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Description  |
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THE PRIOR ART
The action of the known washing agent compositions and washing assistant
compositions is based to a substantial part on the presence of inorganic
or organic sequestering agents for alkaline earth metal ions. These
sequestering agents support the effect of other non-sequestering inorganic
or organic cleaning substances. To such sequestering agents belong, for
example, sodium tripolyphosphate. The use of this sequestering agent in
washing agent compositions and washing assistants has been criticized
publicly in connection with questions of ecology. Frequently, an opinion
has been expressed that the eutrophication of lakes is derived largely
from the phosphorus-containing compounds that come through such washing
agent compositions into the waters. Therefore, a demand has been made for
washing agent compositions with a low content of phosphorus.
OBJECTS OF THE INVENTION
An object of the invention is to replace the known phosphorus-containing
sequestering agents in washing agent compositions and washing assistant
compositions by active sequestering agents that contain phosphorus in a
very much lower amount and possess beyond that a good sequestering power
equal to an equal amount of sodium tripolyphosphate.
A further object of the present invention is the development of washing
agent compositions and washing assistant compositions comprising (a) from
0.5% to 70% by weight of a phosphonopolycarboxylate having the formula
##EQU3##
wherein R.sub.1 is a member selected from the group consisting of hydrogen
and methyl, R.sub.2 is a member selected from the group consisting of
hydrogen, alkyl having 1 to 4 carbon atoms and --CH.sub.2 --CHR.sub.1
--COOMe, X is a member selected from the group consisting of (1) a direct
bond between the carbon and the phosphorus,
##EQU4##
and Me is a member selected from the group consisting of hydrogen and a
cation capable of complex formation with alkaline earth metal ions, (b)
from 0 to 96.5% by weight of customary non-surface-active ingredients for
washing agents and (c) from 3% to 45% by weight of at least one
surface-active compound selected from the group consisting of anionic
surfaceactive compounds and non-ionic surface-active compounds.
A yet further object of the present invention in the development in the
process of washing and cleansing solid materials which comprises
contacting solid materials having soil thereon with an aqueous solution
containing from 0.5 to 80 gms/liter of a cleansing agent consisting of
from 30% to 99.5% by weight of at least one compound having a cleaning
action and from 70% to 0.5% by weight of a sequestering agent capable of
sequestering alkaline earth metal ions, for a time sufficient to disperse
and dissolve said soil in said aqueous solution and removing said cleansed
solid materials, the improvement consisting of utilizing, as said
sequestering agent, at least one phosphonopolycarboxylate sequestering
agent capable of sequestering alkaline earth metal ions having the formula
##EQU5##
wherein R.sub.1 is a member selected from the group consisting of hydrogen
and methyl, R.sub.2 is a member selected from the group consisting of
hydrogen, alkyl having 1 to 4 carbon atoms and --CH.sub.2 --CHR.sub.1
--COOMe, X is a member selected from the group consisting of (1) a direct
bond between the carbon and the phosphorus,
##EQU6##
and Me is a member selected from the group consisting of hydrogen and a
cation capable of complex formation with alkaline earth metal ions.
These and other objects of this invention will become more apparent as the
description thereof proceeds.
DESCRIPTION OF THE INVENTION
This invention relates to washing agent compositions or washing assistant
compositions, containing sequestering agents for alkaline earth metal
ions, being present as solids, pastes, dispersions or solutions containing
as a low phosphoruscontaining sequestering agent, at least one
phosphonopolycarboxylic acid of the formula I
##EQU7##
or water-soluble salts thereof, where R.sub.1 denotes a hydrogen or
methyl, R.sub.2 a hydrogen, an alkyl with 1 to 4 carbon atoms, or the
radical --CH.sub.2 --CHR.sub.1 --COOH, and X is a direct bond or the group
##EQU8##
where preferably a maximum of three carboxyl groups are present.
The phosphonopolycarboxylic acids of formula I and their water-soluble
salts, hereafter called "phosphonopolycarboxylic acids",
"phosphonopolycarboxylates" or "PPC", are the free acids and those
compounds where the hydrogen of the phosphonic acid group or groups and of
the carboxyl groups is substituted completely or partly by an alkali
metal, particularly sodium, or by ammonium. The water-soluble salts with
organic bases, particularly with aliphatic amines and alkylolamines with
not more than 6 carbon atoms in the molecule, can also be used.
PPC can represent the sole builder. It can also be used in combination with
alkaline-reacting salts which have little or no sequestering power for
alkaline earth metal ions to prevent the precipitation of alkaline earth
metal salts.
The washing agent compositions and washing assistant compositions according
to the invention are characterized in that they contain:
0.5% to 70% by weight of a phosphonopolycarboxylic acid of the above
defined formula I
0 to 96.5% by weight of other sequestering and nonsequestering, preferably
phosphorus-free builder salts.
3% to 45% by weight of at least one surface-active compound of the groups
of soaps, synthetic carboxylates, sulfates, sulfonates and of the
non-ionic polyglycolethers,
where the constituents of the washing agent compositions and washing
assistant compositions, particularly the phosphonopolycarboxylic acid and
other builder salts, are so selected that the preparations have a pH value
in a 1% aqueous solution of between 6 and 11.5, preferably between 7 and
11.
Preferably, the invention consists of washing agent compositions and
washing assistant compositions comprising (a) from 0.5% to 70% by weight
of a phosphonopolycaboxylate having the formula
##EQU9##
wherein R.sub.1 is a member selected from the group consisting of hydrogen
and methyl, R.sub.2 is a member slected from the group consisting of
hydrogen, alkyl having 1 to 4 carbon atoms and --CH.sub.2 --CHR.sub.1
--COOMe, X is a member selected from the group consisting of (1) a direct
bond between the carbon and the phosphorus,
##EQU10##
and Me is a member selected from the group consisting of hydrogen and a
cation capable of complex formation with alkaline earth metal ions. More
particularly, the phosphonocarboxylate has a maximum of three carboxyl
groups in the molecule. Me is selected from the group consisting of
hydrogen, alkali metal and H.NR.sub.3 where R.sub.3 is selected from the
group consisting of hydrogen, alkyl having 1 to 6 carbon atoms and alkylol
having 2 to 6 carbon atoms, and the pH of a 1% aqueous solution of the
compositions is between 6 and 11.5, preferably between 7 and 11.
The preparations according to the invention contain in addition other known
washing agent components, such as a bleaching component, textile
softeners, optical brighteners, soil suspension agents, foam regulators,
enzymes, dyes and perfumes, and water. Suitable according to the invention
are, for example, the following phosphonopolycarboxylic acids:
1-phosphonoethane-1,2-dicarboxylic acid
2-phosphonopropane-2,3-dicarboxylic acid
1-phosphonopropane-1,2,3-tricarboxylic acid
1-phosphonopropane-1,2-dicaboxylic acid
1-phosphono-2-methyl-propane- 1,2,3-tricarboxylic acid
2-phosphonobutane-2,3-dicarboxylic acid
2-phosphonobutane-2,3,4-tricarboxylic acid
2-phosphonobutane-1,2,4-tricarboxylic acid
1-phosphonobutane-1,2,3-tricarboxylic acid
1-phosphono-2-methyl-butane-1,2,3-tricarboxylic acid
2-phosphono-3-methyl-butane-2,3,4-tricarboxylic acid
2-phosphonopentane-2,3,4-tricarboxylic acid
2-phosphono-3-methyl-pentane-2,3,4-tricarboxylic acid
1,1-diphosphonopropane-2,3-dicarboxylic acid
1,1-diphosphono-2-methyl-propane-2,3-dicarboxylic acid
2,2-diphosphonobutane-3,4-dicarboxylic acid
1,1-diphosphonobutane-2,3-dicarboxylic acid
2,2-diphosphono-3-methyl-butane-3,4-dicarboxylic acid
2,2-diphosphonopentane-3,4-dicarboxylic acid
1,1-diphosphono-2-methyl-butane-2,3-dicarboxylic acid
2,2-diphosphono-3-methyl-pentane-3,4-dicarboxylic acid.
The phosphorus content of the phosphonopolycarboxylic acids to be used
according to the invention is mostly less than half the phosphorus content
of an equal amount of sodium tripolyphosphate, based on the sodium salts.
In the washing agent compositions, according to the invention, the total
phosphorus content depends on whether the lowphosphorus builder component
of these compositons consists of PPC alone or of a combination of PPC with
other builders, preferably alkali metal carbonates and/or silicates. The
phosphorus content of the compositions according to the invention is not
more than 4% by weight, preferably not over 2% by weight. It is thus less
than 2/5, mostly less than 1/5 of the total phosphorus content of a
comparable detergent containing sodium tripolyphosphate.
Preferably the low phosphorus builder component of the composition
according to the invention contains PPC together with alkali metal
carbonates and/or silicates whereby the weight ratio of PPC to carbonates
and/or silicates is between 1:100 and 4:1, preferably between 1:50 and
4:1, and particularly between 1:20 and 1:1.
The composition of the washing agent compositions and washing assistant
compositions according to the invention depends to a great extent on their
use. Products according to the invention, which are to be used as soaking
agents and those which are to be used as prewashing agents have, as a
rule, like the high-temperature universal or full washing agents, a pH of
between 9.5 and 11 in 1% aqueous solution. This is mostly achieved by a
higher content of alkaline-reacting builder salts. Products which are used
as fine or low temperature washing agents are usually neutral to weakly
alkaline in 1% aqueous solution (pH 9.5), but sometimes also weakly acid
(pH 6-7). The high temperature or universal or full washing agents also
differ from the other preparations by their content of a bleaching
component consisting of peroxide compounds, stabilizers and activators, if
necessary. The bleaching component can represent 10% to 50% by weight,
preferably 15% to 40% by weight of the entire composition.
Of particular importance in practice are the low foaming washing agents
used preferably in washing machines, where the surface-active component
has the following composition:
8% to 95%, preferably 25% to 75%, by weight of anionic surface-active
compounds of the sulfonate and/or sulfate type,
0% to 80%, preferably 10% to 50%, by weight of soap, including a portion of
low-foaming soap of saturated fatty acids with 20 to 24 carbon atoms,
where the quantitative ratio (sulfonate + sulfate):soap is 10:1 and 1:10,
preferably between 5:1 and 1:2,
0% to 80%, preferably 5% to 40%, by weight of non-ionic surface-active
compounds,
0% to 6%, preferably 0.5% to 3%, by weight of foam stabilizers,
0% to 8%, preferably 0.5% to 5%, by weight of non-surface-active foam
inhibitors,
where the foaming power of the surface-active component is reduced by the
presence of at least one foam inhibitor (low foaming soap and/or
non-surface-active foam inhibitor).
Washing agent compositions according to the invention which contain the
above-mentioned surface-active components can correspond, for example, to
the following recipes:
A. Full washing agent
0.5% to 40% by weight of PPC
5% to 60% by weight of other builder salts
8% to 35% by weight of surface-active components
10% to 40% by weight of bleaching components
1% to 5% by weight of magnesium silicate, and up to 15% by weight of other
customary constituents.
B. Prewashing agents:
0.5% to 30% by weight of PPC
10% to 70% by weight of other builder salts
3% to 10% by weight of surface-active components, and up to 15% by weight
of other customary ingredients.
C. Fine and low-temperature washing agents:
3% to 30% by weight of PPC
10% to 60% by weight of other builder salts
10% to 40% by weight of surface-active components, and up to 15% of other
customary ingredients.
The present invention, therefore, also includes in the process of washing
and cleansing solid materials which comprises contacting solid materials
having soil thereon with an aqueous solution containing from 0.5 to 80
gms/liter of a cleansing agent consisting of from 30% to 99.5% by weight
of at least one compound having cleaning action and from 70% to 0.5% by
weight of a sequestering agent capable of sequestering alkaline earth
metal ions, for a time sufficient to disperse and dissolve said soil in
said aqueous solution and removing said cleansed solid materials, the
improvement consisting of utilizing, as said sequestering agent, a least
one copolymer-carboxylate sequestering agent capable of sequestering
alkaline earth metal ions having the formula
##EQU11##
wherein R.sub.1 is a member selected from the group consisting of hydrogen
and methyl, R.sub.2 is a member selected from the group consisting of
hydrogen, alkyl having 1 to 4 carbon atoms and --CH.sub.2 --CHR.sub.1
--COOMe, X is a member selected from the group consisting of (1) a direct
bond between the carbon and the phosphorus,
##EQU12##
and Me is a member selected from the group consisting of hydrogen and a
cation capable of complex formation with alkaline earth metal ions.
The soaking, prewashing, fine-washing, washing and bleaching agent
compositions, according to the invention, containing
phosphonopolycarboxylates, can be used with textiles derived from the most
varied fibers of natural or synthetic origin. To them belong, for
instance, cotton, viscose or linen as well as textiles, that contain
highly processed cotton or synthetic fibers, such as polyamide, polyester,
polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene
chloride fibers. The washing agent compositions of the invention can also
be used for laundering of textiles, designated as "easy care",
occasionally also as "no-iron", of synthetic fiber-cotton-mixed fabrics.
The sequestering power of the phosphonopolycarboxylic acids is particularly
pronounced with respect to the alkaline earth metals, so that they can
support and enhance the washing and cleansing processes. On the other
hand, their sequestering power for heavy metals is, likewise as in other
known sequestering builders, only slight. It is, therefore, recommended to
add to the washing agents, according to the invention, such sequestering
agents for heavy metals in slight amounts of, for instance, from 0.1% to
5%, preferably 0.1% to 2% by weight. As sequestering agents for heavy
metals, particularly for copper, for instance, ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid or hydroxyethane-diphosphonic
acid or their salts are suitable.
The other customary ingredients of the above recipes A to C are the
following components, of which at least one is contained in the washing
agents according to recipes A to C in the indicated quantities:
0.1% to 5% by weight of a sequestering agent for heavy metals,
0.2% to 3% by weight of a soil suspension agent,
0.7% to 3% by weight of enzymes,
2% to 8% by weight of a textile softener,
0.1% to 1% by weight of an optical brightener,
0.01% to 1% by weight of dyes and perfumes,
0.2% to 2% by weight of antimicrobial compounds,
0 to 15% by weight of water.
The washing agent compositions and washing assistant compositions according
to the invention containing phosphonopolycarboxylic acids of formula I are
characterized, in the washing of textiles of various fibers of natural or
synthetic origin, by insensitivity to water hardness, even at high
temperatures, and by excellent washing power. A particular advantage of
the builder sequestering agents used according to the invention is their
insensitivity under conditions where sodium tripolyphosphate is already
partly or completely hydrolyzed. This insensitivty of the
phosphonopolycarboxylic acids to be used according to the invention is of
particular importance in the production most widely used today for solid
detergents and washing aids, namely, the hot-drying of a paste-like
aqueous solution of the ingredients.
The solid washing agents according to the invention are mostly available as
flowable products in the form of powders, granules, agglomerates or hollow
beads. However, they can also be present in many other forms, for example,
as rods, needles or flakes.
The most widely used method for the production of the powders is
spray-drying. The components, which are present at first in the form of a
powder or aqueous solution, are mixed to a slurry or solution. This
mixture is sprayed in a drying tower through nozzles into a hot air
current. The powder thus produced is mixed subsequently with other
powdered washing agent components, if necessary, which are less suitable
for spray-drying, such as the bleaching component, for example. Individual
washing agent ingredients can also be sprayed on the powders obtained in
the production of the detergents. Thus, for example, the non-ionic
surfaceactive compounds are frequently not added to the slurry, but
sprayed on a powdered washing agent component. This procedure is
particularly recommended for the non-surface-active foam inhibitors which
are sprayed preferably on a finished powder.
All other methods for the producton of flowable washing agent compositions
can be used as long as they ensure the composition of the washing agents
according to the invention.
In the following, the ingredients contained in the washing, rinsing and
cleansing agent compositions according to the invention, as arranged by
substance classes, are described more particularly.
The tensides or surface-active components in the washing agent composition
or washing assistant composition of the invention contain in the molecule
at least one hydrophobic organic residue and at least one anionic or
non-ionic water-solubilizing group. The preferably saturated hydrophobic
residue is mostly aliphatic, of mostly 8 to 26, preferably 10 to 22 and
especially 12 to 18, carbon atoms, or possibly also an alkyl aromatic
residue with 6 to 18, preferably 8 to 16, aliphatic carbon atoms. It may
be combined directly with the water-solubilizing groups or through
intermediate members, such as through benzene rings, carboxylic acid ester
links, carbonamide links or sulfonic-acid amide links as well as through
ester- or ester-like residues of polyhydric alcohols.
Soaps, which are derived from natural or synthetic fatty acids, possibly
also from resin acids or naphthenic acids, are utilizable as anionic
detergent substances, especially if these acids have iodine values of not
more than 30 and preferably less than 10.
Among the synthetic anionic tensides, the sulfonates and sulfates possess
particularly practical importance.
The sulfonates include, for example, alkylbenzenesulfonates with preferably
straight-chain C.sub.9 -.sub.15, especially C.sub.10 -.sub.14 alkyl
residues, alkanesulfonates, obtainable from preferably saturated aliphatic
C.sub.8 -.sub.18 especially C.sub.12 -.sub.18 hydrocarbons by
sulfochlorination or sulfoxidation or by the additions of bisulfite to an
olefin, mixtures of alkanesulfonates, hydroxyalkanesulfonates and
alkanedisulfonates, know under the name of "olefinsulfonates", which are
formed by acidic or alkaline hydrolysis of the sulfonation products which
first result from terminal or non-terminal C.sub.18 -.sub.18 and
preferably C.sub.12 -.sub.18 olefins by sulfonation with sulfur trioxide.
The sulfonates, utilizable according to the invention, include also salts,
preferably alkali metal salts of .alpha.-sulfo fatty acids and salts of
esters of these acids with mono or polyhydric alcohols with 1 to 4, and
preferably 1 to 2 carbon atoms.
Preferable are the carboxylate esters of .alpha.-sulfo, hydrogenated,
coconut fatty acids, palm kernel fatty acids or tallow fatty acids with
methanol or ethanol.
Tensides of the sulfate type include primary fatty alcohol monosulfates,
especially those derived from coconut fatty alcohols, tallow fatty
alcohols or from oleyl alcohol, are those of secondary alkanols having 9
to 26 carbon atoms. Also suitable are sulfatized fatty acid alkylolamides
or fatty acid monoglycerides and sulfated alkoxylation products of
alkylphenols (C.sub.8 -.sub.15 alkyl), primary fatty alcohols, or
secondary alkanols with 1 to 4 ethylene glycol residues in the molecule.
An anionic tensides of the carboxylate type, for example are the fatty acid
esters or amides of hydroxycarboxylic acids and aminocarboxylic acids or
hydroxysulfonic acids and aminosulfonic acids, such as the condensations
of fatty acids with sarcosine, glycollic acid, lactic acid and taurides or
isethionates.
The anionic tensides are mostly present as salts of the alkali metals,
particularly of sodium or potassium, as well as the ammonium salts and
salts of alkylamines or alkylolamines having 1 to 6 carbon atoms such as
mono, di or triethanolamine.
The nonionic tensides, for the sake of simplicity called hereafter
"Nonionics", include the polyethyleneglycol ethers, obtained by addition
of from 4 to 40, preferably 4 to 20 mols of ethylene oxide to 1 mol of
fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides
or alkane sulfonic acid amides. Particularly important are the addition
products of 5 to 16 mols of ethylene oxide adducted onto lauryl or stearyl
alcohols, oleyl alcohol, or onto secondary alkanols with 8 to 18,
preferably 12 to 18 carbon atoms, as well as on monoalkylphenols or
dialkylphenols with 6 to 14 carbon atoms in the alkyls. In addition to
these water-soluble non-ionics, also of interest are polyglycol ethers
with 1 to 4 ethylene glycol ether radicals in the molecule, which are not
soluble or not completely soluble in water, particularly if they are used
together with water-soluble, non-ionic or anionic surface-active
substances.
Furthermore the water-soluble, addition products of ethylene oxide, which
contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene
glycol ether groups, adducted onto polypropylene glycol ("Pluronics"),
alkylene diamine polypropylene-glycol ("Tetronics"), and alkyl
polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain can
also be used, where the polypropylene glycol chain acts as a hydrophobic
radical.
Further useful Nonionics are fatty acid alkylolamides or sulfonic acid
alkylolamides, derived, for example, from mono- or diethanolamine, from
dihydroxypropyl amine or other polyhydroxyalkyl amines, such as the
glycamines. Also the oxides of higher tertiary amines with a hydrophobic
alkyl residue and two shorter alkyl and/or alkylol residues, with up to 4
carbon atoms each, can be considered as Nonionics.
The foaming power of the tenside can be increased or reduced by combination
of suitable tenside types, as well as changed by additions of
non-surface-active organic substances.
Suitable foam stabilizers, particularly with anionic sides of the sulfonate
or sulfate type, are surface-active carboxy or sulfo betaines, as well as
the above-named nonionics of the alkylolamide type. Moreover, fatty
alcohols or higher terminal diols have been suggested for this purpose.
A reduced foaming power, that is desirable for the use in washing machines,
is often attained by combination of different tenside types, such as of
sulfates and/or sulfonates and/or of nonionics, on the one hand, with
soaps, on the other hand. In soaps, the foam inhibition with the degree of
saturation and the number of carbons in the fatty acid residue. Soaps
derived from saturated C.sub.20 -.sub.24 fatty acids have been proven good
as foam inhibitors.
The non-tenside foam inhibitors included N-alkylated aminotriazines,
optionally containing chlorine, which are obtained by the reaction of 1
mol of cyanuric acid chloride with 2 to 3 mols of a mono- and/or
dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl
radicals. Similarly effective are propoxylated and/or butoxylated
aminotriazines, such as, products that are obtained by the addition of
from 5 to 10 mols of propylene oxide to 1 mol of melamine and further
addition of from 10 to 50 mols of butylene oxide to this propylene-oxide
derivative.
Other non-tenside foam inhibitors are water-insoluble organic compounds,
such as paraffins or halogenated paraffins with melting points below
100.degree.C, aliphatic C.sub.18 to C.sub.40 ketones as well as aliphatic
carboxylic acid esters which contain in the acid or alcohol residue,
optionally also in both of these residues, at least 18 carbon atoms (such
as triglyceride or fatty acid/fatty alcohol esters). These compounds can
be used for the inhibition of foam, above all in combinations of tensides
of the sulfate and/or sulfonate type with soaps.
As particularly low-foaming nonionics which can be used both alone, and
also in combination with the abovementioned anionic, and nonionic tensides
and to reduce the foaming power of better foaming tensides, the addition
products of propylene oxide to the above-described surface-active
polyethyleneglycol ethers are suitable as well as the addition products
ethylene oxide with the above-described polypropylene glycols,
alkylenediamine polypropylene glycols or the C.sub.1 -.sub.10 -alkyl
polypropylene glycols.
All weakly acidic, neutral and alkaline reacting inorganic or organic
salts, particularly the alkali metal salts of compounds which can
precipitate or sequester calcium ions, are suitable as builders in
combination with the phosphonopolycarboxylates.
Weakly acidic, neutral or alkaline reacting salts which are usable are, for
example, the bicarbonates, carbonates, or silicates of the alkali metals,
such as sodium silicates with a Na.sub.2 O:SiO.sub.2 ratio of from 1:1 to
1:3.5. The alkali metal sulfates and borates are also suitable.
Among the suitable organic salts, that is the alkali metal salts of organic
acid compounds, are the non-surface-active sulfonic acid, carboxylic acid
and sulfocarboxylic acid salts containing from 1 to 8 carbon atoms, for
example, the alkali metal salts of benzenesulfonic acid, toluenesulfonic
acid or xylenesulfonic acid, sulfobenzoic acid, sulfophthalic acid,
sulfoacetic acid, sulfosuccinic acid or other sulfocarboxylic acids, as
well as the alkali metal salts of acetic acid or lactic acid.
Other suitable builder salts are the nitrogen and phosphorus free compounds
of the type of the polycarboxylic acids or their alkali metal salts which
form complexing salts with calcium ions. This type also includes polymers
containing carboxyl groups. Suitable are, for example citric acid,
tartaric acid, benzene-hexacarboxylic acid, polycarboxylic acids
containing carboxymethylether groups such as diglycolic acid,
2,2'-oxydisuccinic acid, as well as polyhydric alcohols or
polyhydroxycarboxylic acids partly or completely etherified with glycolic
acid, for example, bis(O-carboxymethyl)-ethylene glycol, mono or
bis-(O-carboxymethyl) glyceric acid, or carboxymethylated or oxidized
polysaccharides. Suitable are also the polymeric carboxylic acids with a
molecular weight of at least 350, such as polyacrylic acid,
poly-.alpha.-hydroxyacrylic acid, polymaleic acid, etc., as well as the
water-soluble salts, such as the alkali metal salts of copolymers of
maleic acid anhydride with ethylene, propylene or vinylmethyl ether and
the practically uncrosslinked polyhydroxycarboxylic acids and
polyaldehydecarboxylic acids containing C--C bonds in the principal chain,
which are composed substantially of ethylene units with one
carboxylformyl-, hydroxymethyl or hydroxyl group each. The
polyhydroxycarboxylic acids have a ratio of carboxyl groups to hydroxyl
groups of 1.1 to 15, preferably 2 to 9, and a degree of polymerization of
preferably 3 to 600 units. They can be produced, for example, by
copolymerization of acrolein and acrylic acid in the presence of hydrogen
peroxide and subsequent Cannizzaro reaction.
The polyaldehydecarboxylic acids have a ratio of carboxyl to formyl groups
of at least 1, and a degree of polymerization of preferably 3 to 100
units, optionally the polymers have terminal hydroxyl groups. They can be
produced, for example, by oxidative-polymerization of acrolein with
hydrogen peroxide.
The ingredients of the washing agents and washing auxiliaries of the
invention, particularly the builders are mostly so selected, that the
preparations react weakly acidic to distinctly alkaline in aqueous
solution. Preferably, the pH-value of a 1% solution of the preparation
mostly lies in the range from 6 to a maximum of 11.5. Fine-washing and low
temperature washing agents have mostly a weakly acidic to weakly alkaline
reaction (pH-value = 6 to 9.5), while soaking pre-washing and
boiling-washing agents are more strongly alkaline (pH-value = 9.5 to 11.5,
preferably 10 to 11).
Soil-suspension agents which keep the dirt, loosened from the fiber,
suspended in the liquor, and thus preventing graying, can also be utilized
in the washing agents and washing auxiliaries of the invention. For this,
water-soluble colloids, mostly organic in nature, are suitable, such as
this water-soluble salts of polymeric carboxylic acids, glue, gelatins,
salts of ethercarboxylic acids or ethersulfonic acids of starch or
cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
Also water-soluble polyamides, containing acidic groups, are suitable for
this purpose. Furthermore, soluble starch preparations and starch products
other than the above-named, such as degraded starch, aldehyde starches,
etc. may be used. Also polyvinylpyrrolidone is usable. Soil suspension
properties are also found in the addition products of 1 to 4 mols of
ethylene oxide adducted onto 1 mol of fatty alcohol with 8 to 18 carbon
atoms, described above a non-ionic surface-active compound.
Among the compounds serving as bleaching agents, releasing H.sub.2 O.sub.2
in water, sodium perborate tetrahydrate (NaBO.sub.2.H.sub.2 O.sub.2.3
H.sub.2 O) and the monohydrate (NaBO.sub.2.H.sub.2 O.sub.2) have
particularly practical importance. But also other H.sub.2 O.sub.2
releasing borates are usable, such as perborax Na.sub.2 B.sub.4
O.sub.7.4H.sub.2 O. These compounds may partly or completely be replaced
by other carriers of active oxygen, particularly by peroxyhydrates, such
as percarbonates, (Na.sub.2 CO.sub.3. 1.5H.sub.2 O.sub.2),
peroxypyrophosphates, citrate perhydrate, percarbamide, (urea-H.sub.2
O.sub.2) or melamine H.sub.2 O.sub.2 compounds as well as by H.sub.2
O.sub.2 releasing peracidic salts, such as caroates (KHSO.sub.5),
perbenzoates or perphthalates.
It is recommended to incorporate conventional water-soluble and/or
water-insoluble stabilizers for percompounds in amounts from 0.25% to 10%
by weight. Water-insoluble percompound stabilizers, which amount to, for
example, from 1% to 8%, preferably 2% to 7% of the weight of the whole
preparation, are, for example, the magnesium silicates, mostly obtained by
precipitation from aqueous solutions, MgO : SiO.sub.2 = 4:1 to 1:4,
preferably 2:1 to 1:2 particularly 1:1. In their place, other alkaline
earth metal, cadmium or tin silicates of a corresponding composition are
usable. Also water containing oxides of tin are suitable as stabilizers.
Water-soluble stabilizers which may be present together with the
water-insoluble ones, are the organic sequestering agents whose quantity
may amount to 0.25% to 5%, preferably 0.5% to 2.5% of the weight of the
whole preparation.
In order to obtain a satisfactory bleaching effect when washing at
temperatures below 80.degree.C, particularly in a range of 60.degree.C to
40.degree.C, bleach activator components are preferably incorporated in
the preparations.
Certain N-acyl-O-acyl compounds, forming with the H.sub.2 O.sub.2 organic
peracids, as well as carbonic acid or pyrocarbonic acid esters, whose
activation value for the percompounds ( = titer) is at least 3, preferably
at least 4.5 serve as activators for the percompounds, releasing H.sub.2
O.sub.2 in water. This activation value is determined in the following
manner.
Solutions that contain 0.615 gm/liter of NaBO.sub.2.H.sub.2
O.sub.2.3H.sub.2 O (4 m mol/liter) and 2.5 gm/liter of Na.sub.4 P.sub.2
O.sub.7 .10 H.sub.2 O are treated, after heating to 60.degree.C, with 4 m
mol/liter of activator and kept for 5 minutes at this temperature with
stirring. Then 100 ml of this liquid is added to a mixture of 250 gm of
ice and 15 ml of glacial acetic acid and titrated, immediately after the
addition of 0.35 gm of potassium iodide, with 0.1N sodium thiosulfate
solution with starch as indicator. The amount of thiosulfate solution used
in ml is the activation value ( = titer). At a 100% activation of the
peroxide used, it would amount to 8.0 ml.
Of the types of activators described below, particularly those compounds
are suitable which have a melting point of at least 70.degree.C,
preferably at least 100.degree.C, and especially at least 150.degree.C.
Furthermore, the equivalent weight of these compounds (under equivalent
weight is here understood the quotient from the molecular weight and the
number of acyl residues, or carbonic acid or pyrocarbonic acid residues in
the molecule) should be at most 170, preferably at most 130 and especially
at most 110.
The activators, usable according to the invention, include:
a. the N-diacylated and N,N'-tetraacylated amines, such as
N,N,N',N'-tetraacetyl-methylenediamine,
N,N,N',N'-tetraacetyl-ethylenediamine, N,N-diacetylaniline and
N,N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, such as the
compounds 1,3-diacetyl-5,5-dimethylhydantoin and
1,3-dipropionyl-hydantoin;
b. the N-alkyl-N-sulfonyl-carbonamides, for example, the compounds
N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide,
N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl-p-methoxybenzamide;
c. the N-acylated cylic hydrazides, acylated triazoles or urazoles, such as
the monoacetylmaleic acid hydrazide;
d. the O,N,N,-tri-substituted hydroxyl amines, such as
O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamine,
O-p-methoxybenzoyl-N,N-succinylhydroxylamine,
O-p-nitrobenzoly-N,N-succinylhydroxylamine and
O,N,N-triacetylhydroxylamine;
e. the N,N-diacyl-sulfurylamides, such as
N,N-dimethyl-N,N'-diacetyl-sulfurylamide and
N,N'-diethyl-N,N'-dipropionyl-sulfurylamide;
f. the triacylcyanurates, such as triacetylcyanurate and
tribenzoylcyanurate;
g. the carboxylic acid anhydrides, such as benzoic acid anhydride,
m-chlorobenzoic acid anhydride, phthalic acid anhydride, 4-chlorophthalic
acid anhydride;
h. the sugar esters, such as glucosepentaacetate;
i. the 1,3-diacyl-4,5-diacyloxy-imidazolidines, such as the compounds
1,3-diformyl-4,5-diacetoxyimidazolidine,
1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy
imidazolidine;
j. the acylated glycoluril compounds, such as tetraacetylglycoluril and
tetrapropionylglycoluril;
k. the diacylated 2,5-diketopiperazines, such as
1,4-diacetyl-2,5-diketo-piperazine, 1,4-dipropionyl-2,5-diketo-piperazine,
1,4-dipropionyl-3,6-dimethyl-2,5-diketo-piperazine.
l. the acylation products of propylenediurea or 2,2-dimethylpropylenediurea
(2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonane-3,7-dione or its 9,9-dimethyl
derivative), particularly tetraacetyl-propylenediurea,
tetrapropionyl-propylenediurea or their dimethyl derivatives;
m. the carbonic acid esters, for example, the sodium salts of
p-(ethoxycarbonyloxy)-benzoic acid and
p-(propoxycarbonyloxy)-benzenesulfonic acid.
Of particularly practical interest are the activator types named under (a),
(j), (k) a | | |
