U.S. patent application number 11/578948 was filed with the patent office on 2008-01-31 for method for the treatment of flexible substrates.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Tibor Duris, Andreas Fechtenkotter, Holger Schopke, Dominik Winter.
Application Number | 20080022466 11/578948 |
Document ID | / |
Family ID | 34968550 |
Filed Date | 2008-01-31 |
United States Patent
Application |
20080022466 |
Kind Code |
A1 |
Winter; Dominik ; et
al. |
January 31, 2008 |
Method for the Treatment of Flexible Substrates
Abstract
A process for treating substrates comprises contacting (A) at
least one substrate selected from substrates composed of (A1)
polyacrylic, polyester, silicone, polyamide or (A2) one or more
polymers based on a monomer of the general formula I ##STR1## in
each of which R.sup.1 is selected from --Cl,
C.sub.1-C.sub.10-alkyl, --CH.dbd.CH.sub.2, --C(Cl).dbd.CH.sub.2,
--C(CH.sub.3).dbd.CH.sub.2 and --COOC.sub.1-C.sub.10-alkyl, with at
least one aqueous formulation comprising (B) at least one ethylene
copolymer wax comprising from 60% to 95% by weight of ethylene and
from 5% to 40% by weight of at least one ethylenically unsaturated
carboxylic acid in interpolymerized form, further at least one
colorant selected from (C) at least one pigment and (D) at least
one dye.
Inventors: |
Winter; Dominik;
(Ludwigshafen, DE) ; Duris; Tibor; (Ludwigshafen,
DE) ; Schopke; Holger; (Neckargemund, DE) ;
Fechtenkotter; Andreas; (Ludwigshafen, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
67056
|
Family ID: |
34968550 |
Appl. No.: |
11/578948 |
Filed: |
May 4, 2005 |
PCT Filed: |
May 4, 2005 |
PCT NO: |
PCT/EP05/04809 |
371 Date: |
October 19, 2006 |
Current U.S.
Class: |
8/501 ;
8/557 |
Current CPC
Class: |
D06P 1/5257 20130101;
D06P 1/5207 20130101; D06P 1/44 20130101; D06P 3/79 20130101; D06P
1/525 20130101 |
Class at
Publication: |
008/501 ;
008/557 |
International
Class: |
D06P 1/39 20060101
D06P001/39 |
Foreign Application Data
Date |
Code |
Application Number |
May 12, 2004 |
DE |
10 2004 023 894.4 |
Claims
1. A process for treating flexible substrates, which comprises
contacting (A) at least one flexible substrate selected from
substrates composed of (A1) polyacrylic, polyester, silicone,
polyamide or (A2) one or more polymers based on a monomer of the
general formula I ##STR11## in each of which R.sup.1 is selected
from --Cl, C.sub.1-C.sub.10-alkyl, --CH.dbd.CH.sub.2,
--C(Cl).dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 and
--COOC.sub.1-C.sub.10-alkyl, with at least one aqueous formulation
comprising (B) at least one ethylene copolymer wax comprising from
60% to 95% by weight of ethylene and from 5% to 40% by weight of at
least one ethylenically unsaturated carboxylic acid in
interpolymerized form, further at least one colorant selected from
(C) at least one pigment and (D) at least one dye.
2. The process according to claim 1 wherein at least one
ethylenically unsaturated carboxylic acid is a carboxylic acid of
the general formula II ##STR12## where R.sup.2 is selected from
hydrogen, branched or unbranched C.sub.1-C.sub.10-alkyl or COOH,
COOCH.sub.3, COOC.sub.2H.sub.5, R.sup.3 is selected from hydrogen,
branched or unbranched C.sub.1-C.sub.10-alkyl.
3. The process according to claim 1 wherein flexible substrates are
selected from foils and textile substrates.
4. The process according to claim 1 wherein flexible substrates are
selected from (A2) polypropylene.
5. The process according to claim 1 wherein flexible substrates are
selected from wovens, formed-loop knits and nonwovens.
6. The process according to claim 1 wherein at least one aqueous
formulation comprises (A) at least one further material selected
from thickeners, crosslinkers, film inhibitors, fastness improvers,
plasticizers, defoamers, wetting agents and leveling agents.
7. The process according to claim 1 wherein treated flexible
substrate is dried after said contacting.
8. Textile three-dimensional structures treated by a process
according to claim 1.
9. Print pastes comprising (B) at least one aqueous formulation
which comprises at least one ethylene copolymer wax comprising from
60 to 95% by weight of ethylene and from 5 to 40% by weight of at
least one ethylenically unsaturated carboxylic acid, in
interpolymerized form, and (C) at least one pigment.
10. Dyeing liquors comprising (B) at least one one aqueous
formulation which comprises at least one ethylene copolymer wax
comprising from 60 to 95% by weight of ethylene and from 5 to 40%
by weight of at least one ethylenically unsaturated carboxylic
acid, in interpolymerized form, and (C) at least one pigment or (D)
at least one dye.
Description
[0001] The present invention relates to a process for treating
flexible substrates, which comprises contacting [0002] (A) at least
one flexible substrate selected from substrates composed of [0003]
(A1) polyacrylic, polyester, silicone, polyamide or [0004] (A2) one
or more polymers based on a monomer of the general formula I
##STR2## [0005] in each of which R.sup.1 is selected from --Cl,
C.sub.1-C.sub.10-alkyl, --CH.dbd.CH.sub.2, --C(Cl).dbd.CH.sub.2,
--C(CH.sub.3).dbd.CH.sub.2 and --COOC.sub.1-C.sub.10-alkyl, [0006]
with at least one aqueous formulation comprising [0007] (B) at
least one ethylene copolymer wax comprising from 60% to 95% by
weight of ethylene and from 5% to 40% by weight of at least one
ethylenically unsaturated carboxylic acid in interpolymerized form,
further at least one colorant selected from [0008] (C) at least one
pigment and [0009] (D) at least one dye.
[0010] Processes for coating, dyeing and printing flexible
substrates such as for example foils or fibrous substrates such as
for example wovens, formed-loop knits or nonwovens have demanding
formulation requirements. One particular challenge relates to
formulations relating to the printing of polypropylene for example.
Polypropylene substrates printed with conventional formulations
often exhibit inadequate fastnesses, for example as far as wash
fastness and wet rub fastness are concerned. Similarly, other
flexible substrates, composed of polyvinyl chloride or silicone for
example, require treatment processes permitting for example
printing or dyeing with good fastnesses.
[0011] Furthermore, there are for example limits to the adhesive
bonding of polypropylene when temperatures above the melting or
softening point of polypropylene are to be avoided in forming the
adhesive bond. True, polypropylene can be modified by corona
treatment such that an adhesive will subsequently hold. However,
corona treatments are typically costly, usually not very efficient
and have but limited stability for the modification in storage.
[0012] The present invention therefore has for its object to
provide a process for treating flexible substrates without prior
art disadvantages. The present invention further has for its object
to provide treated flexible substrates. The present invention
further has for its object to provide print pastes and dyeing
liquors using which flexible substrates can be treated.
[0013] We have found that this object is achieved by the process
defined at the beginning.
[0014] The process of the present invention starts from at least
one substrate (A), substrates being preferably flexible substrates,
i.e., substrates which can be manually deformed nondestructively,
for example kinked, wound up, wound off, folded or bent, at room
temperature at least once. Preferred examples of flexible
substrates are textiles, hereinafter also referred to as textile
substrates, foils and manually deformable hollow structures such as
bottles for example.
[0015] Textiles or textile substrates for the purposes of the
present invention are textile fibers, textile intermediate and end
products and finished textile articles manufactured therefrom
which, as well as textiles for the apparel industry, also include
for example carpets and other home textiles and also textile
structures for industrial purposes such as for example awnings.
These also include unshaped structures such as for example staples,
linear structures such as twine, filaments, yarns, lines, strings,
cordage, threads and also three-dimensional structures such as for
example felts, wovens, formed-loop knits, nonwovens, fleecestuffs
and waddings.
[0016] Flexible substrates (A) are selected from substrates made
from [0017] (A1) polyacrylic, polyesters, silicones, polyamide, for
example polycondensates of .alpha.,.omega.-diamides with
.alpha.,.omega.-dicarboxylic acids or cyclic amides such as for
example .epsilon.-caprolactam, or preferably [0018] (A2) one or
more polymers based on a monomer of the general formula I ##STR3##
in each of which R.sup.1 is selected from [0019] chlorine, [0020]
C.sub.1-C.sub.10-alkyl, branched or unbranched, such as for example
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl and tert-butyl and most preferably
methyl, [0021] --CH.dbd.CH.sub.2, --C(Cl).dbd.CH.sub.2,
--C(CH.sub.3).dbd.CH.sub.2 [0022] and --COOC.sub.1-C.sub.10-alkyl,
wherein C.sub.1-C.sub.10-alkyl can be branched or unbranched and as
defined above.
[0023] Substrates composed of one of the foregoing polymers also
include substrates comprising a certain fraction, for example not
less than 30% by weight and preferably not less than 50% by weight,
of at least one of the aforementioned polymers. Illustrative
examples are blend fabrics composed of cotton-polyester or
cotton-polyamide.
[0024] Polymers based on at least one monomer of the general
formula I shall for the purposes of the present invention be taken
to include not just homopolymers but also copolymers which may
comprise a significant fraction, for example not less than 50 mol
%, of at least one monomer of the general formula I in
interpolymerized form. Useful copolymers also include for example
ethylene-propylene copolymers which may contain not less than 50
mol % of propylene in interpolymerized form.
[0025] Very particular preference is given to substrates composed
of polyvinyl chloride (PVC) and polypropylene (PP), which can each
have been produced by any desired processes. Polypropylene for
example can be produced by Ziegler-Natta catalysis or by
metallocene catalysis.
[0026] According to the invention, at least one flexible substrate
is contacted with at least one aqueous formulation comprising at
least one ethylene copolymer wax comprising from
[0027] 60% to 95% by weight and preferably from 65% to 85% by
weight of ethylene and from 5% to 40% by weight and preferably from
15% to 35% by weight of at least one ethylenically unsaturated
carboxylic acid in interpolymerized form, the weight %ages being
based on the entire ethylene copolymer wax.
[0028] Preferably, at least one ethylenically unsaturated
carboxylic acid is a carboxylic acid of the general formula II
##STR4## where [0029] R.sup.2 is selected from hydrogen, [0030]
C.sub.1-C.sub.10-alkyl, such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,
sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more
preferably C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; [0031]
COOH, COOCH.sub.3, COOC.sub.2H.sub.5. [0032] R.sup.3 is selected
from hydrogen, [0033] C.sub.1-C.sub.10-alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl and tert-butyl.
[0034] Most preferably, R.sup.2 is hydrogen and R.sup.3 is hydrogen
or methyl.
[0035] Ethylene copolymer waxes included in aqueous formulations
used according to the present invention may comprise up to 40% by
weight and preferably up to 35% by weight (each %age being based on
the sum total of ethylene and interpolymerized ethylenically
unsaturated carboxylic acid or acids) of one or more further
monomers in interpolymerized form, for example [0036] vinyl
acetate, [0037] one or more ethylenically unsaturated carboxylic
esters, preferably of the formula III ##STR5## [0038] R.sup.4 is
selected from hydrogen, [0039] C.sub.1-C.sub.10-alkyl, such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl and tert-butyl; [0040] R.sup.5 is
selected from hydrogen, [0041] C.sub.1-C.sub.10-alkyl, such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl,
1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl; more preferably
C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl and tert-butyl; [0042] COOH,
COOCH.sub.3, COOC.sub.2H.sub.5, [0043] R.sup.6 is selected from
C.sub.1-C.sub.10-alkyl, such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,
sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; more
preferably C.sub.1-C.sub.4-alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
[0044] Most preferably, R.sup.5 is hydrogen and R.sup.4 is hydrogen
or methyl.
[0045] Most preferably, R.sup.5 is hydrogen and R.sup.4 is hydrogen
or methyl and R.sup.6 is selected from methyl, ethyl, n-butyl and
2-ethylhexyl.
[0046] Foregoingly described ethylene copolymer waxes of ethylene
and ethylenically unsaturated carboxylic acids can be prepared with
advantage by free-radically initiated copolymerization under
high-pressure conditions, for example in stirred high-pressure
autoclaves or in high-pressure tubular reactors. The preparation in
stirred high-pressure autoclaves is preferred. Stirred
high-pressure autoclaves are known per se, a description is to be
found in Ullmann's Encyclopedia of Industrial Chemistry, 5th
edition, headwords: Waxes, Volume A 28, pages 146 et seq., Verlag
Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. Their
length/diameter ratio varies predominantly in intervals from 5:1 to
30:1 and preferably 10:1 to 20:1. High-pressure tubular reactors,
which can likewise be used, are likewise to be found in Ullmann's
Encyclopedia of Industrial Chemistry, 5th edition, headwords:
Waxes, Volume A 28, pages 146 et seq., Verlag Chemie Weinheim,
Basel, Cambridge, New York, Tokyo, 1996.
[0047] Suitable pressure conditions for the polymerization are 500
to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures
range from 170 to 300.degree. C. and preferably from 200 to
280.degree. C.
[0048] The polymerization can be carried out in the presence of a
regulator. Useful regulators include for example hydrogen or an
aliphatic aldehyde or an aliphatic ketone of the general formula IV
##STR6## or mixtures thereof.
[0049] In the formula, R.sup.7 and R.sup.8 are the same or
different and each selected from [0050] hydrogen; [0051]
C.sub.1-C.sub.6-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,
sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,
isohexyl, sec-hexyl, more preferably C.sub.1-C.sub.4-alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl
and tert-butyl; [0052] C.sub.3-C.sub.12-cycloalkyl such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl;
preference is given to cyclopentyl, cyclohexyl and cycloheptyl.
[0053] In one particular embodiment R.sup.7 and R.sup.8 are
covalently bonded together to form a 4- to 13-membered ring. For
example, R.sup.7 and R.sup.8 can conjointly be:
--(CH.sub.2).sub.4--, --(CH.sub.2).sub.5--, --(CH.sub.2).sub.6,
--(CH.sub.2).sub.7--,
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH(CH.sub.3)-- or
--CH(CH.sub.3)--CH.sub.2--CH.sub.2--CH.sub.2--CH(CH.sub.3)--.
[0054] Very useful regulators include alkylaromatic compounds, for
example toluene, ethylbenzene or one or more isomers of xylene. It
is preferable not to use aldehydes and ketones of the general
formula IV as regulator. It is particularly preferred not to add
any further regulators with the exception of so-called
phlegmatizers, which can be added to
[0055] organic peroxides to improve handling and can likewise have
the function of a molecular weight regulator.
[0056] Useful initiators for the free-radical polymerization
include the customary free-radical initiators such as for example
organic peroxides, oxygen or azo compounds. Mixtures of two or more
free-radical initiators are also suitable.
[0057] Suitable peroxides selected from the commercially available
substances are [0058] didecanoyl peroxide,
2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl
peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl
peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate,
tert-butyl peroxydiethylisobutyrate,
1,4-di(tert-butylperoxycarbonyl)cyclohexane in the form of a
mixture of isomers, tert-butyl perisononanoate,
1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
1,1-di(tert-butylperoxy)cyclohexane, methyl isobutyl ketone
peroxide, tert-butyl peroxyisopropyl carbonate,
2,2-di-tert-butylperoxybutane or tert-butyl peroxyacetate; [0059]
tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumyl peroxide,
the isomeric di(tert-butylperoxyisopropyl)benzenes,
2,5-dimethyl-2,5-di-tert-butylperoxy-hexane, tert-butyl cumyl
peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne,
di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide,
cumene hydroperoxide or tert-butyl hydroperoxide; or [0060] dimeric
or trimeric ketone peroxides of the general formula V a to V c.
##STR7##
[0061] In these formulae R.sup.9 to R.sup.14 are the same or
different and are each selected from [0062] C.sub.1-C.sub.8-alkyl
such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl,
n-heptyl, n-octyl; preferably linear C.sub.1-C.sub.6-alkyl such as
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, more
preferably linear C.sub.1-C.sub.4-alkyl such as methyl, ethyl,
n-propyl or n-butyl, very particular preference being given to
ethyl; [0063] C.sub.6-C.sub.14-aryl such as phenyl, 1-naphthyl,
2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl,
2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl,
preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably
phenyl.
[0064] Peroxides of the general formulae V a to V c and also
processes for preparing them are known from EP-A 0 813 550.
[0065] Particularly suitable peroxides are di-tert-butyl peroxide,
tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or
dibenzoyl peroxide or mixtures thereof. Illustrative of an azo
compound is azobisisobutyronitrile ("AIBN"). Free-radical
initiators are added in amounts customary for addition
polymerizations.
[0066] Numerous commercially available organic peroxides are
admixed with so-called phlegmatizers prior to sale in order to
improve their handling. Examples of suitable phlegmatizers include
white oil or hydrocarbons such as isododecane in particular. Under
the conditions of free-radical high-pressure addition
polymerization, such phlegmatizers can act to regulate molecular
weight. For the purposes of the present invention, any reference to
the use of molecular weight regulators should be taken to mean the
additional use of further molecular weight regulators above and
beyond the use of such phlegmatizers.
[0067] The ratio of the ethylene and ethylenically unsaturated
carboxylic acid or acids monomers in the feed does not normally
correspond exactly to the ratio of the units in the ethylene
copolymer waxes included in the formulations used according to the
present invention, since, generally speaking, ethylenically
unsaturated carboxylic acids are more readily incorporated into
ethylene copolymer waxes than is ethylene.
[0068] The monomers are typically metered together or
separately.
[0069] The monomers can be brought to the polymerization pressure
in a compressor. In another embodiment of the process according to
the present invention the monomers are first brought to an elevated
pressure of for example 150 to 400 bar, preferably 200 to 300 bar
and especially 250 bar by means of a pump and are then brought to
the actual polymerization pressure using a compressor.
[0070] The polymerization can be selectively carried out in the
absence and in the presence of solvents; in this context, for the
purposes of the present invention, mineral oils, white oil and
other solvents which are present in the reactor during the
polymerization and have been used to phlegmatize the free-radical
initiator or initiators are not considered to be solvents.
[0071] In one embodiment the polymerization is carried out in the
absence of solvents.
[0072] It is also possible, of course, to prepare ethylene
copolymer wax by first copolymerizing ethylene with at least one
ethylenically unsaturated carboxylic ester of the general formula
III and then to saponify the ester groups in a polymer-analogous
reaction, for example with aqueous potassium hydroxide solution or
aqueous sodium hydroxide solution.
[0073] Aqueous formulations used according to the present invention
preferably comprise from 0.05% to 40% by weight and preferably from
10% to 35% by weight of one or more ethylene copolymer waxes,
preferably in fully or partially neutralized form.
[0074] To effect partial or full neutralization, aqueous
formulations used according to the present invention typically
comprise one or more substances having a basic action, for example
hydroxides and/or carbonates and/or bicarbonates of alkali metals,
ammonia, organic amines such as for example triethylamine,
diethylamine, ethylamine, trimethylamine, dimethylamine,
methylamine, ethanolamine, diethanolamine, triethanolamine,
methyldiethanolamine, n-butyldiethanolamine,
N,N-dimethylethanolamine. Aqueous formulations used according to
the present invention preferably comprise a sufficient amount of
basic substance or substances that at least half and preferably at
least three quarters of the carboxyl groups of the ethylene
copolymer wax or waxes are neutralized. Basic substances can be
added to formulations used according to the present invention
during the dispersing of ethylene copolymer wax for example.
[0075] In one embodiment of the present invention aqueous
formulations used according to the present invention comprise a
sufficient amount of basic substance or substances that the
carboxyl groups of the ethylene copolymer wax or waxes are
quantitatively neutralized.
[0076] Aqueous formulations used according to the present invention
typically have a basic pH, preferably a pH in the range from 7.5 to
14, more preferably a pH of 8 or higher and most preferably a pH of
8.5 or higher.
[0077] Aqueous formulations used according to the present invention
preferably do not include protective colloids. Aqueous formulations
used according to the present invention are stable even without
such surface-active auxiliaries; i.e., when sheared at 100
cm.sup.-1 the light transmissivity of a dispersion having a solids
content of 0.1% will not change by more than 2%, measured against
pure water as reference.
[0078] Aqueous formulation used according to the present invention
as well as ethylene copolymer wax (B) comprises
at least one colorant selected from
[0079] (C) at least one pigment and [0080] (D) at least one
dye.
[0081] Pigments (C) for the purposes of the present invention are
virtually insoluble, finely dispersed, organic or inorganic
colorants as per the definition in German Standard Specification
DIN 55944. It is preferable to select at least organic pigment
and/or metal pigment.
[0082] Illustrative examples of organic pigments are TABLE-US-00001
monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13,
36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31,
48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1,
63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3,
73, 74, 65, 97, 151 and 183; disazo pigments: C.I. Pigment Orange
16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment
Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174,
176 and 188; anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat
Orange 3); anthraquinone pigments: C.I. Pigment Yellow 147 and 177;
C.I. Pigment Violet 31; anthraquinone pigments: C.I. Pigment Yellow
147 and 177; C.I. Pigment Violet 31; anthrapyrimidine pigments:
C.I. Pigment Yellow 108 (C.I. Vat Yellow 20); quinacridone
pigments: C.I. Pigment Red 122, 202 and 206; C.I. Pigment Violet
19; quinophthalone pigments: C.I. Pigment Yellow 138; dioxazine
pigments: C.I. Pigment Violet 23 and 37; flavanthrone pigments:
C.I. Pigment Yellow 24 (C.I. Vat Yellow 1); indanthrone pigments:
C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6);
isoindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260;
C.I. Pigment Yellow 139 and 185; isoindolinone pigments: C.I.
Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment
Yellow 109, 110, 173 and 185; isoviolanthrone pigments: C.I.
Pigment Violet 31 (C.I. Vat Violet 1); metal complex pigments: C.I.
Pigment Yellow 117, 150 and 153; C.I. Pigment Green 8; perinone
pigments: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment
Red 194 (C.I. Vat Red 15); perylene pigments: C.I. Pigment Black 31
and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190
(C.I. Vat Red 29) and 224; C.I. Pigment Violet 29; phthalocyanine
pigments: C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and
16; C.I. Pigment Green 7 and 36; pyranthrone pigments: C.I. Pigment
Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange 4); thioindigo
pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1); C.I.
Pigment Violet 38 (C.I. Vat Violet 3); triarylcarbonium pigments:
C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment
Red 81, 81:1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I.
Pigment Black 1 (aniline black); C.I. Pigment Yellow 101 (aldazine
yellow); C.I. Pigment Brown 22.
[0083] Examples of particularly preferred pigments (C) are: C.I.
Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19,
C.I. Pigment Blue 15:3 and 15:4, C.I. Pigment Black 7, C.I. Pigment
Orange 5, 38 and 43 and C.I. Pigment Green 7.
[0084] Further suitable pigments (C) are metallic pigments such as
for example gold bronze, silver bronze, Iriodin pigments, mica.
[0085] The median diameter of pigment (C) used in the process of
the present invention is typically in the range from 20 nm to 1.5
.mu.m and preferably in the range from 300 to 500 nm.
[0086] In one embodiment of the present invention pigment (C) used
in the process of the present invention is present in a spherical
or substantially spherical particulate form, i.e., the ratio of
longest diameter to smallest diameter is in the range from 1.0 to
2.0 and preferably up to 1.5.
[0087] In another embodiment of the present invention pigment (C)
used in the process of the present invention is present in the form
of needles or pins.
[0088] Suitable dyes (D) are all textile dyes, for example vat dyes
such as for example indigo and its derivatives, direct dyes,
disperse dyes, acid dyes, metallized dyes, naphthol dyes, sulfur
dyes, reactive dyes and pigment dyes.
[0089] Aqueous formulations used according to the present invention
may be produced for example as described hereinbelow. One option is
first to disperse one or more ethylene copolymer waxes in water.
One or more of the ethylene copolymer waxes described above can be
used for this. This is placed in a vessel, for example a flask, an
autoclave or a tank. In one version the ethylene copolymer wax or
waxes heats to above its melting point. It is advantageous to heat
to a temperature not less than 10.degree. C. and more
advantageously to a temperature not less than 30.degree. C. above
the melting point of the ethylene copolymer wax or waxes. When a
plurality of different ethylene copolymer waxes are used, they are
heated to a temperature above the melting point of the ethylene
copolymer wax melting at the highest temperature. In the case of a
plurality of different ethylene copolymer waxes being used, it is
advantageous to heat to a temperature not less than 10.degree. C.
above the melting point of the ethylene copolymer wax melting at
the highest temperature. In the case of a plurality of different
ethylene copolymer waxes being used, it is particularly
advantageous to heat to a temperature not less than 30.degree. C.
above the melting point of the ethylene copolymer wax melting at
the highest temperature.
[0090] Water and one or more basic substances and if appropriate
further constituents such as for example ethylene glycol are then
added in any order for the addition of water and the addition of
basic substance or substances and also of further constituents.
When the temperature is above 100.degree. C., it is advantageous to
operate under elevated pressure and to select the vessel
accordingly. The resulting emulsion is homogenized, for example by
mechanical or pneumatic stirring or by shaking. The aqueous
formulation thus produced can subsequently be cooled down.
[0091] Thereafter, at least one colorant selected from (C) at least
one pigment and (D) at least one dye can be added. Thereafter,
water, ethylene copolymer wax (B) and colorant are mixed.
[0092] To add at least one pigment (C) as colorant, it is
preferable to add pigment (C) in the form of a so-called pigment
preparation, i.e., a form dispersed with water and if appropriate
at least one surface-active material.
[0093] The present invention's process for treating flexible
substrates is carried out by contacting at least one flexible
substrate (A) with at least one aqueous formulation used according
to the present invention.
[0094] In one embodiment of the present invention (A) is contacted
with aqueous formulation at temperatures in the range from 20 to
100.degree. C. and preferably at room temperature.
[0095] In one embodiment of the present invention the contacting is
effected at pressures in the range from 0.5 bar to 10 bar and
especially at atmospheric pressure.
[0096] In one embodiment of the present invention (A) is contacted
with aqueous formulation at temperatures in the range from 70 to
180.degree. C. and preferably from 90.degree. C. to 120.degree. C.
and pressures above atmospheric pressure, for example up to 10 bar,
are employed for this.
[0097] Contacting according to the present invention can be done
for example for a period in the range from 0.1 second to 60 minutes
and preferably from 0.5 second to 30 minutes.
[0098] The contacting of substrate (A) with aqueous formulation
used according to the present invention can be done for example by
spraying on, padding, coating, impregnating and printing, for
example by the inkjet process.
[0099] Substrate (A) can be contacted one or more times in
succession with aqueous formulation used according to the present
invention.
[0100] The process of the present invention is preferably carried
out by flexible substrate being contacted with at least one aqueous
formulation used according to the present invention and
subsequently dried.
[0101] It is particularly preferable for the actual drying to be
preceded by predrying substrate treated according to the present
invention, for example to a residual moisture content in the range
from 0.5% to 2% by weight.
[0102] Predrying/drying can be carried out on commonly used
apparatuses. To treat textile substrates, for example,
predrying/drying can be carried out on all setting and drying
assemblies customary in the textile industry. Suitable drying or
predrying temperatures range for example from 50 to 300.degree. C.,
and preferably from 70 to 180.degree. C.
[0103] This may be followed by a thermal treatment at temperatures
in the range from 50 to 300.degree. C., preferably in the range
from 100 to 160.degree. C. and more preferably in the range from
110 to 130.degree. C. for a period ranging for example from 10
seconds to 60 minutes, preferably from 0.5 minute to 7 minutes.
Polyamide, polyester, polyvinyl chloride, modified polyesters,
polyester blend fabrics, polyamide blend fabrics,
polyacrylonitrile, polycarbonate are advantageously treated
thermally at temperatures in the range from 130 to 250.degree. C.
Polypropylene fabrics preferably between 80 and 130.degree. C. and
more preferably between 110 and 130.degree. C. Here temperature
generally refers to the temperature of the medium surrounding the
flexible substrate to be treated.
[0104] In one embodiment of the present invention aqueous
formulation used according to the present invention comprises at
least one further material (E) which can be selected from
thickeners, crosslinkers, fastness improvers, plasticizers,
defoamers, wetting agents and leveling agents.
[0105] Useful crosslinkers include for example urea-formaldehyde
and melamine-formaldehyde addition products, if appropriate in
combination with inorganic salts such as for example MgCl.sub.2.
6H.sub.2O or NH.sub.4Cl. Useful crosslinkers further include for
example free or blocked isocyanates or polyisocyanates such as for
example compounds of the general formula VI ##STR8## where [0106]
Y.sup.1 is selected from N--R.sup.15, oxygen and N--H, [0107]
Z.sup.1 is selected from hydrogen and CO--O--R.sup.15, [0108]
R.sup.15 is at each occurrence the same or different and selected
from C.sub.1-C.sub.10-alkyl, particular preference being given to
methyl and n-butyl.
[0109] Useful crosslinkers further include multiply functional
epoxides such as for example polyglycidyl ethers of polyols, for
example pentaerythritol polyglycidyl ether, and also multiply
functional aziridines such as for example trimethylolpropane
tris(beta-aziridinyl propionate).
[0110] Film inhibitors can be added for example to inhibit the
formation of films on rolls of for example pad-mangles during
contacting. Useful film inhibitors include for example mixtures of
multiply alkoxylated alcohols, especially mixtures of multiply
ethoxylated fatty alcohols.
[0111] As thickeners (thickening agent) there may be used natural
or synthetic thickeners. Examples of natural thickeners are
alginate, guar, starch, carob bean flour ether, cassia, tamarind
cellulose ether, dextrins such as for example natural gums,
galactomannan, xanthan, polysaccharide and mixtures thereof.
Preference is given to the use of synthetic thickeners, for example
to the use of room temperature liquid solutions of synthetic
(co)polymers in for example white oil or as aqueous solutions or as
water-in-oil emulsions, preferably comprising about 40% by weight
of (co)polymer.
[0112] Preferred examples of thickeners are copolymers comprising
from 85% to 95% by weight of acrylic acid, from 4% to 14% by weight
of acrylamide and about 0.01-1% by weight of the (meth)acrylamide
derivative of the formula VII ##STR9## and having molecular weights
M.sub.w in the range from 100,000 to 200,000 g/mol, in each of
which R.sup.16 is methyl or preferably hydrogen.
[0113] Formulations according to the present invention may comprise
from 30% to 70% by weight of white oil. Aqueous thickeners comprise
typically in total up to 25% by weight of (co)polymer and in some
cases up to 50% by weight (so-called thickener dispersions), based
on the entire thickener. When it is desired to use aqueous
formulations of a thickener, aqueous ammonia is generally added.
Even the use of granular, solid formulations of a thickener are
conceivable in order to be able to produce pigment prints
emissionlessly for example.
[0114] Useful fastness improvers include for example room
temperature liquid silicone oils and polysiloxanes. In a preferred
version of the present invention the use of fastness improvers can
be dispensed with.
[0115] Examples of suitable plasticizers are ester compounds
selected from the groups of the aliphatic or aromatic di- or
polycarboxylic acids fully esterified with alkanols and of at least
singly alkanol-esterified phosphoric acid.
[0116] In one embodiment of the present invention alkanols are
C.sub.1-C.sub.10-alkanols.
[0117] Preferred examples of fully alkanol-esterified aromatic di-
or polycarboxylic acids are fully alkanol-esterified phthalic acid,
isophthalic acid and mellitic acid; illustrative examples are:
di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate,
di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl
isophthalate.
[0118] Preferred examples of fully alkanol-esterified aliphatic di-
or polycarboxylic acids are for example dimethyl adipate, diethyl
adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl
glutarate, diethyl glutarate, di-n-butyl glutarate, diisobutyl
glutarate, dimethyl succinate, diethyl succinate, di-n-butyl
succinate, diisobutyl succinate and also mixtures thereof.
[0119] Preferred examples of at least singly alkanol-esterified
phosphoric acid are C.sub.1-C.sub.10-alkyl di-C.sub.6-C.sub.14-aryl
phosphates such as isodecyl diphenyl phosphate.
[0120] Further suitable examples of plasticizers are aliphatic or
aromatic di- or polyols at least singly esterified with
C.sub.1-C.sub.10-alkylcarboxylic acid at least singly.
[0121] 2,2,4-Trimethylpentane-1,3-diol monoisobutyrate is preferred
examples of aliphatic or aromatic di- or polyols esterified with
C.sub.1-C.sub.10-alkylcarboxylic acid at least singly.
[0122] Further suitable plasticizers are polyesters obtainable by
polycondensation of aliphatic dicarboxylic acid and aliphatic diol,
for example adipic acid or succinic acid and 1,2-propanediol,
preferably having an M.sub.w of 200 g/mol, and polypropylene glycol
alkylphenyl ether, preferably having an M.sub.w of 450 g/mol.
[0123] Further suitable plasticizers are polypropylene glycols
etherified with two different alcohols and having a molecular
weight M.sub.w in the range from 400 to 800 g/mol, wherein
preferably one of the alcohols may be an alkanol, especially a
C.sub.1-C.sub.10-alkanol, and the other alcohol may preferably be
an aromatic alcohol, for example o-cresol, m-cresol, p-cresol and
especially phenol.
[0124] Useful defoamers include for example silicone-containing
defoamers such as for example those of the formula
HO--(CH.sub.2).sub.3--Si[OSi(CH.sub.3).sub.3].sub.2. Silicone-free
defoamers are also suitable, such as for example multiply
alkoxylated alcohols, for example fatty alcohol alkoxylates,
preferably 2 to 50-tuply ethoxylated preferably unbranched
C.sub.10-C.sub.20-alkanols, unbranched C.sub.10-C.sub.20-alkanols
and 2-ethylhexan-1-ol.
[0125] Useful wetting agents include for example nonionic, anionic
or cationic surfactants, especially ethoxylation and/or
propoxylation products of fatty alcohols or propylene
oxide-ethylene oxide block copolymers, ethoxylated or propoxylated
fatty or oxo alcohols, also ethoxylates of oleic acid or
alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides,
alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates or
alkylphenyl phosphates.
[0126] Useful leveling agents include for example block copolymers
of ethylene oxide and propylene oxide having molecular weights
M.sub.n in the range from 500 to 5000 g/mol, and preferably in the
range from 800 to 2000 g/mol. Particular preference is given to
block copolymers of propylene oxide/ethylene oxide for example of
the formula EO.sub.8PO.sub.7EO.sub.8, where EO represents ethylene
oxide and PO represents propylene oxide.
[0127] The present invention further provides substrates treated by
the process of the present invention. Substrates according to the
present invention comprise at least one ethylene copolymer wax in
crosslinked or uncrosslinked form. Substrates according to the
present invention have good performance characteristics, for
example good fastnesses, especially wash fastnesses and rub
fastnesses such as for example dry and wet rub fastness.
[0128] A specific embodiment of the present invention is a process
for producing printed flexible substrates and especially printed
textile by the process of the present invention, hereinafter also
referred to as inventive textile printing process.
[0129] The inventive textile printing process can be carried out
for example by processing at least one inventive aqueous
formulation to form a print paste, hereinafter also referred to as
inventive print paste, and thereafter printing textile substrates
by methods known per se.
[0130] Inventive print pastes are advantageously produced by mixing
at least one aqueous formulation used according to the present
invention with common printing-process auxiliaries and at least one
pigment (C). The depth of shade is advantageously controlled by
adjusting the ratio of pigment (C) to aqueous formulation used
according to the present invention.
[0131] Pigment is preferably added to the inventive print paste in
the form of pigment preparations. Pigment preparations customarily
comprise from 20% to 60% by weight of pigment, water and one or
more surface-active compounds, for example one or more emulsifiers,
examples being multiply alkoxylated C.sub.10-C.sub.30-alkanols.
[0132] The ratio of pigment to aqueous formulation used according
to the present invention can be varied within wide limits. For
instance, pigment and aqueous formulation used according to the
present invention can be used in a weight ratio of 20:1 to 1:100.
In a preferred embodiment of the present invention the ratio of
pigment to aqueous formulation used according to the present
invention is adjusted such that the weight ratio of pigment to
solids fractions of aqueous formulation used according to the
present invention is in the range from 1:1 to 1:30.
[0133] It is also possible, of course, first to premix pigment and
aqueous formulation used according to the present invention in a
weight ratio in the range from 20:1 to 10:1 and to add further
aqueous formulation used according to the present invention or a
conventional acrylate binder only just before printing.
[0134] Further common auxiliaries for print pastes in textile
printing are known from Ullmann, Handbuch der technischen Chemie
und Verfahrenstechnik, compare for example Ullmann's Encyclopedia
of Industrial Chemistry, 5th edition, headword: Textile
Auxiliaries, Volume A26, pages 286 ff and 296 ff, Verlag Chemie,
Weinheim, Deerfield/Fla., Basel; 1996, and from
Textil-Hilfsmittel-Katalog, Konradin Verlag Robert Kohlhammer GmbH,
D-70771 Leinfelden-Echterdingen. As common auxiliaries there may be
mentioned by way of example thickeners, fixatives, hand improvers,
defoamers, rheology improvers, acid donors and emulsifiers.
[0135] In a further improved embodiment of the present invention
inventive print pastes further comprise hand improvers selected
from silicones, especially polydimethylsiloxanes, and fatty acid
C.sub.1-C.sub.10-alkyl esters. Examples of commercially available
hand improvers which can be added to the inventive print pastes are
Acramin.RTM. Weichmacher SI (Bayer AG), Luprimol SIG.RTM., Luprimol
TX 4732 and Luprimol CW.RTM. (BASF Aktiengesellschaft).
[0136] In a preferred embodiment of the present invention inventive
print pastes include as further ingredients one or more
emulsifiers, especially when the print pastes contain white
oil-containing thickeners and are obtained as an oil-in-water
emulsion. Examples of suitable emulsifiers are aryl- or
alkyl-substituted polyglycol ethers. Commercially available
examples of suitable emulsifiers are Emulgator W.RTM. (Bayer),
Luprintol PE New.RTM. und Luprintol MP.RTM. (BASF
Aktiengesellschaft).
[0137] Inventive print pastes can be produced for example by
admixing water if appropriate with a defoamer, for example a
silicone-based defoamer, and adding at least one aqueous
formulation used according to the present invention with mixing,
for example by stirring. Thereafter, one or more emulsifiers and
the pigment or pigments can be added.
[0138] Next it is possible to add one or more hand improvers, for
example one or more silicone emulsions.
[0139] Subsequently it is possible to add one or more thickeners
and to homogenize by further mixing, for example stirring.
[0140] A typical print paste according to the present invention
comprises (per kilogram of inventive print paste in each case)
[0141] 0.5 to 400 g and preferably 10 to 250 g of ethylene
copolymer wax (B),
[0142] 0 to 100 g and preferably 1 to 5 g of emulsifier,
[0143] 1 to 500 g and preferably 3 to 100 g of thickener,
[0144] 0 to 500 g, preferably 0.1 to 250 g and preferably 0.5 to
120 g of pigment (C),
[0145] if appropriate further auxiliaries;
[0146] the balance is preferably water.
[0147] In one embodiment of the present invention inventive print
pastes have a 20.degree. C. viscosity in the range from 0.3 to 4000
dPas, preferably in the range from 20 to 200 dPas and more
preferably in the range from 60 to 100 dPas. Viscosities can be
determined by common methods, especially for example with a rotary
viscometer, for example the VT02 or VT24 Viscotester from Haake
Mess-Technik GmbH u. Co., Karlsruhe.
[0148] Pigment printing using at least one inventive print paste
can be carried out according to various processes known per se. It
is customary to use a screen through which the inventive print
paste is forced with a squeegee. This process belongs to the screen
printing processes. Inventive pigment printing processes using at
least one inventive print paste provide printed substrates
combining particularly high brilliance and depth of shade for the
prints with excellent hand for the printed substrates. The present
invention accordingly provides flexible substrates printed by the
inventive printing process using the inventive print pastes.
[0149] Another embodiment of the present invention is a pigment
dyeing process utilizing at least one inventive formulation,
hereinafter also referred to as inventive pigment dyeing process.
The inventive dyeing process is preferably carried out by treating
at least one flexible substrate, preferably a textile substrate,
with at least one dyeing liquor which comprises at least one
inventive formulation. Dyeing liquors comprising at least one
inventive formulation are hereinafter also referred to as inventive
dyeing liquors.
[0150] Inventive dyeing liquors may further comprise wetting agent
additives, preferably wetting agents which are considered to be
low-sudsing wetting agents, since sudsing due to the high
turbulence in the dyeing operation causes the quality of the dye to
be impaired from formation of unlevelnesses.
[0151] Dry textile wovens, formed-loop knits or fleece of the kind
used in continuous pigment dyeing contain a large amount of air.
The inventive pigment dyeing process is therefore advantageously
practised using deaerators. These are based for example on
polyethersiloxane copolymers. They can be included in the inventive
dyeing liquors in amounts from 0.01 to 2 g/l.
[0152] Inventive dyeing liquors may further comprise antimigration
agents. Useful antimigration agents include for example block
copolymers of ethylene oxide and propylene oxide having molecular
weights M.sub.n in the range from 500 to 5000 g/mol and preferably
in the range from 800 to 2000 g/mol.
[0153] The inventive dyeing liquors may further include an addition
of one or more hand improvers. Hand improvers are generally
polysiloxanes or waxes. Polysiloxanes have the advantage in this
context of being permanent, whereas waxes are gradually washed off
in use.
[0154] The viscosities of the inventive dyeing liquors are
preferably in the range below 100 mPas. The surface tensions of the
inventive dyeing liquors are to be adjusted such that wetting of
the material is possible. Surface tensions of less than 50 mN/m are
commercially utilized.
[0155] In one embodiment of the present invention a typical
inventive dyeing liquor will comprise per liter
[0156] 0.5 to 400 g and preferably 20 to 300 g of ethylene
copolymer wax (B),
[0157] 0 to 100 g and preferably 0.1 to 10 g of wetting agent,
[0158] 0 to 100 g and preferably 0.1 to 10 g of defoamer,
[0159] 0 to 300 g and preferably 1 to 20 g of antifilm agent,
[0160] 0 to 100 g and preferably 1 to 50 g of antimigration
agent,
[0161] 0 to 100 g and preferably 1 to 50 g of leveling agent,
[0162] 0.5 to 25 g and preferably 1 to 12 g of pigment (C).
[0163] A further aspect of the present invention is a process for
producing inventive dyeing liquors. The process of the present
invention comprises mixing colorant, for example pigment (C),
preferably in the form of pigment preparations which comprise one
or more surface-active compounds as well as pigment and water with
above-recited additives such as further solvents, defoamers, hand
improvers, emulsifiers and/or biocides and making up with water. To
practise the process for producing inventive dyeing liquors, it is
customary to stir the components of the inventive dyeing liquors in
a mixing vessel, the size and shape of which are not critical.
Stirring is preferably followed by a clarifying filtration.
[0164] A further aspect of the present invention is a process for
dyeing flexible substrates using the above-described inventive
dyeing liquors, hereinafter also referred to as inventive dyeing
process, especially as inventive pigment dyeing process. The
inventive dyeing process can be carried out in commonly employed
dyeing machines. Preference is given to pad-mangles where the
essential element is two squeeze rollers through which flexible
substrate and especially textile is led. Inventive dyeing liquor is
introduced above the rollers and wets flexible substrate or the
textile. The pressure of the rollers causes the flexible substrate
or the textile to be squeezed off and ensures a constant add-on
level.
[0165] The actual dyeing is customarily followed by a thermal
drying step and optionally a setting step. Drying is preferably
done at temperatures in the range from 25 to 300.degree. C. for a
period of time in the range from 10 seconds to 60 minutes and
preferably in the range from 30 seconds to 10 minutes. Setting, if
setting is desired, is done at temperatures in the range from
150.degree. C. to 190.degree. C. for a period of time in the range
from 30 seconds to 5 minutes.
[0166] Preference is given to a process for pigment dyeing by
padding.
[0167] Substrates printed and dyed according to the present
invention are notable for brilliance of color coupled with good
hand for the respectively printed and dyed substrates. A further
aspect of the present invention is therefore substrates dyed by the
above-described process by using the inventive dyeing liquors.
[0168] The present invention further provides dyed flexible
substrates obtainable by the inventive pigment dyeing process.
Inventive dyed flexible substrates are notable for example for good
wash fastnesses, good dry and wet rub fastnesses and also for good
fastnesses, especially due to minimal reductions in depth of shade
which are incurred in the course of the boil brush wash.
[0169] In another embodiment of the present invention flexible
substrates (A) and especially foils or textile composed of
polypropylene are contacted with pigment-free aqueous formulation
and subsequently dried. Uncrosslinked ethylene copolymer wax
uniformly distributed on flexible substrate acts as a primer and
makes adhesive bonding to any other materials possible.
[0170] In another embodiment of the present invention the present
invention's process for printing flexible substrates can be carried
out as a transfer printing process. To this end, a paper coated
with wax, for example with silicone wax, is printed with at least
one inventive print paste and thereafter the printed paper is dried
at from room temperature to 300.degree. C. and preferably at from
room temperature to 180.degree. C. The dried and printed paper is
treated with the textile material on a hot press or on a hot
calender at 70 to 300.degree. C., preferably for 10 to 100 s at 100
to 120.degree. C. During this operation, the print paste
softens/melts and transfers and fixes from paper onto the two- or
three-dimensional flexible substrate, for example textile substrate
or foil, to be printed.
[0171] Working examples illustrate the invention.
WORKING EXAMPLES
[0172] 1. Preparation of Ethylene Copolymer Wax
[0173] In a high-pressure autoclave as described in the literature
(M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), ethylene and
acrylic acid or methacrylic acid as per Table 1 were copolymerized.
Ethylene was fed into the autoclave under the reaction pressure of
1700 bar at a rate of 12.0 kg/h. Separately, the Table 1 amount of
acrylic acid or methacrylic acid was initially compressed to an
intermediate pressure of 260 bar and subsequently fed into the
autoclave under the reaction pressure of 1700 bar. Separately,
initiator solution consisting of tert-butyl peroxypivalate in
isododecane (amount and concentration see Table 1) was fed into the
autoclave under the reaction pressure of 1700 bar. Separately, the
Table 1 amount of regulator consisting of propionaldehyde in
isododecane, concentration see Table 1, was initially compressed to
an intermediate pressure of 260 bar and subsequently fed with the
aid of a further compressor into the high-pressure autoclave. The
reaction temperature was 220.degree. C. Ethylene copolymer waxes
were obtained as per Table 1 which had the analytical data evident
from Table 2.
[0174] The level of ethylene and acrylic acid or methacrylic acid
in the ethylene copolymer wax was determined by NMR spectroscopy
and by titration (acid number) respectively. The acid number of the
ethylene copolymer wax was determined titrimetrically according to
German standard specification DIN 53402. The KOH consumption
corresponds to the acrylic acid or methacrylic acid level in the
ethylene copolymer wax. MFI was determined according to German
standard specification DIN 53735 at 160.degree. C. under a load of
325 g. TABLE-US-00002 TABLE 1 Preparation of ethylene copolymer
waxes PO PA in in ECW T.sub.reactor Ethylene AS AS MAS MAS ID ID
Conversion product No. [.degree. C.] [kg/h] [l/h] [kg/h] [l/h]
[kg/h] [ml/h] c(PA) [l/h] c(PO) [wt %] [kg/h] 1.1 220 12 0.79 0.80
-- -- 650 25 1.95 0.07 23 3.0 1.2 220 12 -- -- 1.01 1.03 600 25
2.10 0.07 25 3.2 T.sub.reactor refers to the maximum internal
temperature of the high-pressure autoclave.
[0175] TABLE-US-00003 TABLE 2 Analytical data of ethylene copolymer
waxes Ethylene Acid number level AS level MAS level [mg KOH/g MFI
.rho. No. [wt %] [wt %] [wt %] ECW] [g/min] T.sub.melt [.degree.
C.] [g/cm.sup.3] 1.1 79.0 21.0 -- 165 10 78-88 0.96 1.2 73.4 --
26.6 173 10 65-80 n.d. "Level" refers to the fraction of
interpolymerized ethylene or acrylic acid or methacrylic acid in
the respective ethylene copolymer wax. Abbreviations: AS: acrylic
acid, MAS: methacrylic acid, PA: propionaldehyde, ID: isodothecane,
PO: t-butyl hydroperoxide, ECW: ethylene copolymer wax.
[0176] 2. Production of Aqueous Dispersions of Ethylene Copolymer
Waxes
[0177] A 2-liter autoclave equipped with anchor stirrer was charged
with the Table 3 amount of ethylene copolymer wax according to
Example 1. The Table 3 amounts of deionized water and also ammonia
were added and the temperature was raised to 120.degree. C. with
stirring. After 30 minutes at 120.degree. the temperature was
lowered to room temperature in the course of 15 minutes to obtain
dispersions 2.1 and 2.2. TABLE-US-00004 TABLE 3 Production of
aqueous dispersions of ethylene copolymer wax ECW NH.sub.3 Water
ECW amount amount amount Solids Viscosity No. No. [g] [g] [g]
content [%] [s] pH 2.1 1.1 25.0 3.4 71.6 25 85 9.0 2.2 1.2 25.0 3.4
71.6 25 40 8.8 The viscosity was determined using a 5-mm cup at
23.degree. C. to ISO 2431 "NH.sub.3 amount" refers to the amount of
25% by weight aqueous ammonia solution.
[0178] 3. Production of Inventive Print Pastes
[0179] 3.1 Production of a Blue Pigment Preparation
[0180] The following were ground together in a Drais DCP SF 12
Superflow stirred ball mill: [0181] 2640 g of Pigment Blue 15:3
[0182] 460 g of n-C.sub.18H.sub.37O(CH.sub.2CH.sub.2O).sub.25H
[0183] 600 g of glycerol [0184] 2300 g of distilled water
[0185] Grinding was continued until the pigment particle had a
median diameter of 100 nm.
[0186] 3.2. Production of Stock Pastes
[0187] The ingredients as per Table 4 were stirred together in a
stirred vessel and the stock pastes 3.1 to 3.4 were obtained by the
ingredients being combined with each other, and stirred together,
in the order recited in Table 4. This was followed by 15 minutes of
stirring with a high-speed stirrer of the Ultra-Turrax type at
about 6000 revolutions/min before the pH was tested. When the pH
was below 8, a pH of 8.5 was set by adding concentrated aqueous
ammonia. TABLE-US-00005 TABLE 4 Production of stock pastes 3.1 to
3.4 Stock paste Ingredient [g] 3.1 3.2 3.3 3.4 Distilled water --
380 -- 380 2.1 980 600 -- -- 2.2 -- -- 980 600 Thickener 20 20 20
20 Sum total 1000 1000 1000 1000
[0188] 2.1 and 2.2 refer to the respective aqueous dispersion 2.1
or 2.2 from Example 2.
[0189] The thickener used in each case was:
[0190] dispersion of
[0191] copolymer of acrylic acid (92% by weight), acrylamide (7.6%
by weight), methylenebisacrylamide (0.4% by weight), quantitatively
neutralized with ammonia (25% in water), molecular weight M.sub.w
about 150,000 g/mol
[0192] as water-in-mineral oil dispersion (volume ratio 2.6:1)
(boiling point of mineral oil: 190-230.degree. C.), solids content:
24% by weight; stabilized with sorbitan monooleate (2.5% by weight,
based on total thickener).
[0193] 3.3. Mixing of stock Pastes with Blue Pigment Preparation
from Example 3.2.
[0194] Inventive print pastes as per Table 5 were produced by
mixing in each case 970 g of stock paste as per Table 4 with in
each case 30 g of blue pigment preparation from Example 3.1.
[0195] Inventive print pastes 4.1 to 4.4 as per Table 5 were
obtained. TABLE-US-00006 TABLE 5 Production of inventive print
pastes Stock paste No. Print paste No. 3.1 4.1 3.2 4.2 3.3 4.3 3.4
4.4
[0196] 4. Printing Experiments, Tests of Prints
[0197] Substrates composed of woven polypropylene fabric, basis
weight 170 g/m.sup.2, were screen printed.
[0198] The printing parameters were: 15 mm squeegee, ESTAL MONO E
55 screen gauze, magnet pull level 6, simple print, no pattern.
[0199] Drying at 80.degree. C. in a drying cabinet was followed by
fixing on a fixing cabinet by heating with hot air at 110.degree.
C. for 5 minutes.
[0200] This gave the inventive substrates 5.1 and 5.2, also
referred to respectively as substrates 5.1 and 5.2 printed
according to the present invention.
[0201] For comparison, a print was performed with a comparative
print paste V4.5 which had been produced similarly to inventive
print paste 4.1 except that ethylene copolymer wax dispersion 2.1
had been replaced by a dispersion (acrylate binder dispersion) of
the following copolymer: [0202] n-butyl acrylate (66% by weight),
[0203] styrene (31% by weight), [0204] acrylic acid (1% by weight),
[0205] methylolacrylamide (1% by weight), acrylamide (1% by
weight), quantitatively neutralized with ammonia (25% by weight in
water), with 2% by weight, based on copolymer, of ##STR10## as an
emulsifier; solids content: 35% by weight.
[0206] Comparative substrate V5.5 is obtained.
[0207] The inventive substrates were tested for dry and wet rub
fastness to DIN EN ISO 105-X12 and wash fastness to DIN EN ISO
105-C03. Best possible result: a rating of 5, worst possible
result: a rating of 1.
[0208] The following inventive substrates and test results as per
Table 6 were obtained. TABLE-US-00007 TABLE 6 Substrates printed
according to invention and test results Rub fastness Rub fastness
Wash Print paste No. Substrate No. dry wet fastness 4.1 5.1 3-4 4 3
4.2 5.2 3-4 3-4 3 4.3 5.3 3-4 4 3 4.4 5.4 3-4 3-4 3 V4.5 V5.5 3 1
1-2
[0209] 6. Production of Inventive Dyeing Liquors and Pigment
Dyeing
[0210] 6.1. Production of Inventive Dyeing Liquors
[0211] General Recipe:
[0212] The following were mixed together by being stirred together
in a stirred vessel: TABLE-US-00008 fully desalted water 774 g
pigment preparation of 20 g/l (reckoned on pigment Example 3.1
preparation) aqueous dispersion 2.1 or 2.2 180 g/l (reckoned on
solids content) EO.sub.8PO.sub.7EO.sub.8 20 g/l as antimigration
agent n-C.sub.12H.sub.25O(C.sub.2H.sub.4O).sub.7H 4 g/l as antifilm
agent HO--(CH.sub.2).sub.3--Si[OSi(CH.sub.3).sub.3].sub.2 20 g/l as
defoamer
and made up to one liter with fully desalted water. Using aqueous
dispersion 2.1 gives inventive dyeing liquor F6.1; using aqueous
dispersion 2.2 gives inventive dyeing liquor F6.2.
[0213] Antimigration agent: In the EO.sub.8PO.sub.7EO.sub.8
antimigration agent used in the general recipe EO is always
ethylene oxide and PO propylene oxide. It has the following
properties: a 40.degree. C. cloud point in water, an average molar
mass M.sub.w of 1100 g/ml, solidification point<5.degree. C.,
25.degree. C. viscosity: 175 mPas.
[0214] 6.2. Dyeing of Substrates with Inventive Dyeing Liquors
[0215] A Mathis HVF12085 pad-mangle was used to dye a textile
substrate (woven polypropylene) with in each case an inventive
liquor produced according to 6.1. The nip pressure of the rolls was
2.6 bar. The resulting wet pickup was 55%. The application speed
was 2 m/min. The textile was subsequently dried in an LTF89534
circulating air cabinet from Mathis at 80.degree. C. for 60 s (air
circulation 50%). The subsequent setting was carried out at
110.degree. C. with air circulation (100%) in the course of 5
minutes.
[0216] This gave the following inventive substrates, also referred
to as substrates dyed according to invention, and test results as
per Table 7.
[0217] The comparative substrate was produced by dyeing with a
comparative liquor which corresponded to inventive dye liquor F6.1
except that, instead of dispersion 2.1, an identical amount of
acrylate binder dispersion as also used for producing the
comparative print paste V4.5 was used. TABLE-US-00009 TABLE 7
Substrates dyed according to invention and test results Rub
fastness Rub fastness Wash Dye liquor No. Substrate No. dry wet
fastness F6.1 7.1 3-4 4 3 F6.2 7.2 3-4 3-4 3 Comparative V7.3 2 1
1-2 dye liquor
[0218] 7. Production of Transfer Prints
[0219] 7.1 Production of Inventive Transfer Printing Colors
TABLE-US-00010 TABLE 8 Production of inventive transfer printing
colors 8.1 to 8.2 Transfer printing color Ingredient [g/kg] 8.1 8.2
2.1 958 -- 2.2 -- 600 Fully desalted water -- 358
HO--(CH.sub.2).sub.3--Si[OSi(CH.sub.3).sub.3].sub.2 2 2 Thickener
of Example 3.2 20 20 Blue pigment preparation 3.1 20 20 Sum total
1000 1000
[0220] 7.2. Production of Transfer Prints
[0221] A paper coated with silicone wax was printed with the
inventive print pastes, for example 8.1 and 8.2, and thereafter
dried at 100.degree. C. The printed and dried paper is treated on a
hot press at 120.degree. C. for one minute together with textile.
During this operation, the print paste softens/melts and transfers
and fixes from paper onto the textile to be printed.
* * * * *