Note: Descriptions are shown in the official language in which they were submitted.
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Graft copolymers based on mono-, oligo- and
polysaccharides, process for preparing the same
and their use
S This invention relates to graft copolymers based on
natural raw materials, the graft copolymers being
obtainable by the copolymerisation of ethylenically
unsaturated monomers in the presence of saccharides or
derivatives thereof. This invention also relates to a
process for producing copolymers of this type and to the
use of the graft copolymers as a water treatment agent,
an incrustation inhibitor and as a detergent additive,
namely as a so-called cobuilder.
The use of copolymers, which are obtained by grafting
acrylic acid and methacrylic acid on to starch or other
hydroxy compounds, in detergents for inhibiting re-
soiling is known from US 3,558,499.
According to JP-A-55/155 097, an oxidised starch grafted
with sodium acrylate, an oxidised starch grafted with
hydroxypropyl methacrylate, or a maize starch-polyvinyl
alcohol graft copolymer are used in an amount of 0.05 to
5 ~ by weight in detergent formulations to prevent the
re-soiling of laundry during washing.
Copolymers of acrylic acid with other unsaturated
compounds, which can be produced by polymerisation in the
presence of monosaccharides which are capable of enolate
formation, are known from EP 0 239 895 B1. The
aforementioned patent also describes their use as
cobuilders in detergents and cleaning materials.
DE 40 03 172 A1 or EP 0 441 197 discloses graft
copolymers of monosaccharides, oligosaccharides and
polysaccharides which are obtainable by radical-initiated
graft copolymerisation from
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_W0 96/37530 PCT/EP96/01922
A) monomer mixtures comprising
a) 90 to 10 ~ by weight of monoethylenically
unsaturated C4 to C8 dicarboxylic acids, or
anhydrides or alkali and/or ammonium salts
thereof,
b) 10 to 90 ~ by weight of monoethylenically
unsaturated C3 to C10 carboxylic acids, or
alkali and/or ammonium salts thereof,
c) 0 to 40 ~ by weight of other monoethylenically
unsaturated monomers which are copolymerisable
with monomers (a) and (b), and~5
d) 0 to 5 ~ by weight of monomers containing at
least two ethylenically unsaturated
unconjugated double bonds in their molecule,
in the presence of
B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically
decomposed polysaccharides; oxidised, hydrolytically
decomposed or oxidised, enzymatic.ally decomposed
polysaccharides; chemically modified mono-, oligo-
and polysaccharides or mixtures of the said
compounds in a weight ratio (A) : (B) of (95 to
20) : (5 to 80).
DE 40 38 908 A1 relates to the use of graft copolymers
according to DE 40 03 172 A1 as cobuilders.
Graft copolymers are known from DE 42 21 381 C1 which are
obtainable by the radical copolymerisation of an
ethylenically unsaturated monocarboxylic acid or a salt
thereof and monomers containing monoethylenically
unsaturated sulphonic acid groups, and optionally of -~
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_WO 96/37530 PCT/EP96/01922
other water-soluble monomers. The use of graft
copolymers of this type as cobuilders is also described.
.
DE 23 57 036 relates to polycarboxylates having a defined
biodegradability. These known polycarboxylates are used
as builders in the formulation of solid or liquid
cleaning materials. They are produced by the oxidative
polymerisation of acrolein, on its own or in the presence
OL aclylic acid, in the presence of thioethylene glycol.
DE 23 30 260 discloses a process for producing
polycarboxylates by the oxidative polymerisation of
acrolein on its own or together with acrylic acid,
polymerisation being carried out with the addition of
n-dodecylmercaptan.
EP 0 609 777 relates to detergent compositions having an
improved dirt-carrying capacity, with the use of a
suitable polycarboxylate. The co-builders disclosed are
obtained by the copolymerisation of acrolein and acrylic
acid, for example, under suitable conditions.
In Polym. J. 11 (1979) 85, G. Maher describes graft
copolymers which are produced by the polymerisation of
vinyl monomers on to starch xanthate. Acrolein,
acrylamide, acrylic acid, acrylonitrile, methyl acrylate
or styrene were investigated as the vinyl monomers. In
the course of this procedure, the respective monomer was
reacted with an aqueous system comprising completely
soluble starch xanthate and hydrogen peroxide (at an
alkaline pH), and a gel-like,-crosslinked product was
formed in each case, comprising graft copolymers in a
self-generated acidic medium. For example, a gel-like
product was formed with acrolein, and vigorous gas
evolution occurred during the polymerisation reaction,
with the formation of bubbles which could not escape
rapidly enough on account of the rapid formation of gel.
This effect led to the proposal that this reaction and -~
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the products thereof be employed in the production of
foam rubber (US-4,005,040).
Polycarboxylates are known from DE 44 17 734.8 which are
produced by the polymerisation of acrolein and vinyl
acetate in aqueous solution in the presence of hydrogen
peroxide and optionally of other batch materials. The
polymers exhibit a biodegradability of , 30 ~.
Derwent Abstract 86-085028/13 of JP-61 031 498 discloses
graft polymers of acrylic acid or maleic acid on glucose,
fructose or other defined sugars. As mixtures of
cobuilders, these are claimed to provide enhanced washing
power and improved biodegradability.
It has in fact been shown that the incrustation of
textiles during washing can be reduced by the
polycarboxylate products which are commonly available on
the market. However, further optimisation of cobuilders
is desirable in order to increase the efficacy of
detergents and thus further to improve the usage
properties of textiles at the same time. The underlying
object of the invention described below is accordingly to
provide polymers, which as far as possible are based on
reproductively grown raw materials and inexpensive batch
materials, which exhibit an incrustation-inhibiting
effect which is better than or at least as good as that
of the products used hitherto, and which at the same time
exhibit outstanding biodegradability.
The said object, and other objects not mentioned in
detail, are achieved by means of the water-soluble graft
copolymers of monosaccharides, oligosaccharides,
polysaccharides and derivatives thereof according to the
invention, which are obtainable by the radical-initiated
copolymerisation of
A) monomer mixtures comprising -~
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a) more than 40 - 100 ~ by weight of at least one
~ unsaturated aldehyde of general formula I
R2
.~,0
R1 _ GH = C - C (I),
H
where Rl represents hydrogen or a linear or
branched Cl-C4 alkyl, and R2 represents hydrogen
or methyl,
b) ~ ~ 60 ~ by weight of a) different
monoethylenically unsaturated monomers which
are copolymerisable with a), and
c) 0 - 5 ~ by weight of monomers containing at
least two ethylenically unsaturated,
unconjugated double bonds in their molecule,
in the presence of
B) monosaccharides, oligosaccharides, polysaccharides;
oxidatively, hydrolytically or enzymatically
decomposed polysaccharides; chemically modified
mono-, oligo- or polysaccharides; or mixtures of the
said compounds, and
C) one or more oxidising agents,
wherein the weight ratio of A) to B) extends from
(95 : 20) to (5 : 80) and the weight ratio of C) to
- A) + B) extends from (5 : 100) to (50 : 50).
Because the graft copolymers of the present invention are
based on natural, reproductively grown raw materials,
namely the said saccharides and their derivatives B),
they give little cause for concern ecologically and they
are relatively inexpensive. The ~,~-unsaturated
aldehydes of formula I, which as component (a) constitute -~
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WO 96/37530 . PCT/EP96/01922
the major part of the monomer mixtures A) which are
grafted on to component B), are also relatively
inexpensive raw materials, particularly acrolein.
However, the graft copolymers which are obtainable in
this manner exhibit a good incrustation-inhibiting effect
and at the same are outstandingly biodegradable.
The ~,~-unsaturated aldehydes of formula I which can
successfully be used according to the invention comprise
those in which R1 is hydrogen, methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl and/or tert.-butyl, whilst R2
represents hydrogen or methyl.
One or more compounds of formula I may be used in
admixture with each other as component (a).
Acrolein and/or methacrolein are particularly suitable as
monomers of group (a). The use of acrolein is
particularly advantageous on economic grounds.
Monoethylenically unsaturated C3 to C10 monocarboxylic
acids and alkali and/or ammonium salts thereof are
suitable as monomers of group (b). Examples of these
monomers include acrylic acid, methacrylic acid,
ethylacrylic acid, allylacetic acid and vinylacetic acid.
From this group of monomers, acrylic acid, methacrylic
acid, mixtures thereof and their sodium, potassium or
ammonium salts or mixtures thereof are preferably used.
These monomers are either polymerised on their own as
component (b), or are polymerised in admixture with
monoethylenically unsaturated dicarboxylic acids or
anhydrides thereof as component (b), together with (a)
and optionally (c) in the presence of natural products
(B) under oxidising conditions. In this respect, the
expression "under oxidising conditions" is to be
understood as the use of an oxidising agent C) in a
weight ratio of C) to A) + B) of (5 : 100) to (50 : 50),
wherein C) has sufficient oxidising power to effect the -~
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WO 96/37530 PCT/EP96/01922
oxidation of carbonyl groups and the oxidation and
decomposition of the polysaccharide used and thus to
initiate the polymerisation of mixture a) to c) star~ing
from the polysaccharide.
Suitable unsaturated dicarboxylic acids contain 4 to 8 C
atoms, e.g. maleic acid, fumaric acid, itaconic acid,
methylenemalonic acid, citraconic acid, maleic anhydride,
itaconic anhydride and methylenemalonic anhydride. The
monoethylenically unsaturated C4 to C8 dicarboxylic acids
may be used in the graft polymerisation in the form of
the free acids or in the form in which they are
neutralised with alkali metal bases, ~mmo~; a or amines.
Of the dicarboxylic acids or anhydrides thereof which are
suitable, maleic acid, maleic anhydride, itaconic acid or
itaconic anhydride and the sodium, potassium or ammonium
salts of maleic acid or itaconic acid are preferably
used. These salts can be obtained, for example, from
maleic anhydride or itaconic anhydride by neutralising
the said anhydrides in aqueous solution with sodium
hydroxide solution or potassium hydroxide solution, or
with ammonia or amines.
Examples of monomers of group (b) which can also be used
in the graft polymerisation include C1 to C6 alkyl esters
and hydroxyalkyl esters of the said compounds, e.g.
methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl
methacrylate, maleic acid monomethyl ester, maleic acid
diethyl ester, hydroxyethyl acrylate, hydroxypropyl
acrylates, hydroxybutyl acrylates, hydroxyethyl
methacrylate and hydroxypropyl methacrylate. The amides
and N-substituted alkyl amides of the said compounds are
also suitable as monomers of group (b), e.g. acrylamide,
methacrylamide, N-alkylacrylamides containing 1 to 18 C
atoms in the alkyl group, such as N-methylacrylamide,
N-dimethylacrylamide, N-tert.-butylacrylamide,
N-octadecylacrylamide, maleic acid monoethylhexylamide,
maleic acid monododecylamide, dimethylaminopropyl -
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WQ 96/37530 PCT/EP96/01922
methacrylamide and acrylamidoglycolic acid.
Alkylaminoalkyl (meth)acrylates are also suitable as
monomer (b), e.g. dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl
acrylate, diethylaminoethyl methacrylate,
dimethylaminopropyl acrylate and dimethylaminopropyl
methacrylate.
Monomers which contain sulphonic acid groups are also
suitable as monomers of group (b), such as
vinylsulphonic acid, allylsulphonic acid,
methallylsulphonic acid, styrenesulphonic acid, acrylic
acid-3-sulphopropylester, methacrylic acid-3-sulphopropyl
ester and acrylamidomethyl-propanesulphonic acid for
example, as well as monomers containing phosphonic acid
groups, such as vinylphosphonic acid, allylphosphonic
acid and acrylamidomethylpropane-phosphonic acid for
example. This group of monomers also includes
N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide,
N-vinyl-N-methylformamide, 1-vinylimidazole, 1-vinyl-2-
methylimidazole, vinyl acetate and vinyl propionate.
Also suitable as monomers of group (b) are the esters of
alkoxylated C1 to C18 alcohols which are reacted with 2 to
50 moles of ethylene oxide, propylene oxide, butylene
oxide or mixtures thereof, with the monoethylenically
unsaturated carboxylic acids of group (a), e.g. the
esters of acrylic acid, methacrylic acid or maleic acid
with a C13/C1s oxoalcohol which has been reacted with
different amounts of ethylene oxide, e.g. 3 moles,
5 moles, 7 moles, 10 moles or 30 moles of ethylene oxide.
Both the mono- and diesters of the dicarboxylic acids are
suitable as the esters.
The basic monomers are preferably used in the form of
their salts with mineral acids, e.g. hydrochloric acid,
sulphuric acid or nitric acid, or in quaternarised form -~
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WQ 96/37530 PCT/EP96/01922
(examples of suitable quaternarisation agents include
dimethyl sulphate, diethyl sulphate, methyl chloride,
ethyl chlQride or benzyl chloride).
Amides of monoethylenically unsaturated C3 to C8
carboxylic acids with amide groups of the said structure
are also suitable as monomers of group (b).
-The prefer.ed monomers of group (b) are acrylic acid,
methacrylic acid, maleic acid, hydroxyethyl acrylate,
hydroxypropyl acrylate, vinyl acetate, N-vinyl
pyrrolidone, acrylamidomethyl-propanesulphonic acid and
N-vinyl-imidazole.
A further modification of the graft copolymers can be
obtained by conducting the graft polymerisation in the
presence of monomers of group (c). In this case, the
monomer mixtures contain up to 5 ~ by weight of a monomer
having at least two ethylenically unsaturated
unconjugated double bonds in its molecule. These
compounds are usually employed as crosslinking agents in
copolymerisation reactions. They may be added to the
monomers of group (a) or to the monomer mixtures of (a)
and (b) used for copolymerisation. When they are used,
the amount of monomers (c) which is used is preferably
0.05 to 2 ~ by weight. The use in conjunction of
monomers of group (c) during the copolymerisation effects
an increase in the molecular weight of the copolymer.
Examples of suitable compounds of this type include
methylene-bis-acrylamide, esters of acrylic acid and
methacrylic acid with polyhydric alcohols, e.g. glycol
diacrylate, glycerine triacrylate, glycol dimethacrylate,
glycerine trimethacrylate, and polyols which are
esterified at least twice with acrylic acid or
methacrylic acid, such as pentaerythritol and glucose.
In addition, divinylbenzene, divinyldioxane,
pentaerythritol triallyl ether and pentaallyl sucrose are
suitable crosslinking agents. Water-soluble monomers, --
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such as glycol diacrylate or diacrylates of polyethylene
glycols having a molecular weight up to 3000, are
preferably used from this group of compounds.
s Polymerisation of monomers (a) and optionally of (b) and
(c) in addition is effected in the presence of natural
products based on polysaccharides, oligosaccharides,
monosaccharides and derivatives thereof. These natural
products may, for example, be saccharides of vegetable or
~n;m~l origin or products of the metabolism of
microorganisms, or decomposition and modification
products thereof which are already dispersible or soluble
in water or alkali, or which, during the polymerisation
of monomers (a) and optionally (b) and (c), become
directly, completely or partially dispersible or soluble
in the form in which they are neutralised with alkali,
ammonia or amines.
Examples of these substances include starch, pectin,
algin, chitin, chitosan, heparin, carrageenan, agar, gum
arabic, gum tragacanth, karaya gum, ghatti gum, carob
seed grain, guar gum, Tara gum, inulin, xanthan, dextran,
saccharose, nigeran and pentosans such as xylan and
araban, the major constituents of which consist of
D-glucuronic acid, D-galacturonic acid, D-galacturonic
acid methyl ester, D-mannuronic acid, L-guluronic acid,
D- and L-galactose, 3,6-anhydro-D-galactose, L-arabinose,
L-rhamnose, D-glucoronic acid, D-xylose, L-fucose,
D-mannose, D-fructose and D-glucose, 2-amino-2-desoxy-D-
glucose and 2-amino-2-desoxy-D-galactose and the N-acetyl
- derivatives thereof.
Considered from an economic standpoint, the following are
preferably used as polysaccharides of component (B)
during the graft copolymerisation: starch, thermally
and/or mechanically treated starch, starches decomposed
oxidatively, hydrolytically or by enzymatic oxidation,
oxidised starches decomposed by enzymatic hydrolysis or -~
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11
by enzymatic oxidation, and also chemically modified
starches and chemically modified monosaccharides and
oligosaccharides.
In principle, all starches are suitable. Starches from
maize, wheat, rice or tapioca, and starches from potatoes
in particular, are preferred, however. Starches are
practically insoluble in water and can be converted into
a water-soluble form in the known manner by thermal
and/or mechanical treatment or by enzyme- or acid-
catalysed decomposition. Oxidatively decomposed starches
are also suitable as component (B). The following
compounds should be cited as examples of starch
decomposition products which are obtainable by the
oxidative, hydrolytic or enzymatic decomposition of
starch: dextrins such as white and yellow dextrins,
maltodextrins, glucose syrups, maltose syrups,
hydrolysates with a high content of D-glucose, products
of the conversion of starches into sugars, and maltose
and D-glucose and their isomerisation product fructose.
Mono- and oligosaccharides are also of course suitable as
component (B), such as galactose, mannose, ribose,
saccharose, raffinose, lactose and trehalose, as well as
decomposition products of cellulose, for example
cellubiose and oligomers thereof.
Oxidised starches are also suitable as component (B),
such as dialdehyde starch and oxidised starch
decomposition products, for example gluconic acid and
glucuronic acid. Compounds such as these are obtained,
- for example, by the oxidation of starch with periodate,
chromic acid, hydrogen peroxide, nitrogen dioxide,
nitrogen tetroxide, nitric acid or hypochlorite.
Chemically modified polysaccharides, particularly
chemically modified starches, are also suitable as
component (B), e.g. starches and starch decomposition
products which are reacted with acids to form esters and -~
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which are reacted with alcohols or alkyl halides, such as
chloroacetic acid, for example, to form ethers. It is
possible to esterify these substances both with inorganic
and with organic acids or anhydrides or chlorides
thereof. Phosphated and acetylated starches,
carboxymethyl starch and starch decomposition products
are of particular commercial interest. The commonest
method of etherifying starch is the treatment of starch
and of starch decomposition products with organic-halogen
compounds, epoxides or sulphates in aqueous alkaline
solution. Bxamples of starch ethers include the alkyl
ethers, hydroxyalkyl ethers, carboxyalkyl ethers and
allyl ethers of starch. In relation to component (B),
the expression "chemically modified starches" should also
be understood as comprising cationically modified
starches, e.g. starches reacted with 2,3-epoxypropyl-
trimethylammonium chloride, such as those described in
US-PS 3,649,616 for example.
Examples of chemically modified polysaccharides also
include carboxymethylcellulose, hydroxyethylcellulose,
hydroxypropylcellulose, carboxymethyl-
hydroxyethylcellulose, sulphoethylcellulose,
carboxymethyl-sulphoethylcellulose, hydroxypropyl-
sulphoethylcellulose, hydroxyethyl-sulphoethylcellulose,
methyl-sulphoethylcellulose and ethyl-
sulphoethylcellulose.
Chemically modified decomposed starches are also suitable
as component (B), for example the hydrogenatio~ products
of starch hydrolysates, such as sorbitol and mannitol,
maltitol and hydrogenated glucose syrups, or oxidised,
hydrolytically decomposed starches or oxidised,
enzymatically decomposed starches.
All the oxidising agents familiar to one skilled in the
art are suitable as component (C). These comprise,
amongst others, hydrogen peroxide, hypochlorite, nitrogen
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dioxide, nitrogen tetroxide, nitric acid, chromic acid
and/or periodate. Hydrogen peroxide is preferably used
as the oxidising agent. Mixtures of a plurality of
oxidising agents may also be used.
The graft copolymers according to the invention are
preferably composed of 20 to 95 ~ by weight of monomer
mixture (A) and 5 to 80 ~ by weight of component (B). In
this connection, products containing 25 to 70 ~ by weight
of monomer mixture (A) and 30 to 75 ~ by weight of
component (B) are particularly preferred.
If the content of monomer mixture is less than 20 ~ by
weight, the washing properties are unsatisfactory. On
the other hand, if the content of monomer mixture is
greater than 95 ~ by weight the biodegradability is
unsatisfactory.
The present invention also relates to a process for
producing graft copolymers of monosaccharides,
polysaccharides and derivatives thereof by the radical-
initiated copolymerisation of A) 95 to 20 ~ by weight of
ethylenically unsaturated monomers in the presence of B)
5 to 80 ~ by weight of at least one monosaccharide,
oligosaccharide, polysaccharide, decomposed or chemically
modified mono-, oligo- and polysaccharide or mixtures
thereof, and C) one or more oxidising agents in an inert
diluent at temperatures up to 180~C, wherein mixtures
comprising
a) 40 - 100 ~ by weight of at least one ~,~-unsaturated
aldehyde of general formula I
R2
R1 _ CH=C-C (I),
H
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14
where R1 represents hydrogen or a linear or branched
C1-C4 alkyl, and R2 represents hydrogen or methyl,
.
b) ~ ~ 60 ~ by weight of a) different monoethylenically
unsaturated monomers which are copolymerisable with
a), and
c) 0 - 5 ~ by weight of monomers containing at least
two ethylenically unsaturated, unconjugated double
bonds in their molecule,
are used as the ethylenically unsaturated monomers A),
and the one or more oxidising agents C) are used in a
weight ratio of C) to A) + B) of (5 : 100) to (50 : 50).
If the oxidising agent is present in a weight ratio of C)
to A) + B) which is less than (5 : 100), insufficient
carboxyl groups are produced in the molecule to achieve
satisfactory washing properties. However, if the weight
ratio of C) to A) + B) is greater than (50 : 50), the
molecular weight of the graft polymer is too low due to
oxidative decomposition and no advantageous washing
properties are obtained.
Polymers are obtained by the polymerisation of
~,~-unsaturated aldehydes under oxidising conditions
which can still contain, as structural elements, free
aldehyde groups or the acetal thereof, acid groups, acid
groups esterified with 3-hydroxypropionic acid, alcohol
groups, and also ether groups. A precise determination
of the structure of the polymers is difficult, however.
The production of the polymers according t-o the invention
also results in the oxidation of the mono- or
polysaccharides used, wherein carboxyl groups, which
presumably also contribute to the observed washing
effect, are incorporated therein, and radicals on to
which ~,~-unsaturated aldehydes and other monomers can
polymerise are produced on the saccharide molecules. In
addition, bonding of component (B) to the polymers formed --
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WO 96/37530 _ 15 PCT/EP96/01922
from (A) can occur via the aldehyde groups of component
(A) with the formation of a semi-acetal or acetal.
As mentioned above, the preceding statements are merely
an attempted explanation; the technical teaching given in
the claims is independent of the correctness thereof,
however.
Suitable initiators for the polymerisation comprise
hydrogen peroxide, persulphuric acid and the sodium,
potassium and ammonium salts thereof, and percarbonic
acid, perboric and perphosphoric acid, peroxycarboxylic
acids and salts thereof. Hydrogen peroxide is preferably
used as the initiator.
Since hydrogen peroxide is also a preferred oxidising
agent, in one advantageous embodiment of the invention
hydrogen peroxide is most preferably used both as an
initiator and as an oxidising agent.
Production of the polymer according to the invention is
preferably conducted in aqueous solution, wherein
components (A) and (B) and the oxidising agent may be
placed in the reaction vessel or added during the
reaction. Preferably, component (B) is placed in the
reaction vessel and (A) is added. Oxidising agent (C)
may be placed in the vessel or added during the reaction,
according to choice. The mono- or polysaccharide B) may
also firstly be pre-oxidised and partially decomposed
with oxidising agent C) before commencing the addition of
monomer mixture A). The temperature range which is
suitable for the reaction is between 50 and 100~C;
temperatures between 65 and 85~C are preferred. The
components are typically added at a metered rate over a
period of 1 to 6 hours. Heating is then continued for a
further 1 to 6 hours at temperatures between 70 and 100~C
in order to ensure that the reaction proceeds to
completion. --
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16
The product obtained may be used without further
treatment or may be concentrated before use, or may be
dried by methods known to one skilled in the art, such as
spray-drying for example. In particular, it may also be
mixed with other detergent and cleaning material
components before work-up.
The graft copolymers according to the invention are
polycarboxylates which have the advantage~that in
addition to a good bonding capacity for lime they exhibit
outstanding biodegradability and effect an outstanding
inhibition of incrustation.
The polycarboxylates according to the invention may be
used both as cobuilders and as builders in detergents.
When employed as cobuilders, they can be used in addition
to known builders such as zeolite A for example, or layer
silicates such as SKS-6, or amorphous disilicates.
They can be used in combination with water-soluble or
water-insoluble, inorganic and/or organic builder
materials. Examples of suitable inorganic builder
substances include zeolites, phosphates and sodium
silicates.
The zeolite used is preferably finely divided zeolite
NaA. Zeolite NaX and Zeolite NaP and mixtures of these
three zeolites are also suitable, however. In
particular, zeolites of this type have an average
30 particle size less than 10 ~m and preferably contain 18
to 22 ~ by weight of water (determined as the loss on
ignition at 1000~C for one hour). The zeolites may also
be used as a stabilised suspension, however. In this
connection, small amounts of added nonionic surfactants
35 effect stabilisation of the suspension.
Amorphous or crystalline alkali silicates may be present
as a replacement or partial replacement for phosphates --
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W0 96/37530 17 PCT/EP96/01922
and zeolites. The preferred alkali silicates are sodium
silicates, particularly amorphous sodium silicates, with
an Na2O : SiO2 molar ratio of 1.5 to 3. Amorphous alkali
silicates of this type are obtainable under the name
Portil~ (Henkel), for example. Co-granulates of soda
and amorphous sodium disilicates, which are known by the
trade name Nabion 15~ (Rhone-Poulenc), for example, may
also be used. Crystalline layer sodium silicates of
general formula NaMSix02x+l.yH2o~ where-M denotes sodium or
hydrogen, x is a number from 1.9 to 4, y is a number from
0 to 20, and a preferred value of x = 2, are preferably
used as crystalline silicates which may be present on
their own or in admixture with amorphous silicates.
Crystalline layer silicates of this type are described in
European Patent EP 0 164 514. Both ~- and ~-sodium
disilicates are particularly preferred.
Examples of organic builders which can be used include
polycarboxylic acids, which are preferably used in the
form of their sodium salts, such as polyacrylic acid,
polymethacrylic acid and copolymers thereof with maleic
acid, as well as tartaric acid, citric acid, succinic
acid, adipic acid, glutaric acid, saccharic acids,
aminocarboxylic acids, nitrilotriacetic acid and mixtures
of these, for example.
In a combination of the compound according to the
invention with the aforementioned inorganic and/or
organic builders, it is immaterial whether the compound
is introduced into the detergent preparation in the form
of spray-dried compounds or compounds premixed in another
manner with the said builders or is introduced directly.
The present invention also relates to methods of washing
and cleaning textile fabrics in which the graft polymers
according to the invention are used as a builder.
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WO 96/37530 18 PCT/EP96/01922
The present invention further relates to detergents and
cleaning materials which contain the graft polymers
according to the invention.
The invention is described in detail below with reference
to examples.
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I. Methods:
A) Molecular weight determination
Molecular weight determination was effected via gel
permeation chromatography (GPC) on LiChrospher Diol
columns (Merck) using phosphate buffer (pH = 7) as the
eluent solution. Calibration can best be effected with
closely distributed polyacrylic acid. In this
connection, the fact that the chemical composition of the
copolymers according to the invention was not constant
resulted in an error in the absolute value of the
molecular weight. This source of error, which is
generally known, could not easily be eliminated, so that
all the molecular weight data given here are to be
understood as being relative to the calibration with
polyacrylic acid.
B) Determination of the lime bo~; n~ capacity
The lime bonding capacity (LBC) is a numerical measure
which indicates how many grams of calcium carbonate
(CaCO~) are held in solution or are dispersed to a certain
degree per gram of complex-former. It was determined by
turbidimetric titration.
200 mg of the polymer (calculated as solid) were
dissolved in 100 ml deionised water. The pH of this
solution should be > 6 and had to be correspondingly
corrected with sodium hydroxide solution if necessary.
Thereafter, 10 ml of 2 % soda solution were added and the
pH was adjusted to 10 with sodium hydroxide solution or
acetic acid. This solution was titrated with calcium
acetate (44.1 g/l) and the turbidity caused by
precipitated calcium carbonate was measured and recorded
using a fibre optic measuring cell (wavelength = 650 nm).
The transmission of the measuring cell was adjusted to
100 ~ before the titration. The LBC was determined at 50
% transmission.
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WO 96/37530 _ PCT/EP96/01922
C) Determination of the Zahn-Wellens biodegradability
The Zahn and Pellens decomposition test is a means of
assessing the biodegradability of a substance or liquid
effluent. It operates at a fixed ratio of COD to
biomass.
About 2 litres of biomass suspension were stirred and
aerated via glass frits in a tall 3 litre glass beaker.
385 mg NH4Cl and 89 mg NaH2PO4.H2O were weighed in, mixed
with the calculated amount of polymer and made up to
about 2 litres with cold tap-water. The activated sludge
from a commlln~l sewage works was allowed to settle for 30
- 60 minutes so that it thickened by about half. The
supernatant water was removed by decantation and the
sludge was kept stirred and aerated. A portion of sludge
was removed for each test and centrifuged at 2000 rpm for
5 minutes. 24 g of the centrifuged sludge from a 2 litre
batch gave a solids content of 1 g/l (~ 20 ~). Before
adding the sludge to the polymer solution, the pH was
adjusted to 6.5 - 7.0 and a sample was analysed for COD
content. A sample could be taken again after the
activated sludge had become finely distributed. The
height of the liquid in the beaker was then marked. A
test liquid was used for comparison which contained
nutrient salts and activated sludge only, and no polymer.
This batch was used to determine the COD due to the
activated sludge. Each day, the bio-sludge deposited on
the rim of the beaker was transferred back into the
solution with a rubber wiper, the pH was adjusted again
and the water lost by evaporation was replaced by
demineralised water. Two samples, a filtered sample and
an unfiltered sample, were analysed for their COD content
in order to determine the substance adsorbed on the bio-
sludge. The unfiltered sample was taken directly from
the well-mixed reaction vessel and measured. For the
filtered sample an aliquot portion, 40 ml for example,
was taken, allowed to settle, and filtered using a --
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21
Millipore 2.5 ~ filter (Millipore Millex GS, for
example). The clear solution was likewise analysed for
its COD_content.
Calculation
In order to determine the COD content of the substance
which was adsorbed on the biomass, the COD value of the
filtered sample and the blank value with biomass were
subtracted from the COD in the sample solution with
biomass.
P1 unfiltered sample solution with biomass
P2 filtered sample solution
Bls unfiltered blank value
ad adsorbed substance
P1 - P2 - Bls = ad.
The dissolved substance was obtained by subtracting the
filtered blank value from the filtered sample P2.
Bl filtered blank value
S dissolved substance
P2 - Bl = S.
The adsorbed and dissolved substance together gave the
initial content of substance to be decomposed or the
current content .
The degree of decomposition ~ was calculated from
A- (ad+S) .100
where
A is the initial value, and
~ is the degree of decomposition.
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II. Examples
Example 1
1260 g deionised water, 105 g of 50 ~ hydrogen peroxide
and 240 g Aeromyl 115 (starch soluble in cold water,
supplied by Sudstarke) were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered a-ddition, and were heated
to 70~C. A mixture of 189 g acrolein and 21.6 g acrylic
acid was added at a metered rate, with stirring, over a
period of 3.5 hours. In parallel with this, a further
105 g of 50 ~ hydrogen peroxide were added at a metered
rate. The reaction batch was then heated to 90~C over a
period of 1 hour and was maintained at this temperature
for a further 4 hours. A pH of 1.5 was measured after
cooling to room temperature. The reaction batch was
adjusted to pH 10 with 50 ~ NaOH and was concentrated to
a solids content of 40 ~.
LBC(23~C) = 820 mg CaCO3/g, LBC(60~C) = 150 mg CaCO3/g,
molecular weight (GPC) = 27,900 g/mole
Example 2
630 g deionised water, 51 g of 50 ~ hydrogen peroxide and
79.4 g Aeromyl 115 (starch soluble in cold water,
supplied by Sudstarke) were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered addition, and were heated
to 70~C. A mixture of 91.7 g acrolein and 13.1 g acrylic
acid was added at a metered rate, with stirring, over a
period of 3 hours. In parallel with this, a further 51 g
of 50 ~ hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was
maintained at this temperature for 4 hours.
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23
LBC(23~C) = 1200 mg CaC03/g, LBC(60~C) = 180 mg CaCO3/g,
molecular weight (GPC) = 8050 g/mole, degree of
decomposition ~ after 28 days = 63 %.
Example 3
630 g deionised water, 44.9 g of 50 % hydrogen peroxide
and 79.4 g Aeromyl 115 (starch soluble in cold water,
supplied by Sudstarke) were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered addition, and were heated
to 70~C. A mixture of 80. 2 g acrolein and 25.2 g acrylic
acid was added at a metered rate, with stirring, over a
period of 3 hours. In parallel with this, a further 44.9
g of 50 % hydrogen peroxide were added at a metered rate.
The reaction batch was then heated to 95~C and was
maintained at this temperature for 4 hours.
LBC(23~C) = 1280 mg CaC03/g, LBC(60~C) = 200 mg CaCO3/g,
molecular weight (GPC) = 10,450 g/mole, degree of
decomposition ~ after 28 days = 52 %.
Example 4
630 g deionised water, 30.3 g of 50 % hydrogen peroxide
and 79.4 g Aeromyl 115 (starch soluble in cold water,
supplied by Sudstarke) were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered addition, and were heated
to 70~C. A mixture of 54.1 g acrolein, 28.0 g vinyl
acetate and 23.2 g acrylic acid was added at a metered
rate, with stirring, over a period of 3 hours. In
parallel with this, a further 30.3 g of 50 % hydrogen
peroxide were added at a metered rate. The reaction
batch was then heated to 95~C and was maintained at this
temperature for 4 hours. -
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24
LBC(23~C) = 1350 mg CaCO3/g, LBC(60~C) = 140 mg CaCO3/g,
molecular weight (GPC) = 7835 g/mole, degree of
decomposition ~ after 28 days = 62 ~.
Exampl-e 5
1200 g deionised water, 150 g of 50 ~ hydrogen peroxide
-and 234 g potato flour were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered addition, and were heated
to 70~C. The reaction batch was maintained at this
temperature for 2 hours. A mixture of 180 g acrolein and
20.0 g acrylic acid was then added at a metered rate,
with stirring, over a period of 3.5 hours. In parallel
with this, a further 50 g of 50 ~ hydrogen peroxide were
added at a metered rate. The reaction batch was then
heated to 95~C and was maintained at this temperature for
4 hours.
(GPC) = 17300 g/mole
Example 6
865 g deionised water, 150 g of 50 ~ hydrogen peroxide
and 200 g white dextrin were placed in a reactor fitted
with a condenser, a stirrer, and with a device for
controlled heating and metered addition, and were heated
to 70~C. A mixture of 180 g acrolein and 20 g acrylic
acid was then added at a metered rate, with stirring,
over a period of 3.5 hours In parallel with this, a
further 50 g of 50 ~ hydrogen peroxide were added at a
metered rate. The reaction batch was then heated to 95~C
and was maintained at this temperature for 4 hours.
LBC(23~C) = 1360 mg CaCO3/g, LBC(60~C) = 825 mg CaCO3/g
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WO 96/37530 25 PCT/EP96/01922
Example 7
268.5 g deionised water, 238.8 g of S0 ~ hydrogen
peroxide and 108.0 g white dextrin were placed in a
reactor fitted with a condenser, a stirrer, and with a
device for controlled heating and metered addition, and
were heated to 70~C. A mixture of 262.8 g acrolein and
29.2 g acrylic acid was then added at a metered rate,
~ with stirring, over a period of 3.5 hours. In paral-lel
with this, a further 79.6 g of 50 ~ hydrogen peroxide
were added at a metered rate. The reaction batch was
then heated to 90~C over 1 hour and was maintained at
this temperature for 4 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding
50 ~ sodium hydroxide solution. A clear, yellowish
solution with a solids content of 43 ~ was obtained.
LBC(23~C) = 1600 mg CaCO3/g, LBC(60~C) = 300 mg CaCO3/g,
pour point = -19~C,
degree of decomposition ~ after 28 days = 45 ~.
Example 8
320.5 g deionised water, 196.6 g of 50 ~ hydrogen
peroxide and 177.4 g white dextrin were placed in a
reactor fitted with a condenser, a stirrer, and with a
device for controlled heating and metered addition, and
were heated to 70~C. A mixture of 216 g acrolein and 24
g acrylic acid was then added at a metered rate, with
stirring, over a period of 3.5 hours. In parallel with
this, a further 65.5 g of 50 ~ hydrogen peroxide were
added at a metered rate. The reaction batch was then
heated to 90~C and was maintained at this temperature for
3 hours.
After cooling, the pH was adjusted to pH = 8.6 by adding
50 ~ sodium hydroxide solution. A clear, yellow solution
with a solids content of 45 ~ was obtained.
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26
LBC(23~C) = 1220 mg CaCO3/g, LBC(60~C) = 160 mg CaCO3/g,
pour point = -16~C,
degree of decomposition ~ after 28 days = 45 ~.
Comparative example 1
420 parts by weight deionised water and 307 parts of 50 %
hydrogen peroxide were placed in a reactor fitted with a
condenser, a stirrer, and with a device for controlled
heating and metered addition, and were heated to 70~C.
1012 parts acrolein and 338 parts vinyl acrylate,
together with 922 parts hydrogen peroxide (50 ~) were
steadily metered in, with stirring, over a period of 4
hours. After the addition was complete, a further 120 g
of hydrogen peroxide (50 ~) were added and the
temperature was increased to 90~C over 1 hour. The batch
was maintained at this temperature until the excess
hydrogen peroxide had decomposed. After cooling to room
temperature, the polymer solution had a pH of 1.4. The
pH was adjusted to pH 10 with 50 ~ NaOH solution.
LBC(23~C) = 1060 mg CaCO3/g, LBC(60~C) = 80 mg CaCO3/g,
molecular weight (GPC) = 2790 g/mole, degree of
decomposition ~ after 28 days = 37 ~.
Comparative example 2 (EP-A-0 441 197)
253.4 g water, 89.7 g white dextrin (89.2 ~ solids
content), 63.8 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 94 g
of 50 ~ aqueous sodium hydroxide solution were heated to
boiling in a heatable reactor fitted with a stirrer,
reflux condenser, thermometer, admission devices, and
nitrogen inlet and outlet devices. After the reaction
mixture had started to boil, a solution of 178.2 g
acrylic acid in 141.9 g water was steadily added over 5
hours, with boiling, and a solution of 16.6 g of 50 ~ --
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WO 96/37530 _ 27 PCT/EP96/01922
hydrogen peroxide in 44.4 g water was steadily added over
6 hours, with boiling. After the metered addition of
hydrogen peroxide was complete, the reaction mixture was
heated to boiling for a further 1 hour and was thereafter
neutralised to a pH of 7.3 by adding 50 ~ aqueous sodium
hydroxide solution and cooled. A clear, viscous, dark
brown solution was obtained, with a solids content of
42.8 ~.
LBC(23~C) = 1010 mg CaC03/g, LBC(60~C) = 950 mg CaCO~/g,
pour point = -6~C,
degree of decomposition ~ after 28 days = 16 ~.
Comparative example 3 (EP-A-0 441 197)
248.6 g water, 134.5 g white dextrin (89.2 ~ solids
content), 55.9 g maleic anhydride, 3.5 g of a 0.1 ~
aqueous solution of iron(II) ammonium sulphate and 82.2 g
of 50 ~ aqueous sodium hydroxide solution were placed in
the reactor described in comparative example 2 and heated
to boiling. Immediately after the commencement of
boiling, a solution of 155.9 g acrylic acid in 141.9 g
water was steadily added over 5 hours, and, separately
from this, a solution of 14.5 g of 50 ~ hydrogen peroxide
in 44.9 g water was steadily added over 6 hours, the
reaction mixture being heated to its boiling point with
stirring. After the addition of hydrogen peroxide was
complete, the reaction mixture was heated to boiling for
a further 1 hour and was thereafter neutralised to a pH
of 7 by adding 132. 5 g of 50 ~ aqueous sodium hydroxide
solution. A turbid, highly viscous, light brown solution
was obtained, with a solids content of 43.7 ~.
LBC(23~C) = 920 mg CaC03/g, LBC(60~C) = 660 mg CaCO~/g,
pour point = -5~C,
degree of decomposition ~ after 28 days = 26 ~.
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28 -
Comparative example 4 (EP-A-0 441 197)
254.7 g water, 160 g maltodextrin with a DE value of
about 3, 47.9 g maleic anhydride, 3.5 g of a 0.1 %
aqueous solution of iron(II) ammonium sulphate and 70.5 g
of 50 % aqueous sodium hydroxide solution were placed in
the reactor described in comparative example 2 and heated
to boiling. Immediately after the commencement of
boiling, a solution of 133. 6 g acrylic acid in 141.9 g
water was steadily added at a metered rate over 5 hours,
and a solution of 12.45 g of 50 % hydrogen peroxide in
44.4 g water was steadily added over 6 hours, whilst
keeping the reaction mixture boiling. After the addition
of hydrogen peroxide was complete, the reaction mixture
was heated to boiling for a further 1 hour. A turbid,
brown gel was obtained.
LBC(23~C) = 770 mg CaC03/g, LBC(60~C) = 650 mg CaC03/g,
degree of decomposition ~ after 28 days = 29 %.
Comparative example 5 (JP-A-61 03 1498)
253.4 g water, 89.7 g white dextrin (89.2 % solids
content) and 3.5 g of a 0.1 % aqueous solution of
iron(II) ammonium sulphate and 82.2 g of 50 % aqueous
sodium hydroxide solution were heated to boiling in the
reactor described in comparative example 2. After
reaction mixture had started to boil, a solution of 178.2
g acrylic acid in 141.9 g water was steadily added over 5
hours, and a solution of 16.6 g of 50 % hydrogen peroxide
in 44.4 g water was steadily added over 6 hours, with
boiling. After the addition of hydrogen peroxide was
complete, the reaction mixture was heated to boiling for
a further 1 hour, and was thereafter neutralised to a pH
of 7.2 by adding 50 ~ aqueous sodium hydroxide solution
and cooled. A turbid, viscous, brown solution was
obtained, with a solids content of 38.4 %. -
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29
LBC(23~C) = 1230 mg CaCO3/g, LBC(60~C) = 500 mg CaCO3/g,
pour point = -8~C,
degree of decomposition ~ after 28 days = 25 ~.
Consistency and colour:
The products from the comparative examples were intensely
coloured and were mostly turbid. They were viscous
liquids, and a gel was even formed in one case.
The products which are claimed exhibited properties which
were surprisingly more favourable. They were clear
liquids with only a slight yellow coloration.
Pour point:
The pour points of the products were measured following
ISO 3016-19741. The flow point denotes the temperature at
which the substance clearly still exhibits perceptible
flow after it has been cooled under specified conditions.
The flow behaviour of the solutions on cooling is
surprisingly better for the compounds claimed than for
the comparative products. Due to this effect, they can
still be handled satisfactorily even under unfavourable
external conditions (cold), i.e. they can be pumped and
conveyed even at low temperatures. The pour points of
the examples and comparative examples are compared in
Table la.
1 In departure from the Standard, a test tube with a
round bottom was used instead of a test tube with a flat
bottom. The effect of this alteration on the measured
results was judged to be negligible, particularly since
all the tests were performed in the same vessel and are
thus comparable with each other in each case. The error
in measurement within a series of measurements is quoted
as + 3~C.
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Table la: Flow points
Product Pour point [~C]
Example 7 -19
Example 8 -16
Comparative example 2 -6
Comparative example 3 -5
Comparative example 4 A gel even at RT
Comparative example 5 -8
RT = room temperature
Zahn-Wellens biodegradability:
The claimed products were decomposed considerably better
than those of the comparative tests. The degree of
decomposition of the examples and comparative examples is
compared in Table 2a.
Table 2a: Degree of decomposition ~ in the Zahn-Wellens
test after 28 days
Product Degree of decomposition
after 28 days [%]
Example 2 63
Example 3 52
Example 4 62
Example 7 45
Example 8 45
Comparative example 1 37
Comparative example 2 16
Comparative example 3 26
Comparative example 4 29
Comparative example 5 25
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Washing tests
In order to characterise the graft polymers according to
the invention as regards their incrustation-inhibiting
effect, they were incorporated in detergent compositions.
Test fabrics comprising huckaback towelling, white cotton
textile and cotton textile with green stripes were washed
with each of these detergent formulations. 25 wash
~ cycles were performed. The fabric was dry-ironed after
each wash. After each 10 and 25 washes the test fabric
was ashed (double determination). 2 g fabric in each
case were calcined in a pre-incinerator at 500~C for 1
hour, and were then ashed in a muffle furnace at 800~C
for 1 hour. The crucibles were re-weighed and the ash
contents were determined as a percentage. The more
effective a polymer is, the lower is the ash content.
The LSD values (least significant deviations) were
calculated according to DIN 44 983, Part 50. A ranking
was obtained by assigning marks to the individual
measured values determined for different fabrics.
Detergent A
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5
6.00 ~ Dehydrol LT7
1.00 ~ Edenor HT35
0.15 ~ Blankophor MBBH-766
0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda
2.70 % Portil N
1.10 ~ Relatin DM 4050
2.50 ~ sodium perborate tetrahydrate
11.70 ~ sodium perborate monohydrate
30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent
6.00 ~ EDTA
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WO 96/37530 _ 32 PCT/EP96/01922
5.40 ~ graft copolymer according to Example 1
(solids content)
0.50 ~ lipolase
0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate
Detergent B
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5
6.00 ~ Dehydrol LT7
1.00 ~ Edenor HT35
0.15 ~ Blankophor MBBH-766
0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda
2.70 ~ Portil N
1.10 ~ Relatin DM 4050
2.50 ~ sodium perborate tetrahydrate
11.70 ~ sodium perborate monohydrate
30.30 ~ Wessalith CS
0.60 ~ anti-foaming agent
6.00 ~ EDTA
5.40 ~ copolymer according to comparative example 1
(solids content)
0.50 ~ lipolase
0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate
Detergent C
10.00 ~ Marlon ARL
1.00 ~ Dehydrol TA5
6.00 ~ Dehydrol LT7
1.00 ~ Edenor HT35
0.15 ~ Blankophor MBBH-766
0.02 ~ Tinopal CBS-X
0.23 ~ Trilon B
12.00 ~ soda
2.70 ~ Portil N .-
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1.10 ~ Relatin DM 4050
2.50 ~ sodium perborate tetrahydrate
11.70 ~ sodium perborate monohydrate
30.30 ~ Wessalith CS
0.60 ~ anti-foaming a~ent
6.00 ~ EDTA
5.40 % Sokalan CP5 (solids content; widely-used
commercial product)
0.50 ~ lipolase
0.70 ~ Esperase 4.0 T
0.36 ~ sodium sulphate
Washing conditions
Secondary wash capacity: 1 cycle corresponding to 25
washes
Temperature / hardness: 60~ Celsius / 20~ dH
Washing machine type: Miele W 763
Program: boiling/coloured wash without
pre-wash
Amount of detergent: 80.0 g (6.15 g/l)
Ballast material: 18 pieces of white cotton
(about 2.7 kg) 3 pieces of terry cloth
3 pieces of towelling (on to
which the soiling materials
were sewn)
White fabric: 1 piece of terry cloth in each
case
(about 0.8 kg) 1 piece of towelling in each
case
2 pieces of white cotton in
each case (cotton / white)
2 pieces of green striped
cotton in each case (cotton /
GS)
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34 -.
Soiling material: blood (EMPA 111)
standard (EMPA 101)
cutaneous fat (WFK 10 G)
tea (WFK 10 G)
Hardening: in each odd washing operation
blood (EMPA 111)
standard (EMPA 101)
cutaneous fat (WFK 1-0 G)
tea (WFK 10 G)
Waschereiforschung Krefeld (WFK) [Krefeld Laundry
Research] (WFK) and the Eidgenossische Material
Prufanstalt (EMPA) Schweiz [Swiss Material Testing
Institute] sell test soiling materials for washing tests.
These test soiling materials are designated, for example,
as EMPA 111 for blood soiling material.
Table 1
Incrustation-inhibiting effect of the polymer according
to the invention from Example 1
Number of washes Fabric Detergent A
ash content [~]
terry cloth 0.62
towelling 0.47
cotton / GS 0.58
cotton / white 0.68
mean value 0.59
terry cloth 1.40
towelling 1.13
cotton / GS 1.15
cotton / white 1.31
mean value 1.25
LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
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Table 2
Incrustation-inhibiting effect of the comparative
examples
5 Number of FabricDetergent B Detergent C
washes ash content [~] ash content [~]
terry cloth 0.67 1.06
towelling 0.74 0.67
cotton / GS 0.79 ~ 1.14
cotton / 0.97 0.72
white
mean value 0.79 0.90
terry cloth 1.61 1.58
towelling 1.47 1.60
cotton / GS 1.74 1.88
cotton / 1.68 1.45
white
mean value 1.63 1.63
LSD values: F: 0.06 ~; HT: 0.08 ~; cotton/GS 0.04 ~;
cotton / white: 0.18 ~
The following ranking for the effectiveness of the
various polymers was obtained from the test results given
in Tables 1 and 2:
After 10 washes:
graft copolymer according to the invention more effective
than that of comparative example 1, which was more
effective than the commercial product Sokalan CP 5.
and after 25 washes:
graft copolymer according to the invention more effective
than that of comparative example 1, the effectiveness of
which was similar to that of the commercial product
Sokalan CP 5.
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- 36
Other advantages and embodiments of the invention follow
from the following claims.
