U.S. patent application number 10/416024 was filed with the patent office on 2004-01-29 for highly branched polymers for wrinkleproofing cellulosic textiles.
Invention is credited to Bruchmann, Bernd, Detering, Jurgen, Neumann, Peter.
Application Number | 20040016060 10/416024 |
Document ID | / |
Family ID | 7663118 |
Filed Date | 2004-01-29 |
United States Patent
Application |
20040016060 |
Kind Code |
A1 |
Detering, Jurgen ; et
al. |
January 29, 2004 |
Highly branched polymers for wrinkleproofing cellulosic
textiles
Abstract
A process for wrinkleproofing cellulosic textiles by treating
the textiles with a finish and drying the treated textiles, which
comprises using a finish comprising one or more highly branched
polymers in dissolved or dispersed form.
Inventors: |
Detering, Jurgen;
(Limburgerhof, DE) ; Neumann, Peter; (Mannheim,
DE) ; Bruchmann, Bernd; (Freinsheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
7663118 |
Appl. No.: |
10/416024 |
Filed: |
May 13, 2003 |
PCT Filed: |
November 8, 2001 |
PCT NO: |
PCT/EP01/12938 |
Current U.S.
Class: |
8/115.51 ;
252/8.91 |
Current CPC
Class: |
D06M 15/564 20130101;
D06M 2101/06 20130101; C11D 3/37 20130101; C11D 3/3726 20130101;
D06M 2200/20 20130101 |
Class at
Publication: |
8/115.51 ;
252/8.91 |
International
Class: |
D06M 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 13, 2000 |
DE |
100 56 183.7 |
Claims
We claim:
1. A process for wrinkleproofing cellulosic textiles by treating
the textiles with a finish and drying the treated textiles, which
comprises using a finish comprising one or more highly branched
polymers in dissolved or dispersed form.
2. A process as claimed in claim 1, wherein the highly branched
polymers are highly branched polyurethanes.
3. A process as claimed in either of claims 1 and 2, wherein the
highly branched polymers contain one or more functional groups
selected from the group consisting of --COOH, --COOR, --CONHR,
--CONH.sub.2, --OH, --SH, --NH.sub.2, --NHR, --NR.sub.2,
--NR.sub.3.sup.+, --SO.sub.3H, --SO.sub.3R, --NHCOOR,
--NHCONH.sub.2, --NHCONHR and salts thereof.
4. A process as claimed in claim 3, wherein the functional groups
are selected from the group consisting of --COOH, CONH.sub.2, --OH,
--NH.sub.2, --NHR, --NR.sub.2, --NR.sub.3.sup.+, --SO.sub.3H and
salts thereof.
5. A process as claimed in claim 4, wherein the functional groups
are selected from the group consisting of --COOH, --OH, --SO.sub.3H
and salts thereof.
6. A process as claimed in claim 4, wherein the functional groups
are selected from the group consisting of --NH.sub.2, --NHR,
--NR.sub.2, --NR.sub.3.sup.+ and salts thereof.
7. A process as claimed in any of claims 1 to 6, wherein the highly
branched polymers contain on average at least 4 functional
groups.
8. A process as claimed in claim 7, wherein the highly branched
polymers contain on average from 4 to 100 functional groups.
9. The use of highly branched polymers as defined in any of claims
1 to 8 in textile treatments, solid and liquid laundry detergents
and laundry refreshers.
10. The use of finishes comprising highly branched polymers as
defined in any of claims 1 to 8 in the manufacture of textiles,
textile treatment, main laundry cycle, final laundry rinse cycle
and ironing.
11. A finish for wrinkleproofing cellulosic textiles, comprising
highly branched polymers as defined in any of claims 1 to 8.
12. A textile treatment comprising a) from 0.1-40% by weight of at
least one highly branched polymer as defined in any of claims 1 to
8, b) from 0 to 30% by weight of one or more silicones, c) from 0
to 30% by weight of one or more cationic and/or nonionic
surfactants, d) from 0 to 60% by weight of further ingredients such
as further wetting agents, softeners, lubricants, water-soluble,
film-forming and adhesive polymers, scents, dyes, stabilizers,
fiber and color protection additives, viscosity modifiers, soil
release additives, corrosion control additives, bactericides,
preservatives and spraying assistants, and e) from 0 to 99.9% by
weight of water, components a) to e) adding up to 100% by
weight.
13. A solid laundry detergent comprising a) from 0.05 to 20% by
weight of at least one highly branched polymer as defined in any of
claims 1 to 8, b) from 0 to 20% by weight of one or more silicones,
c) from 0.1 to 40% by weight of at least one nonionic and/or
anionic surfactant, d) from 0 to 50% by weight of one or more
inorganic builders, e) from 0 to 10% by weight of one or more
organic cobuilders, f) from 0 to 60% by weight of other customary
ingredients such as standardizers, enzymes, perfume, complexing
agents, corrosion inhibitors, bleaches, bleach activators, cationic
surfactants, bleach catalysts, dye transfer inhibitors,
antiredeposition agents, soil release polyesters, dyes,
bactericides, dissolution improvers and/or disintegrants,
components a) to f) adding up to 100% by weight.
14. A liquid laundry detergent comprising a) from 0.05 to 20% by
weight of at least one highly branched polymer as defined in any of
claims 1 to 8, b) from 0 to 20% by weight of one or more silicones,
c) from 0.1 to 40% by weight of at least one nonionic and/or
anionic surfactant, d) from 0 to 20% by weight of one or more
inorganic builders, e) from 0 to 10% by weight of one or more
organic cobuilders, f) from 0 to 60% by weight of other customary
ingredients such as sodium carbonate, enzymes, perfume, complexing
agents, corrosion inhibitors, bleaches, bleach activators, bleach
catalysts, cationic surfactants, dye transfer inhibitors,
antiredeposition agents, soil release polyesters, dyes,
bactericides, unaqueous solvents, solubilizers, hydrotropes,
thickeners and/or alkanolamines, g) from 0 to 99.85% by weight of
water, components a) to g) adding up to 100% by weight.
15. A laundry refresher comprising a) from 0.05 to 40% by weight of
at least one highly branched polymer, especially of at least one
highly branched polyurethane, b) from 0 to 20% by weight of one or
more silicones, c) from 0.1 to 40% by weight of at least one
cationic surfactant, d) from 0 to 30% by weight of one or more
nonionic surfactants, e) from 0 to 30% by weight of other customary
ingredients such as silicones, other lubricants, wetting agents,
film-forming polymers, scents, dyes, stabilizers, fiber and color
protection additives, viscosity modifiers, soil release additives,
corrosion control additives, bactericides and preservatives, and f)
from 0 to 99.85% by weight of water, components a) to f) adding up
to 100% by weight.
Description
[0001] This invention relates to processes for wrinkleproofing
cellulosic textiles, wrinkleproofing finishes comprising highly
branched polymers, the use of the finishes and of the highly
branched polymers, and also textile treatments, solid and liquid
laundry detergents and laundry refreshers comprising highly
branched polymers.
[0002] Cellulosic textiles are given easy care properties by
treatment with condensation products of urea, glyoxal and
formaldehyde, for example. The finish is applied during the
manufacture of textile materials. Softening compounds are
frequently further applied with the finish. Thus finished textiles
are less wrinkled and creased, easier to iron and softer and
smoother after laundering compared with untreated cellulose
textiles.
[0003] WO 92/01773 discloses the use of microemulsified
aminosiloxanes in fabric conditioners to reduce wrinkling and
creasing during the laundering process. In addition, the use of
aminosiloxanes is said to facilitate ironing.
[0004] WO 98/4772 discloses a process for pretreating textile
materials by applying a mixture of polycarboxylic acid and a
cationic softener to the textile materials. Wrinkle control is
obtained as a result.
[0005] EP-A 0 300 525 discloses fabric conditioners based on
crosslinkable amino-functionalized silicones that impart wrinkle
control or an easy-iron effect to textiles treated therewith.
[0006] WO 99/55953 discloses fabric wrinkle control compositions.
They comprise lubricants, shape retention polymers, lithium salts
and optionally further ingredients such as softeners, ionic and
nonionic surfactants, odor control agents and bactericides. The
formulation is preferably applied to the textile material by
spraying.
[0007] EP-A 0 978 556 describes a mixture of a softener and a
crosslinker component having cationic properties as a fabric
wrinkle and crease control composition and also a method of
wrinkleproofing textiles.
[0008] It is an object of the present invention to provide a
further process for wrinkleproofing cellulosic textiles and also
further finishes for wrinkleproofing such textiles.
[0009] We have found that this object is achieved by a process for
wrinkleproofing cellulosic textiles by treating the textiles with a
finish and drying the treated textiles, which comprises using a
finish comprising one or more highly branched polymers in dissolved
or dispersed form.
[0010] The invention also provides a wrinkleproofing finish for
cellulosic textiles that comprises these highly branched
polymers.
[0011] Highly branched polymers are known per se. Dendrimers,
arborols, starburst polymers and hyperbranched polymers are
designations for polymeric structures distinguished by a branched
structure and a high functionality.
[0012] Dendrimers are molecularly and structurally uniform
macromolecules having a highly symmetrical construction. They are
constructed in multistage syntheses and are very costly as a
result.
[0013] In contrast, hyperbranched polymers are both molecularly and
structurally nonuniform. They have branches that differ in length
and the degree of branching. The highly branched polymers used
according to the invention are preferably such hyperbranched
polymers in the narrower sense. But it is also possible to use
structurally and molecularly uniform dendrimeric polymers. "Highly
branched polymers" for the purposes of this invention therefore
includes hyperbranched and dendrimeric polymers.
[0014] The highly branched polymers used according to the invention
can be prepared in particular from AB.sub.x monomers. These have
two different functional groups A and B which are capable of
reacting with each other to form a linkage. There is only one
functional group A per molecule, while B is present two or more
times. The AB.sub.x monomers react with each other to form
uncrosslinked polymers having regularly disposed branching sites.
There are almost exclusively B groups at the polymer chain ends.
More particular details are described for example in J.M.S.--Rev.
Macromol. Chem. Phys., C37(3), 555-579 (1997).
[0015] Highly branched polymers having functional groups may be
synthesized in a principally known manner using AB.sub.x,
preferably AB.sub.2, monomers. The AB.sub.2 monomers may be
completely incorporated in the form of branchings; they can be
incorporated as terminal groups, i.e. still have two free B groups;
or they can be incorporated as linear groups having a free B group.
The highly branched polymers obtained have a certain number of B
groups, either terminally or as side groups, depending on the
degree of polymerization. Further particulars concerning
hyperbranched polymers and their synthesis are to be found for
example in J.M.S.--Rev. Macromol. Chem. Phys., C37(3), 555-579
(1997) and the references cited therein.
[0016] The choice of highly branched polymers for use in the
wrinkleproofing process of the invention is in principle not
limited to a specific class of polymers. Useful polymers include
highly branched polyesters, highly branched polyethers, highly
branched polyurethanes, highly branched polyureaurethanes, highly
branched polyamines, highly branched polyamides, highly branched
polysiloxanes, highly branched carbosilanes, highly branched
polyetheramides and also highly branched polyesteramides. But
highly branched polyurethanes, highly branched polyesters, highly
branched polyethers, highly branched polyesteramides and highly
branched polyamines are particularly useful. Among highly branched
polyatnines, it is specifically the highly branched
polyethyleneimines which are suitable. Very particular preference
is given to highly branched polyurethanes.
[0017] Highly branched polymers are preparable for example as
follows:
[0018] highly branched polyurethanes according to WO 97/02304 or
according to DE 199 04 444
[0019] highly branched polyesters according to SE 468771 or
according to SE 503342
[0020] highly branched polyesters according to DE 199 47 631
[0021] highly branched polyesteramides according to WO 99/16810
[0022] highly branched polyamines according to WO 93/14147
[0023] Highly branched and highly functional polymers obtained by
polymerization of AB.sub.2 molecules may in principle be used as
such in the finishes of the invention, provided the functional
groups obtained in the train of the particular embodiment of the
synthesis are suitable for application of the polymers in dissolved
or dispersed form.
[0024] However, the B groups originally present may also be
transfunctionalized by polymer-analogous reaction with suitable
compounds.
[0025] Examples of suitable functional groups for introduction by
means of suitable reaction partners include especially acidic or
basic groups that contain H atoms and also derivatives thereof such
as --COOH, --COOR, --CONHR, --CONH.sub.2, --OH, --SH, --NH.sub.2,
--NHR, --NR.sub.2, --NR.sub.3.sup.+, --SO.sub.3H, --SO.sub.3R,
--NHCOOR, --NHCONH.sub.2, --NHCONHR or salts thereof. The R
radicals are generally straight-chain or branched alkyl radicals
which may be further substituted, for example by
C.sub.1-C.sub.8-alkyl radicals. But other functional groups such as
--CN or --OR, for example, may also be introduced.
[0026] In a preferred embodiment, the highly branched polymers used
according to the invention contain one or more functional groups
selected from the group consisting of --COOH, --COOR, --CONHR,
--CONH.sub.2, --OH, --SH, --NH.sub.2, --NHR, --NR.sub.2,
--NR.sub.3.sup.+, --SO.sub.3H, --SO.sub.3R, --NHCOOR,
--NHCONH.sub.2, --NHCONHR and salts thereof.
[0027] The compounds used for transfunctionalization may contain
not only the desired functional group but also a second group
capable of reacting with the B groups of the highly branched
polymer starting material to form a bond. An example is the
reaction of an isocyanate group with a hydroxycarboxylic acid.
[0028] But it is also possible to use monofunctional compounds with
which existing groups are merely modified. For example, alkyl
halides may be used to quaternize existing amino groups.
[0029] The transfunctionalization of hyperbranched polymers may
advantageously be carried out immediately following the
polymerization reaction or in a separate reaction.
[0030] Functional groups having sufficiently acidic hydrogen atoms
may be converted into the corresponding salts by treatment with
suitable bases. Similarly, basic groups are convertible with
suitable acids into the corresponding salts. This makes it possible
to obtain highly branched polymers that are soluble in water.
[0031] It is also possible to generate highly branched polymers
having different functionalities. This may be effected for example
by reaction with a mixture of various compounds for
transfunctionalization or else by reacting only a portion of the
functional groups originally present.
[0032] The degree of polymerization, the molar mass and the type
and number of functional groups are selectable by the skilled
person according to the intended application.
[0033] Particularly preferred functional groups are --COOH,
--CONH.sub.2, --OH, --NH.sub.2, --NHR, --NR.sub.2, --NR.sub.3.sup.+
and --SO.sub.3H and salts thereof.
[0034] In an advantageous embodiment, the highly branched polymers
used according to the invention contain one or more functional
groups selected from the group consisting of --COOH, --OH,
--SO.sub.3H and salts thereof.
[0035] In a further advantageous embodiment, the highly branched
polymers used according to the invention contain one or more
functional groups selected from the group consisting of --NH.sub.2,
--NHR, --NR.sub.2, --NR.sub.3.sup.+ and salts thereof.
[0036] The highly branched polymers used according to the invention
have on average at least 4 functional groups per molecule. The
number of functional groups has in principle no upper limit.
However, products having an excessively large number of functional
groups frequently have undesirable properties, for example poor
solubility or a very high viscosity. Therefore, the highly branched
polymers used according to the invention preferably do not have
more than 200 functional groups on average. Preferably the highly
branched polymers have from 4 to 150, particularly preferably from
4 to 100, functional groups on average.
[0037] The molar masses of the highly branched polymers used
according to the invention depend on the particular class of
polymer and are chosen accordingly by one skilled in the art.
Suitable products have a weight average molecular weight M.sub.w of
from 1 000 to 20 000 g/mol, preferably of from 1 000 to 100 000
g/mol.
[0038] Preferred highly branched polymers for use in the finishes
of the invention are highly branched polyurethanes.
[0039] As used herein, the term "polyurethanes" extends beyond the
customary understanding and includes polymers which are obtainable
by reaction of di- or polyisocyanates with active-hydrogen
compounds and which are linkable together by urethane structures,
but also for example by urea, allophanate, biuret, carbodiimide,
amide, uretonimine, uretidione, isocyanurate or oxazolidone
structures.
[0040] The hyperbranched polyurethanes used according to the
invention are preferably synthesized using AB.sub.x monomers
containing not only isocyanate groups but also groups capable of
reacting with isocyanate groups to form a linkage. x is a natural
number between 2 and 8, preferably 2 or 3. Either A is an
isocyanate group and B an isocyanater-reactive group, or vice
versa.
[0041] Isocyanate-reactive groups are preferably OH, NH.sub.2, NHR
or SH groups.
[0042] AB.sub.x monomers are preparable in a conventional manner.
AB.sub.x monomers are synthesizable for example by the method
described in WO 97/02304 using protective group techniques. This
technique may be illustrated with reference to the preparation of
an AB.sub.2 monomer from 2,4-toluylene diisocyanate (TDI) and
trimethylolpropane. First, one of the isocyanate groups of the TDI
is blocked in a conventional manner, for example by reaction with
an oxime. The remaining free NCO group is reacted with
trimethylolpropane, although only one of the three OH groups reacts
with the isocyanate group, the other two OH groups being blocked
via acetalization. Elimination of the protective group leaves a
molecule having one isocyanate group and two OH groups.
[0043] A particularly advantageous way to synthesize AB.sub.x
molecules is by the method described in DE-A 199 04 444, where no
protective groups are required. Di- or polyisocyanates are used in
this method and reacted with compounds having at least two
isocyanate-reactive groups. At least one of the reactants has
groups having a reactivity that differs with regard to the other
reactant. Preferably, both reactants have groups that differ in
reactivity with regard to the other reactant. The reaction
conditions are chosen in such a way that only certain reactive
groups can react with each other.
[0044] Useful di- and polyisocyanates include the aliphatic,
cycloaliphatic and aromatic isocyanates known from the prior art.
Preferred di- or polyisocyanates are 4,4'-diphenylmethane
diisocyanate, the mixtures of monomeric diphenylmethane
diisocyanates and oligomeric diphenylmethane diisocyanates (polymer
MDI), tetramethylene diisocyanate, hexamethylene diisocyanate,
4,4'-methylenebis(cyclohexyl) diisocyanate, xylylene diisocyanate,
tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine
alkyl ester diisocyanate, where alkyl is C.sub.1-C.sub.10-alkyl,
2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate,
1,4-diisocyanatocyclohexane or 4-isocyanatomethyl-1,8-octam-
ethylene diisocyanate.
[0045] Particular preference is given to di- or polyisocyanates
having NCO groups of different reactivities, such as 2,4-toluylene
diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate
(2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI),
2-butyl-2-ethylpentamethylene diisocyanate,
2-isocyanatopropylcyclohexyl isocyanate,
3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate,
1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis(cyclohexyl)
diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI).
Particular preference is further given to isocyanates (b) whose NCO
groups initially have equal reactivity, but where first addition of
an alcohol or amine to an NCO group can be used to induce a
reactivity reduction for the second NCO group. Examples thereof are
isocyanates whose NCO groups are coupled via a delocalized electron
system, for example 1,3- and 1,4-phenylene diisocyanate,
1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine
diisocyanate or 2,6-toluylene diisocyanate.
[0046] It is further possible to use for example oligo- or
polyisocyanates preparable from the di- or polyisocyanates
mentioned or mixtures thereof by linkage by means of urethane,
allophanate, urea, biuret, uretdione, amide, isocyanurate,
carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione
structures.
[0047] Compounds used as having at least two isocyanate-reactive
groups are preferably di-, tri- or tetrafunctional compounds whose
functional groups have different reactivities toward NCO groups.
Preference is given to compounds having at least one primary and at
least one secondary hydroxyl group, at least one hydroxyl group and
at least one mercapto group, particularly preferably having at
least one hydroxyl group and at least one amino group in the
molecule, especially amino alcohols, aminodiols and aminotriols,
since amino is substantially more reactive with isocyanate than
hydroxyl.
[0048] Examples of compounds having at least two
isocyanate-reactive groups are propylene glycol, glycerol,
mercaptoethanol, ethanolamine, N-methylethanolamine,
diethanolamine, ethanolpropanolamine, dipropanolamine,
diisopropanolamine, 2-amino-1,3-propanediol,
2-amino-2-methyl-1,3-propanediol or tris(hydroxmethyl)aminomethane.
Mixtures of the compounds mentioned may also be used.
[0049] The preparation of an AB.sub.2 molecule may be illustrated
for a diisocyanate with an aminodiol. First one mole of a
diisocyanate is reacted with one mole of aminodiol at low
temperatures, preferably in the range from 10 to 30.degree. C. The
urethane-forming reaction is virtually completely suppressed in
this temperature range and the more reactive NCO groups of the
isocyanate react exclusively with the amino group of the aminodiol.
The AB.sub.x molecule formed has one free NCO group and two free OH
groups and can be used for synthesizing a highly branched
polyurethane.
[0050] On heating and/or catalyst addition this AB.sub.2 molecule
can react intermolecularly to form a highly branched polyurethane.
The synthesis of the highly branched polyurethane may
advantageously be effected without prior isolation of the AB.sub.x
molecule in a further reaction step at elevated temperature,
preferably in the range from 30 to 80.degree. C. Using the
above-described AB.sub.2 molecule having two OH groups and one NCO
group provides a highly branched polymer having per molecule one
free NCO group and also--depending on the degree of
polymerization--a certain number of OH groups. The reaction can be
carried on to high conversions to provide very high molecular
weight structures. But it may also be discontinued for example by
addition of suitable monofunctional compounds or by addition of one
of the starting compounds for preparing the AB.sub.2 molecule on
attainment of the desired molecular weight. Depending on the
starting compound used for the termination, this provides either
completely NCO-terminated or completely OH-terminated
molecules.
[0051] Alternatively, it is also possible for example to prepare an
AB.sub.2 molecule from one mole of glycerol and 2 mol of 2,4-TDI.
The primary alcohol groups and the isocyanate group in position 4
react preferentially at low temperature to form an adduct which has
one OH group and two isocyanate groups and which, as described, can
be converted at higher temperatures into a highly branched
polyurethane. This initially provides a highly branched polymer
which has one free OH group and--depending on the degree of
polymerization--a certain number of NCO groups.
[0052] The highly branched polyurethanes may in principle be
prepared without solvent, but are preferably prepared in solution.
Useful solvents include in principle all compounds that are liquid
at room temperature and inert toward the monomers and polymers.
[0053] Other products are obtainable through further synthetic
variants. AB.sub.3 molecules are obtainable for example by reacting
diisocyanates with compounds having at least 4 isocyanate-reactive
groups. An example is the reaction of 2,4-toluylene diisocyanate
with tris(hydroxymethyl)aminomethane.
[0054] The polymerization may also be terminated using
polyfunctional compounds capable of reacting with the respective A
groups. This makes it possible to link a plurality of small highly
branched molecules together to form a large highly branched
molecule.
[0055] Highly branched polymers having chain-extended branches are
obtainable for example by using for the polymerization reaction as
well as the AB.sub.x molecules additionally in a molar ratio of 1:1
a diisocyanate and a compound having two isocyanate-reactive
groups. These additional AA or BB compounds may also have further
functional groups which however must not be reactive toward the A
or B groups under the reaction conditions chosen. This makes it
possible to introduce further functionalities into the
hyperbranched polymer.
[0056] Further synthetic variants for highly branched polyurethanes
are disclosed in the applications DE 100 13 187.5 and DE 100 30
869.4.
[0057] The highly branched and highly functional polyurethanes
obtained may be used as such in the finishes of the invention,
provided the functional groups obtained in the course of the
synthesis are suitable for use with the polyurethanes in dissolved
or dispersed form.
[0058] But, as stated above, the functional groups may also be
hydrophobicized, hydrophilicized or transfunctionalized. This makes
highly branched polyurethanes available that are particularly
suitable for use as solution or aqueous dispersion. Owing to their
reactivity, highly branched polyurethanes containing isocyanate
groups are very particularly useful for transfunctionalization. It
is also possible to transfunctionalize OH-- or NH.sub.2-terminated
polyurethanes by means of suitable reaction partners.
[0059] Preferred groups for introduction into highly branched
polyurethanes are --COOH, --CONH.sub.2, --OH, --NH.sub.2, --NHR,
--NR.sub.2, --NR.sub.3.sup.+, --SO.sub.3H and salts thereof.
--NH.sub.2, --NHR, --NR.sub.2 and --NR.sub.3.sup.+ are particularly
preferred in one embodiment of the invention, and --COOH, --OH and
--SO.sub.3H in another embodiment of the invention.
[0060] Groups having sufficiently acidic hydrogen atoms are
convertible into the corresponding salts by treatment with suitable
bases. Similarly, basic groups are convertible into the
corresponding salts using suitable acids. This makes it possible to
obtain highly branched polyurethanes that are soluble in water.
[0061] By reacting NCO-terminated products with alkanols and
alkylamines, especially alkanols and alkylamines having
C.sub.8-C.sub.40-alkyl radicals, it is possible to obtain
hydrophobicized products.
[0062] Hydrophilicized but nonionic products are obtainable by
reaction of NCO-terminated polymers with polyether alcohols, for
example di-, tri- or tetra- or polyethylene glycol.
[0063] Acid groups are incorporable for example by reaction with
hydroxycarboxylic acids, hydroxysulfonic acids or amino acids.
Examples of suitable reaction partners are 2-hydroxyacetic acid,
4-hydroxybenzoic acid, 12-hydroxydodecanoic acid,
2-hydroxyethanesulfonic acid, glycine or alanine.
[0064] Reaction with acrylate compounds such as alcohols containing
acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl
methacrylate, makes it possible to obtain highly branched
polyurethanes having polymerizable olefinic groups.
[0065] Oxidatively drying highly branched polyurethanes are
obtainable by reacting initially mono- or polyunsaturated fatty
acids, especially C.sub.8-C.sub.40 fatty acids, with an aliphatic
alcohol having at least two OH groups, although at least one OH
group must not be esterified. Linoleic acid, linolenic acid or
eleostearic acid can be reacted by way of example. The fatty acid
ester obtained, which still contains OH groups, is then reacted
with NCO groups.
[0066] It is also possible to generate highly branched
polyurethanes having different functionalities. This can be
accomplished for example by reaction with a mixture of various
compounds or else by reacting only a portion of the functional
groups already present, for example only a portion of the OH and/or
NCO groups.
[0067] Furthermore, one or more functional groups of the highly
branched molecule can be reacted with reagents having affinity for
the fiber, for example polyamines such as polyethyleneimine or
polyvinylamine. A highly branched molecule containing a portion
with affinity for the fiber as an anchoring group for the fiber is
thereby obtained.
[0068] The transfunctionalization of highly branched polyurethane
may advantageously be effected immediately following the
polymerization reaction without the NCO-terminated polyurethane
being isolated beforehand. But the functionalization may also take
place in a separate reaction.
[0069] The highly branched polyurethanes used according to the
invention generally have on average at least 4 and not more than
200 functional groups. Highly branched polyurethanes preferably
have from 4 to 150, particularly preferably from 4 to 100,
functional groups. Preferred highly branched polyurethanes have a
weight average molecular weight M.sub.w of from 1 000 to 200 000
g/mol, preferably of from 1 000 to 100 000 g/mol.
[0070] This invention also provides for the use of highly branched
polymers, especially highly branched polyurethanes, in finishes for
wrinkleproofing cellulosic textiles. Finishes are any liquid
formulations which contain the highly branched polymer, especially
the highly branched polyurethane, in dissolved or dispersed form
for application to the textile material. The finishes of the
invention can be present for example as finishes in the narrower
sense in the manufacture of textiles or in the form of an aqueous
washing liquor or as a liquid textile treatment. Useful solvents
include for example water, alcohols such as methanol, ethanol and
propanol, THF or mixtures thereof. It is possible for example to
treat textiles with the finish in the course of their manufacture.
Textiles which have not been adequately finished, if at all, may be
treated with a textile treatment that contains the highly branched
polymers for example before or after home laundering, for example
during ironing. But it is also possible to treat the textiles with
highly branched polymers in the main wash cycle or after the main
wash cycle in the refresher or rinse cycle of the washing
machine.
[0071] The present invention also provides for the use of the
highly branched polymers, especially the highly branched
polyurethanes, in the manufacture of textiles, textile treatment
before and after laundering, main laundry cycle, laundry
conditioning rinse cycle and ironing. Different formulations are
needed in each case.
[0072] The treatment before or after laundering may utilize a
textile treatment which, as well as a highly branched polymer in
dissolved or dispersed form, contains a surfactant. In this
treatment, the cellulosic textiles are for example sprayed with the
highly branched polymers with an add-on which is generally in the
range from 0.01 to 10% by weight, preferably in the range from 0.1
to 7% by weight, particularly preferably in the range from 0.3 to
4% by weight, based on the weight of the dry textile material. But
the finish may also be applied to the textile material by dipping
the textiles into a bath which contains generally from 0.1 to 10%
by weight, preferably from 0.3 to 5% by weight, based on the weight
of the dry textile material, of a highly branched polymer in
dissolved or dispersed form. The textile material is either dipped
only briefly into the bath or else allowed to dwell therein for a
period of from 1 to 30 min for example.
[0073] Cellulosic textiles which have been treated with the finish
either by spraying or by dipping are if necessary squeezed off and
dried. Drying may take place in air or else in a dryer or else by
subjecting the treated textile material to hot ironing. The finish
becomes fixed on the textile material in the course of drying. The
best conditions in each case are readily ascertainable by
experimentation. The temperatures for drying, including ironing,
are for example in the range from 40 to 150.degree. C. preferably
from 60 to 110.degree. C. For ironing, the cotton program of the
iron is suitable in particular. Textiles treated with the highly
branched polymers in dissolved or dispersed form according to the
above-described process exhibit an excellent level of wrinkle and
crease resistance that is durable to multiple laundering. There is
frequently no longer any need to iron the textiles. The textiles
thus treated additionally possess fiber and color protection.
[0074] The invention also provides a textile treatment
comprising
[0075] a) from 0.1 to 40% by weight, preferably from 0.5 to 25% by
weight, of at least one highly branched polymer, in particular at
least one highly branched polyurethane,
[0076] b) from 0 to 30% by weight of one or more silicones,
[0077] c) from 0 to 30% by weight of one or more cationic and/or
nonionic surfactants,
[0078] d) from 0 to 60% by weight of further ingredients such as
further wetting agents, softeners, lubricants, water-soluble,
film-forming and adhesive polymers, scents, dyes, stabilizers,
fiber and color protection additives, viscosity modifiers, soil
release additives, corrosion control additives, bactericides,
preservatives and spraying assistants, and
[0079] e) from 0 to 99.9% by weight of water,
[0080] components a) to e) adding up to 100% by weight.
[0081] Preferred silicones are amino-containing silicones, which
are preferably present in microemulsified form, alkoxylated,
especially ethoxylated, silicones, polyalkylene
oxide-polysiloxanes, polyalkylene oxide-aminopolydimethylsiloxanes,
silicones having quaternary ammonium groups (silicone quats) and
silicone surfactants. Useful softeners or lubricants include for
example oxidized polyethylenes or paraffinic waxes and oils. Useful
water-soluble, film-forming and adhesive polymers include for
example (co)polymers based on acrylamide, N-vinylpyrrolidone,
vinylformamide, N-vinylimidazole, vinylamine,
N,N'-dialkylaminoalkyl (meth)acrylates,
N,N'-dialkylaminoalkyl(meth)acrylamides, (meth)acrylic acid, alkyl
(meth)acrylates and/or vinylsulfonate. The aforementioned basic
monomers may also be used in quaternized form.
[0082] A pretreatment formulation to be applied to the textile
material by spraying may additionally include a spraying assistant.
In some cases, it can also be of advantage to include in the
formulation alcohols such as ethanol, isopropanol, ethylene glycol
or propylene glycol. Further customary additives are scents, dyes,
stabilizers, fiber and color protection additives, viscosity
modifiers, soil release additives, corrosion control additives,
bactericides and preservatives in customary amounts.
[0083] The textile treatment may generally also be applied by
spraying in the course of ironing after laundering. This not only
substantially facilitates the ironing, but also imparts sustained
wrinkle and crease resistance to the textiles.
[0084] The highly branched polymers may also be used when the
textiles are washed in the main wash cycle of the washing
machine.
[0085] The invention further provides a solid laundry detergent
formulation comprising
[0086] a) from 0.05 to 20% by weight of at least one highly
branched polymer, especially at least one highly branched
polyurethane,
[0087] b) from 0 to 20% by weight of one or more silicones,
[0088] c) from 0.1 to 40% by weight of at least one nonionic and/or
anionic surfactant,
[0089] d) from 0 to 50% by weight of one or more inorganic
builders,
[0090] e) from 0 to 10% by weight of one or more organic
cobuilders,
[0091] f) from 0 to 60% by weight of other customary ingredients
such as standardizers, enzymes, perfume, complexing agents,
corrosion inhibitors, bleaches, bleach activators, bleach
catalysts, cationic surfactants, dye transfer inhibitors,
antiredeposition agents, soil release polyesters, dyes,
bactericides, dissolution improvers and/or disintegrants,
[0092] components a) to f) adding up to 100% by weight.
[0093] Useful anionic surfactants are in particular:
[0094] (fatty) alcohol sulfates of (fatty) alcohols having from 8
to 22, preferably from 10 to 18, carbon atoms, for example C.sub.9-
to C.sub.11-alcohol sulfates, C.sub.12- to C.sub.14-alcohol
sulfates, C.sub.12- to C.sub.18-alcohol sulfates, lauryl sulfate,
cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate
and tallow fatty alcohol sulfate;
[0095] sulfated alkoxylated C.sub.8- to C.sub.22-alcohols (alkyl
ether sulfates). Compounds of this kind are prepared for example by
first alkoxylating a C.sub.8- to C.sub.22-alcohol, preferably a
C.sub.10- to C.sub.18-alcohol, for example a fatty alcohol, and
then sulfating the alkoxylation product. The alkoxylation is
preferably carried out using ethylene oxide;
[0096] linear C.sub.8- to C.sub.20-alkylbenzenesulfonates (LAS),
preferably linear C.sub.9- to C.sub.13-alkylbenzenesulfonates and
-alkyltoluenesulfonates,
[0097] alkanesulfonates such as C.sub.8- to
C.sub.24-alkanesulfonates, preferably C.sub.10- to
C.sub.18-alkanesulfonates
[0098] soaps such as, for example, the sodium and potassium salts
of C.sub.8- to C.sub.24-carboxylic acids.
[0099] The anionic surfactants mentioned are preferably included in
the laundry detergent in the form of salts. Suitable cations in
these salts are alkali metal ions such as sodium, potassium and
lithium and ammonium ions such as hydroxyethylammonium,
di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium.
[0100] Useful nonionic surfactants are in particular:
[0101] alkoxylated C.sub.8- to C.sub.22-alcohols such as fatty
alcohol alkoxylates or oxo alcohol alkoxylates. These may have been
alkoxylated with ethylene oxide, propylene oxide and/or butylene
oxide. Useful surfactants here include all alkoxylated alcohols
which contain at least two molecules of one of the aforementioned
alkylene oxides. Here it is possible to use block polymers of
ethylene oxide, propylene oxide and/or butylene oxide or addition
products which contain the aforementioned alkylene oxides in random
distribution. Nonionic surfactants generally contain from 2 to 50,
preferably from 3 to 20, mol of at least one alkylene oxide per
mole of alcohol. The alkylene oxide component is preferably
ethylene oxide. The alcohols preferably have from 10 to 18 carbon
atoms. Depending on the type of alkoxylation catalyst used to make
them, alkoxylates have a broad or narrow alkylene oxide homolog
distribution;
[0102] alkylphenol alkoxylates such as alkylphenol ethoxylates
having C.sub.6- to C.sub.14-alkyl chains and from 5 to 30 alkylene
oxide units;
[0103] alkylpolyglucosides having from 8 to 22, preferably from 10
to 18, carbon atoms in the alkyl chain and generally from 1 to 20,
preferably from 1.1 to 5, glucoside units;
[0104] N-alkylglucamides, fatty acid amide alkoxylates, fatty acid
alkanolamide alkoxylates and also block copolymers of ethylene
oxide, propylene oxide and/or butylene oxide.
[0105] Useful inorganic builders are in particular:
[0106] crystalline or amorphous aluminosilicates having
ion-exchanging properties such as zeolites in particular. Useful
zeolites include in particular zeolites A, X, B, P, MAP and HS in
their sodium form or in forms in which sodium has been partly
replaced by other cations such as lithium, potassium, calcium,
magnesium or ammonium;
[0107] crystalline silicates such as in particular disilicates or
sheet-silicates, for example .delta.-Na.sub.2Si.sub.2O.sub.5 or
.beta.-Na.sub.2Si.sub.2O.sub.5. Silicates can be used in the form
of their alkali metal, alkaline earth metal or ammonium salts,
preferably as sodium, lithium or magnesium silicates;
[0108] amorphous silicates such as for example sodium metasilicate
or amorphous disilicate;
[0109] carbonates and bicarbonates. These can be used in the form
of their alkali metal, alkaline earth metal or ammonium salts.
Preference is given to sodium, lithium and magnesium carbonates or
bicarbonates, especially sodium carbonate and/or sodium
bicarbonate;
[0110] polyphosphates such as for example pentasodium
triphosphate.
[0111] Useful organic cobuilders include in particular low
molecular weight, oligomeric or polymeric carboxylic acids.
[0112] Useful low molecular weight carboxylic acids include for
example citric acid, hydrophobic modified citric acid such as for
example agaric acid, malic acid, tartaric acid, gluconic acid,
glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic
acid, propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids
and aminopolycarboxylic acids such as for example nitrilotriacetic
acid, .beta.-alaninediacetic acid, ethylenediaminetetraacetic acid,
serinediacetic acid, isoserinediacetic acid,
N-(2-hydroxyethyl)iminodiacetic acid, ethylenediaminedisuccinic
acid and methyl- and ethylglycinediacetic acid;
[0113] useful oligomeric or polymeric carboxylic acids include for
example homopolymers of acrylic acid, oligomaleic acids, copolymers
of maleic acid with acrylic acid, methacrylic acid,
C.sub.2-C.sub.22-olefins such as for example isobutene or
long-chain .alpha.-olefins, vinyl alkyl ethers having
C.sub.1-C.sub.8-alkyl groups, vinyl acetate, vinyl propionate,
(meth)acrylic esters of C.sub.1- to C.sub.8-alcohols and styrene.
Preference is given to using the homopolymers of acrylic acid and
copolymers of acrylic acid with maleic acid. Polyaspartic acids are
also useful as organic cobuilders. Oligomeric and polymeric
carboxylic acids are used in acid form or as sodium salt.
[0114] Useful bleaches include for example adducts of hydrogen
peroxide to inorganic salts such as sodium perborate monohydrate,
sodium perborate tetrahydrate and sodium carbonate perhydrate and
percarboxylic acids such as phthalimidopercapronic acid.
[0115] Useful bleach activators include for example
N,N,N',N'-tetraacetylethylendiamine (TAED), sodium
p-nonanoyloxybenzenesulfonate and N-methylmorpholinium
acetonitrilmethylsulfate.
[0116] Preferable enzymes used in laundry detergents are proteases,
lipases, amylases, cellulases, oxidases and peroxidases.
[0117] Useful dye transfer inhibitors include for example
homopolymers and copolymers of 1-vinylpyrrolidone, of
1-vinylimidazole or of 4-vinylpyridine-N-oxide and homopolymers or
copolymers of 4-vinylpyridine reacted with chloroacetic acid.
[0118] A solid laundry detergent formulation according to the
invention is customarily present in powder or granule form or in
extrudate or tablet form.
[0119] The invention further provides a liquid laundry detergent
comprising
[0120] a) from 0.05 to 20% by weight of at least one highly
branched polymer, especially at least one highly branched
polyurethane,
[0121] b) from 0 to 20% by weight of one or more silicones,
[0122] c) from 0.1 to 40% by weight of at least one nonionic and/or
anionic surfactant,
[0123] d) from 0 to 20% by weight of one or more inorganic
builders,
[0124] e) from 0 to 10% by weight of one or more organic
cobuilders,
[0125] f) from 0 to 60% by weight of other customary ingredients
such as sodium carbonate, enzymes, perfume, complexing agents,
corrosion inhibitors, bleaches, bleach activators, bleach
catalysts, cationic surfactants, dye transfer inhibitors,
antiredeposition agents, soil release polyesters, dyes,
bactericides, unaqueous solvents, solubilizers, hydrotropes,
thickeners and/or alkanolamines,
[0126] g) from 0 to 99.85% by weight of water,
[0127] components a) to g) adding up to 100% by weight.
[0128] The abovementioned silicones, nonionic and anionic
surfactants, builders and cobuilders may be used.
[0129] A detailed description of the laundry detergent ingredients
mentioned is found for example in WO 99/06524 or WO 99/04313 and in
Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol.
67, Marcel Decker, New York, 1997, p. 272-304.
[0130] The concentration of the highly branched polymers in the
wash liquor is for example in the range from 10 to 5 000 ppm,
preferably in the range from 50 to 1 000 ppm. Textiles treated with
the highly branched polymers in the main wash cycle of the washing
machine not only wrinkle substantially less than untreated
textiles, they are also easier to iron, softer and smoother, more
dimensionally and shape stable and, because of their fiber and
color protection, look less used, i.e., exhibit less fluff and
fewer knots and less color damage or fading, after repeated
washing.
[0131] The highly branched polymers may be used in the rinse or
refresher cycle following the main wash cycle. The concentration of
the highly branched polymers in the wash liquor is for example in
the range from 10 to 5 000 ppm, preferably in the range from 50 to
1 000 ppm. The rinse liquor may if desired include ingredients
typical for a fabric conditioner or refresher. Textiles treated in
this way and then dried on the line or preferably in a tumble dryer
likewise exhibit a very high level of crease resistance that is
associated with the positive effects on ironing that were described
above. Crease resistance can be substantially enhanced by briefly
ironing the textiles once after drying. The treatment in the
conditioning or refresher rinse cycle also has a favorable effect
on the shape retention of the textiles. It further inhibits the
formation of knots and fluff and suppresses color damage.
[0132] The invention also provides a laundry refresher
comprising
[0133] a) from 0.05 to 40% by weight of at least one highly
branched polymer, especially of at least one highly branched
polyurethane,
[0134] b) from 0 to 20% by weight of one or more silicones,
[0135] c) from 0.1 to 40% by weight of at least one cationic
surfactant,
[0136] d) from 0 to 30% by weight of one or more nonionic
surfactants and
[0137] e) from 0 to 30% by weight of other customary ingredients
such as silicones, other lubricants, wetting agents, film-forming
polymers, scents, dyes, stabilizers, fiber and color protection
additives, viscosity modifiers, soil release additives, corrosion
control additives, bactericides and preservatives, and
[0138] f) from 0 to 99.85% by weight of water,
[0139] components a) to f) adding up to 100% by weight.
[0140] Preferred cationic surfactants are selected from the group
of the quaternary diesterammonium salts, the quaternary
tetraalkylammonium salts, the quaternary diamidoammonium salts, the
amidoamine esters and imidazolium salts. These are preferably
present in an amount of from 3 to 30% by weight in the laundry
refreshers. Examples are quaternary diesterammonium salts which
have two C.sub.11- to C.sub.22-alk(en)ylcarbo- nyloxy(mono- to
pentamethylene) radicals and two C.sub.1- to C.sub.3-alkyl or
-hydroxyalkyl radicals on the quaternary nitrogen atom and, for
example, chloride, bromide, methosulfate or sulfate as
counterion.
[0141] Quaternary diesterammonium salts further include in
particular those which have a C.sub.11- to
C.sub.22-alk(en)ylcarbonyloxytrimethylene radical bearing a
C.sub.11- to C.sub.22-alk(en)ylcarbonyloxy radical on the central
carbon atom of the trimethylene group and three C.sub.1- to
C.sub.3-alkyl or -hydroxyalkyl radicals on the quaternary nitrogen
atom and, for example, chloride, bromide, methosulfate or sulfate
as counterion.
[0142] Quaternary tetraalkylammonium salts are in particular those
which have two C.sub.1- to C.sub.6-alkyl radicals and two C.sub.8-
to C.sub.24-alk(en)yl radicals on the quaternary nitrogen atom and,
for example, chloride, bromide, methosulfate or sulfate as
counterion.
[0143] Quaternary diamidoammonium salts are in particular those
which bear two C.sub.8- to C.sub.24-alk(en)ylcarbonylaminoethylene
radicals, a substituent selected from hydrogen, methyl, ethyl and
polyoxyethylene having up to 5 oxyethylene units and as fourth
radical a methyl group on the quaternary nitrogen atom and, for
example, chloride, bromide, methosulfate or sulfate as
counterion.
[0144] Amidoamino esters are in particular tertiary amines bearing
a C.sub.11- to C.sub.22-alk(en)ylcarbonylamino(mono- to
trimethylene) radical, a C.sub.11- to
C.sub.22-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a
methyl group as substituents on the nitrogen atom.
[0145] Imidazolinium salts are in particular those which bear a
C.sub.14- to C.sub.18-alk(en)yl radical in position 2 of the
heterocycle, a C.sub.14- to C.sub.18-alk(en)ylcarbonyl(oxy or
amino)ethylene radical on the neutral nitrogen atom and hydrogen,
methyl or ethyl on the nitrogen atom carrying the positive charge,
while counterions here are for example chloride, bromide,
methosulfate or sulfate.
[0146] The examples hereinbelow illustrate the invention.
EXAMPLES
[0147] The percentages in the examples are by weight, unless the
context suggests otherwise.
[0148] The following finishes were used:
Finish A
[0149] 1% by weight alkaline solution of the highly branched
polyurethane A, which was prepared as follows:
[0150] 168 g of hexamethylene diisocyanate (HDI), dissolved in 386
g of dimethylacetamide (DMAc), were initially charged at room
temperature under nitrogen. 134 g of dimethylolpropionic acid
dissolved in 313 g of DMAc were then added in the course of 1 min
with intensive stirring. After metered addition of 0.2 g of
dibutyltin dilaurate, the reaction mixture was heated to 70.degree.
C. and the decrease in the NCO content was followed
titrimetrically. When an NCO content of 1.5% by weight had been
reached, the reaction product had an average functionality of 1
with regard to NCO, of 3 with regard to COOH and of 1 with regard
to OH.
[0151] This polyaddition product was then admixed with 22 g of
trimethylolpropane (TMP) dissolved in 50 g of DMAc and subsequently
stirred at 70.degree. C. for 3 h. During this period, the NCO
content of the mixture decreased to 0%. The product was then
stripped of solvent in a rotary evaporator at 80.degree. C. under
reduced pressure.
[0152] The solid end product had the following parameters:
[0153] Average functionality with regard to OH: about 5 and with
regard to COOH: about 9 Average molar mass: 6 018 g/mol
Finish B
[0154] 1% by weight alkaline solution of the highly branched
polyurethane B, which was prepared as follows:
[0155] 336 g of hexarnethylene diisocyanate (HDI), dissolved in 336
g of dimethylacetamide (DMAc), were initially charged at 0.degree.
C. under nitrogen. 105 g of diethanolamine were then added in the
course of 20 min with intensive stirring and stirred at 0.degree.
C. for a further 30 min. Then 134 g of dimethylolpropionic acid,
dissolved in 239 g of DMAc, were added. After metered addition of
0.5 g of dibutyltin dilaurate, the reaction mixture was heated to
60.degree. C. and the decrease in the NCO content was followed
titrimetrically. When an NCO content of 1.2% by weight had been
reached, an excess of methanol was added to convert NCO groups
still present. The product was then stripped of solvent in a rotary
evaporator at 80.degree. C. under reduced pressure.
[0156] The reaction product had the following parameters:
[0157] Average functionality with regard to COOH: about 3 and with
regard to OH: about 4 Average molar mass: 1 757 g/mol
Finish C
[0158] 1% by weight alkaline solution of the highly branched
polyurethane C, which was prepared as follows:
[0159] 222 g of isophorone diisocyanate (IPDI) were initially
charged under nitrogen. A mixture of 67 g of TMP and 67 g of
dimethylolpropionic acid, dissolved in 365 g of DMAc, was then
added in the course of 1 min with intensive stirring. After metered
addition of 0.4 g of dibutyltin dilaurate, the reaction mixture was
heated to 60.degree. C., stirred at this temperature and the
decrease in the NCO content was followed titrimetrically. When an
NCO content of 1.0% by weight had been reached, the reaction
product had an average functionality of 1 with regard to NCO, of 3
with regard to COOH and of 4 with regard to OH.
[0160] This polyaddition product was then admixed with 32 g of
polytetrahydrofuiran with an average molar mass of 250 glmol and
subsequently stirred at 60.degree. C. for 3 h. During this period,
the NCO content of the mixture decreased to 0%. The product was
then stripped of solvent in a rotary evaporator at 80.degree. C.
under reduced pressure.
[0161] The solid end product had the following parameters:
[0162] Average functionality with regard to OH: about 20 and with
regard to COOH: about 15 Average molecular weight: 22 610 g/mol
Finish D
[0163] 1% by weight alkaline solution of the highly branched
polyurethane D, which was prepared as follows:
[0164] 168 g of hexamethylene diisocyanate (HDI), dissolved in 168
g of dimnethylacetamide (DMAc), were initially charged at 0.degree.
C. under nitrogen. 52.5 g of diethanolamine dissolved in 52.5 g of
DMAc were then added at 0.degree. C. in the course of 20 min with
intensive stirring and stirred at 0.degree. C. for a further 30
min. Then 59.9 g of N-methyldiethanolamine, dissolved in 59.5 g of
DMAc, were added. After metered addition of 0.2 g of dibutyltin
dilaurate, the reaction mixture was heated to 40.degree. C. and the
decrease in the NCO content was followed titrimetrically. When an
NCO content of 1.2% by weight had been reached, an excess of
methanol was added to convert NCO groups still present. The product
was then stripped of solvent in a rotary evaporator at 80.degree.
C. under reduced pressure.
[0165] The reaction product had the following parameters:
[0166] Average functionality with regard to NR.sub.2: about 3 and
with regard to OH: about 4 Average molar mass: 1 782 g/mol.
Finishing of Fabric Samples
[0167] Cotton fabrics having the size reported in table 1 and a
basis weight of 160 g/m.sup.2 were sprayed on both sides with the
finishes A, B, C and D in such a way that the add-on was 2%, based
on the particular weight of the dry textile material, and then hot
pressed while still slightly moist.
[0168] The fabric samples thus treated and, for comparison,
untreated fabric samples of the same size were washed in the
presence of ballast fabric with a liquid laundry detergent at
40.degree. C. in an automatic domestic washing machine (load in the
range from 1.5 to 3.0 kg) and then tumble-dried. A standard washing
program and a standard drying program (respectively 40.degree. C.
colored wash and the cupboard dry program) were used. After drying,
the sheetlike fabric samples were visually rated on the lines of
AATCC test method 124, where a rating of 1 indicates that the
fabric is highly wrinkled and has many creases and the rating of 5
was awarded to wrinkle- and crease-free fabric. The fabric samples
pretreated with the finishes A, B and C received ratings between
2.5 and 3.5. In contrast, the untreated fabric samples each
received a rating of 1.
1 TABLE 1 Cotton Cotton Cotton (40 cm .times. 40 cm) (40 cm .times.
40 cm) (40 cm .times. 80 cm) Load 1.5 kg Load 3.0 kg Load 1.5 kg
Untreated 1 1 1 A 3.5 3 3 B 3 2.5 3 C 2.5 2.5 2.5 D 3 2.5 3
* * * * *