I) General procedure for the production of the copolymers
; A'~ to A'~ containing anhydride groups
Part I i5 initially introduced into a 4-liter reaction
vesael equipped with a stirrer, cooling and heating systQm
and heated to the reaction temperature. Part II and Part
~ III are then added at the same time over a total period of
.3 2.5 hours and 3 hours, respectively. The mixture is then
stirred for 2 hours at the reaction temperature.
The reaction temperatures and the compositions of
parts I to III are shown in Table l together with the char-
Le A 26 158 35
.
,
1 32853 ~
acteristic data of the copolymers obtained.
Le A 26 158 36
:
1 32853~
O ~ ~ ~ o o
O O t~ I~ O ~1
o ~ ~o ~ ~ ,,
,, CO
,
o a~ r m u) OD
o 1~ 0 1 ~In u~
O ~ U~
.; t~ .
,:. O ~ ~ ~r In ~ 00 0O~ O
~, N ~ ~ ~ 0 ~ ~1 It~ ~ l~
,1 a~
O ~ ~D ~r In In 0 0a~ co
~ t' ~ ` o ~ N In~1
,, ~ O 1~ ~ ~ ~ ~
I¢
~i o~
O
_
--
~n
r~ ~ ~ :~ ~
~ ~ I ~ r O
.'1 Ql ~ H :1 C~
~ y ~1 U ~U H .q U O , '~
:. j ~ ~ W H 1~ U H I W ~ Ul
~i ~ ~o ~ 3 ~ 8
~ ~ ~ y ~ ~ w~1 Ul
~ ~ X
.,
,
,.,. ~ ,
. . .
` . - ~ .
.
.
. -.~. .
.~, . . .
,.
,-:- r
i
1 32~531
II) General procedure for reaction of the anhydride-func-
tional copolymers A'l to A'4 with hydroxyl or amino-
functional unsaturated (meth)acrylates to form compon-
ents A~ to Al3
: 5 The reaction components shown in Table 2 are intro-
duced into a l-liter reaction vessel equipped with a
stirrer, cooling and heating system and heated to the
reaction temperature, followed by stirring for 4 hours at
that temperature.
Le A 26 1S8 38
.,
. ` ' . ' ~ ':
`- 1 3~.853~
~ ~D O
o ~ o ~ o
o ,~ . o o o In ~
~: ~ - o o~ .1 In ~ rl
N
~ ~ O
N o ~ r-- ~ O O ~
~D ~1 0 1~ ~
O
N
O O U~
_ O U) . Il~ t~ O ~ O
~ OD t`
O o ~r o N O a~
~r o ~7 ,~ ~D tn
~0 ~ ~ u~ u~
0 0 aD N It 0~ O
; ~ 0 ~ ~
N
u~ In
O ~D O u~
O ~ ~O U~ U~
~¢ ~ O ~
O ~ ~
O Ir~ 1~ N O 11~ .1
o r~
O ~ U~
~ o ~ O NO ~ a~
,eC~ ~D ~1 0 ~1 ~1 ~ U~ U~
N ~
O ~ U~ ~
u~ O N 1~') ~O C~ O
N O ~1 ~1~ 10
~-
N ~D
o ~D In
~ O N O ~O O~ ~
fS~ ~D ~ O N rlq' In N
~ - .
N O
O ~D 10 ~
~I O NO O ~D
'~7 ~ O N ~1 U~ U~) In
~^
o ~ . o ~ o a~
~D ~ O
~-
O ~ U~ ~
O N O NO a~ CO
~ ~ ~ ~ O N ~1 U~ N
~1 ~ a v
Q~
~n
~1 ~ I O a~
~ ~ ~ ~ X X I ~ ~ O ~ S ~ d~ `
e
e o ~ o ~ e o ~ ~ e
01 ~ a o ~ o ~ ~ U J~ -- 00
~ ~ ~ S L~ 3 S~ ~ ~ 8 ~ I
N rD ~ ~ ~ ~ ~ ~ ~J 0 ~ ~ 0 _~ ~ 0 e ~ ~ o
X
o _I o o o _I o _I ~ ,, ~ x ~ s~ o ~ ~ ~1 o ~ _I ~ a) ~ ~ o
~1 P~ O ~ ~ U ~ U O S U D~ S ~ ~ U U ~ ~ U
I e ~ ~ ~ ~5 h ~ S ~ ~ O ~ E~ S ~ S J ~ ~ o _~ m
I O O ~ ~ U ~1 U ~ o ~
E~ ~) ~ a u ~ N Q) 3: ~1) m
,
~ .
1 3285~1
III) Preparation of components B) capable of crosslinking
Bl
513 g cyclohexane and 456 g isobutyraldehyde are
introduced under nitrogen into a 2-liter reaction vessel
equipped with a stirrer, cooling and heating system. 529.8
g l-amino-3-methylaminopropane are added dropwise at lO~C
(ice bath cooling), after which the mixture is stirred for
1 hour at lO-C and then heated at the reflux temperature
until no more water is eliminated. Cyclohexane and excess
isobutyraldehyde are then distilled off and the hexahydro-
pyrimidine crosslinker B1 is obtained.
B2
In a 3-liter reaction vessel equipped with a stirrer,
cooling and heating system, 680 g isophoronediamine, 1000
g methyl isobutyl ketone and 560 g toluene are refluxed
under nitrogen on a water separator until the theoretical
guantity of water has been eliminated (144 g) or until no
more water is eliminated. Toluene and excess methyl iso-
butyl ketone are then distilled off and the bisketimine
crosslinker Bz is obtained.
i
; B3
a) 1050 g diethanolamine and 615 g cyclohexane are intro-
duced under nitrogen into a 4 liter reaction vessel equip-
ped with a stirrer, cooling and heating system. 1408 g 2-
ethyl hexanal are then added dropwise at room temperature,
the temperature slowly rising. The mlxture is then kept at
the reflux temperature until the separation of water is
complete. Cyclohexane and excess 2-ethyl hexanal are then
distilled of~. An oxazolane, the intermediate stage B3a),
i8 obtained.
b) Preparation of B3
200.6 g of an isocyanurate polyisocyanate based on
~,
~ Le A 26 444 40
~'
.
. . .
.
1 328531
hexamethylene diisocyanate, consisting essentially of
N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate, and 207 g
butyl acetate are introduced under nitrogen into a reaction
vessel equipped with a stirrer, cooling and heating system
and heated to 60-c. After the dropwise addition of 286.7
g ~f the oxazolane intermediate stage B3a), the mixture is
; kept at 70-C for 10 hours. A 70% solution of the cross-
linker B3, containing 3 oxazolane groups on a statistical
average, is obtained.
IV) Preparation of the binder combinations according to
the invention
The components A) containing anhydride and unsaturated
(meth)acrylate groups and the polyamine components B) are
mixed together at room temperature and adjusted to a
processible viscosity, optionally by addition of more
i auxiliaries C).
The films are coated onto metal test plates using a
film drawing tool (wet film thickness 180 ~m). The films
applied and stored at room temperature were all tack-free
; after 60 minutes at the longest. After ageing, i.e. 24
hours at room temperature, clear, crosslinked, solvent-
resistant films characterized by excellent mechanical
properties and very good optical properties are obtained.
The paint mixtures prepared all had a pot life of
several hours.
The compositions of the binder combinations and the
solvent resistances ~degree of crosslinking) are shown in
Table 3 below.
Solvent resistance is tested by a wiping test using a
cotton wool plug impregnated with methyl isobutyl ketone
(MIBK). The number of double wipes for which the film re-
mains visibly unchanged is shown. No film was subjected to
more than 200 double wipes.
Le A 26 444 41
. .
:' ' . , .
.
1 32~531
~ g ,~
o U~ o ~ ~ -
a~ u7 ~ ~
~ g
o ~ o ~ ~ ..
I` U~
tP ~ ~ ~ o ~
O lo 0 ~ N -
u~ Il) ~
~ ~ .
.~: o
o _l
o ~r o ~r ~ -
In a~
D~ ~ ~ .C O
O ,1
O ~ O ~ ~ -
. ~r ~ A ~
tl~ .C g ,~
o ~r o
~ g ,~
O er O ~r ~ .
U~
~ a~
!
. ~ o ,1
o ~r o ~r ~ -
'I a) ~ o
~1 ~ I
x ~ o
8 ¢ m ~ c~ ~ 3 ~ '~5 0 ~ i
,~ JJ J~) O rl J- a~ ~ ~ ~ _l I
~ c c o o c~
I ~11
3 u o 8 ,~ ,~ 3 g o ,,, :~ ~ I :
,, _, ~ 1 l
, ~ ~ ~3 e J~ ~ m ,1 u~ o ~
t~5 ~ O O ~ O H ~ q-l O ~ ~ l
I ~¢ C~ X tlJ O X
',
;
' ' ~ . . . '' '
'-r . ' ~ ' ' : :
:~ :' ' ' -
1 3~8531
m^
: ~ ~ ~ ~ o -l
It7 o O ~r N -
U~t~ ~ A A ~1
~ m^
~ ~ ~ ~ o
:: ~r o _I
O O ~r N -
~1 1~1` ~ A A ~1
.~
~, ~- mN
t~ ,C O
~r o ~1
O O ~ N -
~1 Ir~I` ~ A A ~1
.,, ~- ~
~ ~ ~ S oO ,~
N O ~1 0 ~ N -
~1 U'lN ~ A A --I
,~ ~ g ~
.1 ~1 O~'7 0 ~ ~ -
~ It~N ~r A A ~1
'.'
~, t7~~ ~ 5 g ,~
o o ~ o ~r ~ -
11~N ell A A ~1
,~ * aS'
., ~ tJ~ S g ,~
! o a~ o ~. N
0~ U~ N ~r A A ~1
,
.3 .
l ~ ~ ~
.', ~ a~
.~ N ~ ,
.'.
~ 0~ ~ ~
o ~ m ~ ~ 3 o ~ m
.~ ~ ~ e
~ 10 C ~ ~1 3 0 ~ N
.~ I .,1 O O _l _l O O Ll ~ ~ O
~ ~ 0~ 0~ ~ ~ m ~ o ~
.~ P~ 1 0 H ~ ~0 1 ~
E~ ~ c~ C~ m ~ x ~ o ~
~.~
.;.
. ! , : '
: ~ .:
''': :
,` ' : ~ ' .
. . , ~
,.. .
f~ff 1 328531
f~f m
o- ~f' s o
f~'ff o ff~
N O flr.' ~' N -
N ~l' N N A A 'f-~
o
fff~ ~
J''3'' CJ'' ''''f O
N O N f
N O ~ d' N -
N 'I~,ffr,' N A A
ff¢f m-
~ ff ~ff.~ff o
f O N O t--t
'.'~1Ittf fr,' 'N A ~ t~
fff~fm-
c~ff ff o
N O ff~
f5ff O ~r~f ~' f~, ..
ff' ~fr,' N A A ff-l'
f~'~'ff rN
CJ''CJ'' ~''rff O
O O ff~,
X 1nfr~ fr.~ A A ff~ ~tf
* mN
. crff trff 'tJ'~ ff O
~ O . o ff~ ff',
ff-~Itlf fX' f~qf~ ~ ff~
f ff¢~ct mN
5ff ~' tJ''S o ff~f
'~' O O ~f f~f ..
ff-~Inf~f,~ frf~ ~ f,
'I
rlf h
3, ''~
f~
~ ~tf ~
f~ fff~f m ~ 3f O ''3 ~ ~ 'X'
O I !f .~ f~U~ ff~ f~ O f~ ~r.
f'~ ~ f f~ fr~t.~f f~ ~f f~-~ f~
f lf e ~f ;Jf f~fc~ ff. ~ ~ fr~f
~Xfl ~ ~ C' '~ aR~,f '''~'~'f~t''~ 'N
'I'l f ~ O O ff'. . I O O ~ ~' ~f U'
ff-~ ff-. ~.~f ~f fY f'., ''~ f~ .~ ' ff~ fff~
R ~ 13.,~. ~'~' mff-tf fV o ~f
f flO ~f O O ~ O t~ ~f f~tf O ,C fff~ f~'
ff~ f¢~t r~f m A ~, fla O ~ '' ff~ 1
, . .
.
