U.S. patent application number 12/519379 was filed with the patent office on 2010-01-28 for hydrophobically modified polyalkylenimines for use as dye transfer inhibitors.
This patent application is currently assigned to BASF SE. Invention is credited to Richard Baur, Heike Becker, Juergen Detering, Gero Nordmann.
Application Number | 20100017973 12/519379 |
Document ID | / |
Family ID | 39367715 |
Filed Date | 2010-01-28 |
United States Patent
Application |
20100017973 |
Kind Code |
A1 |
Detering; Juergen ; et
al. |
January 28, 2010 |
HYDROPHOBICALLY MODIFIED POLYALKYLENIMINES FOR USE AS DYE TRANSFER
INHIBITORS
Abstract
The invention relates to the use of hydrophobically modified
polyalkylenimines as dye transfer inhibitors.
Inventors: |
Detering; Juergen;
(Limburgerhof, DE) ; Becker; Heike; (Mannheim,
DE) ; Baur; Richard; (Mutterstadt, DE) ;
Nordmann; Gero; (Heidelberg, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
39367715 |
Appl. No.: |
12/519379 |
Filed: |
December 21, 2007 |
PCT Filed: |
December 21, 2007 |
PCT NO: |
PCT/EP07/64486 |
371 Date: |
June 16, 2009 |
Current U.S.
Class: |
8/442 |
Current CPC
Class: |
C11D 3/0021 20130101;
C11D 3/3723 20130101 |
Class at
Publication: |
8/442 |
International
Class: |
D06P 5/02 20060101
D06P005/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 22, 2006 |
EP |
06127179.7 |
Claims
1. A method for inhibiting dye transfer during washing of textiles
with a detergent composition, which comprises at least one
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines in an
amount which is effective for inhibiting dye transfer.
2. The method according to claim 1, where, on average, at least 10
mol % of the nitrogen atoms of the
poly-C.sub.2-C.sub.4-alkylenimine carry an aliphatic, saturated or
unsaturated hydrocarbon radical which has at least 8 carbon
atoms.
3. The method according to claim 2, where the fraction of the
hydrocarbon radicals, based on the total weight of the
poly-C.sub.2-C.sub.4-alkylenimine, constitutes 25 to 95% by
weight.
4. The method according to claim 2, where the hydrocarbon radicals
are present in the form of C.sub.8-C.sub.30-alkyl-,
C.sub.8-C.sub.30-alkylcarbonyl, C.sub.8-C.sub.30-alkenyl-,
C.sub.8-C.sub.30-alkenylcarbonyl-, C.sub.8-C.sub.30-alkadienyl-,
C.sub.8-C.sub.30-alkadienylcarbonyl- and/or
hydroxy-C.sub.8-C.sub.30-alkyl groups.
5. The method according to claim 1, where the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimine has a number-average
molecular weight in the range from 3000 to 300 000 Daltons.
6. The method according to claim 1, where the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimine in the
poly-C.sub.2-C.sub.4-alkylenimine moiety is branched.
7. The method according to claim 1, where the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimine has quaternized nitrogen
atoms.
8. The method according to claim 1, where the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimine is obtainable by a
process which comprises the reaction of a nonmodified
poly-C.sub.2-C.sub.4-alkylenimine with a hydrophobicizing
agent.
9. The method according to claim 8, where the hydrophobicizing
agent is selected from saturated, mono- or polyunsaturated
aliphatic C.sub.9-C.sub.31-carboxylic acids, their amide-forming
derivatives and C.sub.8-C.sub.30-alkylene oxides.
10. The method according to claim 8, where the hydrophobicizing
agent, calculated as the parts of the hydrophobicizing agent
remaining in the product, is used in an amount of from 0.35 to 20
parts by weight per part by weight of unmodified
poly-C.sub.2-C.sub.4-alkylenimine.
11. The method according to claim 8, where the preparation of the
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimine
additionally comprises a quaternization.
12. The method according to claim 8, where the unmodified
poly-C.sub.2-C.sub.4-alkylenimine used for the preparation is
branched.
13. The method according to claim 8, where the unmodified
poly-C.sub.2-C.sub.4-alkylenimine used for the preparation has a
number-average molecular weight in the range from 1000 to 200 000
Daltons.
14. The method according to claim 1, where the fraction of nonionic
surfactants in the detergent composition, based on the total amount
of surfactant in the detergent composition, is at least 50% by
weight.
15. The method according to claim 1, where the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimine is used in a
concentration of from 5 to 150 ppm in the wash liquor.
16. A method for inhibiting dye transfer during washing of textiles
with a detergent composition, which comprises contacting a textile
with at least one hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines in an amount which is effective
for inhibiting dye transfer.
Description
[0001] The invention relates to the use of hydrophobically modified
polyalkylenimines as dye transfer inhibitors.
[0002] During the washing process, dye molecules are often detached
from colored textiles; these can in turn attach to other textiles.
In order to counteract this undesired dye transfer, so-called dye
transfer inhibitors are often used. These are frequently polymers
which comprise monomers with nitrogen-heterocyclic radicals in
copolymerized form.
[0003] Thus, for example, DE 4235798 describes copolymers of
1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazolium compounds
or mixtures thereof; further nitrogen-containing, basic
ethylenically unsaturated monomers; and, if appropriate, other
monoethylenically unsaturated monomers and their use for inhibiting
dye transfer during the washing process.
[0004] Similar copolymers are described for this purpose in DE
19621509 and WO 98/30664.
[0005] The copolymers described in these specifications are
characterized in part by good inhibition of dye transfer in washing
processes. However, they generally have poor compatibility with the
other detergent constituents customarily used. Thus, particularly
in the case of liquid detergents, there is the danger of
incompatibilities, for example in the form of opacity or phase
separations.
[0006] On several occasions, the use of hydrophobically modified
polyalkylenimines in detergent and cleaner formulations has been
described.
[0007] DE 2025829 describes reaction products of fatty acid
glycidyl esters with polyethylenimines and their use as fabric
softeners.
[0008] DE 2046304 describes reaction products of fatty acids or
fatty acid esters with polyethylenimines and their use as fabric
softeners.
[0009] DE 2165900 describes reaction products of alkyl glycidyl
ethers with polyethylenimines and their use as graying
inhibitors.
[0010] U.S. Pat. No. 3,576,341 describes alkylated
polyethylenimines in which the alkyl groups have 16 to 30 carbon
atoms, and use as fabric softeners.
[0011] WO 2002/095122 describes the use of hydrophobically modified
polyethylenimines as anticrease additives for detergent
formulations.
[0012] An effect of the hydrophobically modified polyalkylenimines
inhibiting dye transfer during washing is described in none of
these citations.
[0013] It was an object of the present invention to provide
substances with a good dye transfer-inhibiting effect during the
washing process. These substances should additionally have good
compatibility with conventional detergent constituents, especially
in the case of liquid detergent formulations.
[0014] These and further objects are surprisingly achieved through
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines.
[0015] The invention therefore relates to the use of
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines, in
particular hydrophobically modified polyethylenimines, as dye
transfer inhibitors in detergent compositions for textiles.
[0016] Here and in what follows, hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines are to be understood as meaning
poly-C.sub.2-C.sub.4-alkylenimines in which the hydrogen atoms of
the primary and secondary amino groups are partially or completely
replaced by linear or branched aliphatic, saturated or unsaturated
hydrocarbon radicals such as alkyl, alkenyl, alkadienyl or
hydroxyalkyl radicals. The hydrocarbon radicals generally have at
least 8, e.g. 8 to 30, carbon atoms, preferably 10 to 22 carbon
atoms, in particular 10 to 18 carbon atoms.
[0017] Depending on the hydrophobicizing agent used in each case,
the hydrocarbon radicals can be linked to the nitrogen atom of the
poly-C.sub.2-C.sub.4-alkylenimine directly or via a functional
group, e.g. via a carbonyl group (*-C(.dbd.O)-.sup.#), via an
oxycarbonyl group (*-O--C(.dbd.O)-.sup.#), via an aminocarbonyl
group (*-NH--C(.dbd.O)-.sup.#), via a carbonyloxyhydroxypropyl
group (*-C(.dbd.O)--O--CH.sub.2--CH(OH)--CH.sub.2-.sup.#), via a
2-oxycarbonylethylenecarbonyl group
(*-CH(COOH)--CH.sub.2--CO-.sup.#), or via a radical of the formula
*-CH.sub.2--C(.dbd.O)--CH*-C(.dbd.O)-.sup.# (in the formulae given
above, * represents the linkage to the hydrocarbon radical and #
represents the linkage to the nitrogen atom of the
poly-C.sub.2-C.sub.4-alkylenimine). The hydrocarbon radical can
also form an aldimine or ketimine group with the nitrogen of the
poly-C.sub.2-C.sub.4-alkylenimine, or be linked to 2 nitrogen atoms
of the poly-C.sub.2-C.sub.4-alkylenimine via the carbon atom of a
cyclic amidine group.
[0018] Preference is given to those hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines in which the hydrocarbon radical
is linked to one nitrogen atom of the
poly-C.sub.2-C.sub.4-alkylenimine directly or via a carbonyl group,
the latter being particularly preferred.
[0019] Preferably, the hydrocarbon radicals are linear. Preferably,
the hydrocarbon radicals are saturated.
[0020] Accordingly, the hydrocarbon radicals in the preferred
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines are
present in the form of C.sub.8-C.sub.30-alkyl,
C.sub.8-C.sub.30-alkylcarbonyl, C.sub.8-C.sub.30-alkenyl,
C.sub.8-C.sub.30-alkenylcarbonyl, C.sub.8-C.sub.30-alkadienyl,
C.sub.8-C.sub.30-alkadienylcarbonyl and/or
hydroxy-C.sub.8-C.sub.30-alkyl groups, in particular in the form of
C.sub.10-C.sub.22-alkyl, C.sub.10-C.sub.22-alkylcarbonyl,
C.sub.10-C.sub.22-alkenyl, C.sub.10-C.sub.22-alkenylcarbonyl,
C.sub.10-C.sub.22-alkadienyl, C.sub.10-C.sub.22-alkadienylcarbonyl
and/or hydroxy-C.sub.10-C.sub.22-alkyl groups, particularly
preferably in the form of C.sub.10-C.sub.18-alkyl,
C.sub.10-C.sub.18-alkylcarbonyl, C.sub.10-C.sub.18-alkenyl,
C.sub.10-C.sub.18-alkenylcarbonyl, C.sub.10-C.sub.18-alkadienyl,
C.sub.10-C.sub.18-alkadienylcarbonyl and/or
hydroxy-C.sub.10-C.sub.18-alkyl groups, where the alkyl,
hydroxyalkyl, alkenyl, alkadienyl radicals of the aforementioned
groups are preferably linear.
[0021] In the particularly preferred hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines, the hydrocarbon radicals are
present in the form of C.sub.8-C.sub.30-alkylcarbonyl or
C.sub.8-C.sub.30-alkenylcarbonyl groups, in particular in the form
of C.sub.10-C.sub.22-alkylcarbonyl or
C.sub.10-C.sub.22-alkenylcarbonyl groups and specifically in the
form of C.sub.10-C.sub.18-alkylcarbonyl or
C.sub.10-C.sub.18-alkenylcarbonyl groups, where the alkyl und
alkenyl radicals of the aforementioned groups are preferably
linear.
[0022] Preference is furthermore given to those hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimines in which at least 10
mol %, in particular at least 15 mol % and particularly preferably
at least 20 mol %, e.g. 5 to 80 mol %, in particular 15 to 70 mol %
and specifically 20 to 60 mol %, of the nitrogen atoms of the
poly-C.sub.2-C.sub.4-alkylenimine carry a hydrocarbon radical.
[0023] Correspondingly, the fraction of the hydrocarbon radicals
constitutes preferably 25 to 95% by weight, in particular 30 to 90%
by weight and specifically 40 to 80% by weight, based on the total
weight of the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimine.
[0024] The weight-average molecular weight Mw of hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimines suitable according to
the invention is typically in the range from 1000 to 1 000 000
Daltons. For the use according to the invention, it has furthermore
proven advantageous if the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimine has a number-average molecular
weight in the range from 3000 to 300 000 Daltons and in particular
in the range from 6000 to 200 000 Daltons. The molecular weights
given here refer to the molecular weights specified by means of
dynamic light scattering and measured on dilute aqueous solutions
at 25.degree. C. which correspond to the weight-average molecular
weight.
[0025] The hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines used according to the invention,
in particular the hydrophobically modified polyethylenimines, can,
based on the poly-C.sub.2-C.sub.4-alkylenimine on which they are
based, be linear or branched, preference being given to those which
are branched in the poly-C.sub.2-C.sub.4-alkylenimine moiety.
Whereas linear poly-C.sub.2-C.sub.4-alkylenimines are composed
exclusively of repeat units of formula A, in which Q is
C.sub.2-C.sub.4-alkylene, branched
poly-C.sub.2-C.sub.4-alkylenimines have, besides the linear repeat
units, tertiary nitrogen atoms according to the structural unit
B:
##STR00001##
[0026] Preference is given to those branched, hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimines, in particular
branched, hydrophobically modified polyethylenimines, which, based
on the poly-C.sub.2-C.sub.4-alkylenimine on which they are based,
have, on average, per polyalkylenimine molecule at least one,
preferably at least 5 or at least 10, branching points according to
formula B. In particular, at least 5%, in particular at least 10%
and particularly preferably at least 15%, e.g. 5 to 40% and
specifically 15 to 35%, of the nitrogen atoms of the parent
poly-C.sub.2-C.sub.4-alkylenimine are tertiary nitrogen atoms.
[0027] Particularly in the case of relatively high degrees of
branching, i.e. if at least 10%, in particular at least 15%, e.g.
10 to 40%, in particular 15 to 35% of the nitrogen atoms of the
parent poly-C.sub.2-C.sub.4-alkylenimine are tertiary nitrogen
atoms, the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines have a structure similar to a
core-shell structure, where the poly-C.sub.2-C.sub.4-alkylenimine
moieties form the core and the hydrophobic radicals form the
shell.
[0028] The hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines can be present in uncrosslinked
or crosslinked form, and, besides the hydrophobic modification, may
be quaternized and/or modified through reaction with alkylene
oxides, di-C.sub.1-C.sub.4-alkyl carbonates,
C.sub.2-C.sub.4-alkylene carbonates or C.sub.1-C.sub.4-carboxylic
acids.
[0029] Preferably, the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines are uncrosslinked.
[0030] According to a first preferred embodiment of the invention,
the hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines
have no further modification besides the hydrophobic
modification.
[0031] According to a second preferred embodiment of the invention,
the hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines are
quaternized in addition to the hydrophobic modification. Such
quaternized hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines preferably have no further
modification. The degree of quaternization, i.e. the number of
quaternized nitrogen atoms, based on the total amount of the
nitrogen atoms of the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimine, is preferably not more than 80
mol %, in particular not more than 50 mol %, e.g. 1 to 80 mol %, in
particular 5 to 50 mol %, based on the nitrogen atoms of the
poly-C.sub.2-C.sub.4-alkylenimine.
[0032] The hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines which are used according to the
invention are in part known from the prior art cited at the
beginning or can be prepared analogously to the methods described
there. As a rule, hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines are prepared by
polymer-analogous reaction of unmodified
poly-C.sub.2-C.sub.4-alkylenimines with a hydrophobicizing agent.
Accordingly, one embodiment of the invention relates to the use of
a hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimine
obtainable by a process which comprises the reaction of a
nonmodified poly-C.sub.2-C.sub.4-alkylenimine, in particular a
nonmodified, branched poly-C.sub.2-C.sub.4-alkylenimine, and
specifically a nonmodified, branched polyethylenimine, with a
hydrophobicizing agent.
[0033] Examples of suitable hydrophobicizing agents are [0034] i)
long-chain, linear or branched carboxylic acids having 8 to 30
carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to
18 carbon atoms, in the alkyl or alkenyl radical, such as caprylic
acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic
acid, myristic acid, pentadecanoic acid, palmitic acid, margaric
acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid,
palmitoleic acid, oleic acid, linoleic acid, linolenic acid,
arachidonic acid and mixtures thereof, preferably lauric acid,
stearic acid, palmitic acid and oleic acid, or their amide-forming
derivatives, such as acid chlorides, esters or anhydrides of the
specified carboxylic acids and mixtures thereof, [0035] ii) linear
or branched alkyl halides having 8 to 30 carbon atoms, preferably
10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the
linear or branched alkyl radical, such as octyl chloride, nonyl
chloride, decyl chloride, dodecyl chloride, tetradecyl chloride,
hexadecyl chloride, octadecyl chloride and mixtures thereof, [0036]
iii) alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to
22 carbon atoms, in particular 10 to 18 carbon atoms in the linear
or branched alkyl radical, such as hexadecenyl oxide, dodecenyl
oxide and octadecenyl oxide and mixtures thereof, [0037] iv) alkyl
ketene dimers having 8 to 30 carbon atoms, preferably 10 to 22
carbon atoms, in particular 10 to 18 carbon atoms in the linear or
branched alkyl radical, such as lauryl ketene, palmityl ketene,
stearyl ketene and oleyl ketene dimers and mixtures thereof, [0038]
v) cyclic dicarboxylic acid anhydrides, in particular
alkyl-substituted succinic anhydrides having 8 to 30 carbon atoms,
preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon
atoms, in the linear or branched alkyl radical, such as
dodecenylsuccinic anhydride, tetradecylsuccinic anhydride,
hexadecenylsuccinic anhydride and mixtures thereof, [0039] vi)
alkyl isocyanates having 8 to 30 carbon atoms, preferably 10 to 22
carbon atoms, in particular 10 to 18 carbon atoms in the linear or
branched alkyl radical, such as tetradecyl isocyanate, hexadecyl
isocyanate, octadecyl isocyanate and mixtures thereof, [0040] vii)
chloroformic acid esters of linear or branched alkanols or alkenols
having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in
particular 10 to 18 carbon atoms and mixtures thereof, and [0041]
viii) linear or branched aliphatic aldehydes having 8 to 30 carbon
atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18
carbon atoms, and dialkyl ketones having in total 8 to 30 carbon
atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18
carbon atoms, in the two alkyl groups and mixtures thereof.
[0042] Preferred hydrophobicizing agents are long-chain, linear or
branched carboxylic acids having 8 to 30 carbon atoms, preferably
10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the
alkyl or alkenyl radical and amide-forming derivatives thereof, in
particular linear saturated carboxylic acids having 10 to 22 carbon
atoms, in particular 10 to 18 carbon atoms in the alkyl
radical.
[0043] Preferred hydrophobicizing agents are also alkyl epoxides
having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in
particular 10 to 18 carbon atoms.
[0044] The unmodified poly-C.sub.2-C.sub.4-alkylenimines which form
the basis of the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines used according to the invention
comprise homopolymers of ethylenimine (aziridine) and higher
homologs thereof, propylenimine (methylaziridine) and butylenimines
(1,2-dimethylaziridine, 1,1-dimethylaziridine and
1-ethylaziridine), copolymers of ethylenimine with its higher
homologs, and the graft polymers of polyamidoamines or
polyvinylamines with ethylenimine and/or its higher homologs.
[0045] Also suitable are the graft polymers of
C.sub.2-C.sub.4-alkylenimines described in WO 02/095122, such as
ethylenimine onto polyamidoamines or onto polyvinylamines. Such
graft polymers generally have a weight fraction of
C.sub.2-C.sub.4-alkylenimines of at least 10% by weight, in
particular at least 30% by weight, e.g. 10 to 90% by weight in
particular 10 to 85% by weight, based on the total weight of the
unmodified poly-C.sub.2-C.sub.4-alkylenimine.
[0046] In particular, the unmodified
poly-C.sub.2-C.sub.4-alkylenimines are branched
poly-C.sub.2-C.sub.4-alkylenimines, preferably polyethylenimines,
in particular branched polyethylenimines and specifically
homopolymers of ethylenimine, which are in particular branched.
[0047] Preferably, the unmodified poly-C.sub.2-C.sub.4-alkylenimine
used for the preparation is branched, where, with regard to the
degree of branching, that stated above for hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines applies.
[0048] Preferably, the unmodified poly-C.sub.2-C.sub.4-alkylenimine
used for the preparation has a number-average molecular weight in
the range from 1000 to 200 000 Daltons, in particular in the range
from 2000 to 100 000 Daltons.
[0049] The reaction of the unmodified
poly-C.sub.2-C.sub.4-alkylenimine with the hydrophobicizing agent
can take place analogously to known processes in the prior art. The
reaction conditions naturally depend on the type and functionality
of the hydrophobicizing agent.
[0050] The reaction can take place without a diluent or in
solution. The reaction is preferably carried out in a solvent
suitable for the reaction. Examples of suitable solvents are
hydrocarbons, in particular aromatic hydrocarbons, e.g.
alkylbenzenes such as xylenes, toluene, cumene, tert-butylbenzene
and the like.
[0051] If appropriate, the reaction can be carried out in the
presence of catalysts which improve the reactivity of the
hydrophobicizing agent toward the
poly-C.sub.2-C.sub.4-alkylenimine. The type of catalyst depends in
a manner known per se on the type and reactivity of the
hydrophobicizing agent. The catalysts are usually Lewis acids or
Bronstedt acids. Often, for example in the case of carboxylic
acids, it is possible to dispense with the use of catalysts.
[0052] In the case of the carboxylic acids and carboxylic acid
derivatives preferred according to the invention, it has proven
advantageous to remove the low molecular weight products (water,
alcohols or hydrogen chloride) which form during the reaction from
the reaction mixture. For example, in the case of the carboxylic
acids, the water formed will preferably be removed from the
reaction mixture via an entrainer. Typical entrainers are
hydrocarbons, in particular alkyl aromatics such as toluene or
xylenes. Preferably, the reaction will then be carried out in an
organic solvent suitable as entrainer.
[0053] As a rule, the hydrophobicizing agent will be used in an
amount which corresponds to the desired functionality, it also
being possible to use the hydrophobicizing agent in excess. In this
respect, that stated previously for the functionalization of the
hydrophobicized polyalkylenimine applies analogously for the molar
ratio of hydrophobicizing agent to nitrogen atoms in the unmodified
polyalkylenimine. In particular, the hydrophobicizing agent,
calculated as the parts of the hydrophobicizing agent remaining in
the product (thus the amount of hydrophobicizing agent minus any
low molecular weight products such as water), will be used in an
amount of from 0.35 to 20 parts by weight, in particular in an
amount of from 0.5 to 10 parts by weight, per part by weight of
unmodified poly-C.sub.2-C.sub.4-alkylenimine.
[0054] According to a preferred embodiment of the invention, the
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimines are
quaternized. Accordingly, the preparation of the hydrophobically
modified poly-C.sub.2-C.sub.4-alkylenimines additionally comprises
a quaternization. The quaternization can take place before or in
particular after the hydrophobicization.
[0055] For the quaternization, in particular alkylating agents such
as alkyl halides which generally have 1 to 10 carbon atoms in the
alkyl radical, or dialkyl sulfates, which generally comprise alkyl
radicals having 1 to 10 carbon atoms, are used. Examples of
suitable alkylating agents from these groups are methyl chloride,
methyl bromide, methyl iodide, ethyl chloride, ethyl bromide,
propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride,
and dimethyl sulfate and diethyl sulfate. Further suitable
alkylating agents are, for example, benzyl halides, in particular
benzyl chloride and benzyl bromide; chloroacetic acid;
fluorosulfuric acid methyl ester; diazomethane; oxonium compounds,
such as trimethyloxonium tetrafluoroborate; alkylene oxides, such
as ethylene oxide, propylene oxide and glycidol, which are used in
the presence of acids; cationic epichlorohydrins. Preferred
quaternizing agents are methyl chloride, dimethyl sulfate and
diethyl sulfate. During the quaternization, the secondary or in
particular the tertiary nitrogen atoms of the parent
poly-C.sub.2-C.sub.4-alkylenimine moiety are converted into
quaternary nitrogen atoms, ergo ammonium groups, as a result of
which the hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimine is given an overall positive
charge.
[0056] The hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines are generally water-soluble or
water-dispersible and can be used in solid and liquid detergents
and in laundry aftertreatment compositions. They are characterized
in particular by high compatibility with conventional detergent
constituents, in particular with the constituents of liquid
detergent formulations, specifically those which have a low content
of anionic surfactants.
[0057] The incorporation into the respective detergent or laundry
aftertreatment composition formulation takes place in a manner
known per se, the hydrophobically modified polyalkylenimines often
being used in liquid form, i.e. dissolved or dispersed form. The
hydrophobically modified polyalkylenimines can also be used in
powder or granule form.
[0058] The dye transfer onto fabric washed at the same time and the
associated undesired discoloration of this fabric is effectively
inhibited. Even at concentrations of from 10 to 150 ppm of the
hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimine in the
wash or rinse liquor, good to very good dye transfer-inhibiting
effects are achieved which lie significantly above the reference
substances such as polyvinylpyrrolidone.
[0059] The solid detergent formulations comprise in particular the
following components: [0060] (a) 0.05 to 20% by weight of at least
one hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimine,
[0061] (b) 0.5 to 40% by weight of at least one nonionic, anionic
and/or cationic surfactant, [0062] (c) 0.5 to 50% by weight of an
inorganic builder, [0063] (d) 0 to 10% by weight of an organic
cobuilder and [0064] (e) 0.1 to 60% by weight of other customary
ingredients, such as extenders, enzymes, perfume, complexing
agents, corrosion inhibitors, bleaches, bleach activators, bleach
catalysts, further color protection additives and dye transfer
inhibitors, graying inhibitors, soil release polyesters, fiber
protection additives, silicones, dyes, bactericides and
preservatives, dissolution improvers and/or disintegrants, water,
where the sum of components (a) to (e) is 100% by weight.
[0065] The solid detergent formulations may be present in powder,
granule, extrudate or tablet form.
[0066] The liquid detergent formulations preferably have the
following composition: [0067] (a) 0.05 to 20% by weight of at least
one hydrophobically modified poly-C.sub.2-C.sub.4-alkylenimine,
[0068] (b) 0.5 to 70% by weight of at least one nonionic, anionic
and/or cationic surfactant, [0069] (c) 0 to 20% by weight of an
inorganic builder, [0070] (d) 0 to 10% by weight of an organic
cobuilder, [0071] (e) 0.1 to 60% by weight of other customary
ingredients, such as sodium carbonate, enzymes, perfume, complexing
agents, corrosion inhibitors, bleaches, bleach activators, bleach
catalysts, further color protection additives and dye transfer
inhibitors, graying inhibitors, soil release polyesters, fiber
protection additives, silicones, dyes, bactericides and
preservatives, organic solvents, solubility promoters, hydrotropes,
thickeners and/or alkanolamines and [0072] (f) 0 to 99.35% by
weight of water, where the sum of the components (a) to (f) is 100%
by weight.
[0073] The laundry aftertreatment compositions, in particular
laundry care rinse compositions, preferably comprise [0074] (a)
0.05 to 20% by weight of at least one hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimine, [0075] (b) 0.1 to 40% by weight
of at least one cationic surfactant, [0076] (c) 0 to 30% by weight
of at least one nonionic surfactant, [0077] (d) 0.1 to 30% by
weight of other customary ingredients, such as silicones, other
lubricants, wetting agents, film-forming polymers, fragrances and
dyes, stabilizers, fiber protection additives, further color
protection additives and dye transfer inhibitors, complexing
agents, viscosity modifiers, soil release additives, solubility
promoters, hydrotropes, corrosion protection additives,
bactericides and preservatives and [0078] (e) 0 to 99.75% by weight
of water, where the sum of the components (a) to (e) is 100% by
weight.
[0079] Suitable nonionic surfactants (B) here are primarily: [0080]
alkoxylated C.sub.8-C.sub.22-alcohols, such as fatty alcohol
alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol
ethoxylates: the alkoxylation can take place with ethylene oxide,
propylene oxide and/or butylene oxide. Block copolymers or random
copolymers may be present. Per mole of alcohol, they usually
comprise 2 to 50 mol, preferably 3 to 20 mol, of at least one
alkylene oxide. A preferred alkylene oxide is ethylene oxide. The
alcohols preferably have 10 to 18 carbon atoms; [0081] alkylphenol
alkoxylates, in particular alkylphenol ethoxylates, which comprise
C.sub.6-C.sub.14-alkyl chains and 5 to 30 mol of alkylene
oxide/mol; [0082] alkyl polyglucosides which comprise
C.sub.8-C.sub.22-, preferably C.sub.10-C.sub.18-alkyl chains and as
a rule 1 to 20, preferably 1.1 to 5, glucoside units; [0083]
N-alkylglucamides, fatty acid amide alkoxylates, fatty acid
alkanolamide alkoxylates, long-chain amine oxides,
polyhydroxy(alkoxy) fatty acid derivatives, such as, for example,
polyhydroxy fatty acid amides, gemini surfactants, and block
copolymers of ethylene oxide, propylene oxide and/or butylene
oxide; and their mixtures.
[0084] Suitable anionic surfactants are, for example: [0085]
sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18,
carbon atoms, in particular C.sub.9C.sub.11-alcohol sulfates,
C.sub.12C.sub.14-alcohol sulfates, C.sub.12-C.sub.18-alcohol
sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl
sulfate, stearyl sulfate and tallow fatty alcohol sulfate; [0086]
sulfated alkoxylated C.sub.8-C.sub.22-alcohols (alkyl ether
sulfates): compounds of this type are prepared, for example, by
firstly alkoxylating a C.sub.8-C.sub.22-, preferably a
C.sub.10-C.sub.18-alcohol, e.g. a fatty alcohol, and then sulfating
the alkoxylation product. For the alkoxylation, ethylene oxide is
preferably used; [0087] linear
C.sub.8-C.sub.20-alkylbenzenesulfonates (LAS), preferably linear
C.sub.9-C.sub.13-alkylbenzenesulfonates and alkyltoluenesulfonates;
[0088] alkanesulfonates, in particular C.sub.8-C.sub.24-,
preferably C.sub.10-C.sub.18-alkanesulfonates; [0089]
olefinsulfonates; [0090] fatty acid and fatty acid ester
sulfonates; [0091] soaps, such as the Na and K salts of
C.sub.8-C.sub.24-carboxylic acids, and mixtures thereof.
[0092] The anionic surfactants are preferably added to the
detergent in the form of salts. Suitable salts here are, for
example, alkali metal salts, such as sodium, potassium and lithium
salts, and ammonium salts, such as hydroxyethylammonium,
di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.
[0093] Particularly suitable cationic surfactants which may be
mentioned are: [0094] C.sub.7-C.sub.25-alkylamines; [0095]
N,N-dimethyl-N-(hydroxy-C.sub.7-C.sub.25-alkyl)ammonium salts;
[0096] mono- and di(C.sub.7-C.sub.25-alkyl)dimethylammonium
compounds quaternized with alkylating agents; [0097] ester quats,
in particular quaternary esterified mono-, di- and trialkanolamines
which have been esterified with C.sub.8-C.sub.22-carboxylic acids;
[0098] imidazoline quats, in particular 1-alkylimidazolinium salts
of the formulae II or III
[0098] ##STR00002## [0099] in which the variables have the
following meaning: [0100] R.sup.9 is C.sub.1-C.sub.25-alkyl or
C.sub.2-C.sub.25-alkenyl; [0101] R.sup.10 is C.sub.1-C.sub.4-alkyl
or hydroxy-C.sub.1-C.sub.4-alkyl; [0102] R.sup.11 is
C.sub.1-C.sub.4-alkyl, hydroxy-C.sub.1-C.sub.4-alkyl or a radical
R.sup.1--(CO)--X--(CH.sub.2).sub.m--(X: --O-- or --NH--; m: 2 or
3), [0103] where at least one radical R.sup.9 is
C.sub.7-C.sub.22-alkyl.
[0104] Suitable amphoteric surfactants are, for example,
alkylbetaines, alkylamidobetaines, aminopropionates,
aminoglycinates and amphoteric imidazolium compounds.
[0105] The advantages according to the invention of the
hydrophobically modified polyalkylenimines come in useful
especially in those detergent formulations which comprise only a
small fraction of anionic surfactants. Preferably, the fraction of
anionic surfactants, based on the total amount of surfactant in the
detergent or laundry aftertreatment composition formulation, is not
more than 50% by weight, in particular not more than 30% by weight
and specifically not more than 10% by weight. Preferably, the
anionic surfactant constitutes not more than 8% by weight, in
particular not more than 5% by weight, based on the total weight of
the formulation.
[0106] Suitable inorganic builders are, in particular: [0107]
crystalline and amorphous alumosilicates with ion-exchanging
properties, such as in particular zeolites: various types of
zeolites are suitable, in particular the zeolites A, X, B, P, MAP
and HS in their Na form or in forms in which Na is partially
replaced by other cations such as Li, K, Ca, Mg or ammonium; [0108]
crystalline silicates, such as in particular disilicates and sheet
silicates, e.g. .delta.- and .beta.-Na.sub.2Si.sub.2O.sub.5. The
silicates can be used in the form of their alkali metal, alkaline
earth metal or ammonium salts, preference being given to the Na, Li
and Mg silicates; [0109] amorphous silicates, such as sodium
metasilicate and amorphous disilicate; [0110] carbonates and
hydrogencarbonates: these can be used in the form of their alkali
metal, alkaline earth metal or ammonium salts. Preference is given
to Na, Li and Mg carbonates and hydrogencarbonates, in particular
sodium carbonate and/or sodium hydrogencarbonate; and [0111]
polyphosphates, such as pentasodium triphosphate.
[0112] Suitable organic cobuilders are in particular: [0113] low
molecular weight carboxylic acids, such as citric acid,
hydrophobically modified citric acid, e.g. agaricic 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,
e.g. nitrilotriacetic acid, .beta.-alaninediacetic acid,
ethylenediaminetetraacetic acid, serinediacetic acid,
isoserinediacetic acid, N-(2-hydroxyethyl)iminoacetic acid,
ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic
acid or alkali metal salts thereof; [0114] oligomeric and polymeric
carboxylic acids, such as homopolymers of acrylic acid and aspartic
acid, oligomaleic acids, copolymers of maleic acid with acrylic
acid, methacrylic acid or C.sub.2-C.sub.22-olefins, e.g. isobutene
or long-chain .alpha.-olefins, vinyl C.sub.1-C.sub.8-alkyl ethers,
vinyl acetate, vinyl propionate, (meth)acrylic acid esters of
C.sub.1-C.sub.8-alcohols and styrene. Preference is given to the
homopolymers of acrylic acid and copolymers of acrylic acid with
maleic acid. The oligomeric and polymeric carboxylic acids are used
in acid form or as sodium salt; [0115] phosphonic acids, such as,
for example, 1-hydroxyethylene(1,1-diphosphonic acid),
aminotri(methylenephosphonic acid),
ethylenediaminetetra(methylene-phosphonic acid) and
diethylenetriaminepenta(methylenephosphonic acid) and alkali metal
salts thereof.
[0116] Suitable graying inhibitors are, for example,
carboxymethylcellulose and graft polymers of vinyl acetate onto
polyethylene glycol.
[0117] Suitable bleaches are, for example, adducts of hydrogen
peroxide onto inorganic salts, such as sodium perboratemonohydrate,
sodium perboratetetrahydrate and sodium carbonate perhydrate, and
percarboxylic acids, such as phthalimidopercaproic acid.
[0118] Suitable bleach activators are, for example,
N,N,N',N'-tetraacetylethylenediamine (TAED), sodium
p-nonanoyloxybenzenesulfonate and N-methylmorpholinium acetonitrile
methyl sulfate.
[0119] Enzymes preferably used in detergents are proteases,
lipases, amylases, cellulases, oxidases and peroxidases.
[0120] Suitable further dye transfer inhibitors are, for example,
homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone,
1-vinylimidazole or 4-vinylpyridine N-oxide. Homopolymers and
copolymers of 4-vinylpyridine reacted with chloroacetic acid are
also suitable as dye transfer inhibitors.
[0121] Detergent ingredients are otherwise generally known.
Detailed descriptions can be found, for example, in WO-A-99/06524
and 99/04313; in Liquid Detergents, Editor: Kuo-Yann Lai,
Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p.
272-304.
[0122] Application of hydrophobically modified
poly-C.sub.2-C.sub.4-alkylenimines according to the invention.
[0123] Selected colored fabric (EMPA 130, EMPA 132, EMPA 133 or
EMPA 134) was washed in the presence of white test fabric made of
cotton and ballast fabric made of cotton/polyester and also of
polyester using a detergent at 60.degree. C. with the addition of
the LCST polymers. After the washing cycle, the fabrics were
rinsed, spun and dried. In order to determine the dye
transfer-inhibiting effect, the coloration of the white test fabric
was determined photometrically (Photometer: Elrepho.RTM. 2000 from
Datacolor). The reflectance values measured at the test fabric were
used to determine the color intensity of the coloration in
accordance with the method described in A. Kud, Seifen, Ole, Fette,
Wachse, volume 119, pages 590-594 (1993). The color intensity for
the experiment with the respective test substance, the color
intensity for the experiment without test substance and the color
intensity of the test fabric before washing were used to ascertain
the dye transfer-inhibiting effect of the test substance according
to the following formula in %.
DTI effect [ % ] = color intensity ( without polymer ) - color
intensity ( with polymer ) color intensity ( without polymer ) -
color intensity ( before washing ) .times. 100 ##EQU00001##
[0124] The washing conditions are given in Table 1. The composition
of detergent A used is given in Table 2. The test results for the
dye transfer inhibition are listed in Table 3.
TABLE-US-00001 TABLE 1 Washing conditions Washing conditions main
wash cycle Machine Launder-o-meter from Atlas, Chicago, USA
Detergent dosing 5.0 g/l of liquor detergent A Water hardness 3
mmol/l Ca:Mg 4:1 Liquor ratio 1:16 Wash temperature 60.degree. C.
Wash time 30 min Polymer dosing 0.05 g/l liquor Colored fabric 1 g
EMPA 130 (C.I. Direct Red 83:1) 1 g EMPA 132 (C.I. Direct Black 22)
1 g EMPA 133 (C.I. Direct Blue 71) 0.5 g EMPA 134 (C.I. Direct
Orange 39) (all Swiss Federal Laboratories for Materials Testing,
St. Gallen, Switzerland) Test fabric 5 g cotton fabric 221
(bleached) Ballast fabric 5 g blended fabric 768 (65:35
polyester:cotton) + 5 g polyester fabric 854
TABLE-US-00002 TABLE 2 Composition of detergent A (liquid
detergent) Ingredients [% by wt.] C.sub.13C.sub.15-oxo alcohol x 7
EO 12 C.sub.6-alcohol x 5 EO 5 Citric acid 3 Propylene glycol 10
Ethanol 2 Diethylenetriaminepenta(methylenephosphonic acid) 1.0
Water ad 100
[0125] Adjust to pH 9 with sodium hydroxide solution.
Preparation of Hydrophobically Modified Polyethylenimine
Derivatives:
Starting Materials:
[0126] Polyethylenimine A: M.sub.W 25 000 g/mol; amine number:
20.14 mmol/g ratio of primary:secondary:tertiary nitrogen atoms:
1.0:1.1:0.7, determined by means of .sup.13C-NMR.
[0127] Polyethylenimine B: M.sub.W 5000 g/mol; amine number: 9.22
mmol/g ratio of primary:secondary:tertiary nitrogen atoms:
1.0:1.0:0.7, determined by means of .sup.13C-NMR.
Polymer 1
[0128] 350 g of polyethylenimine A were initially introduced into
toluene (300 ml). Heating to 100.degree. C. was then carried out.
After adding palmitic acid (179 g), the reaction mixture was
brought to 120.degree. C. and, while stirring, the water which
formed was distilled off via a water separator (7 h). Toluene was
then removed under reduced pressure. The product was obtained as an
orange, very viscous oil (503 g).
Polymer 2
[0129] 210 g of polyethylenimine A were initially introduced into
toluene (300 ml). Heating to 100.degree. C. was then carried out.
After adding palmitic acid (322 g), the reaction mixture was
brought to 120.degree. C. and, while stirring, the water which
formed was distilled off via a water separator (50 h). Toluene was
then removed under reduced pressure. The product was obtained as an
orange wax (501 g).
Polymer 3
[0130] 200 g of polyethylenimine A were initially introduced into
toluene (700 ml). Heating to 100.degree. C. was then carried out.
After adding palmitic acid (502 g), the reaction mixture was
brought to 120.degree. C. and, while stirring, the water which
formed was distilled off via a water separator (30 h). 400 ml of
toluene were removed from the reaction mixture and then water was
distilled off for a further 12 h. The toluene was then removed
under reduced pressure. The product was obtained as a brown wax
(670 g).
Polymer 4
[0131] 231 g of polyethylenimine A were initially introduced and
heated to 100.degree. C. The C12 epoxide (Vikolox 12; 425 g) was
added dropwise. The mixture was then stirred at 100.degree. C. for
9 h. The yellow, highly viscous oil was obtained (656 g).
Polymer 5
[0132] 199 g of polyethylenimine A were initially introduced into
toluene (400 ml). Heating to 100.degree. C. was then carried out.
After adding dodecylic acid (396 g), the reaction mixture was
brought to 120.degree. C. and, while stirring, the water which
formed was distilled off via a water separator (30 h). The toluene
was then removed under reduced pressure. A viscous reddish-brown
product was obtained (558 g).
Polymer 6
[0133] 149 g of polyethylenimine A were initially introduced into
toluene (400 ml) and heated to 100.degree. C. After adding stearic
acid (424 g), the reaction mixture was brought to 120.degree. C.
and, while stirring, the water which formed was distilled off via a
water separator (30 h). The toluene was then removed under reduced
pressure. The product was obtained as a yellow-pale brown wax (451
g).
Polymer 7
[0134] 550 g of polyethylenimine B were initially introduced into
toluene (500 ml). Heating to 100.degree. C. was then carried out.
After adding palmitic acid (258 g), the reaction mixture was
brought to 120.degree. C. and, while stirring, the water which
formed was distilled off via a water separator (3 d). The toluene
was then removed under reduced pressure. The product was obtained
as an orange wax (510 g).
Polymer 8
[0135] 434 g of polyethylenimine B were initially introduced into
toluene (400 ml). Heating to 100.degree. C. was carried out. After
adding palmitic acid (497 g), the reaction mixture was brought to
120.degree. C. and, while stirring, the water which formed was
distilled off via a water separator (3 d). The toluene was then
removed under reduced pressure. The product was obtained as an
orange wax (680 g).
Polymer 9
[0136] Polymer 8 (666 g) was heated to 75.degree. C. Dimethyl
sulfate was then metered in (71.8 g; Dosimat 2.5 ml/min). The
excess dimethyl sulfate was then removed under reduced pressure.
The product was obtained as a brown amorphous substance (407.5
g).
TABLE-US-00003 TABLE 3 Application liquid detergent A DTI effect
[%] EMPA 130 EMPA 132 EMPA 133 EMPA 134 Polymer 1 53.6 45.6 70.5
67.1 Polymer 2 84.3 64.7 89.1 83.1 Polymer 3 87.9 68.3 91.4 78.7
Polymer 4 66.1 30.8 80.3 68.0 Polymer 5 86.2 62.7 91.1 84.7 Polymer
6 86.9 72.9 90.9 84.7 Polymer 7 51.8 37.4 72.7 62.5 Polymer 8 85.3
63.5 90.1 75.0 Polymer 9 84.1 67.1 91.4 80.3 PEI 25 000 neg. effect
46.1 40.2 41.7 PEI 5000 neg. effect 54.3 25.8 53.2 PVP* 22.9 33.7
94.0 35.8 PVP = polyvinylpyrrolidone with K value 30 PEI 25 000 =
polyethylenimine A PEI 5000 = polyethylenimine B Negative effect:
polymer does not exhibit inhibition of the dye transfer, but favors
it. *Polyvinylpyrrolidone: reference substance
* * * * *