Note: Descriptions are shown in the official language in which they were submitted.
,
CA 02802277 2012-12-11
. PF 70481
1
Polymers with saccharide side groups and their use
Description
The present invention relates to polymers with saccharide side groups and
their use as
graying inhibitors in textile detergents and as antimicrobial coating, and to
textile
detergent compositions which comprise the polymers.
Besides the ingredients indispensible for the washing process, such as
surfactants and
builder materials, detergents generally comprise further washing auxiliaries.
Such
auxiliaries also include substances which impart soil release properties to
the laundry
fibers and assist the soil release of the other detergent constituents. Such
soil release
substances are often referred to as "soil-release" active ingredients or, on
account of
their ability to equip the treated surface, for example the fibers, with a
soil repellent
finish, as "soil repellents".
The term "graying" is understood as meaning the gray coloration of textiles
during
washing, which is brought about inter alia by a reattachment of the already
detached
dirt onto the fabric in finer distribution. The reattachment is probably
triggered by
electrostatic forces. The extent of the reattachment is dependent inter alia
on the type
of fabric and dirt, on the degree of soiling of the fabric, on the amount of
water in the
washing process and on the degree of mechanical agitation in the washing drum.
Soil release and/or graying-inhibiting copolymers and also their use in
detergents have
been known for a long time. On account of their chemical similarity, the known
copolymers exhibit particular affinity to polyester fibers.
Bacterial infections represent a major problem in connection with medical
instruments
and devices, implant materials, wound protection films and dressing materials.
The
bacterial infections are triggered by the adhesion of surface-active bacteria
and the
resulting biofilm development primarily on hydrophobic surfaces. The adhesion
of the
bacteria to surfaces is based on the one hand on nonspecific interactions such
as
electrostatic interactions, Van-der-Waals forces and acid-base interactions
and, on the
other hand, on specific interactions such as receptor/ligand bonds. The
surface of
pathogenic bacteria is covered with adhesins, i.e. proteins which aid adhesion
to
surfaces. The nature of the surface of the materials such as roughness and
surface
tension are decisive criteria for the colonization of surfaces. For this
reason, it is
important, through a modification of the surfaces, to minimize the number of
adhering
bacteria and thus the plaque formation and the infection of adjacent tissue.
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WO 90/10023 describes a copolymer of an N-(meth)acryloylglycosylamine and of a
(meth)acrylamide. The copolymers are said to be suitable for the binding of
antigens in
ELISA tests.
It is the object of the invention to provide polymers which exhibit high
affinity to
inorganic surfaces, such as metals or mineral materials, or hydrophilic
fibers, such as
cotton, and are suitable for modifying the surface properties of these
materials.
It is a further object of the invention to provide soil release and/or graying-
inhibiting
active ingredients which exhibit a high affinity to hydrophilic fibers, such
as in particular
cotton.
It is a further object of the invention to provide polymers which minimize the
risk of
microbial colonization of materials coated therewith.
The object is achieved according to the invention by a water-soluble or water-
dispersible copolymer comprising copolymerized units
a) of at least one ethylenically unsaturated monomer with a saccharide side
group
and
b) of at least one hydrophilic ethylenically unsaturated monomer different
from
(meth)acrylamide,
where the weight fraction of the ethylenically unsaturated monomers with a
saccharide
side group is 5 to 95% by weight, preferably 35 to 90% by weight, in
particular 50 to
85% by weight.
Hydrophilic ethylenically unsaturated monomers are understood as meaning those
which have a solubility in water of at least 50 g/I at 25 C.
The polymers according to the invention are, optionally after neutralization,
water-
soluble or water-dispersible, i.e. they are essentially linear and not
crosslinked.
The hydrophilic ethylenically unsaturated monomer is preferably selected from
b1) methyl acrylate;
b2) anionic/anionogenic monomers;
b3) cationic/cationogenic monomers;
b4) monomers with a hydroxyalkyl side group;
b5) monomers with a polyether side group;
b6) N-vinyl compounds; and
combinations thereof.
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Of these, preference is given to anionic/anionogenic monomers, monomers with a
hydroxyalkyl side group and monomers with a polyether side group and
combinations
thereof.
The weight fractions of the units of copolymerized monomers are stated in the
present
case as fractions by weight, based on the total weight of the units of all of
the
copolymerized monomers in the copolymer.
In general, copolymers according to the invention comprise
a) 5 to 95% by weight, preferably 35 to 90% by weight, in particular 50
to 85% by
weight, of units of at least one ethylenically unsaturated monomer with a
saccharide side group,
b) 95 to 5% by weight, preferably 15 to 50% by weight, of units of at least
one
hydrophilic ethylenically unsaturated monomer different from (meth)acrylamide,
and
c) 0 to 40% by weight, preferably 5 to 20% by weight, of units of at
least one
ethylenically unsaturated monomer different from a) and b).
The copolymers according to the invention generally exhibit high electrolyte
stability
and high colloid stability in hot water. They exhibit high affinity to various
surfaces, such
as cotton, glass, ceramic, metal, such as stainless steel, inorganic
materials, such as
calcium silicate or calcium carbonate.
The copolymers are based on nontoxic starting materials from renewable sources
and
are biodegradable.
Ethylenically unsaturated monomers with a saccharide side group are compounds
with
an ethylenically unsaturated group, such as e.g. a (meth)acrylic, vinyl or
allyl group, to
which a saccharide radical is covalently bonded via a linker. A saccharide
radical is
considered to be a radical with at least three hydroxyl groups, preferably at
least four
hydroxyl groups, which are bonded to adjacent (successive) carbon atoms, where
one
or more hydroxyl groups may be part of a glycosidic bond to further saccharide
units.
The saccharide radical is preferably derived from a saccharide from a natural
source or
a derivative thereof, such as a sugar alcohol, a sugar acid or a glycosamine.
The saccharide radical may be a monosaccharide radical, disaccharide radical
or
oligosaccharide radical. Oligosaccharides are understood as meaning compounds
with
3 to 20 saccharide repeat units. Preferred oligosaccharides are selected from
tri-,
tetra-, penta-, hexa-, hepta-, octa-, nona- and decasaccharides, preferably
saccharides
CA 02802277 2014-03-13
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with 3 to 9 repeat units. The linkage within the chains is preferably 1,4-
glycosidic and
optionally 1,6-glycosidic.
A monosaccharide radical is preferably a radical derived from an aldohexose,
in
particular from arabinose, ribose, xylose, mannose, galactose and in
particular glucose.
A disaccharide radical is preferably a radical derived from lactose, maltose,
isomaltose.
An oligosaccharide radical is e.g. a radical derived from maltotriose,
maltotetraose and
maltopentaose or a radical derived from a saccharide mixture obtainable by
hydrolysis
of a polysaccharide, such as hydrolysis of cellulose or starch. Mixtures of
this type are
obtainable by hydrolysis of a polysaccharide, for example enzymatic hydrolysis
of
cellulose or starch or acid-catalyzed hydrolysis of cellulose or starch.
Vegetable starch
consists of amylose and amylopectin as main constituent of the starch. Amylose
consists of predominantly unbranched chains of glucose molecules which are
linked
together 1,4-glycosidically. Amylopectin consists of branched chains in which,
as well
as the 1,4-glycosidic linkages, there are additionally 1,6-glycosidic linkages
which lead
to branches. According to the invention, hydrolysis products of amylopectin as
starting
compound for the process according to the invention are also suitable and are
encompassed by the definition of oligosaccharides.
The ethylenically unsaturated monomers with a saccharide side group
correspond to one of the formulae (la), (lb) or (lc), (Id) or (le)
OH
OH o0 R4
Z- 0
____________________ -(\NANNH
I ,
OH OH RI R- R3
(la)
CA 02802277 2012-12-11
PF 70481
OH
OH 0 R4
Z
OH OH R- R3
(lb)
OH
0 R4
______________________ 0
Z 0 ____________
I
R3
OH OH
(lc)
OH
0 R4
Z 0 0 A
X
R3
OH OH
(Id)
5
in which
Z is H or a saccharide radical;
A is C2-C10-alkylene which may optionally be interrupted by oxygen in
ether function
and/or may be substituted by one or two carboxyl, hydroxyl and/or carboxamide
groups, or is a cycloaliphatic radical;
X is 0 or NR1, in particular 0 or NH;
R1 and R2, independently of one another, are hydrogen, C1-C4-alkyl or Cl-C4-
hydroxyalkyl;
R3 is H or methyl;
R4 is H, COOH or COO-M+; and
M+ is an alkali metal ion or an ammonium ion.
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. PF 70481
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A is C2-Clo-alkylene which may optionally be interrupted by oxygen in ether
function
and/or may be substituted by one or two carboxyl, hydroxyl and/or carboxamide
groups, or is a cycloaliphatic radical. Preferably, A is C2-C6-alkylene, such
as
1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5-
pentanediyl,
1,6-hexanediyl, or a cycloaliphatic radical, such as 1,2-cyclopentanediyl, 1,3-
cyclo-
pentanediyl, 1,2-cyclohexanediyl, 1,3-cyclohexanediylor 1,4-cyclohexanediyl.
R1 and R2, independently of one another, are hydrogen, C1-C4-alkyl or C1-C4-
hydroxyalkyl, preferably hydrogen, methyl, ethyl or hydroxyethyl, in
particular hydrogen
or methyl.
Z is H or a saccharide radical. The saccharide radical may be a monosaccharide
radical, disaccharide radical or oligosaccharide radical. The saccharide
radical is
generally bonded to the molecule via a glycosidic bond.
If Z is a saccharide radical, it preferably has the general formula
¨
OH _ OH
HO ) 0 _______
¨OH OH ___. n OHOH
in which n is the number 0, 1, 2, 3, 4, 5, 6, 7 or 8.
Compounds of the formula (la) are obtainable by reacting a reaction product of
a
polyhydroxy acid lactone and an aliphatic diamine with the anhydride of a
monounsaturated carboxylic acid, cf. the international patent application
PCT/EP
2010/054208.
Polyhydroxy acid lactone is to be understood as meaning lactones of
saccharides from
a natural or synthetic source oxidized only on the anomeric carbon.
Polyhydroxy acid
lactones of this type can also be referred to as lactones of aldonic acids.
The
polyhydroxy acid lactones can be used individually or in their mixtures.
The saccharides are only selectively oxidized at the anomeric center.
Processes for
selective oxidation are generally known and are described, for example, in
J. Lonnegren, I. J. Goldstein, Methods Enzymology, 242 (1994) 116. Thus, the
oxidation can be carried out with iodine in an alkaline medium or with
copper(II) salts.
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Suitable aliphatic diamines may be linear, cyclic or branched.
Preference is given to using aliphatic C2-C8-diamines and cycloaliphatic
diamines, such
as 1,2-diaminoethane, 1,3-diaminopropane, 1,5-diaminopentane, 1,6-
diaminohexane,
N-methyl-1,3-diaminopropane, N-methyl-1,2-diaminoethane, 2,2-dimethylpropane-
1,3-
diamine, diaminocyclohexane, isophoronediamine and 4,4"-diaminodicyclohexyl-
methane.
The reaction of the diamines with the lactones is described in H. U. Geyer,
Chem. Ber.
1964, 2271. Here, the molar ratio of aliphatic diamine to the polyhydroxy acid
lactone
can vary within a wide range, such as e.g. fluctuate within the ratio 5:1 to
0.3:1, in
particular 3:1 to 0.4:1. Preferably, the aliphatic diamine is added to the
polyhydroxy
acid lactone in a molar ratio of about 2:1 to 0.5:1.
The anhydrides of a monounsaturated carboxylic acid are preferably selected
from
acrylic anhydride, methacrylic anhydride and maleic anhydride.
Compounds of the formula (lb) are obtainable by reductive amination of the
corresponding reducing saccharides and subsequent acrylation with acryloyl
chloride
as described by R. L. Whistler, J. Org. Chem. 26, 1961, 1583-1588.
Compounds of the formula (lc) are obtainable e.g. by the process described in
WO 90/10023. For this, a reducing sugar is reacted in solution with ammonium
hydrogencarbonate to give a glycosylamine, which is reacted with a reactive
derivative
of (meth)acrylic acid to give N-(meth)acryloylglycosylamine.
A particularly expedient process involves reacting a reducing sugar with a
primary
aliphatic amine or ammonia in an aqueous medium and, without intermediate
isolation,
reacting it with the anhydride of a monounsaturated carboxylic acid, cf. the
international
patent application PCT/EP 2010/054211.
Compounds of the formula (le) are obtainable e.g. by glycosidase-catalyzed
reaction of
hydroxyl-group containing ethylenically unsaturated monomers with saccharides,
as
described e.g. by I. Gill and R. Valivety in Angew. Chem. Int. Ed. 2000, 39,
No. 21, pp.
3804-3808.
In certain embodiments, the copolymers according to the invention comprise
units of
methyl acrylate, e.g. in a weight fraction of from 0 to 40% by weight,
preferably 5 to
20% by weight.
In certain embodiments, the copolymers according to the invention comprise
units of
anionogenic/anionic monomers, e.g. in a weight fraction of from 0 to 95% by
weight,
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= PF 70481
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preferably 15 to 50% by weight. "Anionic monomers" are understood as meaning
ethylenically unsaturated monomers with anionic groups. "Anionogenic monomers"
are
understood as meaning monomers with a functional group which can be converted
into
an anionic group depending on the pH in the aqueous medium and is present e.g.
at
pH 12 to more than 90% in anionic form.
The anionic monomers include the salts of the monoethylenically unsaturated
carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof, in
particular
the sodium, potassium and ammonium salts.
The anionogenic/anionic monomers include monoethylenically unsaturated mono-
and
dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can
also be
used in the form of their salts or anhydrides. Examples thereof are acrylic
acid,
methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, maleic
anhydride, itaconic
acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and
fumaric acid.
The anionogenic/anionic monomers also include the half-esters of
monoethylenically
unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon
atoms, e.g. of
maleic acid, such as monomethyl maleate. The anionogenic/anionic monomers also
include monoethylenically unsaturated sulfonic acids and phosphonic acids, for
example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate,
sulfoethyl
methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-
3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid,
styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,
vinylphosphonic acid
and allylphosphonic acid.
Preferred anionogenic/anionic monomers are ethylenically unsaturated
carboxylic
acids, in particular acrylic acid, methacrylic acid, itaconic acid and maleic
acid. Of
these, methacrylic acid is particularly preferred.
In certain embodiments, the copolymers according to the invention comprise
units of
cationic/cationogenic monomers, e.g. in a weight fraction of from 0 to 95% by
weight,
preferably 5 to 50% by weight. "Cationogenic/cationic monomers" are understood
as
meaning ethylenically unsaturated monomers with cationogenic/cationic groups.
"Cationogenic group" is understood as meaning a functional group which can be
converted to a cationic group depending on the pH in the aqueous medium. The
cationogenic and/or cationic groups are preferably nitrogen-containing groups,
such as
amino groups, and also quaternary ammonium groups. Charged cationic groups can
be produced from amine nitrogens either by protonation, e.g. with carboxylic
acids,
such as lactic acid, or mineral acids, such as phosphoric acid, sulfuric acid
and
hydrochloric acid, or by quaternization, e.g. with alkylating agents, such as
C1-C4-alkyl
halides or sulfates. Examples of such alkylating agents are ethyl chloride,
ethyl
bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl
sulfate.
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PF 70481
9
Suitable cationogenic monomers are e.g. N,N-dialkylaminoalkyl (meth)acrylates,
such
as N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl
(meth)acrylate,
N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate,
N,N-
diethylaminopropyl (meth)acrylate, N,N-dimethylaminocyclohexyl (meth)acrylate
etc.
Suitable cationogenic monomers are also N,N-
dialkylaminoalkyl(meth)acrylamides,
such as N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyli-
methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)-
propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N44-
(dimethylamino)-
butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N42-(diethylamino)-
ethylimethacrylamide, N[4-(dimethylamino)cyclohexyl]acrylamide and N44-
(dimethylamino)cyclohexyl]methacrylamide. Preference is given to N,N-
dimethylamino-
propyl acrylate, N,N-dimethylaminopropyl methacrylate, N-[3-(dimethylamino)-
propyl]acrylamide and N[3-(dimethylamino)propyllmethacrylamide.
Further cationogenic monomers are those with primary or secondary amino
groups,
e.g. esters of ethylenically unsaturated mono- and dicarboxylic acids with
amino
alcohols, amides of ethylenically unsaturated mono- and dicarboxylic acids
with
diamines and mixtures thereof.
Of suitability are e.g. the esters of ethylenically unsaturated mono- and
dicarboxylic
acids with amino alcohols, preferably C2-C12-amino alcohols. These can
preferably be
C1-C8-monoalkylated on the amine nitrogen. Suitable acid components of these
esters
are e.g. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic
acid, crotonic
acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is
given to
using acrylic acid, methacrylic acid and mixtures thereof. Preference is given
to
N-methylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate,
N-(n-propyl)aminoethyl (meth)acrylate, N-(n-butyl)aminoethyl (meth)acrylate,
tert-
butylaminoethyl (meth)acrylate. Particular preference is given to N-tert-
butylaminoethyl
methacrylate.
Also suitable are the amides of the aforementioned ethylenically unsaturated
mono-
and dicarboxylic acids with diamines which have at least one primary or
secondary
amino group. Of suitability are e.g. N-methylaminoethyl(meth)acrylamide,
N-ethylaminoethyl(meth)acrylamide, N-(n-propyl)aminoethyl(meth)acrylamide,
N-(n-butyl)aminoethyl(meth)acrylamide and N-tert-
butylaminoethyl(meth)acrylamide.
Suitable cationogenic monomers are also vinyl- and allyl-substituted nitrogen
heterocycles, such as vinylimidazole, N-vinyl-2-alkylimidazoles, e.g. N-vinyl-
2-methyl-
imidazole, and 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts
thereof.
CA 02802277 2012-12-11
PF 70481
Suitable cationic monomers are those with at least one quaternary ammonium
group.
Examples of cationic monomers which may be mentioned are N-trimethylammonium
ethylacrylamidochloride, N-trimethylammonium ethylmethacrylamidochloride,
N-trimethylammonium ethyl methacrylate chloride, N-trimethylammonium ethyl
acrylate
5 chloride, trimethylammonium ethylacrylamidomethosulfate,
trimethylammonium
ethylmethacrylamidonnethosulfate, N-ethyldimethylammonium ethylacrylamido-
ethosulfate, N-ethyldimethylammonium ethylmethacrylamidoethosulfate,
trimethylammonium propylacrylamidochloride, trimethylammonium
propylmethacrylamidochloride, trimethylammonium propylacrylamidomethosulfate,
10 trimethylammonium propylmethacrylamidomethosulfate and N-
ethyldimethylammonium
propylacrylamidoethosulfate. Preference is given to trimethylammonium
propylmethacrylamidochloride.
In certain embodiments, the copolymers according to the invention comprise
units of
monomers with a hydroxyalkyl side group, e.g. in a weight fraction of from 0
to 95% by
weight, preferably 15 to 70% by weight. Preferably, this monomer is selected
from
esters of ethylenically unsaturated mono- and dicarboxylic acids with diols or
amides of
ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
Suitable monomers are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl
methacrylate,
3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl
acrylate,
3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl
methacrylate,
6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl
acrylate
and 3-hydroxy-2-ethylhexyl methacrylate.
Suitable monomers are also 2-hydroxyethylacrylamide, 2-
hydroxyethylmethacrylamide,
2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxy-
propylmethacrylamide, 3-hydroxypropylacrylamide, 3-
hydroxypropylmethacrylamide,
3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide, 4-
hydroxybutylacrylamide,
4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexyl-
methacrylamide, 3-hydroxy-2-ethylhexylacrylamide and 3-hydroxy-2-ethylhexyl-
methacrylamide.
In certain embodiments, the copolymers according to the invention comprise
units of a
nonionic ethylenically unsaturated monomer with a polyether side group, e.g.
in a
weight fraction of from 0 to 95% by weight, preferably 15 to 70% by weight.
Suitable nonionic, ethylenically unsaturated monomers with a polyether side
group are
known per se. These are e.g.
4
CA 02802277 2012-12-11
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=
11
(a) urethane-group-containing reaction products of a monoethylenically
unsaturated
isocyanate and a polyether,
(b) esters of ethylenically unsaturated carboxylic acids and polyethers,
(c) vinyl or allyl ethers of polyethers.
Suitable polyethers are preferably polyalkoxylated Cl-C3o-alcohols, such as
fatty
alcohol alkoxylates or oxo alcohol alkoxylates. At least 2, e.g. 2 to 100,
preferably 3 to
20, mol of at least one C2-C4-alkylene oxide are used per mole of alcohol.
Different
alkylene oxide units can be arranged blockwise or be present in random
distribution.
Preferably, the alkylene oxide used is ethylene oxide and/or propylene oxide.
In preferred embodiments, the nonionic, ethylenically unsaturated monomer with
a
polyether side group has the general formula
R-0-(CH2-CHR1-0)n-CO-CR"=CH2
in which R is H or C1-C30-alkyl, preferably C1-C22-alkyl,
R' is hydrogen or methyl, preferably hydrogen,
R" is hydrogen or methyl, preferably methyl, and
n is an integer from 2 to 100, preferably 3 to 50.
The repeat units in the brackets are derived from ethylene oxide or propylene
oxide.
The meaning of R' in each repeat unit is independent of other repeat units.
Different
alkylene oxide units can be arranged blockwise or be present in random
distribution.
In certain embodiments, the copolymers according to the invention comprise
units of
N-vinyl compounds, e.g. in a weight fraction of from 0 to 40% by weight,
preferably 5 to
20% by weight. Preferably, the N-vinyl compounds are selected from N-
vinyllactams,
N-vinylamides of saturated C1-C8-monocarboxylic acids. These include e.g.
N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-viny1-5-methy1-
2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-
viny1-
6-ethy1-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-
caprolactam.
Suitable open-chain N-vinylamide compounds are, for example, N-vinylformamide,
N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-
vinyl-
N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and
N-vinylbutyramide.
Further hydrophilic ethylenically unsaturated monomers are also acrylamide and
methacrylamide, and N-C1-C8-alkyl- and N,N-di(Ci-C8-)alkylamides of
ethylenically
unsaturated monocarboxylic acids. These include N-methyl(meth)acrylamide,
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PF 70481
12
N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-
isopropyl(meth)acrylamide,
N-(n-butyl)(meth)acrylamide, N-(tert-butyl)(meth)acrylamide, N,N-dimethyl-
(meth)acrylamide, N,N-diethyl(meth)acrylamide, piperidinyl(meth)acrylamide and
morpholinyl(meth)acrylamide.
Furthermore, the copolymers according to the invention optionally comprise
units of a
further monomer which is preferably selected from esters of ethylenically
unsaturated
mono- and dicarboxylic acids with Cl-C30-alkanols, esters of vinyl alcohol or
allyl
alcohol with C1-C30-monocarboxylic acids, vinyl ethers, vinyl aromatics, vinyl
halides,
vinylidene halides, C2-C8-monoolefins, nonaromatic hydrocarbons with at least
two
conjugated double bonds and mixtures thereof.
Suitable monomers are then methyl methacrylate, methyl ethacrylate, ethyl
(meth)acrylate, ethyl ethacrylate, n-butyl (meth)acrylate, tert-butyl
(meth)acrylate, tert-
butyl ethacrylate, n-octyl (meth)acrylate, 1,1,3,3-tetramethylbutyl
(meth)acrylate,
ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylat, n-
undecyl
(meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl
(meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl
(meth)acrylate, arachinyl (meth)acrylate, behenyl (meth)acrylate, lignocerenyl
(meth)acrylate, cerotinyl (meth)acrylate, melissinyl (meth)acrylate,
palmitoleinyl
(meth)acrylate, ()ley' (meth)acrylate, linolyl (meth)acrylate, linolenyl
(meth)acrylate,
stearyl (meth)acrylate, lauryl (meth)acrylate and mixtures thereof. Preferred
monomers
are Ci-C4-alkyl (meth)acrylates. In certain embodiments, the copolymers
according to
the invention comprise units of methyl methacrylate, e.g. in a weight fraction
of from 0
to 40% by weight, preferably 5 to 20% by weight.
Suitable monomers are also vinyl acetate, vinyl propionate, vinyl butyrate and
mixtures
thereof.
Suitable monomers are also ethylene, propylene, isobutylene, butadiene,
styrene,
a-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene
chloride, vinyl
fluoride, vinylidene fluoride and mixtures thereof.
The copolymers according to the invention are prepared for example analogously
to
the processes described in general in "Ullmann's Encyclopedia of Industrial
Chemistry,
Sixth Edition, 2000, Electronic Release, keyword: Polymerisation Process". The
(co)polymerization preferably takes place as free-radical polymerization in
the form of
solution polymerization, suspension polymerization, precipitation
polymerization or
emulsion polymerization or by bulk polymerization, i.e. without solvent.
Particularly for
the preparation of the anionic copolymers it is possible either to directly
use an anionic
monomer for the polymerization or firstly to use an anionogenic monomer for
the
CA 02802277 2012-12-11
PF 70481
13
polymerization and then to neutralize the resulting copolymer with a base
after the
polymerization.
For the polymerization, a suitable polymerization initiator is used. Thermally
activatable
free-radical polymerization initiators are preferred.
Suitable thermally activatable free-radical initiators are primarily those of
the peroxy
and azo type. These include, inter alia, hydrogen peroxide, peracetic acid, t-
butyl
hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide,
2,4-
dichlorbenzoyl peroxide, 2,5-dimethy1-2,5-bis(hydroperoxy)hexane, perbenzoic
acid,
t-butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl
peroxide,
distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate,
didecyl
peroxydicarbonate, dieicosyl peroxydicarbonate, di-t-butyl perbenzoate,
azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, water-soluble
azo initiators,
e.g. 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-
methyl-
propionamidine) dihydrochloride, 2,2'-azobis(1-imino-1-pyrrolidino-2-
ethylpropane)
dihydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide];
ammonium
persulfate, potassium persulfate, sodium persulfate and sodium perphosphate.
The persulfates (peroxodisulfates), in particular sodium persulfate and water-
soluble
azo initiators, in particular 2'-azobis[2-(2-imidazolin-2-yl)propane]
dihydrochloride are
most preferred.
While carrying out the polymerization, the initiator is used in an adequate
amount to
initiate the polymerization reaction. The initiator is usually used in an
amount of from
about 0.01 to 3% by weight, based on the total weight of the monomers used.
The
amount of initiator is preferably about 0.05 to 2% by weight and in particular
0.1 to 1%
by weight, based on the total weight of the monomers used.
According to another preferred type of preparation, the copolymer is obtained
by
polymerization of a monomer mixture in the presence of a redox initiator
system. A
redox initiator system comprises at least one oxidizing agent component and at
least
one reducing agent component, where, in the reaction medium, preferably heavy
metal
ions are additionally present as catalyst, for example cerium salts, manganese
salts or
iron(11) salts.
Suitable oxidizing agent components are, for example, peroxides and/or
hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, cumene
hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide,
dicyclohexyl
percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide.
Hydrogen
peroxide and tert-butyl hydroperoxide are preferred.
CA 02802277 2012-12-11
PF 70481
14
Suitable reducing agent components are alkali metal sulfites, alkali metal
dithionites,
alkalimetal hyposulfites, sodium hydrogensulfite, Rongalit C (sodium
formaldehyde
sulfoxylate), mono- and dihydroxyacetone, sugars (e.g. glucose or dextrose),
ascorbic
acid and its salts, acetone bisulfite adduct and/or an alkali metal salt of
hydroxymethanesulfinic acid. Ascorbic acid is preferred.
Also suitable as reducing agent component or catalyst are iron(II) salts, such
as e.g.
iron(II) sulfate, tin(II) salts, such as e.g. tin(II) chloride, titanium(III)
salts, such as
titanium(III) sulfate.
The use amounts of oxidizing agent are 0.001 to 5.0% by weight, preferably
from 0.005
to 1.0% by weight and particularly preferably from 0.01 to 0.5% by weight,
based on
the total weight of the monomers used. Reducing agents are used in amounts of
from
0.001 to 2.0% by weight, preferably from 0.005 to 1.0% by weight and
particularly
preferably from 0.01 to 0.5% by weight, based on the total weight of the
monomers
used.
A particularly preferred redox initiator system is the system sodium
peroxodisulfate/ascorbic acid. A further particular redox initiator system is
the system
t-butyl hydroperoxide/hydrogen peroxide/ascorbic acid, e.g. 0.001 to 5.0% by
weight of
t-butyl hydroperoxide.
The polymerization preferably takes place as a solution polymerization.
The solution polymerization generally takes place in water or in a mixture of
at least
one organic solvent with water or in an organic solvent or solvent mixture,
preferably in
water or in a mixture of at least one organic solvent with water. Suitable
organic
solvents are those which have at least limited miscibility with water at 20 C,
and are in
particular completely miscible with water at 20 C. This is understood as
meaning a
miscibility of at least 10 vol% solvent, in particular at least 50 vol%
solvent in water at
20 C. By way of example, mention may be made of C1-C3-alcohols, e.g. methanol,
ethanol, propanol, isopropanol, ketones such as acetone, methyl ethyl ketone,
mono-,
oligo- or polyalkylene glycols or thioglycols which have C2-C6-alkylene units,
such as
ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, Cl-
C4-alkyl
ethers of polyhydric alcohols, such as ethylene glycol monomethyl or monoethyl
ethers,
diethylene glycol monomethyl or monoethyl ethers, diethylene glycol monobutyl
ether
(butyl diglycol) or triethylene glycol monomethyl or monoethyl ethers, Ci-C4-
alkyl esters
of polyhydric alcohols, y-butyrolactone or dimethyl sulfoxide or
tetrahydrofuran.
Preference is given to mixtures of the organic solvents with water, in which
case the
water content can be up to 95% by weight. Particular preference is given to
mixtures of
methanol with water.
CA 02802277 2012-12-11
= PF 70481
The solution polymerization usually takes place at 35 to 95 C. It can be
carried out
either as a batch process or else in the form of a feed process. Preference is
given to
the feed procedure in which at least some of the polymerization initiator and
optionally
some of the monomers are introduced as initial charge and heated to the
5 polymerization temperature and then the remainder of the polymerization
batch is
introduced, usually via two or more separate feeds, of which one or more
comprise the
monomers in pure, dissolved or emulsified form, continuously or stepwise to
maintain
the polymerization. Preferably, the monomer feed takes place in the form of an
aqueous monomer emulsion. In parallel to the monomer feed, further
polymerization
10 initiator can be metered in.
During the polymerization, chain transfer agents can optionally be co-used.
Typical
chain transfer agents comprise mercaptans such as, for example, 2-
mercaptoethanol,
thioglycolic acid, n-dodecyl mercaptan and tert-dodecyl mercaptan, alpha-
15 methylstyrene dimer, 1-phenylbutene-2-fluorene, terpinol and chloroform.
The copolymers according to the invention are suitable as soil release and/or
graying-
inhibiting active ingredients in textile detergents.
The copolymers according to the invention are moreover suitable as
antimicrobial
coating.
The coating according to the invention is in particular suitable for the
coating of material
surfaces in the medical-therapeutic application, for example for the coating
of metallic
implants, of wound protection films and dressing material or for the coating
of medical
instruments and devices, such as catheters. In the field of biotechnology, the
coating
according to the invention is suitable in particular for the construction of
apparatuses
(e.g. fermentors), for the coating of seals and for suppressing biofouling.
Moreover, the invention relates to a detergent or cleaner composition which
comprises
a copolymer according to the invention.
Besides the copolymer, the detergents or cleaners comprise surfactant(s),
where
anionic, nonionic, cationic and/or amphoteric surfactants can be used. From an
applications point of view, preference is given to mixtures of anionic and
nonionic
surfactants. The total surfactant content of the liquid detergents or cleaners
is
preferably 5 to 60% by weight and particularly preferably 15 to 40% by weight,
based
on the total liquid detergent or cleaner.
CA 02802277 2012-12-11
PF 70481
16
The nonionic surfactants used are preferably alkoxylated, advantageously
ethoxylated,
in particular primary alcohols having preferably 8 to 18 carbon atoms and on
average 1
to 12 mol of ethylene oxide (E0) per mole of alcohol, in which the alcohol
radical can
be linear or preferably methyl-branched in the 2 position or can comprise
linear and
methyl-branched radicals in the mixture, as are usually present in oxo alcohol
radicals.
In particular, however, preference is given to alcohol ethoxylates with linear
radicals
from alcohols of native origin having 12 to 18 carbon atoms, for example from
coconut
alcohol, palm alcohol, tallow fatty alcohol or leyl alcohol, and on average 2
to 8 EO
per mole of alcohol. Preferred ethoxylated alcohols include, for example, C12-
C14-
alcohols with 3 EO, 4 EO or 7 EO, C5-C11-alcohol with 7 EO, C13-C15-alcohols
with
3 E0, 5 EO, 7 EO or 8 EO, C12-C15-alcohols with 3 EO, 5 EO or 7 EO and
mixtures of
these, such as mixtures of C12-C14-alcohol having 3 EO and C12-C15-alcohol
having
7 EQ. The stated degrees of ethoxylation are statistical average values which
may be
an integer or a fraction for a specific product. Preferred alcohol ethoxylates
have a
narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to
these
nonionic surfactants, it is also possible to use fatty alcohols with more than
12 EQ.
Examples thereof are tallow fatty alcohol having 14 E0, 25 EO, 30 EO or 40 EQ.
It is
also possible to use nonionic surfactants which comprise EO and PO groups
together
in the molecule. In this connection, it is possible to use block copolymers
with EO-P0
block units or PO-E0 block units, but also EO-PO-E0 copolymers or PO-E0-P0
copolymers. It is of course also possible to use mixed alkoxylated nonionic
surfactants
in which EO and PO units are not blockwise, but in random distribution. Such
products
are obtainable through the simultaneous action of ethylene oxide and propylene
oxide
on fatty alcohols.
Moreover, further nonionic surfactants that can be used are also alkyl
glycosides of the
general formula (I)
R10(G). (1)
in which R1 is a primary straight-chain or methyl-branched, in particular 2-
methyl-
branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms,
and G is a
glycoside unit with 5 or 6 carbon atoms, preferably glucose. The degree of
oligomerization x, which indicates the distribution of monoglycosides and
oligoglycosides, is any desired number between 1 and 10; preferably, x is 1.2
to 1.4.
A further class of preferably used nonionic surfactants which are used either
as the
sole nonionic surfactant or in combination with other nonionic surfactants are
alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid
alkyl
esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in
particular fatty acid
methyl esters, as are described, for example, in the Japanese patent
application
=
CA 02802277 2012-12-11
PF 70481
17
JP 58/217598 or which are preferably prepared by the method described in the
international patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-
dimethyl-
amine oxide and N-tallow-alkyl-N,N-dihydroxyethylamine oxide, and of the fatty
acid
alkanolamide type may also be suitable. The amount of these nonionic
surfactants is
preferably not more than that of the ethoxylated fatty alcohols, in particular
not more
than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula
(2),
0
R2/-\ N[Z] (2)
I 3
in which R2C(=0) is an aliphatic acyl radical having 6 to 22 carbon atoms, R3
is
hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z]
is a linear
or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10
hydroxyl
groups. The polyhydroxy fatty acid amides are known substances which can
usually be
obtained by reductive amination of a reducing sugar with ammonia, an
alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a
fatty acid chloride.
The group of polyhydroxy fatty acid amides also includes compounds of the
formula (3)
R-0¨R6
4
RN (3)
[Z]
0
in which R4 is a linear or branched alkyl or alkenyl radical having 7 to 12
carbon atoms,
R5 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms
or an
arylene radical having 6 to 8 carbon atoms and R6 is a linear, branched or
cyclic alkyl
radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms,
where
Ci-C4-alkyl or phenyl radicals are preferred, and [Z]1 is a linear
polyhydroxyalkyl radical
whose alkyl chain is substituted by at least two hydroxyl groups, or
alkoxylated,
preferably ethoxylated or propoxylated derivatives of this radical. [Z]1 is
preferably
obtained by reductive amination of a sugar, for example glucose, fructose,
maltose,
lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted
compounds can then be converted to the desired polyhydroxy fatty acid amines,
for
CA 02802277 2012-12-11
PF 70481
18
example in accordance with WO-A-95/07331, through reaction with fatty acid
methyl
esters in the presence of an alkoxide as catalyst.
The content of nonionic surfactants in the liquid detergents or cleaners is
preferably 1
to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by
weight,
in each case based on the total composition.
The anionic surfactants used are, for example, those of the sulfonate and
sulfate type.
Suitable surfactants of the sulfonate type are preferably C9-C13-
alkylbenzenesulfonates,
olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and
also
disulfonates, as are obtained, for example, from C12-C15-monoolefins with
terminal or
internal double bond by sulfonation with gaseous sulfur trioxide and
subsequent
alkaline or acidic hydrolysis of the sulfonation products. Also suitable are
alkane-
sulfonates which are obtained from C12-C15-alkanes, for example by
sulfochlorination or
sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the
esters of
a-sulfo fatty acids (ester sulfonates), for example the a-sulfonated methyl
esters of the
hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters.
Fatty acid
glycerol esters are to be understood as meaning the mono-, di- and triesters,
and
mixtures thereof, as are obtained in the preparation by esterification of a
monoglycerol
with 1 to 3 mol of fatty acid or during the transesterification of
triglycerides with 0.3 to
2 mol of glycerol. Preferred sulfated fatty acid glycerol esters here are the
sulfation
products of saturated fatty acids having 6 to 22 carbon atoms, for example of
caproic
acid, caprylic acid, capric acid, nnyristic acid, lauric acid, palmitic acid,
stearic acid or
behenic acid.
The alk(en)yl sulfates are preferably the alkali metal and in particular the
sodium salts
of the sulfuric acid half-esters of C12-C15-fatty alcohols, for example of
coconut fatty
alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol
or stearyl
alcohol or of the C10-C20-oxo alcohols and those half-esters of secondary
alcohols of
these chain lengths. Furthermore, preference is given to alk(en)yl sulfates of
the
specified chain length which comprise a synthetic, petrochemical-based
straight-chain
alkyl radical which have an analogous degradation behavior to the equivalent
compounds based on fatty chemical raw materials. From a washing point of view,
the
C12-C16-alkyl sulfates and C12-C15-alkyl sulfates and also C14-C15-alkyl
sulfates are
preferred. 2,3-Alkyl sulfates, which are prepared, for example, in accordance
with the
US patent specifications 3,234,258 or 5,075,041 and can be obtained as
commercial
products from the Shell Oil Company under the name DAN , are also suitable
anionic
surfactants.
CA 02802277 2012-12-11
= PF 70481
19
The sulfuric acid monoesters of the straight-chain or branched C7-C21-alcohols
ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-
C11-
alcohols with on average 3.5 mol of ethylene oxide (EO) or C12-C18-fatty
alcohols with 1
to 4 ED, are also suitable. On account of their high foaming behavior, they
are used in
cleaners only in relatively small amounts, for example in amounts from 1 to 5%
by
weight.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic
acid, which
are also referred to as sulfosuccinates or as sulfosuccinic acid esters and
which
constitute monoesters and/or diesters of sulfosuccinic acid with alcohols,
preferably
fatty alcohols and in particular ethoxylated fatty alcohols. Preferred
sulfosuccinates
comprise C8-C18-fatty alcohol radicals or mixtures thereof. Particularly
preferred
sulfosuccinates comprise a fatty alcohol radical derived from ethoxylated
fatty alcohols.
In this connection, particular preference is in turn given to sulfosuccinates
whose fatty
alcohol radicals are derived from ethoxylated fatty alcohols with a narrow
homolog
distribution. It is likewise also possible to use alk(en)ylsuccinic acid
having preferably 8
to 18 carbon atoms in the alk(en)yl chain or salts thereof.
Particularly preferred anionic surfactants are soaps. Saturated and
unsaturated fatty
acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid,
stearic acid,
(hydrogenated) erucic acid and behenic acid, and also soap mixtures derived in
particular from natural fatty acids, for example coconut, palm kernel, olive
oil or tallow
fatty acids, are suitable.
The anionic surfactants including the soaps can be present in the form of
their sodium,
potassium or ammonium salts, and also as soluble salts of organic bases, such
as
mono-, di- or triethanolamine. Preferably, the anionic surfactants are present
in the
form of their sodium or potassium salts, in particular in the form of the
sodium salts.
The content of anionic surfactants in preferred detergents or cleaners is 2 to
30% by
weight, preferably 2 to 40% by weight and in particular 5 to 22% by weight, in
each
case based on the total composition. It is particularly preferred that the
amount of fatty
acid soap is at least 2% by weight and particularly preferably at least 4% by
weight and
particularly preferably at least 6% by weight.
The viscosity of liquid detergents or cleaners can be measured by means of
customary
standard methods (for example Brookfield viscometer LVT-Il at 20 rpm and 20 C,
spindle 3) and is preferably in the range from 100 to 5000 mPas. Preferred
compositions have viscosities of from 300 to 4000 mPas, with values between
1000
and 3000 mPas being particularly preferred.
CA 02802277 2012-12-11
PF 70481
In addition to the copolymer according to the invention and the surfactant(s),
the
detergents or cleaners can comprise further ingredients which further improve
the
application and/or esthetic properties of the liquid detergent or cleaner. As
a rule,
preferred compositions comprise one or more substances from the group of
builders,
5 bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents,
pH
extenders, fragrances, perfume carriers, fluorescent agents, dyes,
hydrotropes, foam
inhibitors, silicone oils, antiredeposition agents, optical brighteners,
graying inhibitors,
antishrink agents, anticrease agents, color transfer inhibitors, antimicrobial
active
ingredients, germicides, fungicides, antioxidants, corrosion inhibitors,
antistatics,
10 ironing aids, phobicization and impregnation agents, swelling and
nonslip agents, and
also UV absorbers.
Builders which may be present in the detergents or cleaners are, in
particular, silicates,
aluminum silicates (in particular zeolites), carbonates, salts of organic di-
and
15 polycarboxylic acids, and mixtures of these substances.
Suitable low molecular weight polycarboxylates as organic builders are, for
example:
C4-C20-di-, -tri- and -tetracarboxylic acids, such as, for example, succinic
acid,
20 propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid
and alkyl- and alkylenesuccinic acids with C2-C16-alkyl or -alkylene radicals;
C4-C20-hydroxycarboxylic acids, such as, for example, malic acid, tartaric
acid, gluconic
acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, -di- and
-tricarboxylic
acid;
aminopolycarboxylates, such as, for example, nitrilotriacetic acid,
methylglycinediacetic
acid, alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic
acid;
salts of phosphonic acids, such as, for example, hydroxyethanediphosphonic
acid,
ethylenediamine tetra(methylenephosphonate) and diethylenetriamine
penta(methylenephosphate).
Suitable oligomeric or polymeric polycarboxylates as organic builders are, for
example:
oligomaleic acids, as are described, for example, in EP-A 0 451 508 and
EP-A 0 396 303;
co- and terpolymers of unsaturated C4-C8-dicarboxylic acids, where
monoethylenically
unsaturated monomers
from group (i) in amounts of up to 95% by weight
=
CA 02802277 2012-12-11
PF 70481
21
from group (ii) in amounts of up to 60% by weight
from group (iii) in amounts of up to 20% by weight
may be present in copolymerized form as comonomers.
Suitable unsaturated C4-C8-dicarboxylic acids here are, for example, maleic
acid,
fumaric acid, itaconic acid and citraconic acid (methylmaleic acid).
Preference is given
to maleic acid.
Group (i) comprises monoethylenically unsaturated C3-Ca-monocarboxylic acids,
such
as, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic
acid. From
group (i), preference is given to using acrylic acid and methacrylic acid.
Group (ii) comprises monoethylenically unsaturated C2-C22-olefins, vinyl alkyl
ethers
with C1-C8-alkyl groups, styrene, vinyl esters of C1-C8-carboxylic acid,
(meth)acrylamide
and vinylpyrrolidone. From group (ii), preference is given to using C2-C6-
olefins, vinyl
alkyl ethers with C1-C4-alkyl groups, vinyl acetate and vinyl propionate.
Group (iii) comprises (meth)acrylic esters of C1-C8-alcohols,
(meth)acrylonitrile,
(meth)acrylamides, (meth)acrylamides of Cl-Cramines, N-vinylformamide and
vinylimidazole.
If the polymers of group (ii) comprise vinyl esters in copolymerized form,
these may
also be present in partially or completely hydrolyzed form to give vinyl
alcohol structural
units. Suitable co- and terpolymers are known, for example, from US 3,887,806
and
SE-A 43 13909.
Copolymers of dicarboxylic acids suitable as organic builders are preferably:
copolymers of maleic acid and acrylic acid in the weight ratio 10:90 to 95:5,
particularly
preferably those in the weight ratio 30:70 to 90:10 with molar masses of from
10 000 to
150 000;
terpolymers of maleic acid, acrylic acid and a vinyl ester of a C1-C3-
carboxylic acid in
the weight ratio 10(maleic acid):90(acrylic acid + vinyl ester) to 95(maleic
acid):10(acrylic acid + vinyl ester), where the weight ratio of acrylic acid
to vinyl ester
can vary in the range from 20:80 to 80:20, and particularly preferably
terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate
in the
weight ratio 20(maleic acid):80(acrylic acid + vinyl ester) to 90(maleic
acid):10(acrylic
acid + vinyl ester), where the weight ratio of acrylic acid to the vinyl ester
can vary in
the range from 30:70 to 70:30;
CA 02802277 2012-12-11
PF 70481
22
copolymers of maleic acid with C2-C8-olefins in the molar ratio 40:60 to
80:20, where
copolymers of maleic acid with ethylene, propylene or isobutane in the molar
ratio
50:50 are particularly preferred.
Graft polymers of unsaturated carboxylic acids on low molecular weight
carbohydrates
or hydrogenated carbohydrates, cf. US 5,227,446, DE-A 44 15 623, DE-A 43 13
909,
are likewise suitable as organic builders.
Suitable unsaturated carboxylic acids here are, for example, maleic acid,
fumaric acid,
itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid
and vinylacetic
acid, and also mixtures of acrylic acid and maleic acid which are grafted on
in amounts
of from 40 to 95% by weight, based on the component to be grafted.
For the modification, additionally up to 30% by weight, based on the component
to be
grafted, of further monoethylenically unsaturated monomers may be present in
copolymerized form. Suitable modifying monomers are the abovementioned
monomers
in groups (ii) and (iii).
Suitable graft bases are degraded polysaccharides, such as, for example,
acidically or
enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated
or
reductively aminated) degraded polysaccharides, such as, for example,
mannitol,
sorbitol, aminosorbitol and glucamine, and also polyalkylene glycols with
molar masses
up to Mw = 5000, such as, for example, polyethylene glycols, ethylene
oxide/propylene
oxide or ethylene oxide/butylene oxide block copolymers, random ethylene
oxide/propylene oxide or ethylene oxide/butylene oxide copolymers, alkoxylated
mono-
or polybasic Cl-C22-alcohols, cf. US 4,746,456.
From this group, preference is given to using grafted degraded or degraded
reduced
starches and grafted polyethylene oxides, where 20 to 80% by weight of
monomers,
based on the graft component, are used in the graft polymerization. For the
grafting,
preference is given to using a mixture of maleic acid and acrylic acid in the
weight ratio
of from 90:10 to 10:90.
Polyglyoxylic acids as organic builders are described, for example, in EP-B 0
001 004,
US 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the
polyglyoxylic acids can have different structures.
Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic
builders
are known, for example, from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and
EP-A 0 581 452.
CA 02802277 2012-12-11
PF 70481
23
Preferably, the organic builders used are also polyaspartic acid or
cocondensates of
aspartic acid with further amino acids, C4-C25-mono- or -dicarboxylic acids
and/or
C4-C25-mono- or -diamines. Particular preference is given to using
polyaspartic acids
modified with C6-C22-mono- or -dicarboxylic acids or with C6-C22-mono- or -
diamines
and prepared in phosphorus-containing acids.
Condensation products of citric acid with hydroxycarboxylic acids or
polyhydroxy
compounds as organic builders are known, for example, from WO-A 93/22362 and
WO-A 92/16493. Carboxyl-group-comprising condensates of this type usually have
molar masses up to 10 000, preferably up to 5000.
Among the compounds which produce H202 in water and can serve as bleaches,
sodium perborate tetrahydrate and sodium perborate monohydrate have particular
importance. Further bleaches that can be used are, for example, sodium
percarbonate,
peroxypyrophosphates, citrate perhydrates, and peracidic salts or peracids
that
produce H202, such as perbenzoates, peroxophthalates, diperazelaic acid,
phthaloiminoperacid or diperdodecanedioic acid.
In order to achieve an improved bleaching effect during washing at
temperatures of
60 C and below, bleach activators can be incorporated into the detergents or
cleaners.
Bleach activators which can be used are compounds which, under perhydrolysis
conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10
carbon
atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted
perbenzoic acid.
Substances which carry 0- and/or N-acyl groups of the specified number of
carbon
atoms and/or optionally substituted benzoyl groups are suitable. Preference is
given to
polyacylated alkylenediamines, in particular tetraacetylethylenediamine
(TAED),
acylated triazine derivatives, in particular 1,5-diacety1-2,4-dioxohexahydro-
1,3,5-triazine
(DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-
acylimides,
in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in
particular
n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic
acid
anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in
particular
triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to the conventional bleach activators, or instead of them, it is
also possible
to incorporate so-called bleach catalysts into the detergents or cleaners.
These
substances are bleach-boosting transition metal salts or transition metal
complexes,
such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salene complexes or -carbonyl
complexes. It is also possible to use Mn, Fe, Co, Ru, Mo, Ti, V and Cu
complexes with
nitrogen-containing tripod ligands, and also Co-, Fe-, Cu- and Ru-amine
complexes as
bleach catalysts.
CA 02802277 2012-12-11
PF 70481
24
Suitable enzymes are in particular those from the classes of the hydrolases,
such as
the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases
and other
glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases
contribute
during washing to the removal of stains such as protein-, fat- or starch-
containing
stains and graying. Cellulases and other glycosyl hydrolases can moreover
contribute
to the color retention and to increasing the softness of the textile by
removing pilling
and microfibrils. Oxyreductases can also be used for the bleaching or for the
inhibition
of color transfer. Enzymatic active ingredients obtained from bacterial
strains or fungi
such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and
Humicola
insolens are particularly well suited. Preference is given to using proteases
of the
subtilisin type and in particular proteases which are obtained from Bacillus
lentus.
Here, enzyme mixtures, for example of protease and amylase or protease and
lipase or
lipolytic enzymes or protease and cellulase or of cellulase and lipase or
lipolytic
enzymes or of protease, amylase and lipase or lipolytic enzymes or protease,
lipase or
lipolytic enzymes and cellulase, but in particular protease and/or lipase-
containing
mixtures or mixtures with lipolytic enzymes are of particular interest.
Examples of such
lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also
proven
suitable in some cases. Suitable amylases include, in particular, a-amylases,
isoamylases, pullulanases and pectinases. The cellulases used are preferably
cellobiohydrolases, endoglucanases and p-glucosidases, which are also called
cellobiases, or mixtures of these. Since different types of cellulase differ
in their
CMCase and avicelase activities, the desired activities can be established
through
targeted mixtures of the cellulases.
The enzymes can be adsorbed to carriers in order to protect them against
premature
decomposition. The fraction of the enzyme, enzyme mixtures or enzyme granules
can
be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2.5% by
weight.
A broad number of highly diverse salts can be used as electrolytes from the
group of
inorganic salts. Preferred cations are the alkali and alkaline earth metals,
preferred
anions are the halides and sulfates. From the point of view of production, the
use of
NaCI or MgCl2 in the compositions is preferred. The fraction of electrolytes
in the
compositions is usually 0.5 to 5% by weight.
Nonaqueous solvents which can be used in the liquid detergents or cleaners
originate,
for example, from the group of mono- or polyhydric alcohols, alkanolamines or
glycol
ethers, provided they are miscible with water in the stated concentration
range.
Preferably, the solvents are selected from ethanol, n- or isopropanol,
butanols, glycol,
propane- or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene
glycol,
ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol
propyl ether,
ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene
glycol
ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene
glycol
CA 02802277 2012-12-11
PF 70481
monomethyl or -ethyl ether, diisopropylene glycol monomethyl or -ethyl ether,
methoxy-, ethoxy- or butoxytriglycol, isobutoxyethoxy-2-propanol, 3-methy1-3-
methoxybutanol, propylene glycol t-butyl ether, and mixtures of these
solvents.
Nonaqueous solvents can be used in the liquid detergents or cleaners in
amounts
5 between 0.5 and 15% by weight, but preferably below 12% by weight and in
particular
below 9% by weight.
In order to bring the pH of the detergents or cleaners into the desired range,
the use of
pH extenders may be appropriate. All known acids or alkalis can be used here,
10 provided their use is not precluded for applications-related or
ecological reasons or for
reasons of consumer protection. Usually, the amount of these extenders does
not
exceed 7% by weight of the total formulation.
In order to improve the esthetic impression of the detergents or cleaners,
they can be
15 colored with suitable dyes. Preferred dyes, the selection of which
presents no
difficulties at all to the person skilled in the art, have a high storage
stability and
insensitivity toward the other ingredients of the compositions and to light,
and also no
marked substantivity toward textile fibers, in order not to stain these.
20 Suitable foam inhibitors which can be used in the detergents or cleaners
are, for
example, soaps, paraffins or silicone oils, which can optionally be applied to
carrier
materials.
Suitable antiredeposition agents, which are also referred to as "soil
repellents", are, for
25 example, nonionic cellulose ethers, such as methylcellulose and
methylhydroxypropyl-
cellulose with a fraction of methoxy groups of from 15 to 30% by weight and of
hydroxypropyl groups of from 1 to 15% by weight, in each case based on the
nonionic
cellulose ethers. Suitable soil release polymers are, for example, polyesters
of
polyethylene oxides with ethylene glycol and/or propylene glycol and aromatic
dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; polyesters of
polyethylene oxides that are terminally kept at one end with di- and/or
polyhydric
alcohols and dicarboxylic acid, in particular polymers of ethylene
terephthalates and/or
polyethylene glycol terephthalates or anionically and/or nonionically modified
derivatives of these. Of these, particular preference is given to the
sulfonated
derivatives of phthalic acid polymers and terephthalic acid polymers.
Polyesters of this
type are known, for example, from US 3,557,039, GB-A 11 54 730, EP-A 0 185
427,
EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and US-A 5,142,020. Further
suitable soil release polymers are amphiphilic graft polymers or copolymers of
vinyl
and/or acrylic esters on polyalkylene oxides (cf. US 4,746,456, US 4,846,995,
DE-
A 37 11 299, US 4,904,408, US 4,846,994 and US 4,849,126) or modified
celluloses,
such as, for example, methylcellulose, hydroxypropylcellulose or carboxymethyl-
cellulose.
CA 02802277 2012-12-11
PF 70481
26
Optical brighteners (so-called whiteners) can be added to the detergents or
cleaners in
order to eliminate graying and yellowing of the treated textile fabrics. These
substances
attach to the fibers and bring about a brightening and quasi bleaching effect
by
converting invisible ultraviolet radiation into visible longer-wave light,
where the
ultraviolet light absorbed from the sunlight is emitted as pale bluish
fluorescence and
produces pure white with the yellow shade of grayed and/or yellowed laundry.
Suitable
compounds originate, for example, from the substance classes of the 4,4'-
diamino-2,2'-
stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene,
methylumbelliferones,
coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides,
benzoxazole,
benzisoxazole and benzimidazole systems, and the pyrene derivatives
substituted by
heterocycles. The optical brighteners are usually used in amounts between 0.03
and
0.3% by weight, based on the finished composition.
Graying inhibitors have the task of keeping the dirt detached from the fibers
suspended
in the liquor and thus preventing reattachment of the dirt. Of suitability for
this purpose
are water-soluble colloids mostly of an organic nature, for example glue,
gelatin, salts
of ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric
acid esters of
cellulose or of starch. Water-soluble polyamides comprising acidic groups are
also
suitable for this purpose. Furthermore, soluble starch preparations and starch
products
other than those mentioned above can be used, for example degraded starch,
aldehyde starches, etc. It is also possible to use polyvinylpyrrolidone.
However,
preference is given to using cellulose ethers, such as carboxymethylcellulose
(Na salt),
methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxy-
ethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and
mixtures thereof in amounts of from 0.1 to 5% by weight, based on the
compositions.
Since textile fabrics, in particular made of rayon, viscose rayon, cotton and
mixtures
thereof can have a tendency to crease because the individual fibers are
sensitive to
bending, folding, pressing and squeezing at right angles to the fiber
direction, the
compositions can comprise synthetic anticrease agents. These include, for
example,
synthetic products based on fatty acids, fatty acid esters, fatty acid amides,
fatty alkylol
esters, fatty alkylolamides or fatty alcohols, which are mostly reacted with
ethylene
oxide, or products based on lecithin or modified phosphoric acid esters.
To control microorganisms, the detergents or cleaners can comprise
antimicrobial
active ingredients. A distinction is made here, depending on the antimicrobial
spectrum
and action mechanism, between bacteriostats and bactericides, fungistats and
fungicides etc. Important substances from these groups are, for example,
benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol
mercuriacetate.
CA 02802277 2012-12-11
PF 70481
27
In order to prevent undesired changes in the detergents or cleaners and/or the
treated
textile fabrics caused by the effect of oxygen and other oxidative processes,
the
compositions can comprise antioxidants. This class of compound includes, for
example, substituted phenols, hydroquinones, pyrocatechins and aromatic
amines, and
also organic sulfides, polysulfides, dithiocarbamates, phosphites and
phosphonates.
Increased wear comfort can result from the additional use of antistats which
are
additionally added to the compositions. Antistats increase the surface
conductivity and
thus permit an improved discharging of charges formed. External antistats are
generally substances with at least one hydrophilic molecule ligand and produce
a more
or less hygroscopic film on the surfaces. These mostly interface-active
antistats can be
divided into nitrogen-containing antistats (amines, amides, quaternary
ammonium
compounds), phosphorus-containing antistats (phosphoric acid esters) and
sulfur-
containing antistats (alkylsulfonates, alkyl sulfates). External antistats are
described, for
example, in the patent applications FR 1,156,513, GB 873 214 and GB 839 407.
The
lauryl(or stearyl)dimethylbenzylammonium chlorides disclosed here are suitable
as
antistats for textile fabrics and as additive for detergents where a hand-
modifying effect
is additionally achieved.
To improve the water absorption capacity, the rewettability of the treated
textile fabrics
and to facilitate ironing of the treated textile fabrics, silicone
derivatives, for example,
can be used in the detergents or cleaners. These additionally improve the wash-
out
behavior of the compositions through their foam-inhibiting properties.
Preferred silicone
derivatives are, for example, polydialkyl- or alkylarylsiloxanes in which the
alkyl groups
have 1 to 5 carbon atoms and are partially or completely fluorinated.
Preferred
silicones are polydimethylsiloxanes which can, optionally, be derivatized and
then are
aminofunctional or quaternized or have Si-OH, Si-H and/or Si-CI bonds. The
viscosities
of the preferred silicones at 25 C are in the range between 100 and 100 000
mPas, it
being possible to use the silicones in amounts between 0.2 and 5% by weight,
based
on the total composition.
Finally, the detergents or cleaners can also comprise UV absorbers which
attach to the
treated textile fabrics and improve the photostability of the fibers.
Compounds which
have these desired properties are, for example, the compounds and derivatives
of
benzophenone with substituents in the 2 and/or 4 position that are effective
as a result
of nonradiative deactivation. Furthermore, substituted benzotriazoles,
acrylates phenyl-
substituted in the 3 position (cinnamic acid derivatives), optionally with
cyano groups in
the 2 position, salicylates, organic Ni complexes, and natural substances such
as
umbelliferone and the endogenous urocanic acid are also suitable.
In order to avoid the decomposition of certain detergent ingredients catalyzed
by heavy
metals, it is possible to use substances which complex heavy metals. Suitable
heavy
CA 02802277 2012-12-11
PF 70481
28
metal cornplexing agents are, for example, the alkali salts of
ethylenediaminetetraacetic acid (EDTA), of nitrilotriacetic acid (NTA) or
methylglycinediacetic acid (MGDA), and also alkali metal salts of anionic
polyelectrolytes such as polymaleates and polysulfonates.
A preferred class of complexing agents is the phosphonates, which are present
in
preferred detergents or cleaners in amounts of from 0.01 to 2.5% by weight,
preferably
0.02 to 2% by weight and in particular from 0.03 to 1.5% by weight. These
preferred
compounds include, in particular, organophosphonates, such as, for example,
1-hydroxyethane-1, 1-diphosphonic acid (H EDP), aminotri(methylenephosphonic
acid)
(ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP or DETPMP),
and also 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostly
used
in the form of their ammonium or alkali metal salts.
Besides these constituents, a detergent or cleaner can comprise dispersed
particles,
the diameter of which along their largest spatial expansion is 0.01 to 10 000
pm.
Particles may be microcapsules as well as granules, compounds and scented
beads,
with microcapsules being preferred.
The term "microcapsule" is understood as meaning aggregates which comprise at
least
one solid or liquid core which is surrounded by at least one continuous
sheath, in
particular a sheath made of polymer(s). Usually, these are finely dispersed
liquid or
solid phases surrounded by film-forming polymers, during the production of
which the
polymers, following emulsification and coacervation or interfacial
polymerization,
precipitate on to the material to be enveloped. The microscopically small
capsules can
be dried like powders. Besides single-core microcapsules, multicore aggregates
are
also known, also called microspheres, which comprise two or more cores
distributed in
the continuous coating material. Single-core or multicore microcapsules can
additionally be surrounded by an additional second, third etc. sheath.
Preference is
given to single-core microcapsules with a continuous sheath. The sheath can
consist of
natural, semisynthetic or synthetic materials. Natural sheath materials are,
for example,
gum arabic, agar agar, agarose, maltodextrins, alginic acid and its salts,
e.g. sodium
alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen,
chitosan,
lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or
dextran, sucrose
and waxes. Semisynthetic coating materials are, inter alia, chemically
modified
celluloses, in particular cellulose esters and ethers, e.g. cellulose acetate,
ethyl-
cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and
carboxymethylcellulose, and also starch derivatives, in particular starch
ethers and
esters. Synthetic coating materials are, for example, polymers, such as
polyacrylates,
polyamides, polyvinyl alcohol or polyvinylpyrrolidone. In the interior of the
microcapsules, sensitive, chemically or physically incompatible as well as
volatile
CA 02802277 2012-12-11
PF 70481
29
components (= active ingredients) of the aqueous liquid detergent or cleaner
can be
enclosed in a storage-stable and transport-stable manner. For example, optical
brighteners, surfactants, complexing agents, bleaches, bleach activators,
dyes,
fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial
active
ingredients, graying inhibitors, antiredeposition agents, pH extenders,
electrolytes,
foam inhibitors and UV absorbers may be present in the microcapsules.
The microcapsules can also comprise cationic surfactants, vitamins, proteins,
preservatives, detergency boosters or pearlizing agents. The fillings of the
microcapsules can be solids or liquids in the form of solutions or emulsions
or
suspensions.
The microcapsules can have any desired form within the scope of manufacture,
but are
preferably approximately spherical. Their diameter along their largest spatial
expansion
can be between 0.01 pm (not visually recognizable as capsules) and 10 000 pm
depending on the components present in their interior and the application.
Preference
is given to visible microcapsules with a diameter in the range from 100 pm to
7000 pm,
in particular from 400 pm to 5000 pm. The microcapsules are accessible by
known
methods, with coacervation and interfacial polymerization being attributed the
greatest
importance. Microcapsules which can be used are all of the surfactant-stable
microcapsules supplied on the market, for example the commercial products (the
coating material is given in each in brackets) Hal!crest Microcapsules
(gelatin, gum
arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapseln
(alginic acid,
agar agar), Induchem Unispheres (lactose, microcrystalline cellulose,
hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline
cellulose,
hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid
esters,
phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres
(phospholipids).
Alternatively, it is also possible to use particles which do not have a core-
sheath
structure, but in which the active ingredient is distributed in a matrix of a
matrix-forming
material. Such particles are also referred to as "speckles".
A preferred matrix-forming material is alginate. To produce alginate-based
speckies, an
aqueous alginate solution, which also comprises the active ingredient to be
enclosed or
the active ingredients to be enclosed, is dripped and then hardened in a
precipitating
bath comprising Ca2+ ions or Al3+ ions.
Alternatively, instead of alginate, other matrix-forming materials can be
used. Examples
of matrix-forming materials comprise polyethylene glycol,
polyvinylpyrrolidone,
polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid,
polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan,
cellulose,
CA 02802277 2014-03-13
dextran, Ficoll , starch, hydroxyethylcellulose, hydroxypropylcellulose,
hydroxypropylmethylcellulose, hyaluronic acid, carboxymethylcellulose,
deacetylated
chitosan, dextran sulfate and derivatives of these materials. The matrix
formation takes
place for these materials for example via gelling, polyanion-polycation
interactions or
polyelectrolyte-metal ion interactions. The preparation of particles with
these matrix-
forming materials is known per se.
The release of the active ingredients from the microcapsules or speckles
usually takes
place during the application of the compositions comprising them through
decomposition of the sheath or the matrix as a result of mechanical, thermal,
chemical
or enzymatic action.
The invention is illustrated in more detail by the examples below.
Example 1: Copolymerization of methacrylamidoethylgluconamide (MEGA) with
methacrylic acid
The copolymerization was carried out at 60 C under N2. Firstly, 43 g (0.142
mol) of
MEGA were dissolved in water in order to obtain a 25% strength by weight
solution.
0.5 g (0.5% by weight, based on the monomers) of 2-mercaptoethanol was added
as
chain transfer agent. Two feeds were metered into this solution in parallel
over a time
period of 4 h: 58.4 g (0.6780 mot) of methacrylic acid dissolved in 36 g of
methanol;
and 1 g of 2,2'-azobis[2-(2-imidazolin-2-yl)propanej dihydrochloride (VAK0-
44*) as
initiator, dissolved in 60 g of water. When the addition was complete, the
polymerization was continued for 1 h.
This gave a copolymer with 100% monomer conversion (demonstrated by means of
IFI NMR spectrum) and a K value in accordance with Fikentscher of 14 as a
highly
viscous solution in the methanol/water reaction medium. This copolymer was
neutralized with aqueous NaOH solution. The neutralized copolymer dissolved in
the
water.
Example 2: Copolymerization of methacrylamidoethylgluconamide (MEGA) with
sodium methacrylate
The copolymerization was carried out at 60 C under N2. Firstly, 45 g (0.147
mol) of
MEGA were dissolved in water in order to obtain a 15% strength by weight
solution.
0.26 g (0.35% by weight, based on the monomers) of 2-mercaptoethanol was added
as
chain transfer agent. Two feeds were metered into this solution in parallel
over a time
period of 5 h: 30 g (0.349 mol) of sodium methacrylate dissolved in 60 g of
water; and
0.75 g of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAKO-44)
as
*trademark
CA 02802277 2012-12-11
PF 70481
31
initiator (1% by weight, based on the monomers), dissolved in 60 g of water.
When the
addition was complete, the polymerization was continued for 1 h.
This gave a copolymer with 90% monomer conversion (demonstrated by means of
1H NMR spectrum) and a K value in accordance with Fikentscher of 50, as a
slightly
viscous solution in the aqueous reaction medium.
Example 3: Copolymerization of MEGA with methyl acrylate and polyethylene
glycol
monomethyl ether methacrylate (MPEGMA)
The copolymerization was carried out at 60 C under N2. Firstly, 60 g (0.196
mol) of
MEGA were dissolved in water in order to obtain a 25% strength by weight
solution.
0.25 g (0.25% by weight, based on the monomers) of 2-mercaptoethanol was added
as
chain transfer agent. Two feeds were metered into this solution in parallel
over a time
period of 4 h: (i) 20 g (0.2323 mol) of methyl acrylate, dissolved in 54 g of
methanol,
and 209 of MPEGMA (molecular weight 1098) (0.0182 mol), dissolved in 35g of
water; and (ii) 1 g (1% by weight, based on the monomers) of 2,2'-azobis[2-(2-
imidazolin-2-yl)propane] dihydrochloride (VAKO-44) as initiator, dissolved in
74 g of
water/methanol (1/1 weight/weight). When the addition was complete, the
polymerization was continued for 1 h.
This gave a copolymer with 100% monomer conversion (demonstrated by means of
1H NMR spectrum) and a K value in accordance with Fikentscher of 21.
Example 4: Copolymerization of MEGA with methyl acrylate and polyethylene
glycol
monomethyl ether methacrylate (MPEGMA)
The copolymerization was carried out at 60 C under N2. Firstly, 60 g (0.196
mol) of
MEGA were dissolved in water in order to obtain a 25% strength by weight
solution.
0.05 g (0.05% by weight, based on the monomers) of 2-mercaptoethanol was added
as
chain transfer agent. Two feeds were metered into this solution in parallel
over a time
period of 4 h: (i) 20 g (0.2323 mol) of methyl acrylate, dissolved in 54 g of
methanol,
and 20 g of MPEGMA (molecular weight 1098) (0.0182mol), dissolved in 35 g of
water;
and (ii) 1 g (1% by weight, based on the monomers) of 2,2'-azobis[2-(2-
imidazolin-
2-yl)propane] dihydrochloride (VAKO-44) as initiator, dissolved in 74 g of
water/methanol (1/1 weight/weight). When the addition was complete, the
polymerization was continued for 1 h.
This gave a copolymer with 100% monomer conversion (demonstrated by means of
1H NMR spectrum) and a K value in accordance with Fikentscher of 35.
CA 02802277 2012-12-11
PF 70481
32
Example 5: Copolymerization of MEGA with sodium methylacrylate (NaMA) and
polyethylene glycol monomethyl ether methacrylate (MPEGMA) (60:20:20% by
weight)
The copolymerization was carried out at 60 C under N2. Firstly, 45 g (0.147
mol) of
MEGA were dissolved in water in order to obtain a 20% strength by weight
solution.
0.26 g (0.35% by weight, based on the monomers) of 2-mercaptoethanol was added
as
chain transfer agent. Two feeds were metered into this solution in parallel
over a time
period of 4 h: (i) 15 g (0.174 mol) of sodium methylacrylate, dissolved in 60
g of water
and 15 g of MPEGMA (molecular weight 1098) (0.0136 mol), dissolved in 60 g of
water; and (ii) 0.75 g (1% by weight, based on the monomers) of 2,2'-azobis[2-
(2-
imidazolin-2-yl)propane] dihydrochloride (VAKO-44) as initiator, dissolved in
60 g of
water. When the addition was complete, the polymerization was continued for 1
h.
This gave a copolymer with 100% monomer conversion (demonstrated by means of
1F1 NMR spectrum) and a K value in accordance with Fikentscher of 39.
Example 6: Copolymerization of MEGA with methyl acrylate (MA), MPEGMA and
methacrylamidopropyltrimethylammonium chloride (MAPTAC)
The copolymerization was carried out at 75 C under N2. Firstly, 40 g (0.1312
mol) of
MEGA were dissolved in water in order to obtain a 25% strength by weight
solution. 1 g
(1% by weight, based on the monomers) of 2-mercaptoethanol was added as chain
transfer agent. Three feeds were metered into this solution in parallel over a
time
period of 4 h: (i) 25 g (0.2919 mol) of methyl acrylate, dissolved in 54 g of
methanol; (ii)
30 g (0.0274 mol) of MPEGMA (molecular weight 1098), dissolved in 50 g of
water and
5 g of MAPTAC (0.0456 mol), dissolved in 74 g of water; and (iii) 2 g (2% by
weight,
based on the monomers) of 2,2'-azobis[2-(2-imidazolin-2-yl)propane]
dihydrochloride
(VAKO-44) as initiator, dissolved in 74 g of water/methanol (1/1
weight/weight). When
the addition was complete, the polymerization was continued for 1 h.
This gave a copolymer with 100% monomer conversion (demonstrated by means of
1H NMR spectrum) and a K value in accordance with Fikentscher of 22. Mn: 6800,
Mw: 19400.
Example 7: Copolymerization of glucose-1R-ethyl acrylate (GEA) with
hydroxyethyl
acrylate
GEA and 2-hydroxyethyl acrylate (molar ratio 1:1) with a total mass of about
1.5 g were
dissolved in 30 ml of boiling water. 0.2 ml of (NH4)2S208 (12% in water) and
0.2 ml of
K2S205 (6% in water) were added as initiators. The reaction mixture was placed
in an
oil bath at 50 C. The polymerization was continued for 20 h under nitrogen.
The
polymer was then precipitated in acetone and dried at 50 C in vacuo.
CA 02802277 2012-12-11
= PF 70481
33
This gave a copolymer with 80% monomer conversion (weight comparison of the
monomers used and of the resulting polymer). The polymer structure was
confirmed by
1H- and 13C-NMR spectra.
Example 8: Adsorption experiments on cellulose
The experiments were carried out using the quartz microbalance technique. A
QCM-D
D (Q-Sense, Vastra Frolunda, Sweden) was used. The method is based on the
change
in intrinsic frequency of a piezoelectric quartz crystal disk as soon as it is
laden with a
foreign mass. The surface of the quartz can be modified by spin-coating or
vapor
deposition. The oscillating quartz is located in a measuring cell. The
solution to be
investigated is pumped into the measuring cell from a storage vessel. The
pumping
rate is kept constant at 250 I/min during the measurement time and it is
ensured that
hoses and measurement cell are free from air bubbles. Each experiment starts
with the
recording of the base line in demineralized water, with regard to which all
frequency
and dissipation measurement values are set as zero.
In this example, a cellulose-coated QCM-D quartz (low-charged microfibrillar
cellulose,
thickness about 6 nm, surface roughness 3-4 nm RMS (according to AFM),
adhesion
promoter: poly(ethyleneimine)) was used.
Aqueous polymer solutions with a polymer concentration of 10 ppm, 100 ppm and
1000 ppm were investigated. The measurement data was used to calculate the
bonded
mass of polymer. The results are summarized in the table below:
Table 1: Adsorption of copolymers on cellulose
Ex. Monomers Concentration Adsorbed
[PPrn] mass
[ng/cm2]
6 MEGA/MA/MPEGMA/MAPTAC 10 n.d.
(40/25/30/5 % by wt.) 100 n.d.
1000 20
3 MEGA/MA/MPEGMA 10 50
(60/20/20% by wt.) 100 750
1000 750
4 MEGA/MA/MPEGMA 10 n.d.
(60/20/20% by wt.) 100 100
1000 950
n.d. = not detected
CA 02802277 2012-12-11
PF 70481
34
Example 9: Adsorption experiments on stainless steel
An arrangement as in example 5 was used. In this example, a sensor with 50 nm
stainless steel coating (SS2343) was used. Aqueous polymer solutions with a
polymer
concentration of 100 ppm and 1000 ppm were investigated. The results are
summarized in the table below:
Table 2: Adsorption of copolymers on stainless steel
Ex. Monomers Concentration Adsorbed
mass
[ng/cm2]
6 MEGA/MA/MPEGMA/MAPTAC 100 225
(40/25/30/5% by wt.) 1000 275
3 MEGA/MA/MPEGMA 100 450
(60/20/20% by wt.) 1000 500
Example 10: Investigation of the protein repulsion of polymer-coated surfaces
For the investigation of the protein repulsion by a polymer film of
MEGA/MA/MPEGMA
(example 3) adsorbed on cellulose, said film was adsorbed from an aqueous
solution
with a concentration of 500 ppm over 2.5 h, as described in example 8. After
rinsing
with water, the solution which flowed through the measuring cell was switched
to an
aqueous solution of 0.1 g/I of bovine serum albumin (BSA). Upon the switch to
BSA, no
change in frequency was observed, i.e. no BSA was adsorbed.
