Note: Descriptions are shown in the official language in which they were submitted.
Le A 32 400-Foreign CountriesWIM/by/W6/V 13.09.1999
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Biodegradable binders for dyein~
This invention relates to the use of biodegradable binders for dyeing, chiefly
the
dyeing of textiles and leather.
Completely biodegradable and compostable materials of construction will become
increasingly important in the future both economically and technically (T.
Jopski,
Kunststoffe 83 (1993), 10). The challenge is to produce plastics which have
the
necessary performance capability yet degrade under the stimulation of a
biologically
active environment. The initiating factor may be microbiological, enzymatic,
hydrolytic, photolytic or oxidative degradation at a specific site in the main
chain of
the polymer. All the degradation products have to be safe, nontoxic and
nonaccumulable in nature, i.e. undergo complete microbial degradation.
Heretofore
three general categories of completely biodegradable and compostable materials
of
construction have become known: polyesters; plastics based on natural
polymers; and
other degradable plastics, for example polyvinyl alcohol. Polyesters include
polylactic acid, polyhydroxybutyrate, polyhydroxyvalerate, polycaprolactone
and
high molecular weight aliphatic polyesters (EP-A 572 256). To obtain
sufficiently
high molecular weights, the polyesters mentioned in EP-A 572 256 are extended
with
organic diisocyanates to form the end product. The use of thermoplastic
polyester
urethanes as compostable plastics is described in EP-A 593 975.
Thermoplastically
processable and biodegradable polyesteramides form part of the subject-matter
of
EP-A 641 917.
Biodegradable thermoplastic polyurethane filaments are described in
DE-C 4 319 439. The thermoplastically processable polyurethanes are linear,
have
difunctional polyesterdiols and difunctional polyethylene glycols built into
the
polymer chain, and are constructed using hexamethylene diisocyanate and
butanediol
or hexanediol as chain extenders (Examples 1 to 3).
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DE-A 195 17 185 and 195 20 092 disclose biodegradable and compostable articles
based on hydrophilic polyurethanes, the term "polyurethanes" also encompassing
polyurethaneureas. The polyurethanes are reaction products of diisocyanates
and
diols, which to hydrophilicize the end product, also contain built-in radicals
of
diaminosulfonates and polyethers which optionally contain ethylene oxide
groups.
These hydrophilic polyurethanes are useful as coating material for the coating
of any
desired substrates, as adhesive and/or as binder for cellulose for producing
nonwovens from cotton and/or hemp or linen, as polymeric binder for wood,
sawdust
or wood chips, as films in composite materials for the production of
biodegradable
packaging, for producing hygiene articles such as, for example, babies'
diapers, as
seed dressings for immobilizing active substances in the form of slow-release
formulations, as binders for the production of plant pots, as coatings for
paper and for
the engine sizing of paper, for the production of sausage casings and for the
production of cosmetic compositions. Examples of products which can be
produced
therefrom include flat film, injection moldings such as flowerpots, drinking
vessels,
food Grays, thermoformed articles, blister packs, blown films or bottles.
Biodegradability is also becoming increasingly important in relation to
textiles, and
there are still large areas where it has not been achieved.
When dyeing and coating textiles with coating or textile print pastes by the
direct,
reverse, coating or printing process or with pigmented binders by the exhaust
process
it is common to use externally crosslinkable film-forming binders, for example
those
based on polyurethane, polyacrylate or butadiene/acrylonitrile copolymer. The
mixtures of binder and pigment customarily include reactive compounds which,
after
the printing step, crosslink the binder at elevated temperature and thereby
fix the
print or the dyeing. It is only this fixing which provides the desired
waterfastness,
which is important, for example, in relation to the laundering of the dyed or
printed
textiles.
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It has now been determined that the ingredients of post-dyeing liquors or of
wash
liquors of the printed textiles, i.e., the underlying binders and Theological
assistants in
particular, are refractory. Similarly, the assistants needed to finish the
pigments are
usually based on refractory emulsifiers and/or copolymers. But for
satisfactory
performance characteristics it is important that the wetfastnesses of the
materials be
good. Good wetfastnesses are generally obtained through crosslinking. On the
other
hand, it has been determined that crosslinking impairs the biodegradability of
the
articles. The crosslinkers used for the binders used in coating and textile
print pastes
are customarily melamine/formaldehyde condensation products which act above
about 120°C. According to W. Berlenbach in Ullmanns Encyklopadie der
tech-
nischen Chemie, 4th edition, volume 22, page 629, Verlag Chemie, Weinheim
1982,
the crosslinking via N-methylol groups of the binder is catalyzed by acid;
fixing is
preferably accomplished using dry hot air for, for example, S to 10 minutes at
140°C
or 30 to 60 seconds at 175°C.
Pigment dyeing with hydrophilic modified polyisocyanates is described for
example
in EP-B 571 867 and DE-A 4 415 449.
Generally, the coloring materials of the invention are also useful for coating
textiles
in the direct and reverse process, provided, as is known per se, only
biodegradable
components are used. Coating desiderata are high flexibility wet and dry and
also
high abrasion resistance and water and solvent resistance. The binders
therefore have
to be crosslinked. Surprisingly, the coated textiles and the residual liquors
retain their
biodegradability when - based on polymer - 15%, preferably 10%, particularly
preferably 7%, by weight of crosslinker (active material) on binder (as 40%
strength
by weight dispersion) is not exceeded.
It is accordingly an object of the present invention to overcome the
ecological
disadvantages of the prior art. More particularly, the residual and wash
liquors from
the coating and dyeing processes shall be dischargeable into a biological
treatment
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plant and the coated, dyed or printed articles shall be compostable, i.e.,
biodegradable
in a landfill.
This object is achieved according to the invention by using biodegradable
polyurethaneureas, polyesters or polyesteramides.
The invention accordingly provides biodegradable coating, dyeing and print
pastes
for textile substrates and nontextile cellulosic substrates, comprising
(i) biodegradable polyurethaneureas, polyesters or polyesteramides,
(ii) rheological assistants,
(iii) pigments or dyes which, if they have been finished, have been finished
with
finishing agents of natural origin, and optionally
(iv) natural-based plasticizers.
Preferred such pastes include per ~0 parts by weight of (i), based on dye
content of (i)
(ii) up to 10 parts by weight of a mineral and/or natural organic thickener,
(iii) up to 100 parts by weight of an optionally casein- and/or albumin-
finished
pigment or dye,
(iv) up to 30 parts by weight of a natural (vegetable or animal) oil or fat,
and also
(v) up to 25 parts by weight of an N-rnethylol-, aziridine-, epoxide- or
isocyanate-
based crosslinker.
The invention further provides for the use of
A) reaction products obtainable with an equivalents ratio of 1:1 to 2:1 for
isocyanate groups to isocyanate-reactive groups from
a) a diisocyanate component comprising
al) hexamethylene diisocyanate or
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a2) mixtures of hexamethylene diisocyanate with in total up to 60% by weight,
based on mixture a2), of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-
cyclohexane and/or 4,4'-diisocyanatodicyclohexylmethane and/or 1-methyl-
2,4(6)-diisocyanatocyclohexane with
b) a diol component comprising
b 1 ) at least one polyesterdiol having a number average molecular weight of
500 to
10,000 derived from (i) adipic acid and/or succinic acid and (ii) at least one
alkanediol having 2 to 6 carbon atoms or
b2) a mixture of such polyesterdiols with up to 32% by weight, based on the
total
weight of component b), of optionally ether group-containing alkanediols
having 2 to 6 carbon atoms,
i~
;..) a diamine component in an amount of from 2 to SO equivalents %, based on
the total amount of isocyanate-reactive groups present in the components b)
and c), comprising
cl) diaminosulfonates of the formula
H2N (-CH2)n-~ (-CH2)m-S03Me
or
c2) mixtures of diaminosulfonates cl) with up to 90% by weight, based on the
total weight of component c), of ethylenediamine, optionally
d) hydrophilic polyether alcohols of the formula
H-X-O-R
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in an amount of up to 10% by weight, based on the sum total of the
components b), c) and d), and also optionally
e) water, which does not enter into the calculation of the equivalents ratio
of
isocyanate groups to isocyanate-reactive groups,
where in the formulae mentioned
m and n are independently from 2 to 6,
Me is potassium or sodium,
R is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, and
X is a polyalkylene oxide chain of the number average molecular weight range
ti-om 88 to 4000 whose alkylene oxide units are ethylene oxide units to a.n
extent which is not less than 40 mol% and are propylene oxide units as far as
the rest is concerned, and
B. 0 to 30%, preferably 0.1 to 25°~0, by weight, based on A, of
crosslinker for A
as binders for dye andlor pigment preparations for dyeing or printing flexible
substrates, especially textiles and leather.
The diisocyanate component a) is preferably all hexamethylene diisocyanate.
The diol component b) is comprised either of b 1 ) at least one polyesterdiol
or b2) of a
mixture of at least one polyesterdiol b 1 ) with up to 32%, preferably up to
10%, by
weight of at least one optionally ether group-containing alkanediol having 2
to 6
carbon atoms.
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Suitable polyesterdiols bl) have a number average molecular weight (computable
from the hydroxyl group content) of S00 to 10,000, preferably 1000 to 2500,
and are
based on (i) adipic acid and/or succinic acid and (ii) optionally ether group-
containing alkanediols having 2 to 6 carbon atoms, for example ethylene
glycol,
diethylene glycol, 1,4-butanediol, neopentylglycol and/or 1,6-hexanediol.
Polyesterdiols prepared using exclusively ethylene glycol and/or 1,4-
butanediol as
diol are particularly preferred.
The optionally ether group-containing alkanediols of 2 to 6 carbon atoms to be
optionally included as hydroxyl-containing chain extenders are those of the
just
exemplified kind as mentioned for preparing polyesterdiols.
The diamine component c) is comprised either of cl) diaminosulfonates of the
abovementioned general formula or of c2) mixtures of such diaminosulfonates
with
1 ~ ethylenediamine which is employed, if at all, in amounts of up to 90,
preferably up to
i 0, equivalents%, based on the isocyanate-reactive amino groups of component
c).
Very particularly preferred diaminosulfonates are the potassium or sodium
salts of
N-('?-aminoethyl)-2-aminoethanesulfonic acid.
The diamine component c) is generally used in an amount of 1 to 10%,
preferably 2
to S%, by weight, based on the weight of component b).
The optional formative component d) comprises hydrophilic, monohydric
polyether
alcohols of the formula
H-X-O-R
where
R and X are each as defined above.
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Preference is given to those among such polyether alcohols for which
R is an aliphatic hydrocarbyl radical having 1 to 4 carbon atoms, and
S X is a polyalkylene oxide chain of the number average molecular weight range
from 500 to 4000 whose alkylene oxide units are ethylene oxide units to an
extent which is not less than 40 mol%, especially not less than 70 mol% and
particularly preferably l00 mol%, and are propylene oxide units as far as the
rest is concerned.
Monohydric polyether alcohols of this kind are prepared by conventional
alkoxylation of suitable starter molecules R-OH, for example methanol, n-
butanol,
n-hexanol or n-dodecanol, with the preferred use of ethylene oxide and
optionally
propylene oxide in the hereinabove disclosed quantitative ratios of the
alkylene
oxides. The alkylene oxides mentioned can here be used in the form of a
mixture
and/or in succession.
The monohydric polyether alcohols d) are used in the process of the invention,
if at
all, in amounts of up to 10%, preferably up to 3%, by weight, based on the sum
total
of components b), c) and d).
A further optional formative component for preparing the urea group-containing
polyurethanes is e) water, which should be considered for use as a reactant in
particular when, in the preparation of the polyurethanes, the chain extension
reaction
of previously prepared NCO prepolymers is effected in an aqueous medium,
especially when the diamines c) dissolved in the water are used in
subequivalent
amounts, based on the NCO groups of the NCO prepolymers.
As well as these formative components, other compounds suitable in principle
include trifunctional compounds in minor amounts, for example glycerol or
trimethylolpropane, which can either be incorporated into the polyesters bl)
in small
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amounts or be used in free form as part of component b2). The use of such
branching
molecules generally has to be compensated by means of monofunctional compounds
so that, purely arithmetically, linear polymers are again obtained.
The polyurethanes containing urea groups can be prepared from the exemplarily
mentioned formative components by any desired process. Preferably, however,
the
known prepolymer process is used, in such a way that the components b) and
optionally d) and also the diisocyanate component a) are reacted using an
NCO/OH
equivalents ratio of 1.5:1 to 4:1, preferably 1.8:1 to 2.5:1, to prepare an
NCO
prepolymer and this NCO prepolymer is subsequently reacted with the component
c)
to effect chain extension.
In general, the prepolymer is prepared at temperatures of 20 to 150°C
in the absence
of a solvent and is subsequently dissolved in a suitable solvent. It will be
appreciated
tha.,t the prepolymers can also be formed directly in a solvent. Suitable.
solvents
include in particular solvents which are inert toward isocyanate groups and
are
miscible with water in any proportion. The solvent used is preferably acetone.
The thusly prepared prepolymers are reacted, in the second reaction step, with
component c) to effect chain extension. In this step, the equivalents ratio of
isocyanate groups in the prepolymers on the one hand to isocyanate-reactive
amino
groups in component c) on the other is within the range from 1:1 to 20:1,
preferably
1.2:1 to 4:1. The chain extension reaction can be earned out in solution,
preferably in
a solution in acetone, or else in an aqueous medium, by combining the solution
of the
prepolymers in an organic solvent with a solution of component c) in water
with
thorough mixing. As already indicated, this may be accompanied by a chain
extension reaction involving the reaction of the NCO groups in the prepolymers
with
the water. In the abovementioned, preferred 2-step process of preparing the
urea
group-containing polyurethanes, the equivalents ratios between isocyanate
groups
and isocyanate-reactive groups in the two reaction steps are chosen within the
scope
of the disclosure in such a way that the overall ratio of isocyanate groups to
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isocyanate-reactive groups in components b) to d) conforms to the above-
indicated
ratio of 1:1 to 2:1. The water is absolutely excluded from the calculation of
the
equivalents ratios mentioned.
S The chain extension reaction generally takes place within the temperature
range from
20 to 50°C.
A possibility in principle, but in no way preferred, is the alternative of
carrying out
the chain extension reaction in the melt, i.e., in the absence of solvents and
water
(melt dispersion process).
To prepare the polyurethanes A, the abovementioned starting materials a), b),
c) and
optionally d) and/or optionally e) are used in the quantitative ratios
mentioned.
1 S The polyurethanes A are preferably used in the form of aqueous
dispersions. As used
herein, the term "aqueous disperison" shall also encompass aqueous solutions
which
can be present when the concentration of hydrophilic centers in the urea group-
containing polyurethanes is sufficient to ensure solubility in water.
Frequently, the
dispersions are aqueous systems comprising not only dispersed but also
dissolved
urea group-containing polyurethanes.
Aqueous dispersions of polyurethanes in a constitution similar or comparable
to the
polyurethane A are already known from DE-A 2 035 732, 2 651 506, 195 17 185
and
195 20 093.
To prepare the aqueous dispersions, the chain-extended polyurethanes or their
solutions in organic solvents if the chain extension reaction has been carried
out in
the absence of water are mixed with the dispersing water, followed if
appropriate by
the distillative removal of at least a portion of any cosolvent used. If the
chain
extension reaction took place in an aqueous medium, it is possible to add
further
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water if appropriate in order to prepare the aqueous dispersions. In this
case, too, it is
of course possible to distillatively remove the cosolvent used, if desired.
In general, the total amount of water used is such that dispersions from S to
60%
strength by weight (preferably 20 to 55% strength by weight) are present.
The polyurethane dispersion may include customary assistants. However,
particular
preference is given to such assistants as are likewise biodegradable. Such
assistants
are suitably in particular those of natural origin: gelatin, protein
hydrolyzates, guar,
tragacanth, flour, starch, sawdust, cellulose powder, etc.
The crosslinkers B comprise hydrophilic polyisocyanates, polyfunctional
epoxides
and carbodiimides as described for example in DE-A 42 17 716; the content of
DE-A 42 17 716 in this respect is hereby expressly incorporated herein by
reference.
In addition, crosslinkers B can be reactive compounds derived from
formaldehyde,
for example N-methylol group-containing phenol/formaldehyde and
melamine/formaldehyde condensates as described for example in "Methoden der
Organischen Chemie" (Houben-Weyl), volume 14/2, 4th edition, Georg Thieme
Verlag, Stuttgart 1963, page 319 ff. The crosslinking leads to better water
resistance
and higher abrasion resistance, etc.
The mixtures of A and B may have added to them up to 30% by weight, based on
A,
of dyes and/or pigments.
Preferred dyes are alkali-fixable reactive dyes. They may bear any color-
conferring
moiety, for example residues of a sulfo-containing organic dye of the mono- or
polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan,
azomethine,
dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone,
nitroaryl,
naphthoquinone, pyrenequinone or perylenetetracarbimide series.
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The alkali-fixable reactive dyes preferably possess at least one aromatic
heterocyclic
reactive radical and/or at least one reactive radical of the formula -S02M,
where
M = CH2-CH2-OH, CH=CH2 or CH2-CH2-V, wherein V = alkali-eliminable
radical, preferably OS03H, SS03H, OCOCH3, OP03H2, OS02CH3, SCN,
NHS02CH3, C1, Br, F, OCOC6H5, OS02-C6H5, N(CH3)3-anion (anion is
preferably Cl-), which under the dyeing conditions reacts with HO- or NH-
containing fibers to form covalent bonds. Preference is given to those which
contain at least one reactive substituent attached to a S- or 6-membered
aromatic heterocyclic ring, for example to a monoazine, diazine or triazine
ring, especially a pyridine, pyrimidine, pyr-idazine, pyrazine, thiazine,
oxazine
or symmetrical or asymmetrical triazine ring, or to such a rzng system which
has one or more aromatic carbocyclic rings fused on, for example a quinoline,
phthalazine, cinnoline, quinazoline, quinoxaline, acr-idine, phenazine or
phenanthridine ring system, or those which are substituted by additional
reactive groups of the vinyl sulfone type.
The reactive substituents on the heterocycle include for example halogen (C1,
Br or
F), ammonium including hydrazinium, pyridinium, picolinium, carboxypyridinium,
sulfonium, sulfonyl, azido(-N3), thiocyanato, thioether, oxyether, sulfinic
acid and
sulfonic acid.
Specific examples are the following fiber-reactive radicals:
2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl, monohalo-sym-triazinyl
radicals,
especially monochloro- and monofluorotriazinyl radicals, which are optionally
substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino,
arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy,
alkylthio, arylthio, where alkyl is preferably optionally substituted C1-C4-
alkyl,
aralkyl is preferably optionally substituted phenyl-C1-C4-alkyl and aryl is
preferably
optionally substituted phenyl or naphthyl and where preferred substituents for
alkyl
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are halogen, hydroxyl, cyano, dialkylamino, morpholino, C1-C4-alkoxy,
carboxyl,
sulfo or sulfato and preferred substituents for phenyl and naphthyl are sulfo,
C1-C4-alkyl, C1-C4-alkoxy, carboxyl, halogen, acylamino, hydroxyl and amino.
Also possible are 2-amino-4-fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-
6-yl,
2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluorotriazin-6-yl, 2-
dimethyl-
amino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-f3-methoxy-
ethylamino-4-fluorotriazin-6-yl, 2-13-hydroxyethylamino-4-fluorotriazin-6-yl,
2-di-(13-
hydroxyethylamino)-4-fluorotriazin-6-yl, 2-carboxymethylamino-4-fluorotriazin-
6-yl,
2-di-(carboxymethylamino)-4-fluorotriazin-6-yl, 2-sulfomethyl-methylamino-4-
fluorotriazin-6-yl, 2-13-cyanoethylamino-4-fluorotriazin-6-yl, 2-benzylamino-4-
fluorotriazin-6-yl, 2-13-phenylethylamino-4-fluorotriazin-6-yl, 2-benzyl-
methylamino-
4-fluorotriazin-6-yl, 2-(4'-sulfobenzyl)-amino-4-fluorotriazin-6-yl, 2-
cyclohexylamino-4-fluorotriazin-6-yl, 2-(0-, m-, p-methylphenyl)-amino-4-
fluorotriazin-6-yl, 2-(0-, m-, p-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-
(2',5'-disul-
1 ~ fophenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-chlorophenyl)-amino-4-
fluorotriazin-6-yl, 2-(0-, m-, p-methoxyphenyl)-amino-4-fluorotriazin-6-yl,
2-(2'-methyl-4'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-methyl-5'-
sulfophenyl)-
amino-4-fluorotriazin-6-yl, 2-(2'-chloro-4'-sulfophenyl)-amino-4-fluorotriazin-
6-yl,
2-(2'-chloro-S'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-methoxy-4'-
sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-carboxyphenyl)-amino-4-
fluorotriazin-6-yl, 2-(2',4'-disulfophenyl)-amino-4-fluorotriazin-6-yl, 2-
(3',S'-disulfo-
phenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-carboxy-4'-sulfophenyl)-amino-4-
fluorotriazin-6-yl, 2-(2'-carboxy-5'-sulfophenyl)-amino-4-fluorotriazin-6-yl,
2-(6'-sulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(4',8'-disulfonaphth-2'-
yl)-
amino-4-fluorotriazin-6-yl, 2-(6',8'-disulfonaphth-2'-yl)-amino-4-
fluorotriazin-6-yl,
2-(N-methyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-(N-ethyl-N-phenyl)-amino-4-
fluorotriazin-6-yl, 2-(N-f3-hydroxyethyl-N-phenyl)-amino-4-fluorotriazin-6-yl,
2-(N-iso-propyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-morpholino-4-
fluorotriazin-
6-yl, 2-piperidino-4-fluorotriazin-6-yl, 2-(4',6',8'-trisulfonaphth-2'-yl)-
amino-4-
fluorotriazin-6-yl, 2-(3',6',8'-trisulfonaphth-2'-yl)-amino-4-fluorotriazin-6-
yl, 2-(3',6'-
disulfonaphth-1'-yl)-amino-4-fluorotriazin-6-yl, N-methyl-N-(2,4-
dichlorotriazinyl-
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6)-carbamyl-, N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl-,
N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl-, N-methyl- or N-
ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl-, 2-methoxy-4-fluorotriazin-6-
yl, 2-
ethoxy-4-fluorotriazin-6-yl, 2-phenoxy-4-fluorotriazin-b-yl, 2-(0-, m- or p-
sulfo-
phenoxy)-4-fluorotriazin-6-yl, 2-(0-, m- or p-methyl- or -methoxy-phenoxy)-4-
fluorotriazin-6-yl, 2-13-hydroxyethylmercapto-4-fluorotriazin-6-yl, 2-
phenylmercapto-
4-fluorotriazin-6-yl, 2-(4'-methylphenyl)-mercapto-4-fluorotriazin-6-yl, 2-
(2',4'-di-
nitrophenyl)-mercapto-4-fluorotriazin-6-yl, 2-methyl-4-fluorotriazin-6-yl, 2-
phenyl-
4-fluorotriazin-6-yl and also the corresponding 4-chloro- or 4-bromo-triazinyl
radicals and the corresponding radicals obtained by halogen exchange with
tertiary
bases such as trimethylamine, triethylamine, dimethyl-13-hydroxyethylamine,
triethanolamine, N,N-dimethylhydrazine, pyridine, a-, 13- or y-picoline,
nicotinic
acid or isonicotinic acid, sulfinates, especially benzenesulfinic acid or
hydrogen
sulfite, and also di- or trihalopyrimidinyl radicals, such as 2,4-
dichloropyrimidin-6-
yl, 2,4,5-trichloro-pyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-
difluorop~~-imidin-
6-yl; 4,5-difluoro-pyrimidin-6-yl, 4-fluoro-5-chloropyrimidin-6-yl, 2.4-
difluo;-o-5-
chloropyrimidinyl and also 2,3-dichloroquinoxaline-5-carbonyl and 2,3-
dichloroquinoxaline-6-carbonyl.
Alkali-fixable reactive dyes are also to be understood as including mixtures
of
reactive dyes of the abovementioned kind.
The pigments can be organic or inorganic. Suitable organic pigments are those
of the
azo, anthraquinone, thioindigo series, as well as other polycyclic pigments,
for
example of the phthalocyanine, quinacridone, dioxazine,
naphthalenetetracarboxylic
acid, perylenetetracarboxylic acid or isoindoline series and also metal
complex
pigments or laked dyes such as Ca, Mg and Al lakes of sulfo- and/or carboxyl-
containing dyes, and also carbon black, of which a large number are known from
Color Index, 2°d edition, for example. Examples of suitable inorganic
dyes are zinc
sulfides, ultramarine, titanium oxides, mixed-phase pigments such as nickel or
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chromium antimony titanium dioxide, cobalt blue, chromium oxides and chromate
pigments; examples thereof are Pigment Yellow 53, Pigment Brown 24.
Particular preference is given to pigments which are free of lead, manganese,
cadmium, chromium, etc., i.e., free of heavy metals, which, if they are
present in
bioavailable form, inhibit the degradability.
Examples of particularly preferred pigments are phthalocyanine pigments, such
as
Pigment Blue I5, Pigment Green 7, arylamide pigments such as Pigment Yellow
83,
Pigment Yellow 17, monoazo pigments such as Pigment Red 48, lithole pigments,
disazo condensations pigments such as Pigment Red 166, and also carbon blacks,
zinc sulfides and ultramarines.
The dyes or pigments are customarily not added as such to the dye or print
paste, but
1 S they are generally used in the form of aqueous dispersions. To this end,
they have to
be mechanically converted in a suitable manner into the aqueous dispersion
with the
aid of f.nishing agents. The finishing agents substantially enrobe the dyes :
or
pigments and so prevent undesirable sedimentation in storage.
Suitable synthetic finishing agents are carbonyl- and hydroxy-bearing
oligourethanes
as described for example in DE-A 41 12 327. However, finishing agents of
natural
origin have the advantage of biodegradability. A particularly preferred
finishing agent
is casein.
The mixtures of A and B may have up to 500%, preferably 0.15 to 200%,
especially
5 to 150%, by weight of dye and/or pigments, based on the sum (A + B), added
to
them.
The mixtures of A and B may further have added to them up to 30% by weight,
based
on A, of rheological assistants, which can be of mineral, natural organic or
synthetic
organic origin. Examples of preferred rheological assistants are alginates,
carob bean
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flour, the organic, degradable cellulose derivatives, ete., and inorganic,
mineralizable
clays, sheet-silicates, etc.
The mixtures of A and B may also include up to 50% by weight, based on A, of
plasticizers. Preferably, only up to 30% of plasticizes is used. Plasticizers
of natural
origin are preferred, although up to 20% by weight, based on the plasticizers
mentioned, of synthetic organic plasticizes are tolerated. Examples of
preferred
plasticizers are the natural oils and fats of vegetable and animal origin such
as palm
oil dervatives, which are optionally hydrogenated, neatsfoot oil, optionally
sulfonated
or sulfatic castor oil, optionally esterified rapeseed oil, etc.
The components A and B can be dispersed in water in a conventional manner,
optionally through the use of organic solvents (thus, for example, by the
"benzine
emulsion process", whereby oil-in-water emulsions are formed). For reasons of
1S environmental compatibility, however, the use of benzine-free print pastes
is
preferred. The formulation is advantageously prepared without the use of
components
having reactive groups which might interfere with the reaction between binder
and
crosslinker.
The print, dyeing and coating pastes, it will be appreciated, may be prepared
using
further assistants, for example emulsifiers, thickeners, evaporation
inhibitors,
catalysts, hand improvers, antifoams. Preference is likewise given to the use
of
products which have such a structure that they are biodegradable.
The textile print pastes are suitably processed using the customary methods of
printing technology; cf. for example Ullmanns Encyklopadie der technischen
Chemie, 4'h edition, volume 22, page 565 ff. "Textildruck", Verlag Chemie,
Weinheim 1982, and also of coating technology, as are described, for example
in
Kunststoffhandbuch, volume 7, Polyurethane, Carl Hanser Verlag, Munich 1993.
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The applied prints and coatings can be crosslinked at elevated temperatures,
isocyanate crosslinkers permitting the use of relatively low temperatures (for
example room temperature to 100°C), but higher temperatures of up to
170°C are not
harmful either. However, curing conditions of 80 to 100°C (1 to 10
minutes) will
give excellent results in most cases. Similarly, drying at room temperature
for a
prolonged period (1-3 days) can be used to obtain a very good final strength.
Dyeings
can be carried out in known manner by the padding and exhaust process. A
particular
embodiment provides that the mixtures of A and B can be used together with
pigment for dyeing textiles and leather in an aqueous medium.
Percentages and parts in the examples hereinbelow are by weight.
The properties of the products tested in the examples hereinbelow were
appraised on
the following qualitative scale:
Appraisal Abbreviation
similar a
a little superiorw+
a little inferiorw-
somewhat superiore+
somewhat inferiore-
superior +
inferior -
distinctly superior d+
distinctly inferior d-
significantly superior b+
significantly inferior b-
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Examples
The following components were used:
~ACRACONZ BN 20% strength dispersion of the ammonium
salt of a lightly
crosslinked acrylic acidlacrylamide copolymer
in an
isoparaffinic hydrocarbon; Bayer AG
~ACRAFIx MF melamine/formaldehyde condensate, Bayer
AG
~ACRAFIX ML modified melamine resin
~ACRAMIN O/W emulsion of paraffin oils, esters and
Weichmacher ACN silicone oils
~ACRAMIN PUD Ol 40% strength aqueous polyurethane dispersion,
Bayer AG
~ACRAMIN aqueous pigment formulation based on Cu
Marine Blau FBC phthalocyanine
1 SO% and oxazine (P.V.23)/Dystar
~ACRAMIN ALV~I 40% strength aqueous dispersion of an
acrylonitrile/butyl acrylate/styrene/acrylic
acid emulsions
copolymer (83:8:4:3 parts); Bayer AG
~ACRAMIN Weich- aqueous microemulsion of a silicone oil
macher SID
~Bayderm FIX CIN modified aliphatic polyisocyanate, Bayer
AG
~Bentone EW sheet-silicate
~Dialgin HV sodium alginate (Diamalt)
~Emulgator L 42% strength aqueous emulsifier solution
(Bayer AG)
OEmulgator VA 46% strength aqueous emulsifier solution
(Bayer AG)
~Emulgator WN 90% strength aqueous solution of an ethylene
oxide
polyether started on a phenolic component
having an
average molecular weight of about 900 (Bayer
AG)
OO Natrosol MR hydroxyethylcellulose (Hercules Powder)
~RESPUMIT BA 2000 silicone-free, biodegradable nonionic foam
suppressant
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based on natural oil
~RESPUMIT SD silicone oil
~Solvesso 100 aromatic hydrocarbon mixture (bp. 163-181C)
from Esso
Chemie, Cologne
thickener solution 4% strength aqueous solution of a cellulose
derivative
(~Natrosol MR from Hercules Powder)
polyurethaneurea 40% strength aqueous dispersion obtainable
by the process
dispersion indicated hereinbelow
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Preparation of the polyurethaneurea dispersion:
170 g of a polyesterdiol of molecular weight 1700, formed from adipic acid and
a
mixture of 1,6-hexanediol and neopentylglycol in a weight ratio of 1.9:1, are
degassed under reduced pressure at 120°C for 60 minutes. Under
nitrogen, 0.2 ml of
benzoyl chloride and, in one go, 30.1 g of hexamethylene diisocyanate are
added to
the batch. After stirring at 120°C for 30 minutes, the NCO content is
3.2%. The
prepoly~rner is dissolved in 500 g of acetone at 50°C, the solution is
cooled to room
temperature, and is admixed with a mixture of 9.7 g of a 50°.'°
strength aqueous
solution of AAS salt, 1.51 g of ethylenediamine and 20 g of water by rapid
stirring.
After 15 minutes of stirnng, 300 g of water are added, and the acetone is
removed at
up to 60°C and 140 mbar. The distillation residue amounts to 505 g.
Dilution with
11 g of water provides a 40% strength thin white polyurethaneurea dispersion.
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Pigments EUKANOL colors'~>
~EUKANOL Orange contains Pigment Orange 34 & Pigment
Brown 24 and
also 15.6% of casein solution in water
~EUKANOL Schwarz contains Pigment Black 7 and also 15.6%
of casein
solution in water
OEUKANOL Blau N contains Pigment Blue 60 and also 12%
of casein
solution in water
~AC:12AMIN Orange azo pigment preparation based on Pigment
FG Orange 034
*) designations of pigment type from Colour Index.
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Examples 1-6
Batch: 1 2 3 4 5 6
Water 100 80 70 197 177 787
~ACRACONZ BN 20
~Emulgator WN 5 5 5 S S S
~Emulgator VA 3 3 3 3 3 3
~ACRAMIN PUD O1 150 1 SO 1 SO 150 150 150
~ACRAMIN-Marineblau 20
FBC 1 SO%
~EUKANOL Blau N 6.5%130 130 130 130 130
Pigm.
~Dialgin HV 4% 597 597 X97
~Bentone EW 3% 500 500
~ ~P.ESPLTMIT SD 5 5 5 5 5 S
~ACRAMIN- 20 20 20
Weichmacher ACN ~
~BAYDERM FIX CIN 10 10 20 10 10 10
Batch size: 1000 g
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Examples 7-10
Batch 7 8 9 10
Water 197 187 187 187
~Emulgator WN 5 S 5 5
~Emulgator VA 3 3 3 3
~ACRAM1N PUD O1 150 150 150 150
~EUKANOL Blau N 130 130 130 130
6.5% Pigm.
~Natrosol MR 4% 250 250 167 333
~Bentone EW 3% 250 250 333 167
~RESPLTMIT SD 5 5 5 5
~BAYDERM FIX C1N 10 . 20 20 20
Batch size: 1000
g
Appraisal relating to batch 7
Film properties Print dried
5 min
at 80C
Brush wash ( 100) + + +
Rubfastness wet ( 1 Ox) ~ e+ ~ e+ ~ +
Film properties Print
dried
and
fixed
5 min
at 150C
Brush wash ( 100 x) w+ w+ e+
Rubfastness wet (10 x) e+ ~ e+ ~ a
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Examples 11-17
Batch 11 12 13 14 15 16 17
Water 187 167 147 167 147 167 147
~Emulgator WN 5 5 5 5 S 5 5
~Emulgator VA 3 3 3 3 3 3 3
~ACRAMIN PUD O1 150 1 SO 1 150 150 150 150
SO
~EUKANOL Blau N 130 130 130 130 130 130 130
6.5% Pigm.
~Natrosol HR 4% 333 333 333 333 333 333 333
~Bentone EW 3% 167 167 167 167 167 167 167
'~RESPUMIT SD 5 5 5 5 5 5 5
Soybean oil 20 40
Sunflower oil 20 40
Castor oil 20 40
~BAYDERM FIX CIN 20 20 20 20 20 20 20
Batch size 1000
g
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Appraisal relating to batch 11
Film properties Print 5 min
dried at
80C
Rubfastness wet w- w+ w+ w+ w- e-
(10 x)
Color yield ~ ~ w+ w+ w+ e+ w+ w+
( ~ ~ ~ ~
Film properties Print
dried
and
fixed
5
min
at
150C
Rubfastness wet e+ a a w- a w-
(10x)
Hand a a a a a a
Hand after 1 x w+ w+ w+ w+ w+ w+
Household wash
60C
Hand after 3 x w+ e+ e+ + + +
Household wash
60C
Brush wash test
The washfastness of dyeings and prints can be tested using the brush wash
test. The
abrasion can serve as a measure of the degree of crosslinking of the binder.
A sample (ca. 10 x 20 cm) of the dyed and printed fabric is after fixing
placed into a
mixture of
2.5 g/1 of Castile soap ("green soap"),
2 g/1 of anhydrous sodium carbonate, and
2 g/1 of sequestrant (e.g., ~Trilon B)
at 80°C for about 10 minutes, then stretched and brushed with a hard
Perlon
handbrush using constant pressure ( 1 kg). Normally, 50 double strokes are
performed.
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Thereafter, the sample is rinsed and dried. The pigment abrasion of the
brushed
sample is compared with the unbrushed original sample. If no pigment abrasion
is
visible, the binder can be considered fully crosslinked.
Examples 18-21 of rotting tests
Batch 18 19 20 21
Water 105 115 85 804
- - _
~ACRACONZ BN 28
~Emulgator WN 5 5 5 3
~Emulgator VA 5 5 S 3
~ACRAMIN ALW 120
Polyurethaneurea dispersion200 200 200
~ACRAMIN-Marineblau 20
a FBC 1 ~0%
i
~EUKANOL Blau N 6.5% 130 130 130 '
I Pig.
~
~Natrosol MR 4% 1 SO 150 150
~Bentone EW 3% 350 350 350
~RESPLTMIT SD 5 5 5 2
~ACRAMIN 10
Weichmacher SID
Sunflower oil 50 20 50
~ACRAFIX ML 10
~BAYDERM FIX CIN 20 20
1000 g
Print on Zimmer sample table (round sleeve)
CO (Vlisco) R. 10/P.3/G. 40
CO knit R.16/P.5/G. 40
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Woven cotton (CO Vlisco)
Batch 18 19 20 21
Film properties Print
dried
and fixed
5 min
at
150C
Rubfastness dry (10 a w+ w+ comparison
x)
CO knit
S
Batch 18 19 20 21
Film properties Print
dried
and fixed
5 min
at
150C
Rubfastness dry (10x) e+ e+ e+ comparison
The print pastes were knife-coated onto release paper and films prepared
therefrom.
The films were subjected to the following composting test:
The films to be tested were first dried at 80°C to constant weight and
then clamped
into 6 x 6 cm slide frames. Compost from a composter was packed into plastic
bowls
2 cm deep and the films embedded therein. The filled boxes were each incubated
for
4 weeks at 60°C in an incubator. Water losses were determined via the
weight loss
and were made good. During incubation, the pH of the compost was measured once
a
week. After 4 weeks in each case, a batch was discontinued, and the films were
removed, cleaned, dried at 80°C to constant weight and photographed.
Directly after
drying, the weight loss of the films was determined by renewed weighing.
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In the poisoned control, the compost was dried at 105°C and the water
which had
evaporated was then replaced with a 1 % strength HgCl2 solution. Before being
introduced into the compost mixture, the films for the poisoned control were
placed
in the HgCl2 solution, dried and then introduced into the poisoned compost.
The
control batch was incubated in the same way as the other batches.
A film was classified as degradable when it completely vanished in the
microbially
active batches in the same way as a cellulose film used in a parallel test and
remained
intact in the poisoned control.
Result
a) Films
Examples
18-20 fully degraded
21 no degradation
Prints (test analogous to the film composting test)
b) CO Vlisco
Examples
18 fully degraded
19 fully degraded
20 somewhat degraded
21 no degradation
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c) CO knit
Examples
18 substantially degraded
19 slightly degraded
20 slightly degraded
21 no degradation
Beispiel 22 (textile coating)
A release paper is coated with about 80 g wet/m2 of a mixture of 1000 g of
polyurethaneurea dispersion, 100 g of ELTKANOL Schwarz and 6 g of Emulgator
VA. After passing through a drying tunnel at 80°-110°-
125°C the adhesive coating of
100 g of polyurethaneurea dispersion, 55 g of EUKANOL Schwarz and 12 g of
Emulgator VA is applied in a thickness of 150 g/m2 wet, and a cotton fabric is
laminated thereto. After drying at 135°C, the coated fabric was
removable nom the
release paper.
A cellulose fiber nonwoven bonded with polyurethaneurea dispersion in a
conventional manner was provided with a coating in a similar manner.
The coated products had the requisite fastnesses in terms of Flexometer and
adhesion; the products proved to be biodegradable.
Examples 23 and 24 concerning the biodegradation of print pastes
The print pastes 23 (prior art) and 24 (inventive) were subjected to the
biodegradability test for five days (BOD-S, method: LCK 55 Kuvette test from
Lange) four hours after being prepared.
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Print paste 24 exhibited the expected high degradability rate coupled with a
comparable application property profile.
Example 23 24
Water 816 175
~ACRACONZ BN 26
~Emulgator WN 3 5
~Emulgator VA 3 5
~ACRAMIN ALW 120
Polyurethaneurea dispersion 120
~ACRAMIN Orange FG 10
. ~EUKANOL Orange 130
~Natrosol MR 4% 150
~Bentone EW 3%
~RESPLTMIT SD 2
~ --
~RESPUMIT BA 2000 5
~ACRAMIN Weichmacher SID 10
Rapeseed oil 50
~ACRAFIX ML 10
~BAYDERMFIX CIN ( 10 '
Ash 1000C 0.0012/ 0.016/
0.0017 0.016
COD 179 427
BOD 7.62 240 '
BOD in % 4.3 56.7
Print on Zimmer sample table (rotary screen)
Print dried and fixed at 150°C for 5 min
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Batch: ~ 23 24
Fabric: Hilden cheesecloth
Film properties
Brush wash ( 100x) e-
Rubfastness dry ( w-
10x)
Rubfastness wet (10x) e-
Fabric: CO knit
Film properties
Brush wash (50x) e-
Rubfastness dry (lOx) e-
Rubfastness wet (lOx) e-
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