Note: Descriptions are shown in the official language in which they were submitted.
1063275 ~OE 74/~ 907
The present invention provides a ~igh temperature resis-
tant anti-adllesion and slide lacquer ("slide lacquer" meai~ing
that it has smoothing and anti--tack properties), substantial]y
composed of finely distributed lo~ molecl~lar weight polytetra-
~luorethylene, a polytriketo~imidaæolidine resin (hereinaftercalled trion resin) and a solvent or solvent mixture.
Coatings of high mole~ular weight polytetra~luoreth.ylene
(P~E) are generall,y obt;ained from aqueou~ PT~E dispersions.
Since these coatin~s, because o. the ~own ~ntiadhe~i~e pro-
perties o~ PTFE, do not adhere su~icientl~ to the substrate,
this substrate has to be pretreated in a suitable manner, for
example by sandblasting, and furthermore, adhesi~e substances
the ohoice of which depends on the kind of the substrate in
question have to be added to the PT~E dispersion. Ho~vever1
this results in a deterioration of the required properties of
P'~FE such as æntiadhesive behavior, low coeffici.ent ol vis~
cosity etc. In order to maintain these properties at the sur~-
face of tne coatiIlg, a top layer of pure PTl~ containin~
an~, only ver~ small amounts o~ usual additives is coat~d over
the a~o~re primer coatin~ Thus, in order to obtain a coating
having the desired prope.rties 9 tnese s~rste1ns require three
di~ferent oper~tions:
1) pretreatment of` the substrate (~or example sandblasting)
~) coating witl.l a pri~er containin~ a small amount o~ PT~'E and
adhesi~Te substances
3) coa~ing ~ith a top l~;er of essential~y p~!re PT~E,
~ urther~iore t aqueo;ls ~Tl~ disper~ ns ilave the lis~d-
varltat~eolls ter.denc~ to irre~ersi1~1e coagulation, especiall~r
29 on prolon~ed stor~ge. Such co~.~ulati~n ~ay for ex~2lpie
~ ~ 2 ~
HOE 74/~ 907
1063Z75
already occur by simply agitating a dispersion ~hich ha~ di~
integrated, by mec}lanical strain or b~ storage at elevated
temperatures or ten~peratures below the freezing point. Such
irreversible coagulation makes the dispersion unserviceable.
In order to o~Tercome these dis~dYanta~es, PT~E cont~ining
coatin~s have been alread,y d~veloped which ~void the expensive
pretreatment o~ thé substrate and its repeated treatment with
primer and top coatin~. It ha~ been tried to o~tain PTFE
ooatings fro~ stable dispersions o~ PTF~ in or~anic solventQ
~laving no tendency to coagulation. Since the properties of
the coatings obtained when using this material, especially the
adhesion on ~he substrate, are insuf~icient for most appli-
cations, these dispersions are mixad with film-for~ing or
binder resins, whi~h mixture, however, causes the loss or at
least a serious deterioratioll of the excellent allti-adhesion,
a.Ati-tack and smoothing properties proper to P~F~ coatings.
It i~ therefore the object o~ the present invention to
pro~ide a P~'E containing coa-ting composition in the ~orm of a
single-coating s,ystem (i.e. in the for~ of a sy~tem being app-
lied to the substrate in one operation only) ~hich is equi-
valent or superior to tlle usual double-layer PTFE coatings
with respect to anti~adl1esive, smoothing and anti-t,ack behav;for,
as ~rell as adhesion to the substrate, aI~d which further~ore
has an excellent hardness and abrasiorl resista~lce.
In accordance ~ith the ~resent invention, there is pro
~ided a coating compositioIl s1~bstantial'y ccmlfosed of
a) from 10 to 9~ parts by wei~ht of a lo~v molecular weight
polyt~tra~luore-th~Jlene ~aving a melt viscosit~r of from
29 10 to l3 poise~ (mea3ured at 3~0C b~r nleans o~ the hig~
- 1063Z75 H0~ 74/' 937
pressure capillary viscometer), a speoi~ic sur~ace of l~om
1 to 40 m2/g (measured accordin~ to the BET method), and a
mean particle diameter of fron 0.1 to 50 micron~;
b) from 90 to 10 parts by weight of a pol~mer containi-.~g tri-
ketoimidazolidine rings and ~epeatea units Or the formula
. O-C =O O-C C=O
` I `I I I .
~ \ / N ---R'- - ~ / N - n
where
R i~ a mono- to trinuclear, bi- to tetravalent aromatic
radical, the arom~tic radicals optionally ~eing al~o
quinones, and in pol~nuclear s~stems the aromatic radic~ls
optionally being linked b~ aliphatic radicals or hetero
atomsS furthermore the aromatic radicals optionall~ being
mono- or polysubstituted b~ alkyl, cycloalkyl, alkox~,
aryl or ~ono~alent ~unctional radicals,
R' is as de~ined for R or an aliphatic or cycloaliphatic
hydrocarbon radical, R' optionall~ being interrupted b~
one or ~ore of the following groups:
b1) amide, imide and/or amidoimide groups, obtained ~
introduction of polycarboxylic acids, the ratio of
the ~olar equivalents pol~carbox~lic acid : pol~isow
cyar.ate being q : (q + 1), and q being fro~ 1 to 40,
preferabl~ from 2 to 40;
b21) chelate forming azo or azomethine groups;
b22) metal chelates of such azo or azomethine groups;
the ratio of the molar equivalents o~ the oxamide a.cid
ester, used for the preparation of the t~iketo-imidazoli-
-- 4 --
-~ H0~ 74/F 907
1063275
dine rings to che'ate-forming agents and/or m~tal chelate3
~eing (2 to 94) : (0.~ vo 50), and the sum of oxamide acid
ester, chelate-forming agent or chelate and possibl~ present
polycarboxylic acids always bein~ 100 mol %,
n is an integer of ~ro~ o 70, preferabl~ from 1 to 40;
and
! ) an aprot~c ~rganic sol~ent having a surface tension o~ more
than 30 dyn/cm, in an a~ount by wei~ht of from 0.43 to 100
times that of com~onent b); up to 80 % of the amount b~
weight of this aprotlc solvent havin~ a surface tension of
more than 30 d.yn/cm optionally being replaced b~ another
organic solvent not meeting at least one of the two cited
requirements, but necessarily h~ving a lower boiling point
than the aprotic sol~rent.
The low molecular ~eight P~F~ having a melt vi.sco~it~ of
from 101 to 108 poises used as co~ponent a) o~ the coating
composition of the invention is a prodv.ct selected from the
so-called *luoro-carbon wax series. Such flurocarbon waxes
m~y be prepared by thermal degradation of high nolecular PTFE
according to preparation methods known fro~ Ger~an Patent ~o.
1,049,099, U.S. Patent ~o. 2,496,978 and especially fro~
German Of~enlegungsschri~t No. 2,031,046. The latter process
is especiælly advantageous, because a su~tal)le adjustment of
the pressure allows to direct the p~rolysis to the obtention
of products having the desired melt vlsc03i.ty (or the cor~
res~orldin~ rnolecular ~eight range). Also proaucts obtained by
means o~ X or gamma ray irradiation according to k~own proce~
ses ma~ ~e useat Such PTFE degradation wa-xes obtained b~ pyro-
29 lysis or irradiatioll generally must be ground to a mean
~ H0~ 74/~ 90i
1063275
particle size of from 1 to 25 microns, pre~erably from 5 to
10 microns before use in the coating ccmposition of the in-
vention, since they are often obtained in the form of ~ore or
less bulky lumps, which grinding ma~ ~e carried Ollt in a
hammer or jet mill.
As component a) of the coatin~ composition according`to
the invention, there may be used also a synthetic ~E ~vax
obtained according to a known proeess descr~bed in German
Of~enelgungsschrift No. 2,235,885, by telomcri~ation of tetra-
fluorethylene with a suitable tel.ogene. ~he àqueous dispersions
of low molecular PT~E obtained according to this process ~a~
be easily coagulated by means of mechanical forces or electro-
lytes to ~orm finely distributed white powders, and they ma~
then be used directly without further pretreatment i~n the
coating compositions of the invention.
~y low molecular weight pol~tetrafluoreth~lene being
employed as component a) of the coating composition of the
invention, there is to be understood a P~E having an apparent
melt viscosity of from 101 to 1 o8 ~ pre~erably from 102 to
106 poises at 3~0~ (dete:rmined by means of the high pressure
capillar.y viscometer as described below).
Such a lo~;~,nolecular P~ must have furthermore a speci-
fic surface o~ Irom 1 to 40, preferably from 4 to 40 m2/g,
especially froln 5 to 26 m2/g (measured according to the so-
called BET method, see ~runauer, Emmet and Teller, J. Am.
~hem. Soc. 60, 1938, p. 309), and a meal1 particle size of
from 0.1 to 50 microns, prefera~ly from G.5 to 20 microns,
especiall.y from 1 to 12 microns. ~n the case of a synthetic
29 P~E wax coagul.-lted from the dispers;on , ~ mean partic1e
-- 6 --
1063275
size there is to be under3tood the mean si~e of the primar;y
particles.
Component b) of the coatin~ composition of the inventior.
is a so-called "trion resin". By trion resin, therc is to be
understood a polymer containin~ triketo-imida~olidine ring~
and repeated units of ~he formula
O~ C , r o (~--C-- C=O
I I J I .
~ `-R --~N N ~ T N~
\C/ \ C/
. _ ~ O ,~ _ n
_
where R, R' and n`are as defined above.
-
Preferabl~, in these trion resin~, the cited s~mbol~ re-
present the ~ollowing:
R a bi- or triv~lent phenyl radical ~that is, havin~ tVJo or
three radicals capable of bein~ condensed or add~d, see
formula IV below), or a binuclear Pxomatic radical. These
radicals may bc optionally substituted, ~referably once or
twice, by alkyl having preferabl.y fro~ 1 to 6 carbon atom~
(for example methyl, alk~rl? 5 c~rclo~lk.yl or alkylc~Jcloal~rl
havin~ preferabl~ fro~n 6 to 12 carbon atoms, ar~rl. prefer-
ably phenyl, halo-alkyl, esp~ciall~ fluoroal'.{.yl l~aving
preferably from 1 to 5 carbo~ ator.s (for e~ample tr-lfluo~o-
met~-~rl), alkoxy ~lavi~lg pr~ferably from 1 to 5 carbon atoms
(for exainp1e ~1ethox~r5 etho~.~r), ar~rlox~ ha-~ring pr~ferably
frcm 6 ~o 10 carbon atoms, ke'~o&lk~l having preferabJ~ up
to 5 carbon ato~s (for exa~ple CX~-CO-) 9 ketoaryl ~aving
preferab~ up ~o 1;` carbon at;o~.s, carbox~alkyl having pre~
ferably up to 6 ca-bo~ cato~ , carboxyaryl havin~ preferabl~
H0' 74/~` 307
1063275
up to 10 carbon atoms, ester groups h~vin~ p~e~erably up to ~
carbon atoms (~or example ~H~C00- or C2H5-C~0-), al~ylsul~on~l
groups ha~ring preferably from 1 to 5 ca~bon ato~ or
example C~I3~03-), dialkylamino grouos naving preferabiy up
to 6 carbon atoms, diarylamino, pre~erably diphenyla~ino,
alkylarylamino havill~ preferabl~ up to 10 carbon atoms, per-
~luorinated alkoxy, car~oxyalk~l or acyl havin~ preferably
the abovementioned number of carbon atoms, nitro, c~ano or
halo~en, especially ~lurlne, chlorine or bromine.
In the case o~ binuclear aromatic radicàls, the phenyl
nuclei may be directly condensed one to the ot~ler, that is,
form a naph-thyl radical, or they ~ay be linked with each
other via a C-~ bridge, such as biphenyl, or they ~ay be
linked u~ith each other b~ an aliphatic radical prefe~ab].y
having from 1 to 3 carbon atoms, or by hetero atoms 3uGh as
oxygen, .sulfur, or b~ hetero atom containing groups such a~
C0, ~2 or NR (R being alkyl having preferably from 1 to 6
carbon atoms, cycloalk~l ha~ing preferably up to 10 carbon
ato~s, alkylcycloalkyl ha~Ting pre~erably up to 10 carbon
atoms, or aryl ha~-ing preferably from 6 to 10 carbon ~toms,
especially ~henyl).
The mono- or binuclear aromatic radicals may also con~
tain hetero-atoms, ~or e~ample they may be thiophene, ben~o-
thiophene, benzothlazole, p~ridine, quinoline etc.
Especially preferred for R a.re bivalent aromatic radi~
cals of the ~ormula
- 8
1063Z75
~ - ~ X - ~, ) (II)
where R" ! iS H or C~-~3,
X is 0, S, CH2, S02 or zero, pref~rably 0 or CH2,
ls 1 or 2ero, preferably 1,
Z i3 fron~ 1 to 3, prefera~ly 1,
or
- ~ (III)
R' of formula (I) is preferably R as cited abo~e or a bivalent
aliphatic or cycloaliphatic radical, especially alkylene or
cycloalkylene having up to 20, preferably up to 15, espe-
cially from 6 to 12 carbon atoms. Examples are methylene,
alkylene, propylene, 2,2'-dimethylpropylene, 3-methyl-
propyleneg butylene 5 cyclohex,ylene or cyclohexylene sub-
s~ituted by lower alkyl ~1 to 6 carbon atom~). Optionally;
these aliphatic or cycloaliphatic radicals may also be
substituted by one or more monovalent functional groups,
as they are cited abov~ under R, especiall~ trifluoro
methyl or nitro or c~rano or halo~en such as fluorine~ chlo-
rine or bro~ine.
n of` f'ormula (I) is preferab1y from 1 to 40.
The preparation of such trion resins is described in
Ger~lan O~fer.le~lngsschriften `;~os. 1,~20~5 ~nd 2jO30,23
-~OF, 74/~ 907
1063275
and it is carried out by reaction of oxamide acid esters o~
the formula
R - (N~ - CO - COOR")r (IV)
and polyisocyanat,es o~ the formula
R~ - (N = C = )s (V).
R and R' o~ t~ese ~ormulae are a~ defined in formula (I);
R'' is a hydrocarbon radical, pre~erably an al~phatic hydro-
carbon radical having ~rom 1 to 18 carbon atoms, e~peciall,y
from 1 to 6 carbon atoms, a cycloaliphatic or alkyl-
cycloaliphatic hydrocarboll radic~ aving from 3 to ~ car~
bon atoms, especiall,y from 6 to 8 carbon atoms, or phen~l,
cycloaliphatic/alkylcycloaliphatic hydrocarbon and phenyl
optionally being substituted by alkyl radicals each
having ~rom 1 to 14, preferably from 1 to 8 carbon atoms;
R" is especia~ly alkyl ha~ring from 1 to 6 carbon atoms1
for example methyl, ethyl, propyl, butyl, i-butyl, n-hex,~Jl;
r is an integer of *rom 2 to 4, pret`erably 2 (bis-oxamide
acid ester) and
s is an integer of from 2 to 6, preferably from 2 to 4,
especially 2 (di-isocyanates).
Suitable pol~isocyanates are for example 2,4,6-tri-
isocyanato-t.ol~lene, 4,4',4"-tri-isocyanato-triphenylmethane,
2,454'-tri-isocy`anato-dipllenylmethane, 2,2',5,5' tetraiso-
cyanato-diphenyl~ethane, further suitable polyisocyanates
(see Ger~an ~ffe~le~ungsschri~t No. 1,920,84.5~
The reaction of the cited oxamide acid esters with the
cited polyisocyanates is carried out at temperatu-res of from
-10 to ~-280C, preferably f-rom O to 1~0C~ in solutioYl or
~ 10 .- .
106327s HO~ 74/F 907
in the melt, preferably in a so-callea aprotic solvent charac-
terized below. ~he reaction may be carried out with or without
a catalyst. Suitable catalysts are in principle those normally
used also for other reactions of isocyanates ~ith compounds
containing reactive hydrogen atoms, such as e~pecially tertiary
bases, for example tertiary amines or tertiary phosph~nes,
such as triethylamine, tributylamine, ~-isobut~lmorpholine,
piperidine, ~-methylpiperidine, N,N-dimethylaniline, trieth~
lenediamine, triphenylphosphine, trimorpholine-p}losphine.
Other cataly~ts are for example lithiu~ methylate or benzoate,
sodium ethylate, potaqsium tert.-butylate or organic tin com-
pounds such as dibutylstannic oxide, dimethylstannic stearate,
dibutylstannic glycolate, dibutylstannic dilaurate, diphenyl-
stannic oxide or also ferrocene or metal chelates such as iron
acetylacetonate, cobalt complexes; all these cataly~t~ may be _ _.
used individuall~ or in combinations.
The products obtained in these reactions ~hich still con-
tain reactive terminal groups are polymerized by further
heating to 120 - 550C, preferably to 280 - 450C. By poly-
merization there is to be understood in this case a chainlengthening by addition and/or condensation.
~ he molar ratio of oxamide acid ester : polyisocyanate
in the reaction is 1 : (0.8 to 2.2), preferably 1 : (0.9 to
1.5) in tha case of equal functionalit.y of both components
(r = s). In the case of different functionalit~, this molar
ratio has to be varied correspondingl~.
For the exa~ple o~ bis-oxamide acid ester and di-iso-
cyanate, the reæction proceeds according to the following
29 general scheD~e:
_ 11 -
~IOE 74/F 907
1063Z75
n R"OOC OC ~ R ~H CO COOR" ~ -
n OCN ~.' NCO -2~ R"O~
. ~ O=~C=O O-C----C=O
--R ~ ~7, R'-- ~\ N-- (VI)
1 ~ J n
~ he trion resins obtained according to this reaction can
be directly employed for the c~ating co~position of the inven-
tion with very good results. A ~urther improvement of the
advantageous properties is attained when, besideQ the oxamiae
a¢id esters and the polyisocyanates, also polyoarboxylic acids
are reacted, as described in German Offenlegungsschrift No.
2,030,233, so that polycondensation products are formed which
oontain addItior.al amide, imide and/or amidoimide groups.
~ y polycarboxylic acids, there are to be understood
carboxylic acids and/or the anh~drides thereof being at least
dibasic and no more than hexabasic, preferably no more than
tetrabasic, especially di- and tribasic. Advantageously, there
are used above all such trion resins the amide,imide or amido-
imide group forming components, as described in German Of~en-
legungsschrift ~o. 2,303,239, in the form of polycarboxylic
acid~ are reacted in a first step with the isocyanate, thus
forming a precondensate having free ~CO terminal groups, which
precondensate is then reacted with the oxamide acid ester in
a second step. The precondensate is formed at temperatures of
a maximum of 70C, preferably of from 40 to 60C, and the
second step requires temperatures of from 70 to 270C~ pre-
ferably from 100 to 220C. A great number of polycarboxylic
- 12 -
HOE 74/~ 907
.1063Z75
acids (or their anhydrides) suitable for this reaction are
described and proposed in German Offenlegungsschriften ~08.
2,030,233 and 2,303,239, among them ~or example the follo~ing:
isophthalic, trimellitic, pyromellitic, terephthalic, benzo-
phenotetracarboxylic, 1,.~,5,8-naphthalenetetracarboxylic,
furthermore 2,5-dianilinoterephthalic, 2,5-ditoluodinotereph-
thalic, hemimellitic, mellitic, maleic, ~umaric, itaconic,
muconic, hexahydroterephthalic, adipic, glutaric, succinic,
`sebacic, ~uberic, tetrah~drofuranotetracarboxylic, perylene-
tetracarbox~lic acid, the cited acids optionally being sub-
st~tuted by chlorine, bromine and/or alkyl groups having up
to 6 carbon atoms. SuitabIe are also polycarboxylic acids
containing amino groups, for e~ample amide acids optained b~
reaction of maleic anhydride with diamino-diphenylmethane,
diamino-dîphenyl ether, diamino-dimethylsulfone, p-phen~lene-
diamine or m-phenylenediamine with formation of amide and
liberation of a carboxyl group of the maleic anh~dride.
Such dicarbox.ylic acids are preferably used ~or the
reaction the carboxyl groups of which are not in ortho-posi-
tion and/or such at least trivalent carboxylic acids t~o car~boxyl group~ o~ which at least are in ortho-position, because
this ensures the maintenance o~ a high linearit~ of the poly-
mer chain.
Suitable polyisocyanates for the precondensation with the
polycarboxylic acids are those already mentioned above ~or
the reaction with the oxamide acid esters; the di-isoc~anates
having radicals R' according to the ~ormulae (IV) and (V)
being preferred. Thus, structural anits such as (VII), (VIII),
29 (IX) and (X) (see enclosed formula sheets ), where X, R"',
1063275 ~OE ?4/F_907
and y are as defined in formula (IV), are obtained. Among these
structural units, especially suitable are those o~ the for~ulae
(IX) and (X), where R"' is H, CH3; X is 0, CH2 and ~ i9 1.
The cited structural units obtained in thi~ manner ma~ be
repeated several times within R' (see the reaction product o~
equation VI), in which case they are always linked w'ith each
other via amid~, imide or amidoimide group~.
In ¢ase of the same functionalit~ of pol~carbox~ylic acid
and polyisocyanate, the ratio of the molar equi~alents should
be q : (q + 1), q being at least 1 and at most 40, pre~erably
from 2 to 40 and especially frorn 5 to 25. A precondensate is
obtained ha~ing isocyanate terminal groups on the one hand,
and on the other being of linear structure because of the pre-
sence of only one excess isocyanate æroup. In the ca3e of
di~ferent functionality of the components the molar ratio~
vary in corresponding and analogous manner.
The properties of the coating composition of the in-
vention may be very advantageously improved by incorporating
"branching" polycarboxylic acids into the cited precondensate.
Such "branching" polycarboxylic acias may be prepared by con-
densation of polycarboxylic acids with other polycarboxylic
acids having an amino substituent, that is, for example by
condensing trimellitic, trimesic, pyromellitic or benzophenone-
tetracarboxylic acid (or the anhydrides therèo~) with 5-amino~
isophthalic or 4-aminoph~halic acid. ~hus, structura1 uni.ts
such as (XI), (XII) and (XIII) (see enclosed formula sheet~')
are formed, which may be also repeated several times while
being linked via amide, imide or amidoimide groups.
29 A ~urther improvement of the properties o~ the coatin~
- 14 -
~063275 H~E 74/F 907
composition of the invention, especially with respect to sto-
rage stability and adhesion of the coatings to metal sub-
strates, may be attained by introducing chelate-forming azo-
methine groups of the formula
(HOOC)2 - (Ar) - N = CH - RIV
and/or chelate-forming azo groups of the formula
(HOOC)2 - (Ar) - ~ = N _ RV
into the trion resin.
In these iormulae, Ar is an aromatic radical, preferably
mono- or binuclear. Furthermore, both carboxyl groups must
. .
not be in ortho- or peri-position to each other, and no car-
boxyl group should be in ortho-position to the azomethine
and/or azo group.
RIV and RV are aromatic or heteroaromatic radicals, pre-
ferably mono- or binuclear, and having an OH group in ortho-
position to the azomethine or azo group. RI~ and RV may be
optionally mono- or polysubstituted~preferably mono- or bi-
substituted, by alkyl or monovalent functional radicals ac-
cording to the definition gi~en for R.
There are used preferably chelate-forming azo and/or azo-
methlne units of the following for~ulae:
COOH COOHand
(XI~
Similarly suitable are also the corresponding azomethine
and/or azo derivatives of 2-amino- or 3-aminonaphthalenedi-
carboxylic acid -(5,7) and of 2-aminonap~thalenedicarboxylic
_ 15
,
HOE 74/F 907
1063275
acid -(5,8).
In the above formulae (XIV) and (XV), RIV and RV are a
mono- or polynuclear arom~tic or heteroaromatic radical having
from 6 to 14 carbon ato~s, preferably from ~ to 10 carbon
atoms, containing an O~I group in ortho-position to the azo-
methine group, and optionally ~ono- or polysubstituted in the
manner indicated under R, ~peciall~ b~ al~yl or cycloalkyl
each having up to 6 carbon atoms, furthermore aryl, pre-
ferably phenyl, fluroalkyl having prefer~bly from 1 to 6 car-
bon atoms, alkox~ h~ving preferabl~ from 1 to 6 carbon atoms,
ar~loxy, preferably phenoxy, carboxyalk~l ha~ing preferably
from 1 to 6 carbo`n atoms, ketoalkyl having preferably from
1 to 3 carbon atoms, nitro or halogen, preferably fluorine
or chlorine; the radicals RIV or RV including all possible
~ubstituents having from 6 to 22, preferably from 6 to 10
carbon atoms.
Suitable azo~ethine compounds are especially the reaction
products of 5-aminoisophthalic acid with salicylaldehyde,
1-hydroxy-2-naphthaldehyde, ?-hydroxy-1-naphthaldehyde, 4-
methylsalicylaldehyde, 4-carboxyethyl-salicylaldehyde~ 4-
methoxy-salicylaldehyde, 3-chloro- or 3-bromQsalicylaldehyde,
4-acetylsalicylaldehyde, 4-hydroxy diphenyl-3-aldehyde, 3-
hydroxydiphenyl-4-aldehyde, p-benzylsalicylaldenyde.
Suitable azo compounds are -those obtained by rea.ction of
dia~otized 5-aminoisophthalic acid with, for example 9 one of
the followin~ co~pounds: p-cresol, 2,4-dimethylphenol~ 2,4-
ditert.-butylphenol, p-chlorophenol, 2j4-dichlorophenol, p-
hydroxyacetophenone, hydroquinone-monoethyl ether, 1-naphthol,
29 2-naphthol, 4-bromonaphthol, 4-hyaroxyaiphen.yl, 4-h~droxy
_ 16 -
1063Z75 . HOE 74/F 907
4'-ethoxydiphenyl, 4,4'-dihydroxyaiphenylmethane-monomethyl
ether.
The incorporation of such chelate-~or~ine azo and/or azo-
methine compounds is described in German Offenlegungsschrift
~o. 2,139,005. These chelate-for~ing compounds may be intro-
duced into the chain before or after the reaction with the
, oxamide acid ester, optionally in a step~Yise single-vessel
reaction. Gen~rally, the components, that is, oxamide`acid
ester, chelate-forming agent and, optionally, polycarbox.ylic
acid, are dissolved or finely distributed in the solvent, and
then the isocyanate in solid, liquid or dissolved form is
added at temperature3 of from -20 to 380C, preferabl~ from
O to 250~, especially from 50 to 200C. Subsequently, the
condensation is carried out at temperatures of from 100 to
250C. In the case of formation of the preconden~ate of poly-
carboxylic acid and isocyanate, as proposed in German Offen-
legungsschrift No. 2,303,239, the chelate-forming agent may
be introduced before or after this ~ormation, advantageously,
all three components are reacted together.
The ratio of the molar equivalents of oxamide acid ester
to chelate-for~ing azo- or azomethine compounds (or, as de-
scribed below, to the chelates thereof) should be (2 to 94) :
(0.1 to 50?, preferably (1 to 80) : { 5 to 20); the sum of
oxamide acid ester, chelate-forming agent or chelate and
possibly present polycarboxylic acid always being 100 mol ~.
The incorporation o~ the cited structural units, ~hich
are dicarboxylic acids capable of forming chelates improves
especially the storage stability of the trion resins or trion
29 resin solutions obtained, since these chelate-forming ~roups
- 17 -
.
1063Z75 HOE 74/F 907
capture traces of metals possibl~ being present.
As also described in German Offenlegungsschrift ~o.
2,1~9,005, it may be advantageous to directl~ incorporate
metal chelates of such chelate-forming azo or azomethine groups,
which may be carried out b~ reaction with metal compound~. The
time of chelate formation may be chosen as desired, that i~,
before, during or after the synthesis of the total pol~mer
ohain. ~he chelate-forming metal compounds ma~ thus be reacted
either together with the chelate-forming azo or azomethine
compounds or later. Preformation of the metal chelàtes in a
special step i9 also possible, and the chelates may then be
introduced into the reaction. The ratio of metal compound~ to
chelate-forming agents should be about eq~limolar, preferably
slightly less than equirnolar.
Chelate-forming metal compounds ~re for example compounds
of metals of the Ist to VIIIth group of the Periodic ~stem
capable of forming chelate complexes. Preferabl~, compounds of
lithium, sodiuml potassium, zinc, magnesium, barium, aluminum,
titanium, lead, chromium, nickel and especially iron, cobalt
or copper are used for chelate formation. Especial1~ suitable
are the oxides, hydroxides, carbonates, halides, alcoholates,
phenolates, acetates, formates or naphthenates. Also complex
compounds of such metals, for example of acet~lacetone or of
enolized acetoacetic ester are suitable.
~5 The incorporation of such chelate-forming azo or azo-
methine compounds into the trion resin as structural u~its
is for example shown in formulae (~I) and (XVII~, and that
of the chelates in formula (XVIII) (see enclosed forrnula
29 sheets- ).
- 18 -
1063275 OE 74/F 907
For the total reaction of oxamide acid ester A', poly-
isocyanate ~' and optionally polycarboxylic acid C' and op-
tionally chelate-forming agent or chelate D' (when A', ~',
C' and D' each represent the number of the moles in question
and A' through D' have the same functionality), the ~ollo~ing
e~uation is valid:
(A' + ~' ~ D`~ = ~. ~l,
where ~ is 0.95 to 1.07, e~pecially 0.98 to 1.02. The poly-
i~ocyanate component is preferably used in a sllght excess
relative to the three other oomponents. Different functionali-
ties of the components have to be taken into consideration
correspondingly.
The components of the trion resin, that is oxamide acid
ester, polyisocyanate9 polycarboxylic acid, azo or azomethine
compound or the ~tal chelate thereof, may be used per se or
as a mixture.
Component c) o~ the coating composition of the invention
is a solvent in which, on the one hand, the trion resin is
readily soluble, and on the other, the low molecular weight
PT~E is substantially or completely insoluble. This solvent
has to be selected from the group of the so-called aprotic
solvents, that is, solvents not containin~ any reactive pro-
tons. Furthermores such a solvent should have a surface tension
of more than 30 dyn/cm, preferably from 30 to 50 dyn/cm, that
is, they should not ~et the low molecular PT~E.
Suitable solvents of this kind are for example N,N'-di-
methylformamide, N,N'-dimethylacetamide, dimethylsulfoxide,
nitromethane, nitroethane, nitrobenzene, benzonitrile, benzo
.
_ 19 -
~ ~, . ...
- 1063275 HOE 74/~ 907
phenone, acetophenone~ pyridine, quinoline, methylbenzoate,
eth.ylben~oate, 1,1,2,2-tetrabromoethane, 1,1,2,2-tetrachloro-
ethane, N,~ hexamethyl-phosphoric acid-trisamide, tetra-
methyl urea, tetrameth~lsulfone and, preferably, ~-meth~l-
pyrrolidone. It is also possible to use mixtures of suchsolvents.
These aprotic solvents ma~ optionally be replaced b~
other organic solvents in an amount of up to 80 ~, prefera~l.y
up to 60 %, especially up to 40 ~p of their total amount, and
it is not required that these other organic solvents be apro-
tic or have a surface tension of ~ore than 30 d~n/cm at 20C.
However, these other organic solvents must have a lo~Jer boi-
ling point than the aprotic solvent used, at least by 10C,
preferably by about 30C. Examples of such other organic sol-
vents which may be blended with the apr~tic solv-ents used are
aromatic h~drocarbons such as benzene, toluene or xylenes,
furthermore ketones or esters ~ organic acids such as acetone,
methylbutylketone, acetic acid ethyl ester, acetic acid but~l
ester and similar solvents. The component c~ solvent, pre-
ferably its aprotic a~ount, is advantageo~sly used alreadyfor the preparation of the trion resin, although it is in
principle possible to prepare the trion resin in the melt.
Th-~s, the tota; amount of sol~ent, preferably of aprotic sol-
vent, may be added alread.y during the preparation of the
trion resin, but preferably onl~ a portlon of the solvent is
added in an amount which ensures that the trion resin is main-
tained in solution. The remaining portiol1 of sol~ent, especi-
ally of the other organic solvent, is aaded for dilution pur-
29 pQSeS either before the addition of -the fluorocarbon wax
. -20 -
- 1063275 HOE 74i~ 907
or together with the ~luorocarbon wax, after mixing and homo-
genizing, in the form of a paste or suspension; mixing and
homogenizing being carried out for example by high-speed
` agitation or on a roll mill. In the ~i.rst case however, the
required amount of fluorocarbon wax i~ added in solid form to
the solution of the trion resin, in portions and wi~h agitation.
The ratio of fluorocarbon wax component a) to trion resin
component b) oP the coating compo~ition of the invention i~
from 90 : 10 to 10 : 90 parts by weight, preferably from
40 : 60 to 70 : 30 parts by weight.
The total amount b.y weight of solvents (comprising the
aprotic ~olvent and optionally the other solvent having a
lower boiling point), that is, component c),should be 0.43 to
100 times, preferably 1.5 to 10 times, the a~ount of; trion
resin contained in the coatin~ composition of the invention
(which corresponds to a 70 to 1, preferably 40 to 10 % by
weight solution of trion resin).
Additionally, up to 50 weight ~0, preferably from 0.1 to
30 ~veight %, relative to the total amount of low molecular
weight PT~E and trion resin a) ~ b), of usual fillers and/or
pigments ma.y be addea, such fillers and/or pigments being for
example: inorganic oxides such as Al203, TiO2, SiO2, iron
oxide, chromium oxide, or sul~ides such as molybdenum sulfide
or cadmium sulfide. ~urther examples of such usual fillers
and/or pigment3 are ~oot, graphite, cadmium selenide, metal
powder or metal alloy powder, for e~ample powdered copper,
aluminum or bronze powder. These fillers or pigments may be
introduced into the solution of the trion resin in the same
29 manner as described above for the fluorocarbon wax, either
- 21 -
1063Z75 H0~ 74/P ^7
together with the latter or, preferably, separately.
The coating composition of the invention so prepared is
ready ~or coating in this form already. Coating may be carried
` out according to known and usual methods, such as dipping,
spraying or painting. The coating composition may be applied
to surfaces of ~qubstrates having a thermostability dègree
which allows them to withstand the subsequent baking process
without damage, such as metallic substrates, ~or exa~ple alu-
minum or refined steel, or non-metallic substrates, for example
ceramic materials (glaæed or unglazed, such às earthenware or
china), enamel or glass, but also plastic surfaces.
After being applied to the substrate, the coating layer
so obtained is covered automatically by a skin of pure low
molecular weight P~E within 8 few minutes only. Subsequently,
this coating has to be heated for a short time at a tempera-
ture of frcm 320 to 420C, preferably from 340 to 400C, in
order to make the low molecular weight P~E on the surface
melt to form a film, and to eliminate the solvent. ~his baking
optionally causes the polymerization or completion of the
polymerization of the trion resin reacted in the first step.
Because of the incorporated trion resins, the coatings
obtained f~om the coating composition of the invention possess
a number of extraordinarily advantageous properties: excellent
antiadhesion, smoothing and antl-tack properties comparable
with those of ~ure, also high molecular weight, P~E, high
abrasion resistance and resistance to mechanical strain, and
still a surprising tenacity and resistance to deep-drawing.
Simultaneously, the adhesion of the coating to the substra~e
29 is not only equal but even superior to that of known P~F-~
- 22 -
1063Z75 ,OE 74/F gO7
coatings requiring an adhesive, and no roughening pretreat~ent
of the sub~trate whatsoever is required. It is very surprising
that ~hese properties are obtained in a combination of opti-
mum values hitherto unknown.
~he abovementioned melt viscosities of the fluorocar'oon
waxes are determined as follows: a melt extrusion by means of
a high pressure capillary viscometer of Messr~. Gottfert is
carried out under the ~ollowing conditions: 3800, 21 kg/cm2
extrusion pressure, nozzle dimensions: diameter 1mm a~d len~th
10 mm. ~he amount of e~truded melt leaving such a nozzle at
the given temperature and pressure within the unit of time i5
determined, from which the apparent melt viscosit.y is cal-
culated according to the following equation:
. ' ~ , = ~ ;
8 . l . ~l
P = extrusion pressure (dyn/cm2)
r = radius of nozzle (cm)
l = length of nozzle (cm)
q = amount oI d~scharged extrusion product (cm3/sec).
The following examples illustrate the invention. In these
examples, the adhesion o~ the coatings was tested according
to German Industrial Standard DI~ 53 151, the pendulum hard-
ness according to DIN 53 157 and the capability for deep-
dra~ling according to DI~ 53 156 (~richsen test). ~he cited
surface tension data were obtained by measuring according to
the so-called bubble bursting ~ethod (surface tension apparatus
according to Cassel).
E X A M P L E 1:
A mixture of 99.6 g (0.6 mol) o~ isophthalic acid, 57.8 g
- 23 _
1063275 H03 ~4/~ 907
(0.3 mol) o~ tri~ellitic anhydride, 252 g (1 mol) of 4,4'-di-
isocyanato-diphenylmethane and 1 g o~ ~,N'-tetrame-thylhexa-
methylenediamine as catalyst, dissolved in 1360 g of N-~eth~l-
pyrrolidone, is stirred for 5 hours at 95C. Subseque~itly,
43 g ~0.1 mol) of 4,4'-bis-(etho~al~lamino)~diphenyl~ethane i9
added in portions within one hour to the precondensate o~-
tained, and the temperature is raised to 195G. ~en this
temperature is attained, agitation is continued for 6 hours.
112 partY by weight o~ N-methylp~rrolidone are added to 100
parts by weight of the tlion resin solution obtained, and
sùbsequently, 37 parts by weight of fluorocarbon wax are added
in portions with vigorous agitation. This fluorocarbon wa~ is
a low molecular PT~3 prepared by a 30 minutes tempering of
high molecular PT~3 at 520C and grinding of the reaction pro-
duct after cooling in a hammer classifier ~.ill. The mean par-
ticle diameter is 6 microns, the melt viscosit~ 2.9 ~ 102
poises at 380C and the specific surface 9.0 m2/g according
to BE~.
~he lacquer so obtained is sprayed on aluminum plates by
means of a spray gun, and baked for 15 minutes at 150C and
subsequently for a further lO minute~ at 360C. The thickness
of the coating so obtained is 30 microns.
The adhesion, tested according to the grate cutting
method o~ German Industrial Standard DIN 53 151, is evaluated
as being ~1 0, that is, the cut edges are entirel~ smooth and
- no fragment of the coating is chipped off. ~urthermora J the
coating has a endulum hardness of ~5 seconds and and inden-
tation according to Erichsen of 6.5 mm. r,lil~ burnt on the
29 coating until it has beccme blacl~ can be removed by a vlater
- 24
1063275 HOE 74 jF 907
jet OI a normal waterpipe without leaving any traces.
_X A ~ P ~ E 2:
A suspension of 150 parts of ~-methylpyrrolidone and 50
` parts of fluorocarbon wax is prepared by means of a high-speed
agitator (10 000 rpm). The fluorocarbon wax was prepared
according to German OffenlegungsschI~ift ~o. 2,235,885 b~
telomerization of monomer TFE in the presence OI 4 weight %
of ¢hloroform as telogene in an aqueous dispersion. The melt
viscosity of this fluorocarbon wax is 7.4 . 103 poises at
380C, the specific surface according to ~EI~ is 19 m2/g, the
mean size of the primary particle is 2.0 microns. Furthermore,
a trion resin solution is prepared as follo~,vs: 53 g (0.32 mol)
oî isophthalic acid, 55 g (O.28 mol) o~ trimellitic anh~dride,
0.5 g of tributylamine as catal~st, 700 g of N-methylp~yrrol-
idone and 196g(0.7 mol) of 3,3'-dimethyl-4,4'-di-isoc,ranato-
diphenylmethane are stirred for 6 hours at 80C. ~he precon-
densate so obtained is reacted for 6 hours at 200C with 43 g
(0.1 mol) of 4,4'-bis-(ethoxalylamino)-diphenylmethane, until
the separation of C02 has come to an end. 120 parts by weight
of the aboYe flu~rocarbon wax suspension are stirred into
100 parts by weight of the trion resin solution. Cooking pans
are coated with the composition obtained and baked first for
15 minutes at 150C and then for a further 10 minutes at 400C.
A non-marring and durable coating is obtained which prevents
adhesion of îood ~hile cooking. Aluminum plates coated ac-
cording to EY~ample 1 have a grate cutting ~ralue OI G~ O, a
pendulum hardness of 95 seconds and an indentation according
to Erichsen of 4.3 mm.
HOE 74!F 907
1063Z75
E X A M P L E '3:
53 g (0.~2 mol) of isophthalic a~id, ~3 g (0.27 mol)
of trimellitic anhydride, 3 g (Q.01 mol) of an azomethine
obtained by reaction of 5-amino-isophthalic acid with salicyl-
aldehyde, 0.85 g of tributylamlne as catalyst, 196 g (0.7
mol) Or 3,3~-dimethyl 4,4~-di-isocyanato-diphen~lmethane
and 700 ~ of N meth~lpyrrolidone arc stirred ~or 6 hours at
80 C. Subsequently, 43 g (0.1 mol) of 4,4~-bis-(ethoxalyl-
amino)-diphenylmethane aro stirred into the above mixture.
The temperature is then raised to 195 C, and agitation is
continued for a further 6 hours at this temperature. The
fluorocarbon wax suspension as described in Example 2 is
added to the trion resin solution so obtained in the same
weight ratio.
Disks of disk saws are coatod with the coating composi-
tion obtained and baked at 350 C. Bubble-free and durable
coating~having a thickness of up to 40 microns are obtained
which prevent sticking of resin and impart good sliding
properties to the disks. Aluminum plates coated according
to Example 1 have a grate cutting test result of GT 0, a
pendulum hardness of 97 seconds and an indentation according
to Erichsen of 4.3 mm.
- 25 a -
- OE 74/F 907
1063Z75
E X A M P ~ E 4:
. .
A mixture of 41 g (0.55 mol) of isophthalic acid, 58 g
(0.3 mol) of trimellitic anh.ydridel 18 g (0.05 mol) o~ the
acid imide formed by reaction of trimellitic anh~dride with
5-aminoisophthalic acid, 250 g (1 mol) of 4,4'-di-i~oc~anato
diphenylmethane and 1 g N,~'-tetramethylhe~ameth~lenediamine
! as catalyst, dissolved in 1980 g of N-methylp~rrolidone, is
stirred for 5 hours at 95C. Subsequently, 43 g (0.1 mol) of
4,4'-bis-(ethoxalylamino)-diphenylmethane are added in portions
within one hour, and the temperature is raised to 195C.
After this temperature is attained, the reaction is carried
out by further agitation for 6 hours. 90 parts by weight of a
suspension containing 24 weight ~0 of fluorocarbon ~ax, 1
weight ~ of soot and 75 weight ~0 of dimethylformamide are added
with agitation to 100 parts by ~veight of this trion resin
solution. The fluorocarbon wax used was obtained by telomeri-
zation (see Example 2) in the presence of 3.5 weight % of
chloroform. Its melt`viscosity is 12.5 . 103 poises at 380C,
the specific surface 14 m2/g, the mean size of the primary
particles 2.4 microns. An aluminum plate coated according to
~xample 1 has a grate cutting test result of GT 0, a pendulum
hardness of 1tO seconds and an Erichsen indentation of 3.8 mm.
X A M P ~ ~ 5:
100 parts by weight of the trion resin solution as de-
scribed i~ Example 1 are mixed with 112 parts by weignt of
dimethylformamide. 35 parts by weight of fluorocarbon wax
and 5 parts by weight of iron oxide brown are added to this
solution with hi~h-speed agitation. The fluorocarbon wax has
2~ been obtained b~ degradation of high molecular weight
- 26 _
HOE 74/F 907
1063275
disperse P~FE by means of a dose of 5 Mrad of gamma rays. Its
melt viscosity is 104 poises at 380C and its specific surface
according to B~T is 5.7 m2/g. This lacquer yields red-bro-m
coatings havillg good anti-adhesion properties. The results
of a coated aluminum plate are the same as in Example 1.
E X A M P ~ E 6- `
-
! 252 g (1 mol) of 4,4'-di-isocyanato-diphen~lrnethane and
398 g (1 mol) of 4,4'-bis-(ethoxalylamino)-diphenylmethane are
dissolved in 1510 g of N-methylpyrrolidone. Subsequentl~, 3.5
g of dibutylstannic oxide are added as catalyst, and the
solution is heated slowly to 205C with agitation. At this
temperature, agitation is continued until no ethanol is formed
any more.
Furthermore, a sus~ension of 50 g of fluorocarbon wax,
150 g of N-methylpyrrolidone and 50 g of methylethylketone
is prepared by means of high-speed agitation (10 000 rpm).
The fluorocarbon wax corres~onds to that of Example 2.
100 parts by weight of the above trion resin solution
are biended with 120 parts by weight of the fluorocarbon wax
suspension. Aluminum plates coated with this lacquer according
to the conditions given in ~xample 1 have a grate cutting
test result of G~ 0, a pendulum hardness of 85 seconds and
an Erichsen indentation of 2.1 mm. Milk burnt until it has
become black may be removed without traces by means of a
water jet from a normal waterpipe.
E X A ~ P ~ E 7:
199 g (0.5 mol) of 4,4'-bis-(ethoxalylamino)-diphenyl-
methane, 273 g (0~5 mol) of a bis-imide acid prepared by
29 reaction o~ 2 mols of trimelliti~ anhydride ~ith 1 mol of
- 27 -
1063Z75 H0~ 74/F 907
4,4'-diamino-diphenylmethane, and 252 g (1 mol) of di-iso-
cyanato-diphenylmethane ~re dissolved in 1680 g of N-methyl-
pyrrolidone. ~ubsequently, the whole is heated to 110C witn
agitation, and 3.6 g of 1,4-diazabic~clo-~2,2,2]-octane as
catalyst are added. The temperature is slowl~ raised to 190C.
Agitation is continued at this temperature, until no C02 and
ethanol are fo~med any more.
100 parts b~ weigbt of the trion resin solution so ob-
tained are diluted with 50 parts by weight of N-methylpyrroli-
done and 30 p~rts by weight of ethyl acetate, and 20 parts by
weight of fluorocarbon wax are added in portions with vigo-
rous agitation (10 000 rpm). ~he fluorocarbon wax is identical
to that of Example 1. According to Example 1, aluminum plates
are coated with the lacquer obtained, and the foliowing re-
sults are obtained: grate cutting test GT 0, pendulum hard-
ness 83 seconds, Erichsen indentation 2.3 mm. Milk burnt un-
til it has become black may be removed without traces by
means of a water jet from a normal ~aterpipe.
EX A M P ~ ~ 8:
A mixture of 99.6 g (0.6 mol) of isophthalic acid, 57.8 g
(0.3 mol) of trimellitic anhydride, 252 g (1 mol) of 4,4' di-
isocyanato-diphenylether and 1 g of N,N'-tetramethylhexa
methylenediamine as catalyst, dissolved in 1360 g of ~-
methylpyrrolidone, are stirred for 5 hours at 95C. Sub-
sequently, 40 g (0.1 mol) of bis-(ethoxalylamino)-diphenyl
ether are added in portions within one hour to the precon-
densate obtained, and the temperature is raised to 195C.
After having attained this temperature, agitation is continued
29 for 6 hours. 100 par-ts by weight of the trion resin so-ution
- 28 -
1063Z75 ~02 74/~ goi
90 obtained are diluted with 150 parts b~ weight o~ N-meth~l-
pyrrolidone, and 37 parts by weight of fluorocarbon wax are
added with vigorous agitation. ~he fluorocarbQn wa~ corres-
ponds to that of Example 1. ~he lacqu~r obtained is applied to
aluminum plates and baked as indicated in Exa~ple 1.
~ he adhesion, testes according to the grate cutting test,
has a value o~ GT 0. The coating has a pendulum hardness o~
104 seconds and an Erichsen indentation of 7.8 mm. Milk burnt
until it has become black may be removed without traces as in
- the preceding Examples.
E X A M P L E 9:
53 g (0.32 mol) of i~ophthalic acid, 53 g (0.27 mol) of
trimellitic anhydride, 3.1 g (0.01 mol) of an azo compound ob-
tained by coupling p-cresol with 3,5-dicarbox.y-phenyldiazonium
chloride, 0.85 g of tribut~lamine as catalyst, 196 g`(0.7 mol)
of ~,3'-dimethyl-4,4'-di-isocyanato-diphenylmethane and 700 g
of dimethylsulfoxide are stirred for 6 hours at 70C. Sub-
sequently, 43 g (0.1 mol) of 4,4'-bis-(ethoxal~lamino)-di-
phenylmethane are stirred in. The temperature is raised to
155C, and agitation is continued for a further 6 hours at
this temperature. ~he trion resin solution so obtained is blen-
ded with the fluorocarbon wax suspension described in Example
2 in a ~Jeight ratio of 1:1.
Aluminum plates coated according to Example 1 have the follo- -
wing test results: grate cutting l~umb~rG~ 0~ pendulum hardness
95 seconds and Erichsen indentation 3.8 mm. Milk burnt until
it has become black is removed without traces as in the
preceding Examples.
- 2g -
H0~ 74/F 907
~063Z75
E X A ~ P _ 3 10:
A mixture of 91 g (0.55 mol) of isophthalic acid, 58 g
~0.3 mol) o~ trimellitic anh~dride, 3.5 g (0.01 mol) of azo-
methine prepared b~ reaction of 5-aminophthalic acid with 1'-
hydrox~-2'-naphthaldeh~de, 250 g ~1 mol) of 4,~'-di-isocyanato-
diphenylmethane and 1 g of N,N'-~ètramethylhexameth~lenediamine
! as catal~st, dissolved in 1~8C g of diacetamide, is ~tirred
~or 5 hours at 90C. Subsequentl~, 43 g (0.1 mol) of 4,~'-
bis-(ethoxalylamino)-diphen~lmethane are added in portions,
and the temperature is raised to 160~. After this temperature
i~q attained, the reaction is completed b~ continuing the
agitation for a further 6 hours. Subsequentl~, the reaction
product is allowed to cool to 80C, and 1.3 g (0.005 mol) of
cobalt(II)-acetylacetonate are stirred in. Agitation. is then
conti.nued for a further 2 hours at this temperature.
90 parts by weight of a suspension of 20 weight % of
fluorocarbon wax, 2 weight ~p of soot, 3 weigllt ,~ of molyb-
denum(IV) sulfide (microfine), 40 weight ~0 of di~ethylacet-
amide, 10 weight ~0 of N-methylpyrrolidone, 10 weight ~ of
toluene and 15 weight ~ of x~lene are added to 100 parts by
weight of this trion resin solution. The fluorocarbon wax
used is described in Example 4.
~he coatings obtained according to Example 1 usi-ng the
lacquer so obtained have a grate cuttin~ test result of C-~ 0,
a pendulum hardness of 97 seconds and an ~.richsen indentation
of 3.8 mm. ~urnt 1nilk is removed without traces as described
above.
- 30 -
1063Z75
'''~"X~ J~ )''S~
`- O O O
~X~ H ,~C~,~
` R"' R~ S ll R"' R"'
O O
~y~N--C~l--N~ ~y
R"' R"' R"' R"'
-- . .
1063Z75
. ` ` . 1~3 .
W. ~x~ ~
` /2
IZ ZI /Z\
o=l,~,b=o =~ = ~-o
z\ o=(~ ~=o oc~ --o
o=~ o \ ;~/ \z/
~)=0 --~-- ~
3~
1063275
D ~" n ~ D ~' ` D "'
N I N
~CHI ~N
HO~3¦ H0~
............ ~... . .
Ml~ 3 (Me~
33 `
