Note: Descriptions are shown in the official language in which they were submitted.
2~93~
mhe use of oligourethanes a~ forming agents for aqueous
pigment preparations
This invention relates to the use o~ certain oligo-
ur~thanes as forming agents for agueous pigment prepara-
tions. The terms "pigments" and "pigment preparations" inthe context of this invention include matt 7 ng a~ents and
their preparations. The new pi~ment preparations ob-
tainable by means cf the oligourethanes to be used
according to the invention are eminently suitable for the
pigmentation (or matting) of dressing agents for leather
and leather imitations and of textile coating compounds. "Forrning agents" within
the meaning of this invention are the binders of the pigment preparations but not
necessarily also the complete binders of the dressing agents or of the textile coating
compounds.
Dressing agents and textile coating compvunds ~e.g.
textile printing pastes) in most cases contain their own
binders. The forming agent of the pigment preparation
serves to ~acilitate the incorporation of the pigment in
the dressing agent or in the textile coating compound.
The orming agents must not deleteriQusly affect the
properties of the dr0ssing agents and textile coating
compounds.
~5
LÆ A28297-Foreign countries -2-
~ O ~ 5 ~
Aqueous systems are beinq increasingly used for the
dressing o~ leather and the printing of textiles. Aqueous
pigment preparations for colourin~ the dressing agents and
textile coating compounds used are not only required to be
capable of dilution with water ~nd ~ree from migrating
components and to have ~ high pigment content at low
viscosity, high stability and good compatibility with the
other components of the dress~ng agents or textile coating
compounds but are also reguired not to impair the
properties of the dressing agents and textile coating
compounds nor the properties of the finished articles in
which these agents have been used. Thu~, for example, they
must not deleteriously afect the abrasion resi~tance,
bending strength, wet adherence, ironing and embossing
qualitie~, swelling properties and softness and hardness
at different temperatures (and hence also the low
temperatuxe strength).
Agueous pigment preparations are known, for example, from
DE-OS 3 625 605 (= US-PS 4 812 4923. The polyurethane
ureas used as forming agents may be obtained by the poly-
addi$ion of polyester diols or polyether diols and
dimethylol propionic acid to diisocyanates, dispersion of
the resulting polyaddition product in water, neutralisa-
tion and chain lengthening with polyamines. Although these
pigment preparations fulfil many of the requirements, they
are still not quite satisf~ctory in th~ir le~elling
properties and the water resistance of coatin~s prepared
from piqmented dressing agents and pigmented textile
coating compounds.
It has surprisingly been found that oligourethanes which
are obtainable from isocyanate prepolymers and amino
alcohols and carry anionic (or potentially anionic) and
Le A 28 297 3
2 ~ ~ ~ J ~ ~ r 3
ca~onic (OF po~n~ly ca~o~c~ ~oupsin ce~n proponions ~ su~norto ~e
s~te of ~e a~ fon~ng ag~n~.In ~s con~c~on po~nti~lyio~c ~oups ~e
unde~t~ to ~,forex~mple,acid ~oups~nd ~mino ~oupsw~ch ~ ~pableof
fo~ng ionic ~oups by neu~alisa~on, pro~na~on, quaeenNsation or ~ne
fonna~on.
Thep~sent~ventionrelatesto~euseofo~go-
urethanes in the ~olecular weight range of from 5000 to
50,000 which are free ~rom pri~ary and ~econdary amino
groups ~nd contain ethoxy groups incorporated in a
guant~ty of from 5 to 25% by weight, based on the oligo-
urethane, and anionic and cationic groups, the quantity of
anionic groups amounting to 0.2 to O~ mol, preferably
0.25 to 0.7 mol per lO00 g of oligourethane and the molar
ratio of anionic/cationic groups amounting to o.~ to 4,
preferably 0.9 to 3.6, as forming agents for aqueous
pigment preparations.
The moiecular weight~ mentioned for the oligourethanes are
average molecular weights and are calculated from the
nature and quantity of the starting components.
The oligourethanes to be used according to the invention
are ~referably reaction products of
I) polyisocyanates,
II) hydroxyl compounds and
III) aminoalcohols.
The organic polyisocyanates I) may be aliphatic, cyclo-
aliphatic, araliphatic, aromatic or heterocyclic polyiso-
cyanates such as those described, for example, by
W. Siefken in Liebigs Annalen der Chemie ~62, pages 75 to
l36.
Preferred polyisocyanates I) are compounds of the formula
Q(NCO~n having an average molecular weight below 800, n
LeA28297 -4-
2 0 ~
denoting ~ number from 2 to 4 and Q denoting an aliphatic
C2-C~4-hydrocarbon group, a cycloaliphatic C6-C15-
hydrocarbon group, n araliphatic C7-C15-hydrocarbon
group or a heterocyclic C2-C12 group having 1 to 3 hetero
atoms s~lected from oxygen, ~ulphur and nitrogen, for
example- (i) Diisocyanates such n~ ethylene diisocyanate,
1,4-tetramethylene dii~ocyanate, 1,6-hexa~ethylene diiso-
cyanate, 1,12-dodecane dii60cyanate, cyclobutane-1,3
diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and
any ~ixtures of these isomers, 1-isocyanato-2-i ocyanato-
~ethyl-cyclopentane, 1-$socyanato-3,3,5-trimethyl-5-
isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotolyl-
ene diisooyanate and any mixtures of these isomers, hexa-
hydrn-1,3- and/or -1,4-phenylene diisocyanate, perhydro-
2,4'- andlor ~,4'-diphenylmethane-diisocyana~e, 1,3- and
1,4-phenylene-diisocyanate, 2,4- and 2,6-tolylene-
diisocyanate and any mixtures of these isomers, diphenyl-
methane-2,4'- and/or -4,4'-diisocyanate, naphthalene-1,5-
diisocyanate, polyisocyanates containing uretdione groups,
e.g. bis-(6-isocyanatohexyl)-uretdione sr the dimers of
l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
containing the uretdione structure and any mixtures of the
above-mentioned polyisocyanates; (ii) trifunctional and
higher functional polyisocyanates such as the isomers of the
triisocyanato-triph~nyl thiophosphate series and their
mixtures: the isomers of the triisocyanato triphenyl-
methane ~eries (such as triphenylmethane-4,4',4"-triiso-
cyanate) and their mixtures; biurets and isocyanurates or
tris-urethanes of hexamethylene diisocyanate, of isophor-
one diisocyanate or of other ~liphatic isocyanates, andpolyphenyl-polymethylene polyisocyanates as obtained by
aniline/formaldehyde condensation followed by phosgena
tion.
The compounds for reaction with these polyisocyanates I)
Le A 28 297 5
20S~
may be mono- and especially polyhydroxyl compounds IIj
having from 2 to 8, preferably 2 or 3 hydroxyl groups per
molecule and an (average) molecular weight of up to
10,000, preferably up to 6000. Both low molecular weight
polyhydroxyl compounds having molecular weights of from 62
to 499 and relatively high molecular weight polyhydroxyl
compounds having average molecular weights of at least
500, preferably at least 1000 may be used, such as those
described in detail in the above-mentioned publications.
Low molecular weight polyhydroxyl compounds II ("chain
lengthening agents"j include a wide ~ariety of diols such
as, for example,
a) alkanediols such as ethylene glycol, propylene
glycol-~1,3) and propylene glycol-(1,2), butane-
diol-(1,4), pentanediol-(1,5), dimethylolpropane-
diol-(1,3) and hexanediol-(1,6);
b~ ether diols such as diethylene glycol, triethylene
glycol an~ 1,4-phenylene-bis-(~-hydroxyethylether);
c) ester diols corresponding to the general formulae
Ho-(cH2)x-co-o-(cH2)y-oH and
HO-(CH2)X-O-co-R-co-o-(c~2)x-oH
in which
R denotes an alkylene or arylene group having 1
to 10, preferably 2 to 6/ carbon atoms,
x = 2 to 6 and
Le A 28 297
- ~06~3~
y = 3 to 5,
eOg~ ~-hydroxybutyl-~hydroxy-caproic acid ester,
~hydroxyhexyl-~-hydroxybutyric acid ester, adipic
acid~ hydroxyethyl1ester and terephthalic acid-
bis-(~-hydroxyethyl)ester.
Relatively high molecular weight polyhydroxyl compounds II
include those knuwn per se in polurethane chemistry, such
as hydroxypolyesters, hydroxypolyethers, hydroxypolythio
ethers, hydroxypolyacetals, hydroxypolycarbonates and/or
hydroxypolyester amides, preferably those having average
molecular weights of from 600 to 4000, most preferably
those with average molecular weights of from 800 to 2500.
Polyether polyols and polyester polyols are particularly
preferred.
Ethylene oxide polyethers II having an av~rage of 2 to 3
hydroxyl groups per molecule and ~n average molecular
weight of from 250 to 2500 are particularly preferred;
these may also contain polypropylene oxide units. In a
particularly preferred embodiment, ethylene oxide
polyethers are used in a quantity resulting in an oligo-
urethane having 5 to 15, preferably 6 to 10% by weight of
polyethoxy groups, based on the oligourethane.
The hydroxyl group-containing polyesters II may be, for
example, reaction products of polyhydric, preferably
dihydric alcohols, optionally together with trihydric
alcohols, with polybasic, preferably dibasic carboxylic
acids. Instead of using free polycarboxylic acids, the
corresponding polycarboxylic acid anhydrides or corres
ponding polycarboxylic acid C1-C4-alkyl esters or mixtures
thereo~ may be used for the preparation o~ the polyesters.
The polycarboxylic acids may be aliphatic, cycloaliphatic,
aromatic and/or heterocyclic and may be substituted, e.g.
Le A_28 297 7
2 ~ 3
by halogen atoms, and/or unsaturated.
The following are examples of such polycarboxylic acids:
Succinic a~id, adipic acid, suberic acid, azelaic acid,
sebacic acid, phthalic acid, isophthalic acid, trimellitic
acid, phthalic acid anhydride, tetrahydrophthalic acid
anhydride, hexahydrophthalic acid anhydride, tetrachloro-
phthalic acid anhydride, endomethylene tetrahydrophthalic
acid anhydride, glutaric a~id anhydride, maleic acid,
maleic acid anhydride, fumaric acid, dimeric and trimeric
fatty acids such as oleic acid optionally mixed with
monomeric fatty acids, terephthalic acid dimethylester and
carbonic acid.
The following are examples of suitable polyhydric
alco~ 41s: Ethylene glycol, propylene glycol-(1,2) and
-~1,3), butylene glycol-(1,4) and -(2,3), hexanediol-
~1,6), octanediol-(1,8), neopentyl glycol, cyclohexane
dimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-
1,3-propanediol, glycerol, trimethylolpropane, hexane-
triol-(1,2,6), butanetriol-(1,2,4), trimethylolethane,
pentaerythritol, quinitol, mannitol and sorbitol, methyl
glycoside, diethylene glycol, triethylene glycol, tetra-
ethylene glycol, dipropylene glycol, dibutylene glycol and
polybutylene glycols.
Particularly preferred polyesters II contain residues of
polyethylene glycols (e.g. di-, tri- and/or tetraethylene
glycol) with molecular weights of from 106 to 200
incorporated in their structure. Such modified polyesters
are particularly advantageous when no polyethylene glycols
are used for the preparation of the oligourethanes used
according to the invention. The quantity of built-in
polyethylene glycol groups is preferably chosen so that
the ethoxy group content of the oligourethane to be used
Le A 28 297 8
2~ 3
according to the invention is from 5 to 50% by weight,
preferably from 20 to ~0% by weight.
The components incorporated for the introduction of ionic
groups into the oligourethanes may, quite generally
speaking, consist of cationic and anionic startiny
components of the type described for the preparation of
oligourethanes, such as, for example, dihydroxyl compounds
or diisocyanates containing ionic groups.
Preferred starting materials for the incorporation of
anisnic groups in the oligourethanes to be used according
to the invention include dihydroxycarboxylic and sulphonic
acids and their salts.
Preferred dihydroxycarboxylic acids have 4 to 12 carbon
atoms per molecule such as, for example, dihydroxymaleic
acid, dihydroxyfumaric acid, tartaric acid, 2,3-, 2,4-,
2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic acid, 4,6-
dihydroxyisophthalic acid, 2,8-dihydroxynaphthoic acid-(3)
and in particular compounds corresponding to the formula
R
I
HocH2-c-cH2oH
COOH
wherein R stands for Cl-C4-alkyl, in particular methyl
(dimethylolpropionic acid).
Preferred dihydroxysulphonic acids and their salts
correspond to the following formula
Le A 28 297 9
2 ~
H-(OCH-CH2)n~0-(A)o CH-(B)p-O-(CH2-CH-O)mH
R ~CH2~ R
S03e X~
wherein
A and B denote, independently of one another, divalent
aliphatic hydrocarbon groups having 1 to 6
carbon atoms,
10 R stands for hydrogen, an aliphatic hydrocarbon
group having 1 to 4 carbon atoms or a phenyl
group,
X~ stands for an alkali metal cation or an
optionally sub~tituted a~nonium group,
5 n and m denote, independently of one another, zero or
nu~nbers from 1 to 30,
o and p stand for zero or 1 and
stands for zero, 1 or 2.
Such diols are described, for example, in DE-OS
2 446 440.
The most preferred sulphonate diol is the product of
addition of sodium bisulphite to butene-2-diol-1,4.
The diisocyanates containing (potentially) ionic groups
include, for example, modified isocyanates as described in
DE-05 1 939 911, 2 227 111, 2 359 613 and 2 359 614; for
1~ 10
2 ~ 3 ~
example, aromatic diisocyanates containing free sulphonic
acid groups obtainable by the sulphonation of aromatic
diisocyanates, in particular 2,4-diisocyanatotoluene or
4,4'-diisocyanatodiphenylmethane. Diisocyanates which
react as quaternising agents with amines may also be used
as compounds containing (potentially) ionic groups, e.g.
chlorohexylisocyanate, m-chloromethylphenylisocyanate,
2,4-diisocyanatobenzyl chloride or isocyanates containing
alkyl sulphonic acid ester group~, e.g. 4-isocyanato-
benzene sulphonic acid methyl ester, since their reactionwith, for example, tertiary amines also introduces
cationic groups bound in homopolar form into the oligo-
urethane.
Amino alcohols III for the synthesis of the oligourethanes
to be used according to the invention include monohydric
alcohols but are preferably diol~ or triols, in particular
alkoxylated aliphatic, cycloaliphatic, aromatic and
heterocyclic amines, e.g. N,N-dimethylethanolamine,
N-methyldiethanolamine, N-butyldiethanolamine, N-oleyldi-
~0 ethanolamine, N-cyclohexyldiethanolamine, N-methyldiiso-
propanolamine, N-cyclohexyldiethanolamine, N-methyldiiso-
propanolamine, N-cyclohexyldiethanolamine, N~N-dioxy-
ethylaniline, N,N-dioxyethyl m-toluidine, N,N-dioxyethyl-
p-toluidine, N,N-dioxypropylnaphthylamine, dioxyethyl-
piperazine, polyethoxylated butyldiethanolamine, polyprop-
oxylated methyldiethanolamine (the average molecular
weight being preferably from 250 to 3000 in the case of
polyalkoxylated products). ~mino alcohols III having at
least one tertiary nitrogen atom and at least 2 hydroxyl
groups per molecule are particularly preferred. Among
these, aliphatic products are again preferred on account
of the high light fastness required.
Cationic groups within the meaning of the claims include
Le A 28 297 11
the groups incorporated in a homopolar form in the
oligourethane but not the ammonium groups attached in
heteropolar fQrm which may be produced from the neutralis-
ation of the potentially ionic groups.
One possible explanation of the effect according to the
invention, at least within the most preferred range,
namely when the starting products are used in such
arithmetically equivalent ratios that the number of
isocyanate groups corresponds exactly to the nu~ber of
isocyanate~reactive groups, is that isocyanate groups are
lost by side reactions so that a slight excess of
isocyanate-reactive groups results. If the compounds used
as binders for leather dressings or textile coating
compounds are capable of reacting wlth isocyanate-reactive
groups (e.g. polyisocyanates~, then the oligourethanes may
be chemically incorporated in the leather dressing or
textile coating layers by way of the excess isocyanate
reactive groups. If one assumes that from 0.1 to 0.4% of
the isocyanate groups are lost in the reaction of poly-
isocyanates, hydroxyl compounds and amino alcohols, onemay expect an excess of isocyanate reactive groups of
about 25 to 100 mmol per 1000 g of oligourethane to
result.
The oligourethanes to be u~ed according to the invention
may be prepared discontinuously or continuou~ly.
The equivalent ratio of i~ocyanate groups to isocyanate
reactive groups of all the starting components takinq part
in the synthesis of the polyaddition products according to
the invention is generally from 0.8:1 to 1.2:1, preferably
from 0.9:1 to 1:1.
The oligourethanes to be used according to the invention
Le A 28 297 12
2~i33~
are generally prepared without water and in the presence
or absence of organic solvents.
If an organic solvent i8 used, which may sometimes be
indicated for reasons of viscosity, it is best to use
solvents which are also suitable as dispersing agents for
the preparation of the aqueous dispersions. Organic
solvents of this type include water-miscible esters,
ketones, ethers, amides, etc., such as methoxypropylace-
tate, butanone-2, dioxane, dimethylformamide; dimethyl-
sulphoxide, etc..
The aqueous dispersions may be prepared either (i) by
mixing the oligourethane with water and adjusting the
aqueous dispersion to the desired pH or (ii) mixing the
solution of the oligourethane in the organic solvent with
water, adjusting to the required pH and if necessary
partly or completely evaporating o~f the organic solvent.
The aqueous dispersions consisting of oligourethane and
aqueous phase which may contain up to 30% by weight of
organic solvent (based on the sum of water and organic
solvent) generally contain oligourethane in quantities of
from 10 to 80% by weight, preferably from 20 to 40~ by
weight, based on the sum of oligourethane, aqueous phase
and organic solvent.
The aqueous pigment preparations are generally prepared
from
A. 1 to 80 parts by weight of pigment and
B. 99 to 20 parts by weight of aqueous oligourethane
dispersion (as described above).
With the aid of these oligourethane dispersions, the
Le A 28 297 13
2 0 ~ ~ 9 3 ~
pigments can be easily and quickly dispersed by grinding
the components, for example in a rstor-stator mill or a
paarl or ball mill. The particle size of the ground
pigments and the colour yield are excellent.
There is virtually no limitation to the choice of suitable
pigments for the aqueous pigment preparations: they may be
inorganic or organic. Suitable organic pigments include,
for example, those of the azo, anthraguinone, azoporphine,
thioindi~o, dioxazine, naphthalene tetracarboxylic acid
and perylene tetracarboxylic acid series as well as laked
dyes such as calcium, ma~nesium or aluminum lakes of dyes
containing sulphonic acid and/or carboxylic acid groups; a
large number of these is known, for example, from Colour-
Index, 2nd Edition. Examples of suitable inorganic
pigments (or matting agents) include zinc sulphides,
titanium dioxides, ultramarine, iron oxides, nickel and
chromium compounds, carbon blacks, silicon dioxides and
aluminium oxides.
The products may be added in known manner to the appro-
priate dressing preparations (e.g. based on aqueous
butadiene copolymer, polyacrylate and/or polyurethane
dispersions as described, for example, in Ullmanns
Encyklopadie der technischen Chemie, 4th Edition, Volume
16, Verlag Chemie, Weinheim/New York 1978, pages 159 et
seq and the literature cited there) and applied to the
leather by casting, spraying or printing. They may also be
used in the coating of textiles for colouring aqueous
acrylate and/or polyurethane dispersions, in which case
they are applied to a separating paper by spread coating
in known manner, usually in several layers, and then
transferred from the paper to the textile. If the
interlayers or the ttextile~ coatlngs are to
be subsequently cross-linked by means of polyisocyanates
Le A 28 297 14
2 ~ ~ 5 ~ c3 ~
in order to render them water resistant and incre~se their
resistance to solvent~, 1t i~ advi~able to adjust the pH
of the amphoteric ol igoureth~n~ with alkal ie;, tri-
alkylamine (e.g. trimethylamine or triethylamine), alkyl-
alkanolamine, etc.. pH-Value of ~rom 7 to 10, especi~lly
from 8 to 9, are particularly preferred. Textiles ~ay also
be directly coated by ~pread coating with polyurethanes
and/or polyacrylate di persions containing these pigment
preparations to colour them. Pigment printing pa~tes
conventionally used for textile printing and applied to
the textile by screen printing may also b~ coloured with
these pigment preparations.
The oligourethanes to be used according to the invention are ~ree of N-methylol
groups and groups produced by the reaction of such N-methy101 groups with reactive
groups. The pigment formulations prepared with the aid of the oligourethanes
employed according to the invention and the coatings produced with these pigmentforrnulations do not therefore exude any formaldehyde and are thus correspondingly
friendly to the environment.
In the following examples the percentages relating to quantities and concentrations
are in each case based on weight.
~8 297-Ausland 15
ExamDles
The percentages given in the following Examples are
percentages by weight and th~ parts are parts by weight
unle6s otherwise indicated.
The following auxiliary agents were used:
Aqueous ammonia: ~5%
(R)BAYDERM Fix CI: Isocyanate-based cross~linking agent
of Bayer AG
(R~BAYDERM Fix PCL: Carbodiimide-based cross-linking
agent of Bayer AG
(R~Elftex 415: Colour black of Cabot Company,
D-6450 Hanau
(R)Shell-Sol TD: Isoparaffin mixture (b.p. 172-194C)
of Shell, D-6236 Eschborn
5 (R)Eukanol-Paste M: an aqueous shellac/wax dispersion of
Bayer AG produced with acrylate
thickener
(R)Baysin Glanz K: aqueous preparatin of Bayer AG based
on decomposed casein
0 (R)Euderm dispersion 92 A: 35% aqueous dispersion of an
acrylate/acrylic acid copolym-
er, Shore A hardness 92,
product of Bayer AG
Le A 28 297 16
.
~ ~ ~S ~ ~, 3 ~
(R)Euderm wei~ CG: 65% aqueous dispersion of rutile
pigment in acrylate polymer, product
of Bayer AG
~R)BAYFERROX 105 M: Iron oxide red of Bayer AG
(R~BAYERTITAN RFDI: Titanium dioxide (rutile type) of
Bayer AG
(R)BAYDERM Soft V: Aqueous dressing agent based on wool
grease of Bayer AG
(R)BAYDERM Grund 10 UD: 30% aqueous dispersion of an
anionic aliphatic polyurethane,
Shore A hardness 10, product of
Bayer AG
(R)EUDERM Resin 40 B: 40% aqueous dispersion of a
butadiene copolymer, Shore A
hardness 40, product of Bayer AG
(R)EUD~RM Grund 25 A: 40% aqueous dispersion of an
acrylate copolymer, Shore A hardness
25, product of Bayer AG
(R)Nopco 8050: Defoamant of Munzing Company, D-7100
Heilbronn
(R)EMULGATOR WN: Emulsifier of Bayer AG based on an
alkoxylated aromatic compound
(R)ACRACONC B: Thicke~er of Bayer AG based on
polyacrylic acid
5 (R)IMPRANIL DLP Dispersion: 40% aqueous dispersion of an
aliphatic polyurethane, pxoduct of
Le A 28 297 17
2 ~ ~ 5 ~ 3 ~
Bayer AG
~R~ EMIJLGATOR VA: 50% aqueous oligourethane dispersion
of Bayer AG
(R~ACRAMIN BA: 35% aqueous dispersion of Bayer AG
S of a butadiene/acrylonitrile
copolymer
(R) ACRAMIN Wei~hmaçher ACN: Agueous dispersion of E~ayer
AG based on a praffin/silicone oil
mixtur2 .
10 Examples A to D relate to state of the art forming agents.
Example A describes the preparation of a polyether-
urethane containing carboxyl groups.
Example B describes an amphoteric polyester polyurethane
which is insui:`ficiently compatible with water.
15 Example C describes a highly hydrophilic forming agent
with which it is not possible to prepare water-resistant
coatings and clressings.
Example D describes a carboxyl group-containing polyest-
er~polyether polyurethane which is difficult to disperse.
20 Example E and the following are according to the inven-
tion .
Le A 28 297 18
1. PreDaration of the forn~in~ agent
E~asn~le A
1000 g of ~ polypropylene glycol ~'cher (OH number 56;
1000 mmol OH) were dehydrated with ~tirrir:g (45 min~,
100-C, 13 Torr) in a glas~ b~ak~r equipped with stirrer.
67 g (1000 mmol OH) of dimethylolpropionic acid were then
introduced and 333 g of i~ophorone dii~ocyanate (3000 mmol
NCO) were added wit~ stirrlng at 50 to 60-C. stirring was
continued for 4 hours at 80-C arld a sample was removed and
the isocyanate co~tent of the prepol~er obtained was
titrated. The isocyanate content ~f the thin liquid
obtain~d as product was 3.3% (theoretical 3.35%). 74 g of
n-b~tanol (1000 mmol OH) were then added as chain
terminator and the mixture was ~tirred for a ~urther 30
minutes at 90~C and again titrated: The pr~duct contained
no more titratable NCO. 1440 g of demineralised water
were added to this product with stirring, foll~wed by 25 g
of aqueous ammonia within 60 minutes. A polyurethane
dispersion having a solids content of 50% was obtained.
The dispersion had a pH of 7.2 and a viscosity of 200 rnPa.s at 23~C. When attempts
were made tO produce a film from the polyurethane dispersion by applying it to aseparating paper with a doctor knife and then drying, a sticlcy, smeary mass wasobtained which did not form a film. This polyurethane was unsuitable as pigment
forming agent because it did not sufficiently disperse.
~o Example B
770 g of a hexanediol/neopentyl glycolJpolyadipate with OH number 73 (1000 mmol
OH) were reacted with 67 g of dime~hylolpropionic acid (1000 mmol OH) and 333 g
of isophorone diisocyanate (3000 mmol NCO) by a method analogous to that of
Example A. 15 g of triethanolamine (300 mmol OH) and 55.5 g of isobutanol
(750 mmol OH) were introduced into the resulting highly viscous isocyanate
prepolymer (NCO content 3.52%) and ~he mixture was stirred for one
LeA28 297 -19 -
~ O ~ 5 ~ 3 3
hour at 95~C. 3600 g of water were then stirred into this
product at 90~C. The pH was adjusted to 9.4 with aqueous
ammonia. The milky cloudy dispersion had a viscosity of
1000 mPa.s at 23C. A film of this dispersion was dull,
sticky and not clear. The product was not suitable as
forming agent for pigments.
Example~ C
200 g of a polvester which was crystalline at room
temperature, obtained from 146 g (1 mol) of adipic acid,
498 g (3 mol~ of isophthalic acid and 566 g (4.8 mol) of
hexane-1,6-diol and having an OH number of 85 were rapidly
stirred together with 100 g of polyethylene glycol
(molecular weight 400), 25 g of dimethylolprnpionic acid
and 189.4 g of N-methylpyrrolidone. 152.4 g of isophorone
diisocyanate were then run in, the temperature was
maintained at 75C for 2 hours, and 23.6 g of triethyl-
amine were added. 700 g of demineralised water were addedto the resulting resin with vigorous stirring.
9.4 g of diethylenetriamine in 58 g of water were then
added and the mixture was stirred for one hour. A cloudy
35~ oligourethane dispersion having a viscosity of 280
mPa.s at 23C and a pH of 8.8 was obtained. (This disper-
sion corresponds to dispersion E of US Patent 4 812 492~.
A film produced from this dispersion was not smooth
because the polyurethane dried only with considerable
flow disturbances.
Wh~n this film was compared with a film according to
Example G, the following differences were found when the
films were placed in water:
The film from Example C dissolved completely after 5 hours
Le A 28 297 20
3 ~
in water while the film from Example G was only slightly
swelled. Cros~-linking of the oligourethanes with 5% of a
commercial isocyanate-based cross-linking agent
(BAYDERM(R) Fix CI) did not provide any improvement in the
wet fastness of the film of Example C. The good water
resistance of the film of Example E was further improved
by the addition of the cross-linking agent.
Oligourethane C was therefore unsuitable for water-
resistant coatings and prints and dressings.
Example D!
1380g (1800 mmol OH) of neopentyl glycol~hexanediol/poly-
adipate ~OH number 73) were dehydrated together with 222 g
(1200 mmol OH) of octaethylene glycol and to this were
added 200 g of dimethylolpropionic acid (3000 mmol OH~.
685 g (6150 mmol NCO) of isophorone diisocyanate were
added at 65C with stirring. The exothermic reaction which
set in heated the reaction mixture to 120C. The mass
became difficult to stir and highly viscous after 45
minutes.
5520 g of demineralized water and ~0 g of aqueous ammonia
were added. The mixture resulted in a dispersion (pH 10.2;
viscosity 200 mPa.s at 23C) within 2 hours at 80 to 90C.
A film of this product was clear and dry but it was not
very suitable as forming agent for pigments because the
colour intensity of the pigments triturated in this film
was only 34% of that of the Comparison sample (Example 1
of EP-A 0 086 354).
Example E
Example D was repeated with the following modifications:
Le A 28 297 21
2 ~
690 g (900 mmol OH) of neopentyl glycol/hexanediol
polyadipate,
111 g (~00 mmol OH) of octaethylene glycol,
105 g ~1500 mmol OH) of dimethylolpropioni~ acid and
500 g (~500 mmol NCO) of isophorone diisocyanate
were reacted at 100C to ~orm a prepolymer having an
isocyanate value of 3.81% ~theoretical 3.92%). To this
were added 37.5 g (750 mmol OH) of triethanolamine and
55.5 g of n-butanol (750 mmol OH). The reaction, which was
again exothermic, was left to continue for 30 minutes and
the reaction mixture was cooled to 110C. 3490 g of de-
mineralized water and 80 g of aqueous ammonia were poured
into this mass with vigsrous stirring. A 30% oligourethane
dispersion having a pH of 8.8 and a viscosity of 350 mPa.s
at 23C was obtained. A film cast from this clear
dispersion was clear, smooth and dry.
Films were produced from the dispersion and tested as such
and in the cross-linked state:
Le A 28 297 22
3 ~
_
~ ,~ I I
.' ~ ~ o o o o
~ ~ ..
' ~ ~ a~
~ ~ ~ ._
~6,~ ~
îs; K ~ K
. ._ . _ _ _
Le A 28 297 . - 23 -
3 ~
Example E-l
In one variation, n-butanol was replaced in the oligo-
urethane of Example E by the equimolar quantity of
i obutanol as chain terminator. A black pigment prepara-
tion prepared from this oligourethane dispersion wassliqhtly weaker in colour than that obtained when
n-butanol was used.
Example E-2
Example E was repeated with the only difference that the
polyol mixture was dissolved in 665 g of methoxypropyl
acetate before the isocyanate was added. The mixture was
stirred for 90 minute~ at 50-60C after the addition of
500 g of isophorone diisocyanate and the remainder of the
reactants was then added. The reaction mixture was finally
dispersed in a mixture of 85 g of aqueous ammonia and
2650 g of water. The pH of this dispersion was 7.7 and the
viscosity o~ the clear dispersion was 1,200 mPa.s at 23~C.
Example E-3
Example E was repeated except that the pH of the oligo-
urethane dispersion was adjusted with aqueous 25% sodium
hydroxide solution.
The following oligourethanes were prepared analogously to
Example E:
Le ~ 28 297 24
~ 0 ~
_ . ! _
--_ _ __ ..
~1, ..., ~' ~1,
~ C: ~ ~ o
.li -
~. o o ~ o
, . . ~ ,, U~
Le A 28 297 - 25 -
2 ~ t~ ~ ~
'~ ~ O O O O
~ _ _ _ _
_, ~ U~ _ r~
- _ _ _ __
3 - `J o~ o~ ~
..7 ~ _
_ ~ ~ A
r _ I _ .C
U C C ~ ~ ~ U
C Q~ C C~ ~ C1 C ~_.
E ~ E ~ E t., E E c
U C C _ _ _ ~ _
.c al o _~ ~ o ~ -o x o
:: _ _ C E ~: E
Le A 28 297 - 26 -
Examples of practical application:
Pigment preparat on
The colour intensity of the pigment waæ tested as follows:
150 Parts of Eukanol(R)-Paste M
100 parts of Baysin(R) Glanz K
300 parts of Euderm(R)-Dispersion 92A
were thoroughly mixed with
350 parts of water.
10 Parts of the pigment preparation were introduced into
90 parts of this mixture (in the case of ~lack pigments: 1
part of pigment preparation was stirred into 99 parts of
Mixture 1). This coloured mixture was applied to glossy
paper (or to paper with zebra stripes printed thereon if
the pigment preparation was to be tested for its covering
power) in a layer thickness of 100 ~m at the same time as
the comparison trituration, and the layer was then dried
at 80 D C. The covering power was determined by comparison.
To determine the colour intensity of the pigment, 10 parts
of Euderm(~) wei~ CG were stirred into gO parts of the
above mixture. 5 Parts of the pigment trituration were
stirred into 20 parts of this white mixture, applied by
coating knife to form a layer 150 ~m in thickness and
dried. The colour intensity of the pigment was determined
by the intensity with which it was capable of colouring
this white mixture.
Example Pl
300 Parts of a carbon black (Elftex(R) 415), 450 parts of
the polyetherurethane prepared according to Example A,
Le A 28 297 27
3 ~
158 parts of water, 390 parts of aminoethanol and 50 parts
of an aliphatic solvent (Shell-sol(R) TD~ added to prevent
foaming were mixed with vigorous stirring in a dissolver
and the mixture was stirred for 50 minutes. It was then
ground in a laboratory pearl mill (pearls 0.9 to 1.2 mm in
diameter). The resulting pig~ent was dull when spread
coated over a surface and about 20% weaker than a
comparable pigment according to Example 2 of DE OS
32 03 817.
Example P2
Example Pl was repeated with the polyester polyurethane of
Example B. The difficulty occurred in this case that the
~inder was only soluble in a strongly alkaline medium tpH
> 9.4). It was nevertheless used for forming in black
pigment (analogously to Example Pl). After it had been
applied by doctor knife from a standard mixture, the
pigment was dull, sticky and matt and therefore unsuit-
able.
Example P3
The binder of Example C was used analogously to Example
Pl:
450 g of oligourethane C (35% in water) were ground in a
dissolver for 40 minutes with 300 g of Elftex(R) 415,
145 g of water, 15 g of ethanolamine and 50 g of (R)Shell-
sol TD and then ground for 50 minutes in a pearl mill~
The viscosity of the pigment mixture which was at pH 10.4
was 500 mPa.s at 23C. The intensity of the colour was 15%
less than that of pigment preparation P6. Films prepared
from this dispersion were highly sensitive to water and
therefore unsuitable.
Le A 28 297 28
2 0 ~ ~ V ~ ~
Example P4
It was hardly ~ossible to prepare a pigment trituration
with the binder of Example D analogously to Example Pl;
the colour intensity was only 34% of that of the com-
parison according to Example 2 of DE~OS 3 203 817.
Example P5 (according to the invention)
The oligourethane of Example E was formulated with the
following pigments as shown in Table 3:
Le A 28 297 29
r~ ~
V ._
~ ~ U~ ~ 8 ~
.~ ~ ~
. ~ . - . .
;~}
I ~ _ __
3 ~ ooo~
o ~ ~ o ,,
.... _
.~ ~D l _I I N
~ O O O O O
. O O C~ g '-O
~_ ~1 ~ ~ U) ~
I ~ ~
~ . ~ Lr In In
1 ~3 ~_ P~ C4 P~
Le A 28297 - 30 -
2~ i3~j
Pigments formed with the oligourethanes to be used
according to the invention were distinctly superior in
intensity of colour, stability of the mixture in storage
and application properties to analogously formed pigments
in which acrylate polymers had been used as binder (EP-A 0
086 354).
The use of other oligourethanes is described in Table 4:
Le A 28 297 31
2 ~
c~
5 ~ 8~ 8 8 ~
,;~ ,, 5 5 5 u~
5 oo~
~ 'r 5 u~ ~
C ~ o o ~ o
~1 ~ ~ E5
Le A 28_97 - 32
Example~ of use
Example Vl: Pigmentation of an aqueous, unreaGtive binder
150 g of a pigment preparation P5 were stirred together
with 50 g of a softening antistick agent (BAYDERM(R)
Soft U) in 500 g of water. 100 Parts of a polyurethane
dispersion (BAYDERM(R) Grund 10 UD), 150 g of a butadiene
copolymer binder (EUDERM(R) Re6in 40 B) and 50 g of a soft
acrylate copolymer (EUDERM Grund(R) 25 A) were added
thereto. This primer mixture had excellent covering power
and gave rise to dressings with very good wet fastness
properties.
Example V2: Pigmentation of an aqueous dispersion of a
cross-linkable butadiene copolymer
A process for the dressing of leather in which NBR (buta-
diene/acrylonitrile/styrene/methacrylic acid copolymer)latices are cross-linked with the aid of divalent metal
hydroxides is described in DE-OS 2 946 435. 100 g of a
commercial pigment paste based on casein used in Example 1
of this Patent Specification were replaced hy 100 g of
paste P5. The leather obtained was more completely
covered, more elegant in appearance and less sticky than
that of Example 1 of DE-OS-2 946 435.
Example V3: Pigmentation of an aqueous dispersion of a
cross-linkable po]yurethane for a textile
coating
After the addition of 10 g of 10% acetic acid and 1 g of a
defoamant (Nopco(R) 8050) to 1000 g of a 40% aqueous
dispersion of an aliphatic, cross-linkable polyesterureth-
ane prepared according to DE-OS-2 814 173, Example 2,
Le A ?8 297 33
2 ~ 3 ~
100 g of the titanium dioxide pigment preparation P 5.5
followed by 20 g of a 5~% aqueous solution of a partially
etherified melamine-formaldehyde precondensate were added
with ~tirring, using a slow grid stirrer. 17 g of a
copolymer of vinyl pyrrolidine and vinyl acetate were then
added in an evacuation stirrer to adjust the viscosity for
spread coating. After 5 minutes' stirring, a finely
divided, stable pigment dispersion suitable for coating
textiles by the reversal proces~ or the direct process was
obtained. The paste was at pH 6 and had a viscosity of
4300 mPa.s at 23C. The polyurethane films prepared with
the pignlent dispersion by known processes were uniformly
coloured and free from patches. Cross linking was carried
out under heat treatment of the coated and dried goods for
90 seconds at 150C after application of the last coat.
Pigmentation of textile printinq pastes
Example V4
10 g of urea were dispersed in 760 g of water together
with 1.0 g of emulsifier ((R)EMULGATOR WN), ~0 g of
thickener ((R)ACRACONC B), 200 g of a 40% dispersion of
polyurethane :in water ((R)IMPRANIL DLP dispersion) and
80 g of the black pigment preparation P 5.3 to form a
paste. This paste was printed on a cotton fabric.
Example V4A
In a comparison experiment, the 80 g of pigment prepara-
tion P 5.3 in paste V4 were replaced by 80 g of a
commercial aqueous carbon black preparation containing a
dispersing agent based on an aryl polyalXylene ether (e.g.
ethylene oxide polyether started on nonyl phenol)O Both
the printing paste of Example V4 and that of Example V4A
Le A 28 297 34
r
could easily be removed from the sieve and the application
roller by means of water. Both printing pastes w4re fixed
by heating to 150'C (5 min).
The print produced with paste V4 showed distinctly less
damage after it had been washed and brushed with a nylon
brush than the print obtained with paste V4A~
Example V4
10 g of urea, 2 g of emulsifier ((R)EMULGATOR VA), 25 g of
thickener (~R)ACRACONC B), 200 g of a 35% aqueous
dispersion of an acrylonitrile/butadiene copolymer
(R)ACRAMIN BA) and lO g of plasticizer ((R)ACRAMIN Weich-
macher ACN) were mixed together in 753 g of water. 80 g of
the black pigment preparation P 5.3 were added to 920 g of
this printing paste which was then used for printing and
fixed for 5 minutes at 150C.
Example V5A
,~
g of commercial aqueous carbon black preparation
containing a dispersing agent based on an aryl polyalkyl-
ene ether were added to 920 g of the printing paste from
Example V5 and the paste was printed and fixed for 5
minutes at 150~C.
A comparison of the fastness properties of prints V5 and
V5A showed that the wet fastnesses (wet abrasion, washing
with brushing) of print V5 were ~ubstantially better than
those of print V5A.
Le A 28 297 35
2 ~ 3 .~3
E~ample V6
When Examples V4 and V5 were repeated with pigment
preparations P 5.1, P 5.2, P 5.4, P 5.5 and P 6, P 7 and
P 8, the wet fastness properties obtained were in all
S cases substantially superior to those obtained with
conventional pigment preparations.
Le A 28 29? 36
