Note: Descriptions are shown in the official language in which they were submitted.
208~737
91/F 397 - 1 -
Water-dilutable, urethane-modified and hydroxyl group-
containing self-crosslinking bin~er and formu~ations
thereof
The present invention relates to novel, urethane resin-
modified, hydroxyl group-containing binders, which are
dispersed and/or dissolved in a (predominantly) aqueous
medium, and the use thereof, preferably as stoving
coating compositions for the production of coating films
and coatings.
Conventional stoving systems are frequently based on the
combination of a binder with a corresponding crosslinking
component. Incompatibilities between these components can
,arise. An additional factor in the case of aqueous
systems is that the crosslinking component as a rule also
has to be compatible with water or is stabilized in the
aqueous phase by the emulsifier action of the binder.
In the present invention the incompatibility between
crosslinking agents (polyisocyanates in the invention)
and binders (polyester-polyol containing anionic groups
in the invention) is prevented by partial covalent
bonding of the isocyanate components to the polyester
resin, so that a self-crosslinking one-component stoving
system is obtained.
The storage stability of the binder of the present
invention, which is predominantly dispersed in water, is
consequently considerably greater than that of a combina-
tion of the polyester-polyol with the correspondingly
completely capped polyisocyanate. In detail, the subject
of the invention is a water-dilutable, urethane-modified
and hydroxyl group-containing binder which is prepared by
reacting a polyester containing free hydroxyl groups and
neutralized and/or neutralizable acid groups with sub-
stoichiometric amounts (with respect to the number of
- 2 - 208~737
free hydroxyl groups) of a partially blocked polyiso-
cyanate. The binder according to the invention preferably
contains hydroxyl groups of 3-350, in particular
5-170 milliequivalents OHJloo g of binder solid resin.
The proportion of capped isocyanate groups (expressed as
NCO) is preferably between 0.5 and 10% by weight, with
respect to solid resin, and that of the urethane groups
is preferably between 0.5 and 20% by weight, with respect
to solid resin (expressed as -NH-C(O)O-). In order to
obtain the dilutability with water, the resin contains
neutraliæable and/or neutralized acid groups, generally
carboxylic acid, sulfonic acid or phosphonic acid groups.
The content of these groups is customarily between 5 and
200, preferably between 10 and 90 milliequivalents of
sulfonate and/or carboxylate and/or phosphonate in 100 g
of binder solid resin.
The polyester-polyols used as starting material are
prepared by conventional processes by a condensation
reaction of polycarboxylic acids, polyalcohols and
hydroxy carboxylic acids, all of which can optionally
contain further carboxylic acid, sulfonic acid or phos-
phonic acid groups.
The polycarboxylic acids can be of aliphatic, cyclo-
aliphatic, aromatic and/or heterocyclic type and can
optionally be substituted, for example, by halogen atoms.
Examples which may be mentioned of such carboxylic acids
and their derivatives are: succinic acid, adipic acid,
suberic acid, aæelaic acid, sebacic acid, phthalic acid,
terephthalic acid, sulfoterephthalic acid, sulfoiso-
phthalic acid, sulfophthalic acid, isophthalic acid,trimellitic acid, pyromelli~ic acid, tetrahydrophthalic
acid, hexahydrophthalic acid, di- and tetra-
chlorophthalic acid, endomethylenetetrahydrophthalic acid
and its hexachloro derivative, glutaric acid, maleic
acid, fumaric acid and fatty acid dimers and trimers. In
place of these acids it is also possible to use their
anhydrides, insofar as these exist.
3 208~737
The polyalcohols used are preferably low-molecular
polyols, polyhydroxy-polyethers, polylactone-polyols and
polycarbonate-polyols. Suitable low-molecular polyols
are, for example, ethanediol, the various propanediols,
butanediols and hexanediols, dimethylolcyclohexane,
2,2-bis(4-hydroxycyclohex~l)propane, diethylene glycol,
triethylene glycol, glycerol, trimethylolethane or
trimethylolpropane, hexanetriol, pentaerythritol,
dipentaerythritol or sorbitol; in addition, low-molecular
polyols, preferably diols, which also contain an ionic
group in the form of the carboxylic acid, sulfonic acid
or phosphonic acid group are also used. These acid groups
can be free and/or present in salt form. Examples of this
group of monomers are a-C2-C1O-bishydroxy carboxylic
acids, such as, for example, dihydroxypropionic acid, di-
methylolpropionic acid, dihydroxyethylpropionic acid,
dimethylolbutyric acid, tartaric acid, dihydroxymaleic
acid, dihydroxybenzoic acid or 3-hydroxy-2-hydroxymethyl-
propanesulfonic acid and dihydroxybutanesulfonic acids.
Suitable polyhydroxy-polyethers are compounds of the
formula
H -[- O - (CHR)n-]~ OH
in which
R is hydrogen or a lower alkyl radical, optionally
carrying diverse substituents,
n is a number from 2 to 6 and
m is a number from 10 to 120.
Examples are poly~oxytetramethylene)glycols, poly-
(oxyethylene)glycols and poly(oxypropylene)glycols. The
preferred polyhydroxy-polyethers are poly(oxypropylene)-
glycols having a molecular weight in the range from 400
to 5,000.
The polylactone-polyols derived from lactones are
obtained, for example, by reaction an ~-caprolactone with
a polyol. Products of this type are described in
208~737
US Patent 3,169,945.
The polylactone-polyols, which are obtained by this
reaction, are characterized by the presence of a terminal
hydroxyl group and by recurring polyester fractions which
S are derived from the lactone. These recurring molecule
ractions can have the formula
- C -- ( CHR ) n ~ CH20
in which n is preferably 4 to 6 and the substituent R is
hydrogen, an alkyl radical, a cycloalkyl radical or an
alkoxy radical, no substituent containing more than 12
carbon atoms.
The lactone used as starting material can be any lactone
or any combination of lactones and this lactone should
contain at least 6 carbon atoms in the ring, for example
6 to 8 carbon atoms, and 2 hydrogen substituents should
be present on the carbon atom which is bonded to the
oxygen group of the ring. The lactone used as starting
material can be represented by the fcllowing general
formula:
CH2(CR2)n 1
in which n and R have the meaning already indicated.
The lactones preferred in the case of the invention are
~-caprolactones, in which n has the value 4. The most
preferred lactone is unsubstituted ~-caprolactone, in
which n has the value 4 and all R substituents are
hydrogen. This lactone is particularly preferred since it
is available in large amounts and gives coatings which
have excellent properties. In addition, various other
lactones can be used on their own or in combination.
.
208~737
-- 5 --
Examples of aliphatic polyols suitable for the reaction
with the lactone are ethylene glycol, 1,3-propanediol,
1,4-butanediol, hexane-1,6-diol, dimethylolcyclohexane,
trimethylolpropane and pentaerythritol.
The polycarbonate-polyols or polycarbonate-diols are
compounds which have the general formula
HO-R-~ O-C-O-R-)~-OH
in which R is an alkylene radical. These OH-functional
polycarbonates can be prepared by reacting polyols, such
as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol,
diethylene glycol, triethylene glycol, 1,4-bishydroxy-
methylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane,
neopentyl glycol, trimethylolpropane or pentaerythritol,
with dicarbonates, such as dimethyl carbonate, diethyl
carbonate or diphenyl carbonate, or phosgene. ~ixtures of
such polyols can also be used.
The following may be mentioned as preferred examples of
hydroxy carboxylic acids: salicylic acid, sulfosalicylic
acid and salts thereof.
~he polyester-polyols are prepared by known methods in a
multistage process depending on the rate of esterifi-
cation of the carboxylic acids. For the preferred case of
the preparation of a polyester-polyol from a mixture of
aromatic and aliphatic dicarboxylic acids, the aromatic
carboxylic acids are first esterified with the hydroxy-
functional components in the presence of a catalyst and
the aliphatic carboxyl group-containing reactants are
then introduced, since, as is known, the rate of
esterification of aromatic carboxylic acids, such as, for
example, isophthalic acid, is considerably slower than
that of dimethylolpropionic acid and the latter, in turn,
is slower than, for example, that of adipic acid.
2~8~737
In the case of the polyester-polyols containing sulfonic
acid groups it can be necessary, in order to achieve as
~uantitative as possible a condensation reaction of the
sulfo monomer, to carry out the synthesis also in a
~ultistage process. To this end, the entire hydroxyl-
functional components are first reacted with the sulfo
monomers and optionally with the aromatic, carboxylic
acid-containing components in the presence of catalysts,
so that 95% of the amount of distillate calculated for a
quantitative conversion is obtained from the condensation
reaction. The aliphatic carboxylic acid components are
then reacted, where appropriate, the condensation reac-
tion being carried out until a free acid group content of
less than 18 meq (COOH)/100 g is obtained.
The polycondensation reaction takes place at temperatures
between 150 and 230C, preferably between 160 and 21~C.
Suitable catalysts are, preferably, organometallic com-
pounds, in particular zinc-, tin- or titanium-containing
compounds, such as, for example, zinc acetate, dibutyltin
oxide or tetrabutyl titanate. The amount of catalyst is
preferably 0.1 to 1.5% by weight of the total batch.
The polyester-polyols obtained in this way are then
reacted with a partially capped polyisocyanate. Suitable
polyisocyanates are all compounds of this type known
here, for example trimethylene diisocyanate, tetra-
methylene diisocyanate, pentamethylene diisocyanate,
hexamethylene diisocyanate, propylene diisocyanate,
ethylene diisocyanate, 2,3-dimethylene diisocyanate,
l-methyl-trimethylene diisocyanate, l,3-cyclopentylene
diisocyanate, 1,4-cyclohexylene diisocyanate, 1,2-cyclo-
hexylene diisocyanate, 1,3-phenylene diisocyanate,
1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate,
2,6-toluylene diisocyanate, 4,4'-biphenylene diiso-
cyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene
diisocyanate, 1-isocyanatomethyl-5-isocyanato-
1,3,3,3-trimethylcyclohexane, bis(4-isocyanatocyclo-
hexyl)methane, bis(4-isocyanatocyclophenyl)methane,
2084737
4,4'-diisocyanatodiphenyl ether, 2,3-bis(8-isocyanato-
octyl)-4-octyl-5-hexylcyclohexene, trimethylxylylene
diisocyanate or tetramethylxylylene diisocyanate or
mixtures of these compounds.
In addition to these simple polyisocyanates, those which
contain hetero-atoms in the radical linked to the iso-
cyanate groups are also suitable. Examples of such
compounds are polyisocyanates which contain carbodiimide
groups, allophonate groups, isocyanurate groups, urethane
groups, acylated urea groups or biuret groups.
Suitable polyisocyanates are, finally, also those higher
functional isocyanates which are prepared by reacting a
diisocyanate with a polyol (for example trimethylol-
propane or pentaerythritol), as well as the ethoxylated
and/or propoxylated derivatives thereof having a degree
of alkoxylation of 0.5 to 4.5 ethylene oxide and/or
propylene oxide per hydroxyl functional group.
Suitable capping agents are aliphatic, cycloaliphatic or
alkyl-aromatic (monohydric) alcohols, for example lower
aliphatic alcohols, such as methyl alcohol or ethyl
alcohol, the various propyl, butyl and hexyl alcohols,
heptyl alcohol, octyl alcohol, nonyl alcohol, decyl
alcohol and the like, and also unsaturated alcohols such
as propargyl alcohol or allyl alcohols, cycloaliphatic
alcohols, such as cyclopentanol or cyclohexanol, alkyl-
aromatic alcohols, such as benzyl alcohol, p-methylbenzyl
alcohol, p-methoxybenzyl alcohol and p-nitrobenzyl
alcohol, and monoethers of glycols, such as ethylene
glycol monoethyl ether, ethylene glycol monobutyl ether
and the like. ~urther capping agents are phenols,
ketoximes, expediently having 3 to 20 carbon atoms,
preferably 3 to 10 carbon atoms, such as acetone oxime,
methyl ethyl ketone oxime (= butanone oxime), hexanone
oxime (such as methyl butyl ketone oxime), heptanone
oxime (such as methyl n-amyl ketone oxime), octanone
oxime and cyclohexanone oxime, CH-acid compounds, such as
208~737
malonic acid alkyl esters, acetoacetates and also cyano-
acetates, in each case having 1 to 4 carbon atoms in the
ester group, NH-acid compounds, such as caprolactam and
amino alcohols, such as diethylethanolamine.
The polyisocyanates are re~cted in accordance with
methods known per se with an amount of a capping agent
such that the ratio of free isocyanate groups to capped
isocyanate groups is 1:4 to 1:0.5.
These partially capped polyisocyanates are then reacted
in accordance with known methods with the polyester-
polyol described above, specifically in proportions by
weight such that the end product has the parameters
defined initially. Any free acid groups present are then
finally completely or partially neutralized. Aqueous
solutions of alkali metal hydroxides or amines, for
example trimethylamine, triethylamine, dimethylaniline,
diethylaniline, triphenylamine, dimethylethanolamine,
aminomethylpropanol, dimethylisopropanolamine or ammonia,
are used for this purpose.
If the relative reactivities of the polyester-polyol and
the capping agent with respect to the polyisocyanate
permit, there are also the following two process
possibilities:
- the polyisocyanate is added to the capping agent,
which has been initially introduced with the
polyester-polyol, if appropriate in the presence of
a catalyst, and, in the case of appropriate selec-
tivity, the claimed binder can also be obtained in
this way.
0 - the polyester-polyol is reacted with the polyiso-
cyanate, if appropriate in the presence of a
catalyst, until only the required free OH equiva-
lents are still present. The capping agent is then
added to this NCO-functional polymer and in this way
2~737
it is possible to block the isocyanate groups in
order to obtain the claimed binder.
The aqueous dispersions of the binders according to the
invention can be used to prepare coating systems, as
binders for water-dilutable adhesives or as resins for
printing inks.
In the case of appropriate compatibility, they can also
optionally be combined with other aqueous plastic disper-
sions and/or solutions, for example acrylic polymers
and/or methacrylic polymers, polyurethane, polyurea
resins, polyester resins and epoxy resins, thermoplastics
based on polyvinyl acetate, polyvinyl chloride, polyvinyl
ether, polychloroprene or polyacrylonitrile and ethylene-
butadiene-styrene copolymers.
IThe binders according to the invention can be applied to
very diverse substrates, for example ceramics, wood,
glass, concrete and preferably plastics, such as
polycarbonate, polystyrene, polyvinyl chloride,
polyester, poly(meth)acrylates, acrylonitrile-butadiene-
styrene polymers and the like, as well as also preferablymetals and alloys, such as iron, copper, aluminum, steel,
tin, zinc, titanium, magnesium, brass, bronze and the
like.
The binders according to the invention are suitable, for
example, for the production of coating films, coatings
and/or intermediate coatings for very diverse fields of
application. After adding conventional coating additives,
such as flow auxiliaries, wetting auxiliaries and dis-
persing auxiliaries, as well as conventional pigment
formulations (TiO2, BaSO~), they are suitable, in par-
ticular, as aqueous stoving filler coatings, which -
especially in the automobile industry - are applied as
intermediate coating between primer and top coat, stoving
or forced drying being carried out at temperatures of 70
to 200C, in particular of 100 to 180C, under otherwise
208~737
-- 10 --
customary stoving conditions. Compared with aqueous
filler coatings used on the market, they are distin-
guished by very good protection against flying stones,
very good resistance to warm and humid conditions and
very good optical properties (gloss, surface structure).
Although it is not absolutely essential to add a cross-
linking component when formulating water-dilutable
coating compositions containing the binders according to
the invention, it is nevertheless possible to add further
crosslinking agents customary in coating technology, such
as, for example, water-soluble or water-emulsifiable
melamine or benzoguanamine resins, water-emulsifiable
polyisocyanates or water-emulsifiable prepolymers con-
taining terminal isocyanate groups, water-soluble or
water-dispersible polyaziridines and b~ocked polyiso-
cyanates, provided these are compatible.
Because of the high gloss, a good top coat quality can
also be achieved using the binders according to the
invention if suitable pigments are chosen. A prerequisite
is then, however, the use of non-yellowing polyiso-
cyanates (for example aliphatic isocyanates). Short-term
weathering tests show very good results.
A particular advantage of the binders according to the
invention is their storage stability (Table 3).
Examples
1. Polyesters
The preparation of the polyester-polyol~ is carried out
under a Nz atmosphere in a 4 1 four-necked round-bottomed
flask provided with an anchor stirrer, a N2 inlet, a
temperature sensor and a packed column (about 20 cm long
and 3 cm in diameter) fitted with a top thermometer and
a descending condenser.
Polyester 1
1,241 g of hexanediol (HD), 365 g of neopentyl glycol
20~4737
-- 11
(NPG), 440 g of trimethylolpropane (TMP), 312 g of
sulfoisophthalic acid dimethyl ester sodium salt
(5-SIP-DME-Na) and 3 g of anhydrous zinc acetate are
subjected to a condensation reaction at 170C to 220C
and a ma~imum top temperature of 65C until 50 g of
distillate are obtained. The reaction mixture is cooled
to 140C, 445 g of terephthalic acid (TPA), 891 g of
isophthalic acid (IPA) and 2.6 g of dibutyltin oxide
(DBTO) are added and the condensation reaction is carried
out at 200C until a carboxyl group content of 26 meq
(COOH)/100 g is obtained. The reaction mixture is cooled
to 140C, 706 g of adipic acid (ADPA) are added and the
condensation reaction is carried out at temperatures of
165 to 220C (maximum top temperature 100C) until the
carboxyl group content is 7 meq (COOH)/100 g.
Polyester 2
665 g of hexanediol, 195 g of neopentyl glycol and 235 g
of trimethylolpropane are melted, 210 g of terephthalic
acid and 1.2 g of DBTO are then added at 100C and the
condensation reaction is carried out at 220C and a
maximum top temperature of 100C until a clear melt is
obtained. The reaction mixture is cooled to 160C, 455 g
of isophthalic acid and a further 1.2 g of DBTO are added
and the condensation reaction is carried out until a
carboxyl group content of 35 meq (COOH)/100 g is
obtained. The reaction is then cooled to 130C and 910 g
of adipic acid and 505 g of dimethylolpropionic acid
(DMPA) are added and the condensation reaction is carried
out at 160C to 200C (maximum top temperature 100C)
until a value of 90 meq (COOH)/100 g is obtained.
Polyester 3
500 g of hexanediol, 520 g of neopentyl glycol and 235 g
of trimethylolpropane are melted and 300 g of tere-
phthalic acid, 450 g of isophthalic acid and 2.5 g of
DBTO are then added at 100C. The condensation reaction
is carried out at 190C to 200C until a carboxyl group
content of 14 meq (COOH)/100 g is obtained, the reaction
- 12 - 2084737
mixture is cooled to 140C, 900 g of adipic acid are
added and the condensation reaction is carried out at
190C to 200~C until a value of 133 meq (COOH~/100 g is
obtained. The reaction mixture is then cooled to 140C,
300 g of dimethylolpropionic acid are added and the
condensation reaction is carried out at 170C to 180C
Imaximum top temperature 100C) until the carboxyl group
content is 100 meq (COOHj/100 g.
Polyester 4
500 g of hexanediol, 400 g of neopentyl glycol and 350 g
of trimethylolpropane are melted. 300 g of terephthalic
acid, 450 g of isophthalic acid and 2.5 g of DBTO are
added at 100C and the condensation reaction is carried
out at 190C to 200C until the carboxyl group content is
7 meq (COOH)~100 g. ~he reaction mixture is cooled to
140C, 900 g of adipic acid and 300 g of dimethylol-
propionic acid are added and the condensation reaction is
carried out at 160 to 170C until the free carboxyl group
content is 128 meq (COOH)/100 g. The reaction mixture is
then cooled to 140C and a vacuum of 100 mbar is applied
until a value of 110 meq (COOH)/100 g is reached (about
30 min).
2. Self-crosslinking - urethane-~odified - binders
( S~B)
~he synthesis of the binders according to the invention
is carried out in a 2 1 four-necked round-bottomed flask
fitted with a reflux condenser and a temperature sensor.
S~B 1
75.0 g of diphenylmethane 4,4'-diisocyanate (MDI) are
added in the course of 7 min to 43.2 g of diethyl
malonate, 0.8 g of sodium methylate and 74.0 g of methyl
ethyl ketone and the mixture is stirred at 45C, with
cooling, until a NCO content of 5.5% is obtained. A
solution of 269.5 g of polyester 1 in 92.5 g of methyl
ethyl ketone is then added in the course of 2 min, the
temperature is raised to 50C and the reaction mixture is
,
208~737
_ 13 -
stirred until the NCO content is < 0.1%. After further
dilution with 54.4 g of butyl glycol/isopropanol (weight
ratio 3/1), the mixture is dispersed with 675 g of
demineralized water heated to 50C. 170 g of methyl ethyl
ketone are distilled off from the aqueous phase under
250 mbar and at 60C.
SUB 2
66.6 g of isophorone diisocyanate (IPDI) are metered, in
the course of 2 min, into 27.5 g of methyl ethyl ketoxime
(ME~ oxime), 0.4 g of dibutyltin dilaurate (DBTDL) and
55.6 g of methyl ethyl ketone and the mixture is stirred
at 35C, with cooling, until a NCO content of 8.5% is
obtained. A solution of 294 g of polyester 2 in 110 g of
methyl ethyl ketone i then added in the course of 3 min,
the temperature is raised to 50C and the reaction
mixture is stirred until the NCO content is < 0.1%. After
further dilution with 54.4 g of butyl glycol~isopropanol
(weight ratio 3/1), the mixture is neutralized with
20.0 g of triethylamine (TE~) and then dispersed with
675 g of demineralized water heated to 60. 170 g of
methyl ethyl ketone are distilled off from the aqueous
phase under 200 mbar and at 60~C.
SUB 3
435 g of methyl eth.yl ketoxime are added to 1,110 g of
isophorone diisocyanate and 0.75 g of DETDL at 25C to
30C, with cooling, over a period of 75 min, the tempera-
ture is then raised to 40C and the reaction mixture is
stirred for a further 1 h. Isophorone diisocyanate capped
on one side by methyl ethyl ketoxime is thus obtained.
55 g of n-methylpyrrolidone, 237.6 g of polyester 3 and
186.9 g of isophorone diisocyanate capped on one side, as
described above, are stirred at 60C until a NCO content
of 0.4% is obtained. 21.1 g of dimethylethanolamine
(DNEA) are then added and the reaction mixture is stirred
for a further one hour at 60C and dispersed with 715 g
of demineralized water heated to 60C.
.
- 14 - 208~737
SUB 4
42.0 g of n-methylpyrrolidone, 220.0 g of polyester 4 and
92.0 g of isophorone diisocyanate capped on one side with
methyl ethyl ketoxime are stirred at 60C until a NCO
content of 0.1% is obtained. 21.6 g of dimethylethanol-
amine are then added and the reaction mixture is s~irred
for a further one hour at 60C and dispersed with 460 g
of demineralized water heated to 60C.
SUB 5
435 g of methyl ethyl ketoxime are added to 1,220 g of
tetramethylxylylene diisocyanate (TMXDI) and 0.75 g of
DBTL at 25C to 30C, with cooling, over a period of
75 min, the temperature is then raised to 40C and the
reaction mixture is stirred for a further 1 h. TMXDI
capped on one side with methyl ethyl ketoxime is obtained
in this way.
45.0 g of n-methylpyrrolidone, 219.6 g of polyester 4 and
102.2 g of trimethylxylylene diisocyanate capped on one
side with methyl ethyl ketoxime are stirred at 60C until
a NCO content of 0.1% is obtained. 36.2 g of triethanol-
amine tTOLA) are then added and the reaction mixture is
stirred for a further one hour at 60C and dispersed with
400g of demineralized water heated to 60C.
SUB 6
230.0 g of polyester 4, 44.0 g of N-methylpyrrolidone,
27.4 g of methyl ethyl ketoxime and O.OS g of dibutyltin
dilaurate are stirred homogeneously at 35-40C and 69.8 g
of isophorone diisocyanate are metered in at such a rate
that the temperature does not rise above 65C. The
reaction mixture is stirred at 65C until a NCO content
of < 0.10% is obtained. 22.6 g of dimethylethanolamine
are then added at 65C and the reaction mixture is
stirred for a further hour and dispersed with 490 g of
demineralized water heated to 65C~
- 15 - 2084737
Comparison example:
119.0 g of methyl ethyl ketoxime-capped isophorone
diisocyanate (reaction of 1 mol of isophorone diiso-
cyanate with 2 mol of methyl ethyl ketoxime in the
presence of 0 15 g of dibutyltin dilaurate) are stirred
homogeneously with 42.0 g of N-methylpyrrolidone and
220 0 g of polyester 4 at 60C and 21 6 g of dimethyl-
ethanolamine are added at this temperature. The reaction
mixture is stirred for a further hour at 60C and dis-
persed with 515 0 g of demineralized water heated to60C.
3. Example of a stoving filler coating composition
based on SUB 4 (colour shade light gray)
Parts by weight
SUB 4 65 7
Wetting and dispersing auxiliaries
(-Additol XL 250) 0.3
Flow agent (-Additol XW 390) 0.4
Titanium dioxide 12.0
20 Blanc fixe micro 10 0
Talc, Naintsch E 7 2 0
Flame soot 101 0 1
Deionized water 9 5
100 0
Test results: see Table 4
2084737
- 16 -
4. Example of a water-dilutable top coating composition
based on SUB 5
Parts by weight
SUB 5 68.6
Wetting and dispersing auxiliaries
(-Additol XL 250) 0.2
Flow agent ('Additol XW 390) 25~ in H200.5
Light stabilizers (-Sanduvor 3212)
50% in butyl glycol 1.7
10 Titanium dioxide 23.5
Deionized water 5.5
100.O
Test results for SUB_5 in the top coat
Test 20' 130C20' 150C
.
Coating thickness in ~m 31 31
,
Gloss < 20 76% 75%
< 60 88% 89
Pendulum hardness in sec 153 144
Cross-hatch on sheet steel C-H 0 C-H 0
: 25
Erichsen deep drawing on
sheet steel in mm 9.9 9.9
Resistance to solvents
acetone ~ 20 sec< 20 sec
xylene 1 min 1 min
ethanol/water (1:1)9 min15 min
- 17 - 2084737
Test in total process (Gathodic electrocoat~filler/top
coa~)
Cross-hatch C-H O
Erichsen deep drawing
in mm 6
.
208~737
- 18 -
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o _~ o _
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