U.S. patent number 3,779,931 [Application Number 05/184,213] was granted by the patent office on 1973-12-18 for compositions useful in the aqueous cold-bleaching of textiles including optical brighteners.
This patent grant is currently assigned to Henkel & Cie GmbH. Invention is credited to Helmut Bloching, Walter Fries, Dieter Jung.
United States Patent |
3,779,931 |
Fries , et al. |
December 18, 1973 |
COMPOSITIONS USEFUL IN THE AQUEOUS COLD-BLEACHING OF TEXTILES
INCLUDING OPTICAL BRIGHTENERS
Abstract
Compositions useful in the aqueous cold-bleaching of textiles
comprising (1) from 3 to 100 percent by weight of a bleaching
component comprising (a) from 95 to 99.99 percent by weight of a
mixture of (i) a percompound yielding H.sub.2 O.sub.2 in aqueous
solution and (ii) an activator for active oxygen selected from the
group consisting of N-acyl and O-acyl compounds having 2 to 9
carbon atoms in the acyl, said activator having an activating
action of at least 3 in the Per-Acid Formation Test, said
percompound and said activator being present in such ratio that
from 0.01 to 4 mols of said activator are present for each
gram-atom of active oxygen in said percompound, and (b) from 0.01
to 5 percent by weight of at least one optical brightener selected
from the group consisting of
4,4'-bis-(azolyl)-stilbene-2,2'-disulfonic acids,
stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives,
2-benzoxazolyl-4,5-naphthothiophene compounds, diphenyl-distyryl
compounds and water-soluble acid addition salts thereof, and (2)
from 0 to 97 percent of other customary ingredients of bleaching
agents or washing agents having a bleaching effect.
Inventors: |
Fries; Walter
(Erkrath-Unterbach, DT), Bloching; Helmut (Hilden
Rhld, DT), Jung; Dieter (Monheim-Baumberg,
DT) |
Assignee: |
Henkel & Cie GmbH
(Dusseldorf-Holthausen, DT)
|
Family
ID: |
25760165 |
Appl.
No.: |
05/184,213 |
Filed: |
September 27, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Dec 10, 1970 [DT] |
|
|
2060762 |
Jul 12, 1971 [DT] |
|
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2134691 |
|
Current U.S.
Class: |
8/648; 548/219;
548/260; 510/307; 252/186.39; 252/301.22; 8/111; 548/255 |
Current CPC
Class: |
C11D
3/42 (20130101); C11D 3/3917 (20130101) |
Current International
Class: |
C11D
3/40 (20060101); C11D 3/42 (20060101); C11D
3/39 (20060101); C11d 007/54 () |
Field of
Search: |
;252/99,95,102,89
;260/248R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Weinblatt; Mayer
Claims
We claim:
1. A bleaching component composition useful in an aqueous
cold-bleaching treatment consisting essentially of (a) from 95 to
99.9 percent by weight of a mixture of (i) a water-soluble
inorganic percompound yielding H.sub.2 O.sub.2 in aqueous solution
and (ii) an activator for active oxygen having the formula
##SPC25##
wherein R.sub.101, R.sub.102 and R.sub.103 represent a member
selected from the group consisting of alkyl having 1 to 3 carbon
atoms, haloalkyl having 1 to 3 carbon atoms, phenyl, and
phenylalkyl having 7 to 8 carbon atoms and X.sub.101 represents a
member selected from the group consisting of R.sub.101 and
R.sub.101 -CO said activator having an activating action of at
least 3 in the Per-Acid Formation test, said percompound and said
activator being present in such a ratio that from 0.01 to 4 mols of
said activator are present for each gram-atom of active oxygen in
said percompound, and (b) from 0.01 to 5 percent by weight of at
least one optical brightener having a formula selected from the
group consisting of ##SPC26## wherein azolyl represents an azole
structure of the formula selected from the group consisting of
##SPC27## A represents a member selected from the group consisting
of hydrogen and SO.sub.3 H, R represents a member selected from the
group consisting of hydrogen and alkyl having 1 to 5 carbon atoms,
R.sub.1 represents a member selected from the group consisting of
hydrogen and halogen, R.sub.2 represents a member selected from the
group consisting of CN, SO.sub.3 H and SO.sub.2 NHR, R.sub.4
represents a bivalent linkage selected from the group consisting of
--CH=CH--, ##SPC28##
X represents a member selected from the group consisting of --NH--,
--S--, and --O--, R.sub.5 represents a member selected from the
group consisting of hydrogen, alkyl having 1 to 5 carbon atoms and
phenyl, R.sub.6 and R.sub.7 represent members selected from the
group consisting of phenyl and phenyl substituted with at least one
substituent selected from the group consisting of alkyl having 1 to
4 carbon atoms, hydroxyalkyl having 2 to 5 carbon atoms, alkoxy
having 1 to 5 carbon atoms, chloro, CN, COOH, SO.sub.3 H, CO.sub.2
Cl and SO.sub.2 N R.sub.8 R.sub.9, and R.sub.8 and R.sub.9 are
members selected from the group consisting of hydrogen, alkyl
having 1 to 5 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms
and, taken together with the nitrogen, piperidino, piperazino,
morpholino and pyrrolidino, and water-soluble salts thereof.
2. The composition of claim 1 containing from 99.98 to 97.5 percent
by weight of component (a) mixture and 0.02 to 2.5 percent by
weight of component (b) optical brightener.
3. The composition of claim 2 wherein said activator for active
oxygen has an activating action of at least 4.5 in the Per-Acid
Formation Test and said percompound and said activator are present
in such a ratio that from 0.05 to 2 mols of said activator are
present for each gram-atom of active oxygen in said
percompound.
4. The composition of claim 3 wherein said percompound yielding
H.sub.2 O.sub.2 in aqueous solution is a water - soluble
perborate.
5. The composition of claim 1 having an addition content, based on
said total composition, of at least one compound selected (1) from
0 to 5 percent by weight of a corrosion inhibitor selected from the
group consisting of triazoles and tetrazoles containing at least
one of the groups =Nme and =NOMe where Me represents a metal or a
hydrogen atom replaceable by a metal, (2) from 0 to 20% by weight
of water-soluble salts of partial esters of fatty alcohols having
10 to 22 carbon atoms and their ethoxylated and propoxylated
compounds having 1 to 10 alkoxyl groups, with orthophosphoric acid,
pyrophosphoric acid and polyphosphoric acid, and (3) from 0 to 10
percent by weight of an organic sequestering builder salt for heavy
metals.
6. The composition of claim 5 wherein said water-soluble salts of
partial esters has the formula ##SPC29##
wherein A is a member selected from the group consisting of
hydrogen and ##SPC30## with the proviso that one A may be hydrogen,
R.sub.1 is a member selected from the group consisting of hydrogen
and methyl, R.sub.2 is a fatty alcohol moiety having from 10 to 22
carbon atoms, and n is an integer from 0 to 10.
7. The composition of claim 1 wherein said activator for active
oxyten is a member selected from the group consisting of
tetraacetylglycoluril, tetrapropionylglycoluril,
methyltriacetylglycoluril and diacetyldibenzoylglycoluril.
8. A process for the stabilization of optical brighteners against
deterioration in aqueous solutions in the presence of copper ions
and H.sub.2 O.sub.2 which consists essentially of the steps of
adding to an aqueous solution containing (1) small amounts of
copper ions, (2) an effective amount for optical brightening for
textiles of an optical brightener having a formula selected from
the group consisting of ##SPC31##
wherein azolyl represents an azole structure of the formula
selected from the group consisting of ##SPC32##
A represents a member selected from the group consisting of
hydrogen and SO.sub.3 H, R represents a member selected from the
group consisting of hydrogen and alkyl having 1 to 5 carbon atoms,
R.sub.1 represents a member selected from the group consisting of
hydrogen and halogen, R.sub.2 represents a member selected from the
group consisting of CN, SO.sub.3 H and SO.sub.2 NHR, R.sub.4
represents a bivalent linkage selected from the group consisting of
--CH=CH--, ##SPC33##
X represents a member selected from the group consisting of --NH--,
--S--, and --O--, R.sub.5 represents a member selected from the
group consisting of hydrogen, alkyl having 1 to 5 carbon atoms and
phenyl, R.sub.6 and R.sub.7 represent members selected from the
group consisting of phenyl and phenyl substituted with at least one
substituent selected from the group consisting of alkyl having 1 to
4 carbon atoms, hydroxyalkyl having 2 to 5 carbon atoms, alkoxy
having 1 to 5 carbon atoms, chloro, CN, COOH, SO.sub.3 H, CO.sub.2
Cl and SO.sub.2 N R.sub.8 R.sub.9, and R.sub.8 and R.sub.9 are
members selected from the group consisting of hydrogen, alkyl
having 1 to 5 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms
and, taken together with the nitrogen, piperidino, piperazino,
morpholino and pyrrolidino, and their water-soluble salts, and (3)
an effective amount for bleaching of a water-soluble inorganic
percompound yielding H.sub.2 O.sub.2 in aqueous solution, an amount
of an activator for said inorganic percompounds selected from the
group consisting of N-acyl and O-acyl compounds having 2 to 9
carbon atoms in the acyl, said activator having an activating
action of at least 3 in the Per-Acid Formation test, said
percompound and said activator having present in such ratio that
from 0.01 to 4 mols of said activator are present for each
gram-atom of active oxygen in said inorganic percompound.
Description
THE PRIOR ART
It is known to use aqueous solutions of hydrogen peroxide or of
percompounds, yielding hydrogen peroxide in water, as oxidation and
bleaching baths, particularly for fibrous substances and preferably
for textiles. These bleaching baths may also be solutions of
bleaching washing auxiliaries or washing agents. In such aqueous
solutions the active oxygen is effective generally only at
temperatures of from 80.degree.C to 100.degree.C.
It has also been proposed to use organic compounds that belong to
certain types of N-acyl or O-acyl compounds, in such treatment
baths as activators for the percompounds. These activators
transform the hydrogen peroxide present in the washing liquor into
an organic peracid. By the process, the active oxygen is liberated
at substantially lower temperatures of, for instance, 20.degree. to
70.degree.C, preferably 30.degree. to 60.degree.C, in a bleaching
active state. The compositions intended for the preparation of such
treatment baths for textiles may contain optical brighteners.
Unfortunately, however, it was found that the bleaching baths
containing N-acyl or O-acyl activators had undesirable side effects
when utilized in the presence of copper such as is present in most
washing equipment and, in addition, these bleaching baths
containing N-acyl or O-acyl activators had an adverse effect on
many optical brighteners also present in the treatment bath or on
the treated textiles.
OBJECTS OF THE INVENTION
An object of this invention is the development of compositions
useful in the aqueous cold-bleaching treatment which overcome the
drawbacks of the prior art compositions.
Another object of the present invention is the development of a
bleaching component composition useful in an aqueous cold-bleaching
treatment consisting essentially of (a) from 95 to 99.99 percent by
weight of a mixture of (i) a percompound yielding H.sub.2 O.sub.2
in aqueous solution and (ii) an activator for active oxygen
selected from the group consisting of N-acyl and O-acyl compounds
having 2 to 9 carbon atoms in the acyl, said activator having an
activating action of at least 3 in the Per-Acid Formation test,
said percompound and said activator being present in such ratio
that from 0.01 to 4 mols of said activator are present for each
gram-atom of active oxygen in said percompound, and (b) from 0.01
to 5 percent by weight of at least one optical brightener selected
from the group consisting of
4,4'-bis-(azolyl)-stilbene-2,2'-disulfonic acids,
stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives,
2-benzoxazolyl-4,5-naphthothiophene, diphenyl- distyryl compounds
and water-soluble acid addition salts thereof.
A further object of the invention is the development of a bleaching
and optical brightening composition useful in an aqueous
cold-bleaching treatment consisting essentially of (1) from 3 to
99.9 percent by weight of a bleaching component consisting
essentially of (a) from 95 to 99.99 percent by weight of a mixture
of (i) a percompound yielding H.sub.2 O.sub.2 in aqueous solution
and (ii) an activator for active oxygen selected from the group
consisting of N-acyl and O-acyl compounds having 2 to 9 carbon
atoms in the acyl, said activator having an activating action of at
least 3 in the Per-Acid Formation Test, said percompound and said
activator being present in such ratio that from 0.01 to 4 mols of
said activator are present for each gram-atom of active oxygen in
said percompound, and (b) from 0.01 to 5 percent by weight of at
least one optical brightener selected from the group consisting of
4,4'-bis-(azolyl)-stilbene-2,2'-disulfonic acids,
stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives,
2-benzoxazolyl-4,5-naphthothiophene, diphenyl- distyryl compounds
and water-soluble acid addition salts thereof, and (2) from 0.1 to
97 percent by weight of at least one compound selected from the
group consisting of (a) corrosion inhibitors selected from the
group consisting of triazoles and tetrazoles, (b) water-soluble
salts of a phosphorus acid ester selected from the group consisting
of partial esters of fatty alcohols having from 10 to 22 carbon
atoms and their ethoxylates and propoxylates having from 1 to 10
alkoxy units, with orthophosphoric acid, pyrophosphoric acid and
polyphosphoric acids, (c) organic sequestering agents for heavy
metal ions, (d) alkali metal alkaline-reacting inorganic builder
salts, (e) stabiizers for said percompounds, (f) tensides selected
from the group consisting of anionic surface-active compounds,
non-ionic surface-active compounds and amphoteric surface-active
compounds, (g) water-soluble organic builder salts, (h)
antimicrobial agents, (i) soil suspension agents, (j) enzymes, (k)
foam stabilizers, (l) non-surface-active foam inhibitors, (m)
textile softeners, and (n) water.
These and other objects of the invention will become more apparent
as the description thereof proceeds.
DESCRIPTION OF THE INVENTION
The invention relates to activator-containing compositions for the
preparation of cold-bleaching liquors, particularly of
cold-bleaching active washing liquors. These agents are
characterized in that they contain:
3 to 100 percent, preferably 5 to 90 percent, by weight of a
bleaching component, consisting of:
a. 99.99 to 95 percent, preferably 99.98 to 97.5 percent, by weight
of a percompound, yielding H.sub.2 O.sub.2 in aqueous solution, as
well as an N-acyl or O-acyl compound, serving as activator for
H.sub.2 O.sub.2, that possesses an activations value determined by
the Per-Acid Formation Test, for the percompound of at least 3,
preferably of at least 4.5, whereby the percompound and the
activator are present in such amounts, that at least 0.01 and at
most 4, preferably at least 0.05 and at most 2, mols of activator
are present per gram atom of active oxygen in said percompound.
b. 0.01 to 5 percent, preferably 0.02 to 2.5 percent, by weight of
at least one optical brightener of the following types:
4,4'-bis-(azolyl)-stilbene-2,2'-disulfonic acids,
stilbyl-naphthotriazoles,
bis-(benzoxazolyl)-derivatives,
diphenyldistyryl compounds, and/or
2-benzoxazolyl-4,5-naphthothiophene, whereby the named optical
brighteners, insofar as they are acids, particularly sulfonic
acids, are also present in the form of their salts.
97 to 0, preferably 95 to 10 percent by weight of other customary
ingredients of bleaching agents or of bleaching washing agents.
The brighteners named under (b) may be utilized singularly or in
combination.
Insofar as the optical brighteners, to be used according to the
invention, contain sulfonic acid or carboxylic acid residues, they
are preferably utilized in the form of their water-soluble alkali
metal salts, ammonium salts or salts of alkylamines and
alkylolamines with 1 to 6 carbon atoms in the molecule.
For reasons of simplification in the following, by "activators,"
the above-mentioned N-acyl or O-acyl compounds with the activation
value given there are understood.
The products of the invention may be utilized for the bleaching or
bleaching laundering of many different fibers of natural or
synthetic origin. Cotton, regenerated cellulose or linen and
particularly the "easy care" textiles that consist of highly
processed cotton or of synthetic fibers, such as polyamide,
polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or
polyvinylidene chloride fibers or mixtures, may be bleached by the
products of the invention. The textiles designated as "easy care"
or "no iron" include also such synthetic fibers-cotton mixed
fabrics that may be specially finished.
The products of the invention are particularly suitable for the
bleaching and the bleaching laundering of these "easy care"
textiles, since already at temperatures of 20.degree.to
70.degree.C, preferably 30.degree. to 60.degree.C, on the basis of
the bleaching activation, a degree of whiteness is attained such as
can only be attained at temperatures of 70.degree. to 100.degree.C,
preferably 80.degree. to 95.degree.C in the absence of activators.
The high degree of whiteness, attained with active oxygen and
activators at lower temperatures, is above all advantageous for the
effect of the optical brighteners.
It has been found that the effect of conventional optical
brighteners is often impaired in the presence of the "activators."
This impairment is more strongly observed in the presence of heavy
metals, such as copper in the washing liquor. These copper ions may
be naturally present in the water or may come from the cooper
heating bars of the washing machine. These disadvantages and their
cause were not previously known. It is, therefore, a particular
merit of the invention to have found that the effect of the
above-named optical brighteners is not reduced by the presence of
"activators."
Although the effect of the optical brighteners, to be utilized
according to the invention, is not impaired or if impaired only in
a substantially reduced extent than it is the case with other
optical brighteners, it is, however, recommended to add to the
products of the invention the below described phosphoric acid
esters and/or corrosion inhibitors, whose amount may account for up
to 25 percent by weight of the composition, as well as up to 10
percent by weight, preferably 0.1 to 7 percent, by weight of
organic sequestering agents for such ions. The compositions of the
invention may contain as corrosion inhibitors the following
substances in the amounts stated:
0 to 5 percent, preferably 0.1 to 2 percent, by weight of corrosion
inhibitors of the triazole and/or tetrazole types, that contain a
=NMe group or =NOMe group, in which Me is a metal or a hydrogen
atom replaceable by a metal,
0 to 20 percent, preferably 1 to 10 percent, by weight of
water-soluble salts of partial esters of fatty alcohols with 10 to
22, preferably 16 to 18, carbon atoms of their ethoxylation and/or
propoxylation products, containing 1 to 10, preferably 2 to 6,
glycol ether groups in the molecule with ortho-, pyro- or
polyphosphoric acid (hereinafter called "phosphoric acid esters").
During the bleaching process the acyl radicals of the "activators"
are liberated as carboxylic acids. It is recommended, therefore, to
add to the agents, according to the invention, so much of alkali
metal salts of weak acids, that at least a fourth of the carboxylic
acids formed are bound as salts. Such salts are, for instance, the
alkali metal carbonates, alkali metal silicates and alkali metal
borates. Therefore, the formulation of the products of the
invention is advantageously in the following range:
5 to 90 percent, preferably 10 to 70 percent, by weight of the
above described bleaching component, consisting of percompound,
activator and brightener,
0 to 25 percent, preferably 0.1 to 20 percent, by weight of the
above-described corrosion inhibitors, phosphoric acid esters and/or
sequestering agents for heavy metals, particularly copper,
95 to 10 percent, preferably 89.9 to 10 percent, by weight of
neutral, but preferably alkaline-reacting builder salts customary
in washing agents or washing auxiliaries as well as, optionally,
tensides, where such amounts of alkali metal salts of weak acids
are present, that the acyl groups contained in the activators on
liberation are bound, at least to one fourth the total amount in
the form of salts.
Bleaching textile treating agents, composed according to the above
formulation may be marketed as special products for the textile
industry or for commercial laundries or as soaking, prewash and
washing agents, preferably usable in the home.
The special products for commercial use contain mostly more than 50
percent by weight of the bleaching component of the invention, this
amount being based on the pure activator, the pure percompound and
the pure brightener without further additives. Of course, such
products may also be used at home for special purposes, for
instance, as soaking or washing agents with increased bleaching
effect, that may be of interest as cold-washing agent, or as
bleaching rinsing agent for the washed laundry.
The products, to be used as soaking, prewash and washing agents for
home use, contain mostly lesser amounts of percompounds, activators
and optical brighteners. These are present mostly in amounts of
from 5 to 50 percent preferably of from 10 to 35 percent by weight.
In addition, these agents contain as further essential ingredients
alkaline-reacting, non-sequestering builder salts as well as
tensides. The above-described phosphoric acid esters are at the
same time tensides and may, for this reason, be contained in larger
amounts than given in the above formulation. The same goes
accordingly for the sequestering agents for copper. For this
reason, in the following formulation for soaking, prewash and
washing agents, the phosphoric acid esters are assigned to the
tensides and the sequestering agents for copper are assigned to the
sequestering builder salts.
The products, according to the invention, can also be used
advantageously as soaking agents, particularly if the laundry
remains for a longer time in the solutions of the soaking agents.
Such soaking agents have approximately the following
composition:
0 to 5 percent by weight of tensides, including the optionally
present phosphoric acid esters,
95 to 45 percent by weight, preferably 90 to 60 percent, by weight
of preferably alkaline-reacting builder salts, as well as the
optionally present corrosion inhibitors and/or the optionally
present sequestering agents for heavy metals,
5 to 50 percent by weight, preferably 10 to 35 percent by weight,
of the bleaching component of the invention.
In addition, the below described washing agent ingredients, mostly
used in smaller amounts, may be present in such soaking agents,
such as antimicrobial acting compounds, soil suspension agents,
enzymes, perfumes, dyes, etc.
Since the effect of the activators is connected with a use of an
alkali, the builder salts ought to contain sufficient amounts of
strongly alkaline-reacting salts, such as alkali metal carbonates,
in order to prevent a lowering of the pH value of the bleaching or
washing liquor below the desired value.
A preferred application field of the invention are the
cold-bleaching prewashing and washing agents, whose composition
lies generally in the range of the following formula:
5 to 40 percent, preferably 7 to 30 percent, by weight of a tenside
component, containing at least one tenside from the type of the
sulfonates, sulfates, soaps, non-ionics and/or of the phosphoric
acid esters as well as, optionally, one or more of the following
substances:
0 to 10 percent, preferably 0.5 to 8 percent, by weight of foam
stabilizers,
0 to 10 percent, preferably 0.5 to 8 percent, by weight of
non-surface-active foam inhibitors,
10 to 90 percent, preferably 30 to 55 percent, by weight of
sequestering and/or non-sequestering builder salts, including the
alkali metal salts of weak acids intended for the binding of the
acids liberated by the activator as well as optionally present
corrosion inhibitors and/or sequestering agents for heavy metals,
whereby at least a part of these builder salts, preferably, the
greatest amount, react alkaline, and whereby the amount of the
alkaline to neutral-reacting builder salts preferably amounts to
0.5 to 7 times, and particularly 1 to 5 times the amount of the
total tenside component,
5 to 50 percent, preferably 10 to 35 percent, by weight of the
bleaching component according to the invention,
0 to 20 percent, preferably 2 to 15 percent, by weight of other
washing agent ingredients, such as textile softeners, corrosion
inhibitors, antimicrobial active compounds, soil suspension agents,
enzymes, perfumes, dyes, water.
Fine washing agents, to be applied at temperatures up to
70.degree.C, whose tenside content is mostly in the range of from 8
to 40 percent, preferably 12 to 40 percent, by weight, also fall
within this general formulation. Insofar as these fine washing
agents are not intended for use in washing machines, particularly
in drum-washing machines, they need not contain foam
inhibitors.
Of particular practical significance are the washing agents,
intended for the use in washing machines, preferably in drum
washing machines, in which the tenside component amounts mostly to
7 to 30 percent by weight. The tenside component contains mostly at
least one of the three following tenside types in the amounts
given:
15 to 99 percent, preferably 35 to 90 percent, by weight of
sulfonates and/or sulfates with preferably 8 to 18 carbon atoms in
the hydrophobic moiety,
10 to 60 percent, preferably 10 to 50 percent, by weight of
non-ionic surface-active compounds,
1 to 60 percent, preferably 3 to 50 percent, by weight of
phosphoric acid esters as well as, optionally one or several of the
following compounds:
5 to 70 percent, preferably 10 to 60 percent, by weight of
soap,
0 to 10 percent, preferably 0.5 to 8 percent, by weight of foam
stabilizers,
0 to 10 percent, preferably 0.5 to 8 percent, by weight of
non-surface-active foam inhibitors,
whereby, however, the foaming power of the tenside components is
reduced either by the simultaneous presence of different tensides,
diminishing reciprocally the foaming power and/or of foam reducing
soap and/or of non-surface-active foam inhibitors.
Of the, preferably inorganic, per-compounds yielding H.sub. 2
O.sub.2 in aqueous solution, sodium perborate tetrahydrate
(NaBO.sub.2.sup.. H.sub.2 O.sub.2.sup.. 3H.sub.2 O) is of special
practical importance. Partly or completely dehydrated perborates,
i.e., up to NaBO.sub.2.H.sub.2 O.sub.2, may be used in its place.
Borates such as NaBO.sub.2.sup.. H.sub.2 O.sub.2, described in
German Pat. No. 901,287 and U.S. Pat. No. 2,491,789, in which the
ratio Na.sub.2 O:B.sub.2 O.sub.3 is less than 0.5:1 and preferably
lies in the region of 0.4 to 0.15:1, while the ratio H.sub.2
O.sub.2 :Na lies in the region of 0.5 to 4:1 are also useful. All
these perborates may be wholly or partly replaced by other
inorganic per-compounds, especially by peroxyhydrates, such as the
peroxyhydrates of ortho-, pyro- or polyphosphates, especially of
the tripolyphosphates, as well as the carbonates.
It is advisable to incorporate in the compositions from 0.25 to 10
percent by weight of the usual water-soluble and/or water-insoluble
stabilizers for the stabilization of the per-compounds. Suitable
water-insoluble per-compound stabilizers which, for example,
constitute 1 to 8 percent, preferably 2 to 7 percent, of the weight
of the total preparation, are the magnesium silicates
(MgO:SiO.sub.2 = 4:1 to 1:4, preferably 2:1 to 1:2 and especially
1:1), mostly obtained by precipitation from aqueous solutions.
Other alkaline earth metal, cadmium or tin silicates of
corresponding composition are utilizable in their place. The
above-mentioned organic sequestering agents for copper are useful
as water-soluble per-compound stabilizers.
The activators to be used according to the invention should have,
according to the above definition, an activation value of at least
3, preferably of at least 4.5 in the Per-Acid Formation Test.
Per-Acid Formation Test
The activation value (= titre) for the activators is determined in
the following way:
Solutions which contain 0.615 gm/liter of NaBO.sub.2.sup.. H.sub.2
O.sub.2. 3H.sub.2 O (4 mMol/liter) and 2.5 gm/liter of Na.sub.4
P.sub.2 O.sub.7.sup.. 10 H.sub.2 O, are heated to 60.degree.C, and
then are mixed with 4 mMol/liter of activator and maintained at the
said temperature for 5 minutes 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 addition of 0.35 gm of
potassium iodide with 0.1 N sodium thiosulfate solution, using
starch as indicator. Under the given experimental conditions, for a
100 percent activation of the peroxide used, 8.0 ml of thiosulfate
solution are consumed, the titre is 8.0. This maximum value is, of
course, seldom attained. Good activators have a titre of at least
4.5, preferably from 5 to 7. Useful results are often obtained with
activators having a titre of at least 3.0.
Activators of the N-acyl or O-acyl compounds type contain an acyl
residue R--CO--, in which R represents optionally substituted
hydrocarbon residues with 1 to 8 carbon atoms. If the residues R
are aliphatic, they preferably have 1 to 3 carbon atoms, and if
they are aromatic, they may contain up to 8 carbon atoms.
Consequently, the residue R is preferably one of the following:
lower alkyl, such as methyl, ethyl, N-propyl or isopropyl; phenyl;
alkylphenyl such as toluyl or xylyl residues. Suitable substituents
are C.sub.1.sub.-3 alkoxy groups, halogen atoms, nitro or nitrile
groups; when Ris an aromatic residue it may be chloro- and/or
nitro-substituted, especially m-chloro or m- or
p-nitro-substituted. Such substituents are, for example,
chloroalkyl having 1 to 3 carbon atoms, m-chlorophenyl,
p-nitrophenyl, and p-methoxyphenyl.
Of the activators described below, compounds with a melting point
of at least 70.degree.C, preferably at least 100.degree.C and
especially at least 150.degree.C, are specially suitable. Further
the equivalent weight of these compounds should be not more than
170, preferably not more than 130 and especially not more than 110
(the equivalent weight is here the quotient of the molecular weight
and the number of R--CO-- residues present in the molecule where
the compound is N-acylated or O-acylated).
The types of compound mentioned under (a) to (1) are useful
activators according to the invention. In the formulae the numbered
residues R have the meaning given for R above unless specifically
otherwise indicated. If several residues R are present in a
molecule, they may be the same or different.
a. N-diacylated amines of the formula I, in which X represents a
residue R or one of the residues Ia, Ib, or Ic. ##SPC1##
From this class of compounds, N,N,N',N'-tetraacetylmethylenediamine
(melting point 92.degree.-95.degree.C), N,N,N',N'-
tetraacetylethylenediamine, N,N-diacetylaniline and
N,N-diacetyl-p-toluidine are named as examples.
b. N-alkyl-N-sulfonyl-carbonamides of formula II, in which R.sub.23
preferably signifies a C.sub.1.sub.-3 alkyl residue. ##SPC2##
Activators of this type are, for example,
N-methyl-N-mesylacetylamide (melting point 73.degree.-79.degree.C),
N-methyl-N-mesyl-benzoylamide (m.p. 116.degree.-118.5.degree.C),
N-methyl-N-mesyl-p-nitrobenzoylamide (m.p.
159.degree.-160.degree.C) and
N-methyl-N-mesyl-p-methoxybenzoylamide (m.p.
117.degree.-117.5.degree.C).
c. N-acylhydantoins of formula III, in which at least one of the
residues X.sub.31 and X.sub.32 represent an R--CO-- residue, while
the other may also represent a residue R or a carboxymethyl or a
lower alkoxycarbonylmethyl residue; Y.sub.31 and Y.sub.32 represent
hydrogen or alkyl residues with 1 to 2 carbon atoms. ##SPC3##
Suitable compounds are, for example, 1,3-diacetyl-5,5-
dimethylhydantoin, 1,3-dipropionylhydantoin (m.p. 104.5.degree.to
106.degree.C) and 3-benzoylhydantoin-1-acetic acid ethyl ester.
d. Cyclic N-acylhydrazides of formula IV, in which the two nitrogen
atoms are part of a 5- or 6-membered hetero-ring from the group of
maleic acid hydrazide, phthalic acid hydrazide, triazole or
urazole. ##SPC4## A suitable compound is, for example,
mono-acetyl-maleic acid hydrazide.
e. Triacyl-cyanurates of formula VI ##SPC5##
For example, triacetyl- or tribenzoyl-cyanurate.
f. Optionally substituted anhydrides of benzoic or phthalic acids,
especially benzoic anhydride itself or m-chlorobenzoic anhydride
(m.p. 95.degree.C).
g. O,N,N-trisubstituted hydroxylamines of formula VII, in which
R.sub.73 represents a residue R, preferably a methyl or ethyl
residue, an optionally substituted aryl residue or the group VIIa,
while X.sub.71 and X.sub.72 represent one of the residues R--CO--,
R--SO.sub.2 -- or one of the above-described aromatic residue, or
each can be linked with the corresponding residue R.sub.71 or
R.sub.72 to give a succinyl or phthalyl residue and n signifies a
whole number from 0 to 2. ##SPC6##
Activators of this type are, for example,
O-benzoyl-N,N-succinyl-hydroxylamine (m.p.
137.degree.-139.degree.C), O-acetyl-N,N-succinyl-hydroxylamine
(m.p. 132.degree.-134.degree.C),
O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine (m.p.
142.degree.-145.degree.C),
O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine (m.p.
212.degree.-215.degree.C) and O,N,N-triacetyl-hydroxylamine.
j. N,N'-diacyl-sulfurylamides of formula VIII, in which R.sub.81
and R.sub.83 preferably represent C.sub.1-4 alkyl residues or aryl
residues such as phenyl, while R.sub.82 and R.sub.84 preferably
represent C.sub.1-5 alkyl residues, especially C.sub.1-3 alkyl
residues. ##SPC7##
N,n'-dimethyl-N,N'-diacetyl-sulfurylamide (m.p. 58.degree. to
60.degree.C) and N,N'-diethyl-N,N'-dipropionyl-sulfurylamide (m.p.
95.degree.-97.degree.C) may be mentioned as examples.
k. 1,3-Diacyl-4,5-diacyloxy-imidazolidines of formula IX, in which
X.sub.90 represents hydrogen or R,and R.sub.90 and R.sub.93
represent hydrogen or R. ##SPC8##
To these belong: 1,3-diformyl-4,5-diacetoxy-imidazolidine (m.p.
160.degree.-165.5.degree. C),
1,3-diacetyl-4,5-diacetoxyimidazolidine (m.p.
139.degree.-140.5.degree.C),
1,3-diacetyl-4,5-dipropionyloxy-imidazolidine (m.p.
85.degree.-87.degree.C).
1. acylated glycolurils of the general formula X, in which
X.sub.101 represents the residue R or R-CO. ##SPC9##
Tetraacylated glycolurils and especially tetraacetylglycoluril
(m.p. 233.degree.-240.degree.C) are preferably used. In addition,
the following acylated glycolurils are suitable:
di-(chloracetyl)-diacetyl-glycoluril (m.p.
267.degree.-269.degree.C), tetrapropionyl-glycoluril (m.p.
144.degree.-146.degree.C), 1-methyl-3,4,6-triacetylglycoluril (m.p.
179.degree.-180.degree.C), diacetyldipropionylglycoluril (m.p.
144.degree.-146.degree.C) and diacetyl-dibenzoyl-glycoluril (m.p.
244.degree.-249.degree.C). The acylated glycolurils are not only of
special practical importance on account of their excellent
properties as activators, but owing to their high melting point
they are very suitable for the preparation of pulverulent products
which are stable on storage.
It is often sufficient to activate only a part of the active oxygen
present. For this, additions of activotor of at least 0.05,
preferably of at least 0.1 mol of activator per gram-atom of active
oxygen are sufficient. If the greatest possible activation of the
active oxygen is required, the addition of activator can be
increased up to 4 mols, preferably up to 3 mols. However, it is
preferred to work with 0.3 to 2 mols of activator per gram-atom of
the active oxygen. These amounts can, of course be varied according
to the activity of the particular activator used.
The activators may be provided with a coating of substances which
are inert towards the activators. This prevents a contact of the
activators with the strongly alkaline-reacting alkali metal
silicates, according to the above definition, and possibly with the
percompounds, which contributes to the stability in storage of the
products of the invention.
The optical brighteners utilized in the compositions of the
invention are those of the
4,4'-bis-(azolyl)-stilbene-2,2'-disulfonic acid type (I), the
stilbyl-naphthotriazole type (II), the
bis-(benzoxazolyl)-derivative type (III), the
2-benzoxazolyl-4,5-naphthothiophene type (IV), and the
diphenyldistyryl type (V). These optical brighteners are compounds
of the formulae selected from the group consisting of ##SPC10##
wherein azolyl represents an azole structure of the formula
selected from the group consisting of ##SPC11##
A represents a member selected from the group consisting of
hydrogen and SO.sub.3 H, R represents a member selected from the
group consisting of hydrogen and alkyl having 1 to 5 carbon atoms,
R.sub.1 represents a member selected from the group consisting of
hydrogen and halogen, R.sub.2 represents a member selected from the
group consisting of CN, SO.sub.3 H and SO.sub.2 NHR, R.sub.4
represents a bivalent linkage selected from the group consisting of
--CH=CH--, ##SPC12##
X represents a member selected from the group consisting of --NH--,
--S--, and --O--, R.sub.5 represents a member selected from the
group consisting of hydrogen, alkyl having 1 to 5 carbon atoms and
phenyl, R.sub.6 and R.sub.7 represent members selected from the
group consisting of phenyl and phenyl substituted with at least one
substituent selected from the group consisting of alkyl having 1 to
4 carbon atoms, hydroxyalkyl having 2 to 5 carbon atoms, alkoxy
having 1 to 5 carbon atoms, chloro, CN, COOH, SO.sub.3 H, SO.sub.2
CL and SO.sub.2 N R.sub.8 R.sub.9, and R.sub.8 and R.sub.9 are
members selected from the group consisting of hydrogen, alkyl
having 1 to 5 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms
and, taken together with the nitrogen, piperidino, piperazino,
morpholino and pyrrolidino.
Among the compounds of the above formulae are, for example:
4,4'-bis-(4-phenyl-vic-tri-azol-2-yl)-stilbene-2,2'-disulfonic acid
and its alkali metal salts such as the sodium salt,
4,4'-bis-(naphthotriazol-2-yl)-stilbene-2,2'-disulfonic acid and
its sodium salt,
4,4'-bis-(5-phenyl-pyrazol-2-yl)-stilbene-2,2'-disulfonic acid and
its sodium salt, 4-(4,5-naphthotriazol-2-yl)-stilbene-2-sulfonic
acid and its sodium salt,
4-(4,5-naphthotriazol-2-yl)-4'-chlorostilbene-2-sulfonic acid and
its sodium salt, 4-(4,5-naphthotriazol-2-yl)-stilbene-2-sulfamide,
2,5-bis-(benzoxazol-2-yl)-thiophene,
1,2-bis-(5-methyl-benzoxazol-2-yl)-ethylene,
4,4'-bis-(5-phenyl-benzoxazol-2-yl)-stilbene, 2-benzoxazolyl-4,5
-naphthothioprene, diphenyldistyryl-2,2'-disulfonic acid and its
sodium salt, diphenyldistyryl-2-chloro-2'-sulfonic acid and its
sodium salt, di-2-chlorophenyldistyryl, etc.
The otpical brighteners of formulas I to IV in the compositions of
the invention may be optionally replaced wholly or in part with the
diphenyldistyryl compounds of the formula ##SPC13##
where each of the radicals R.sub.12 or R.sub.13 may represent a
hydrogen atom or a sulfonic acid radical. Like the radicals
R.sub.12 and R.sub.13, also the radicals R.sub.10 and R.sub.11 may
be identical or different. R.sub.10 and R.sub.11 are phenyl
radicals or substituted phenyl radicals, where as substituents the
following atoms or atom groups are possible: alkyl, hydroxyalkyl,
or alkoxy radicals with 1 to 5 carbon atoms; furthermore, chloro,
nitrile, carboxyl, sulfonic acid, chlorosulfonyl, or sulfonamide
radicals, whereby one of the aminohydrogen atoms or both may be
substituted by alkyl radicals with 1 to 5 carbon atoms or
hydroxyalkyl radicals with 2 to 4 carbon atoms or whereby the amide
nitrogen may be part of a heterocyclic ring. Preferably as radicals
R.sub.10 or R.sub.11 are chlorophenyl, nitrilo-phenyl, alkylphenyl,
hydroxyalkylphenyl, alkoxyphenyl, carboxyphenyl and sulfophenyl,
where all these phenyl radicals may contain as second substituent
also a sulfonic acid group. Like the sulfonic acid group, also the
substituents --Cl, --CN and --COOH may be present twice on one
phenyl radical. Further R.sub.10 and R.sub.11 may preferably
represent the radicals sulfamidophenyl (--C.sub.6 H.sub.4
--SO.sub.2 --NH.sub.2) and morpholinosulfophenyl (--C.sub.6 H.sub.4
--SO.sub.2 --NC.sub.4 H.sub.4 O).
Insofar as the optical brighteners to be used, according to the
invention, contain sulfonic acids or carboxylic acids, they are
preferably utilized in the form of their water-soluble salts of the
alkali metals, ammonium salts or salts of amines or alkylolamines
with 1 to 6 carbon atoms in the molecule.
The products of the invention may also contain combinations of
optical brighteners of the above-named types. Insofar as the
products of the invention are soaking or washing agents, in which
the bleaching component, according to the invention, is present in
amounts of 5 to 50 percent, preferably 10 to 35 percent, by weight,
the content of optical brightener of these agents lies preferably
in the range of 0.002 to 1.5 percent by weight.
Triazoles and tetrazoles, known as anti-corrosion agents, with the
groups =Nme or =NOMe, are the following compounds, for instance,
benzotriazole, methylbenzotriazole, 1,2- and 1,8-naphthotriazoles,
nitrobenzotriazole, tetrazole, 5-aminotetrazole,
alkylene-5,5'-ditetrazole, 5-alkylenetetrazoles,
5-dialkyl-aminotetrazoles, and 5-alkyl-4-hydroxytetrazoles, where
the alkyl or alkylene radicals may contain 1 to 5 carbon atoms.
Triazoles that contain an aromatic nucleus, such as a benzene or
napthalene nucleus, are particularly effective. For this reason,
for the practical application benzotriazole and the
naphthotriazoles are preferred.
The organic sequestering agents for heavy metals include the
water-soluble, preferably alkali metal salts of aminotriacetic
acid, ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid and
amino-triethylidene-diphosphonic acid. In their place also other
sequestering agents may be used, insofar as their sequestering
power, particularly for copper, is not substantially below that of
the named compounds.
The named sequestering agents have already been recommended as
organic builder salts for soaking, prewashing and washing agents.
For this reason, the above application amounts for these
sequestering agents are only valid in the case that not already
larger amounts of such sequestering agents are already present as
organic builder salts.
The higher fatty alcohols or their ethoxylation products, used for
the preparation of the ortho-, pyro- or polyphosphoric acid partial
esters, are substantially the same as are also used for the
preparation of other tensides. In this connection, the following
enumeration of the synthetic tensides, optionally contained in the
products of the invention are to be considered.
These "phosphoric acid esters" may be prepared according to various
known procedures, such as by direct esterification of the alcohol
component with the correspoonding acids of phosphorus, with the
halogen derivatives of phosphorus or with the corresponding
phosphoric acid anhydrides, particularly with phosphorus
pentoxide.
Above all the last-named reaction represents a practically useful
preparation method for such esters. By this reaction, in addition
to the partial esters of ortho-phosphoric acid also partial esters
of anhydric acids of phosphorus are formed, particularly of the
pyro- and polyphosphoric acids, where, however, the esters of
ortho-phosphoric acid, optionally also the esters of ortho- and
pyro-phosphoric acids represent the main product. The salts of the
partial esters of the named acids, to be used according to the
invention, may contain on each phosphorus atom, one or two higher
fatty alcohol radicals bound as an ester. Often in the
transesterification of fatty alcohols or of their alkoxylation
products, mixtures of esters are formed with one or with two
alcohol radicals per phosphorus atom.
Preferably the partial esters of phosphoric acid have the formula
##SPC14##
wherein A is a member selected from the group consisting of
hydrogen and ##SPC15##
with the proviso that one A may be hydrogen, R.sub.1 is a member
selected from the group consisting of hydrogen and methyl, R.sub.2
is a fatty alcohol residue having from 10 to 22 carbon atoms, and n
is an integer from 0 to 10. These partial esters of phosphoric acid
are utilized in the form of their water-soluble salts, especially
their alkali metal and ammonium salts where the hydrogen of A is
replaced by alkali metal or ammonium, or their mono-, di- or
triethanolamine salts.
The salts of orthophosphoric acid diesters of ethoxylated fatty
alcohols, with 2 to 6 ethyleneglycol ether radicals in the
molecule, for instance, as obtained from coconut, palm kernel or
tallow fatty acids, with 12 to 18 carbon atoms in the fatty alcohol
radical have been proven preferable.
These partial esters of phosphoric acids also have tenside
properties and may, therefore, be utilized in larger amounts as
such than would be necessary from the point of view of corrosion
protection.
The products of the invention can be prepared by all procedures,
customary in the production of oxidizing agents, bleaching agents,
washing auxiliaries and washing agents. For instance, the single
ingredients can be mixed with each other in a dry, powdery or
granular state. These mixtures can be granulated or agglomerated,
according to known processes, by spraying them, while being
agitated, with water or with aqueous solutions containing active
substances. This process is above all recommended when anhydrous
salts are present in the mixture that crystallize with binding of
water of crystallization.
In all of these processes it is recommended to avoid a direct
contact of the activators and percompounds in the presence of
water, since the activator effect already takes place at that time,
and a part of the activators or of the active oxygen is
consumed.
This is particularly valid for the heat-drying processes, customary
in the production of washing auxiliaries and washing agents. Mostly
only those ingredients are incorporated into the aqueous charge to
be heat-dried, that are not changed by water and/or heat, and the
other ingredients are admixed with the thus-obtained initial
powder. In the process, it is immaterial for the effect of the
combinations of the invention in which partial powder the single
ingredients are present. Thus, for instance, the phosphoric acid
esters of optionally ethoxylated fatty alcohols and the
sequestering agents can be incorporated, together with the other
ingredients of the product, particularly of washing auxiliary or
washing agents, into an aqueous charge and then by known processes,
preferably by heat drying, transformed to a powder. This powder is
then mixed with the other ingredients, sensitive to moisture and/or
heat, such as the activator, the percompound and optionally other,
for the same reason separately to be incorporated, ingredients,
such as enzymes.
An enumeration of the other ingredients present in the products of
the invention, particularly in the washing auxiliaries and washing
agents, such as tensides, builders, soil suspension agents,
enzymes, etc. follows.
The anionic, amphoteric or non-ionic tensides contain in the
molecule at least one hydrophobic residue mostly containing 8 to
26, preferably 10 to 22 and especially 10 to 18, carbon atoms and
at least one anionic, non-ionic or amphoteric water-solubilizing
group. The preferably saturated hydrophobic residue is mostly
aliphatic, but possibly also alicyclic in nature. It may be
combined directly with the water-solubilizing group or through
intermediate members. Suitable intermediate members are, for
example, benzene rings, carboxylic acid ester or carboxylic acid
amide groups, residues of polyhdric alcohols linked in ether or
ester-like form, such as, for example, those of ethylene glycol,
propylene glycol, glycerine or corresponding polyether
residues.
The hydrophobic residue is preferably an aliphatic hydrocarbon
residue with 10 to 18, preferably 12 to 18, carbon atoms but
deviations from the preferred range of carbon atoms are possible,
depending on the nature of the surface-active compound in
question.
Soaps from natural or synthetic fatty acids, possibly also from
resin or naphthenic acids, are utilizable as anionic detergent
substances, especially when these acids have iodine values of not
more than 30, and preferably of less than 10.
Of the synthetic anionic surface-active compounds, the sulfonates
and sulfates possess special practical importance.
The sulfonates include, for example, the alkylaryl sulfonates,
especially alkylbenzene sulfonates, which are obtained from
preferably straight-chain aliphatic hydrocarbons having 9 to 15,
especially 10 to 14 carbon atoms, by chlorinating and alkylating
benzene or from corresponding terminal or non-terminal olefins by
alkylation of benzene and sulfonation of the alkylbenzenes
obtained. Further, aliphatic sulfonates are of interest, such as
are obtainable, for example, from preferably saturated hydrocarbons
containing 8 to 18 and preferably 12 to 18 carbon atoms in the
molecule by sulfochlorination with sulfur dioxide and chlorine or
sulfoxidation with sulfur dioxide and oxygen, and conversion of the
products thereby obtained into the sulfonates. As aliphatic
sulfonates, mixtures containing alkene sulfonates, hydroxyalkane
sulfonates and disulfonates are useful, which are obtained from
terminal or non-terminal C.sub. 8.sub.-18 and preferably
C.sub.12.sub.-18 olefins by sulfonation with sulfur trioxide and
acid or alkaline hydrolysis of the sulfonation products. In the
aliphatic sulfonates thus prepared, the sulfonate group is
frequently found attached to a secondary carbon atom; however,
sulfonates with a terminal sulfonate group obtained by reaction of
terminal olefins with bisulfite can also be used.
Furthermore, salts, preferably dialkali metal salts of
.alpha.-sulfo-fatty acids, and aalts of esters of these acids with
mono- or poly-hydric alcohols containing 1 to 4, and preferably 1
to 2 carbon atoms belong to the sulfonates to be used according to
the invention.
Further useful sulfonates are salts of fatty acid esters of
hydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the
salts of the fatty alcohol esters of lower aliphatic or aromatic
sulfomono- or di-carboxylic acids containing 1 to 8 carbon atoms,
alkylglycerylether sulfonates and the salts of the amide-like
condensation products of fatty acids or sulfonic acids with
aminoethane-sulfonic acid.
As tensides of the sulfate type are fatty alcohol sulfates,
especially those prepared from coconut fat alcohols, tallow fat
alcohols or oleyl alcohol. Useful sulfonation products of the
sulfate type are also obtainable from terminal or non-terminal
C.sub.8.sub.-18 olefins. Sulfated fatty acid alkylolamides or fatty
acid monoglycerides, and sulfated alkoxylation products of
alkylphenols (C.sub.8.sub.-15 alkyl), fatty alcohols, fatty acid
amides or fatty acid alkylolamides, which may contain in the
molecule 0.5 to 20, preferably 1 to 8 and especially 2 to 4
ethylene and/or propylene glycol residues, also belong to this
group of surface-active compounds.
Suitable anionic surface-active compounds of the carboxylate type
are the fatty acid esters of fatty alcohol ethers of
hydroxycarboxylic acids, and the amide-like condensation products
of fatty acids or sulfonic acids with aminocarboxylic acids, for
example, with glycocoll, sarcosin or protein hydrolysates.
The non-ionic surface-active compounds, here called "non-ionics,"
for the sake of simplicity, include products which owe their
solubility in water to the presence of polyether chains,
amineoxide, sulfoxide, or phosphine-oxide groups, alkylolamide
groups and very generally, to an accumulation of hydroxyl
groups.
The products obtainable by addition of ethylene oxide and/or
glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines,
fatty acid and sulfonic acid amides are of special practical
interest. These non-ionics may contain per molecule 4 to 100,
preferably 6 to 40 and especially 8 to 20 ether residues,
particularly ethylene glycol ether residues. Moreover, propylene or
butylene glycol ether residues or polyether chains may be present
in or at the ends of these polyether residues.
Further, products known by the trade name of "Pluronics" or
"Tetronics" belong to the non-ionics. They are obtained from
water-insoluble polypropylene glycols or from water-insoluble
propoxylated lower aliphatic alcohols containing 1 to 8, preferably
3 to 6 carbon atoms and/or from water-insoluble propoxylated
alkylenediamines. These water-insoluble (i.e. hydrophobic)
propylene oxide derivatives are converted into the said non-ionics
by ethoxylation until they become soluble in water. Finally, the
reaction products of the above-mentioned aliphatic alcohols with
propylene oxide known as "Ucon-Fluid" some of which are still
water-soluble, are useful as non-ionics.
The non-ionics also include fatty acid or sulfonic acid
alkylolamides which are derived, for example, from mono- or
di-ethanolamine, dihydroxypropylamine or other
polyhydroxyalkylamines, for example the glycamines. They can be
replaced by amides from higher primary or secondary alkylamines and
polyhydroxycarboxylic acids.
The surface-active amineoxides include, for example, the products
derived from higher tertiary amines having a hydrophobic alkyl
residue and two shorter alkyl and/or alkylol residues containing up
to 4 carbon atoms, each.
Amphoteric surface-active compounds contain in the molecule both
acid and basic hydrophilic groups. Carboxyl, sulfonic acid,
sulfonic acid half ester, phosphonic acid and phosphoric acid
partial ester groups are the acid groups. Basic groups include
primary, secondary, tertiary and quaternary ammonium groups.
Amphoteric compounds with quaternary ammonium groups belong to the
betaine type.
Carboxy, sulfate and sulfonate betaines have particular practical
interest on account of their good compatibility with other
surface-active compounds. Suitable sulfobetaines are obtained, for
example, by reacting tertiary amines containing at least one
hydrophobic alkyl residue with sultones, for example propane- or
butane-sultone. Corresponding carboxybetaines are obtained by
reacting the said tertiary amines with chloracetic acid, or its
salts or with chloracetic acid esters and splitting the ester
linkage.
The foaming power of the surface-active compounds can be increased
or reduced by combination of suitable types of surface-active
compounds, just as it can be changed by additions of
non-surface-active organic substances.
Suitable foam stabilizers, above all in the case of surface-active
compounds of the sulfonate or sulfate type, are surface-active
carboxy or sulfo-betaines and also the above-mentioned non-ionics
of the alkylolamide type. Moreover, fatty alcohols or higher
terminal diols can be utilized for this purpose.
Products with a reduced foaming power are primarily intended for
use in washing and dishwashing machines, where sometimes a limited
repression of foam is sufficient while in other cases a stronger
foam repression may be desired. Products which foam in the middle
range of termperature up to about 65.degree.C, but at higher
temperatures (70.degree. to 100.degree.C) develop less and less
foam are of special practical importance.
A reduced foaming power is frequently obtained with combinations of
different types of surface-active compounds, especially with
combinations of synthetic anionic surface-active compounds,
particularly of (1) sulfates and/or sulfonates or of (2) non-ionics
on the one hand and (3) soaps on the other hand. With combinations
of the components (1) and (2) or (1), (2) and (3), the foaming
power can be affected by the particular soap used. The inhibition
of foam is smaller with soaps from preferably saturated fatty acids
with 12 to 18 carbon atoms, while a greater inhibition of foaming,
particularly in the higher temperature range, is obtained by soaps
from saturated fatty acid mixtures having 20 to 26, preferably 20
to 22 carbon atoms, used in an amount of from 5 to 10 percent by
weight of the total soap fraction present in the combination of
surface-active compounds.
The foaming power of the surface-active compounds can also be
reduced, by the addition of known, non-surface-active foam
inhibitors. These include optionally chlorine-containing
N-alkylated aminotriazines, which are obtained by reacting 1 mol of
cyanuric chloride with 2 to 3 mols of a mono- and/or di-alkylamine
having 6 to 20, preferably 8 to 18 carbon atoms in the alkyl
residue. Aminotriazine or melamine derivatives which contain
propylene glycol or butylene glycol ether chains, in an amount of
10 to 100 of such glycol residues per molecule, have a similar
action. Such compounds are obtained, for example, by addition of
corresponding amounts of propylene and/or butylene oxide to
aminotriazines, especially to melamine. The reaction products from
1 mol of melamine with at least 20 mol of propylene oxide or at
least 10 mol of butylene oxide are preferred. Products which are
obtained by addition of 5 to 10 mol of propylene oxide to 1 mol of
melamine and further addition of 10 to 50 mol of butylene oxide to
this propylene oxide derivative have proved particularly
effective.
Other non-surface-active 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 and aliphatic
carboxylic acid esters, which contain at least 18 carbon atoms in
the acid or alcohol residue, possibly also in both of these two
residues (for example triglycerides or fatty acid-fatty alcohol
esters), can be used as foam inhibitors, particularly in
combinations of anionic synthetic surface-active compounds and
soaps.
The non-surface-active foam inhibitors are frequently only
completely effective at temperatures at which they are present in
the liquid state, so that the foaming behaviour of the products can
be controlled by choice of suitable foam inhibitors in a similar
way to that by the choice of soaps from fatty acids of suitable
chain lengths.
When foam stabilizers are combined with foam inhibitors dependent
upon temperature, good foaming products are obtained at lower
temperatures which, as the temperature approaches the boiling
temperature, foam less and less.
Suitable weakly-foaming non-ionics, which can be used both alone
and in combination with anionic, amphoteric and non-ionic
surface-active compounds and which reduce the foaming power of more
strongly foaming surface-active compounds, are products of addition
of propylene oxide to the above-described surface-active
polyethylene glycol ethers as well as the also above-described
Pluronic, Tetronic and Ucon-Fluid types.
Suitable builders are weakly acid, neutral and alkaline reacting
inorganic or organic salts, especially inorganic or organic
complex-foaming substances.
Useful, weakly acid, neutral or alkaline reacting salts according
to the invention are, for example, the alkali metal bicarbonates,
carbonates, borates or silicates, mono-, di- or tri-alkali metal
orthophosphates, di- or tetra-alkali metal pyrophosphates, alkali
metal metaphosphates known as complex-forming substances, alkali
metal sulfates and the alkali metal salts of organic,
non-surface-active sulfonic acids, carboxylic acids and
sulfocarboxylic acids containing 1 to 8 carbon atoms. These
include, for example, water-soluble salts of benzene-, toluene- or
xylene-sulfonic acid, water-soluble salts of sulfoacetic acid,
sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts
of acetic acid, lactic acid, citric acid and tartaric acid.
Further, the water-soluble salts of higher molecular weight
polycarboxylic acids are utilizable as builders, especially
polymerizates of maleic acid, itaconic acid, mesaconic acid,
fumaric acid, aconitic acid, methylene-malonic acid and citraconic
acid. Co-polymerizates of these acids with one another or with
other polymerizable substances, as for example, with ethylene,
propylene, acrylic acid, methacrylic acid, crotonic acid,
3-butene-carboxylic acid, 3 -methyl-3-butenecarboxylic acid and
with vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and
styrene, are utilizable.
Suitable complex-forming builders are also the weakly acid reacting
metaphosphates and the alkaline reacting polyphosphates, especially
tripolyphosphate, in the form of their alkali metal salts. They may
be wholly or partly replaced by organic complex forming
substances.
The organic complex-forming substances include, for example,
nitrilotriacetic acid, ethylenediaminetetraacetic acid,
N-hydroxyethyl-ethylenediaminetriacetic acid,
polyalkylene-polyamine-N-polycarboxylic acids and other known
organic complex-forming substances, while combinations of different
complex-forming substances may also be used. Di- and
poly-phosphonic acids of the following constitutions also belong to
the other known complex-forming substances: ##SPC16##
in which R represents alkyl and R' alkylene radicals with 1 to 8,
preferably 1 to 4 carbon atoms, X and Y represent hydrogen or alkyl
radicals with 1 to 4 carbon atoms and Z represents --OH, --NH.sub.2
or NXR. For a practical application above all the following
compounds are considered: methylene-diphosphonic acid,
1-hydroxyethane-1,1-diphosphonic acid,
1-aminoethane-1,1-diphosphonic acid,
amino-tri-(methylene-phosphonic acid), methylamino- or
ethylamino-di-(methylene-phosphonic acid as well as
ethylenediamine-tetra-(methylene-phosphonic acid). All these
complexing compounds may be present as free acids or preferably as
the alkali metal salts.
Further, soil suspending agents or greying inhibitors may be
contained in the preparations according to the invention, which
hold the dirt loosened from the fiber suspended in the bath and
thus prevent greying. Water-soluble colloids of mostly organic
nature are suitable for this purpose, for example, the
water-soluble salts of polymeric carboxylic acids, glue, gelatine,
salts of ether-carboxylic acids or ether-sulfonic acids of starch
or cellulose or salts of acid sulfuric acid esters of cellulose or
starch. Water-soluble polyamides containing acid 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, and aldehyde starches.
Polyvinylpyrrolidone is also useful.
The constituents of the bleaching treatment compositions according
to the invention, especially washing compositions and washing
assistants of this kind, and particularly the builder substances,
are usually chosen so that the preparations have a neutral to
distinctly alkaline reaction, so that the pH value of a 1 percent
solution of the preparation mostly lie in the region from 7 to 12.
Fine washing compositions usually have a neutral to weakly alkaline
reaction (pH value 7 to 9.5), while soaking, prewashing and boiling
washing compositions are adjusted to be more strongly alkaline (pH
value 9.5 to 12, preferably 9.5 to 10.5). The action of the
activators is combined with a certain consumption of alkali.
Therefore, it has been already recommended to incorporate strongly
alkaline-reacting builder salts, such as alkali metal carbonates in
order to bind the acid liberated or to buffer the liquor
sufficiently to prevent the pH value from falling below the given
minimum values during the whole period of treatment.
The enzymes to be used are mostly a mixture of different enzymic
substances. They are called proteases, amylases, carbohydrases,
esterases, lipases, oxidoreductases, catalases, peroxidases,
ureases, isomerases, lyases, transferases, desmolases or nucleases,
depending upon their action. The enzymic substances obtained from
strains of bacteria of fungi such as Bacillus subtilis and
Streptomyces griseus are of particular interest, especially
proteases or amylases. Preparations obtained from Bacillus subtilis
have the advantage compared with others that they are relatively
stable towards alkali, percompounds and anionic detergent
substances and are still active at temperatures up to
70.degree.C.
Enzyme preparations are usually marketed by the manufacturers as
aqueous solutions of the active substances or with the addition of
diluents, as powders. Suitable diluents are sodium sulfate, sodium
chloride, alkali metal ortho-, pyro- or polyphosphates, especially
tripolyphosphate. Frequently moist enzyme preparations are mixed
with calcined salts, which then bind water of crystallization
present and the enzymic substance, possibly with agglomeration of
the particles to larger particles.
When the enzymic substances are present as dry powders, liquid,
paste-like and possibly also solid, non-ionic, preferably
surface-active, organic compounds, especially the above-described
non-ionics, can be used at the usual room temperatures to bind the
enzymes to the powders of the washing compositions or washing
assistants. For this purpose a mixture of the respective product
and the enzymic substance is preferably sprayed with the
above-mentioned non-ionic substances, or the enzyme preparations is
dispersed in the said non-ionic substance and this dispersion is
united with the other constituents of the product. When these other
constituents are solids, the dispersion of the enzymic substances
in the non-ionic component can also be sprayed on the other solid
constituents. The enzymes may also be incorporated as granulates or
as products dispersible in cold solutions. Such enzyme preparations
are coated and thus protected against a rapid loss of activity.
The enzymes, or combinations of enzymes with different actions, are
generally used in quantities such that the finished products have
protease activities of 50 to 5,000, preferably 100 to 2,500 LVE/g
and/or amylases activities of 20 to 5,000, preferably 50 to 2,000
SKBE/g and/or lipase activities of 2 to 1,000, preferably 5 to 500
IE/g.
These data on enzyme activities result from the activities of those
enzyme preparations which at the present time seem to be suitable
from the economic standpoint for use in the washing composition
field. From the chemical-technical standpoint the enzyme activities
of the preparations can be increased as desired, so that the
activities in the case of proteases and amylases may be raised, for
example, up to five times, and in the case of lipases, for example,
up to ten times, the highest values given above. If, therefore, in
the future preparations with such high activities should be
available which also economically appear appropriate for the use in
the application fields, named at the beginning, products with
respective higher enzyme activities can be prepared.
With reference to the determination of the enzyme activities, the
following literature references are given: Determination of the
activity of proteases according to Lohlein-Volhard:
A.kunzel, "Chemical Tanning Pocketbook," 6th Ed., Dresden and
Leipzig, 1955;
Determination of the activity of amylases:
J. wohlgemuth, "Biochemische Zeitschrift," Vol. 9, (1908), pp.
1-9;
R. m. sandstedt et al., "Cereal Chemistry," Vol. 16, (1939), pp.
712-723;
Determination of the activity of lipases:
R. willstatter et al., "Hoppe-Seyler's Zeitschrift fur
Physiologiche Chemie," Vol. 125 (1923), pp. 110-117;
R. boissonas, "Helvetica Chimica Acta," Vol. 31 (1948), pp.
1571-1576.
The products according to the invention may also contain
antimicrobial substances. As such, the 2-hydroxy-2',
4,4'-trichloro-diphenylether has been proven good.
The following examples illustrate the practice of the invention
without being limitative in any respect.
EXAMPLES
The salt-like constituents contained in the following, such as
salt-like surface-active compounds, other organic salts as well as
inorganic salts, are present as the sodium salts, unless otherwise
stated. The expressions and abbreviations used have the following
meanings:
"ABS" is the salt of an alkylbenzene sulfonic acid with 10 to 15,
preferably 11 to 13, carbon atoms in the alkyl chain, obtained by
condensing straight-chain olefins with benzene and sulfonating the
alkylbenzene thus formed.
"Alkanesulfonate" is a sulfonate obtained from paraffins with 12 to
16 carbon atoms by the sulfoxidation method.
"HPK-sulfonate" of "HT-sulfonate" are the sulfonates in the
.alpha.-position, obtained from the methyl esters of a hardened
palm kernel fatty acid or a hardened tallow fatty acid by
sulfonation with SO.sub.3.
"Olefin sulfonate" is a sulfonate obtained from mixtures of olefins
with 12 to 18 carbon atoms by sulfonating with SO.sub.3 and
hydrolyzing the sulfonation product with an alkaline liquor, which
sulfonate consists substantially of alkenesulfonate and
hydroxyalkanesulfonate, but contains in addition small quantities
of disulfonates. Products are useful which have been made from
.alpha.- or from non-terminal olefins.
"KA-sulfate" and "TA-sulfate" are the salts of sulfated
substantially saturated fatty alcohols, prepared by reduction of
coconut fatty acid and tallow fatty acid, respectively.
"KA-EO-sulfate" is the sulfated product of addition of 2 mols of
ethylene oxide to 1 mol of fatty alcohol.
"KA-EO-phosphate" or "TA-EO-phosphate" are the orthophosphoric acid
diesters of the addition products of about 4 mols ethylene oxide to
1 mol of coconut or tallow alcohol. When these tensides are
utilized as the diethanolamine or triethanolamine salts, the
percentage figures in the table are marked by a (D) or (T),
respectively.
"OA + 10 EO", "KA + 20 EO" or "Fs-amide + 8 EO" are the addition
products of ethylene oxide (EO) to technical oleyl alcohol (OA) or
coconut alcohol (KA) or coconut fatty acid amide, respectively,
where the numbers represent the molar amounts of ethylene oxide
added to 1 mol of starting material.
"KA + 9 EO + 12 PO" is a non-ionic obtained by reaction of 1 mol of
"KA + 9 EO" with 12 mols of propylene oxide.
"Carboxybetaine" or "Sulfobetaine" are the betaines obtained by
reaction of 1 mol of coconut alkyldimethylamine with 1 mol of
chloroacetic acid or with 1 mol of propanesultone,
respectively.
"CMC" is the salt of carboxymethylcellulose.
"NTA," "EDTA," "DETP," "HEDP," or "ATMP" are the salts of
nitrilotriacetic acid, ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid
or aminotrimethylene phosphonic acid, respectively.
The composition of fatty acid mixture from which the Soaps B, C and
D was prepared, and the composition of fatty acid mixtures the Soap
G which may be used instead of the other soaps, are seen from the
following Table I.
TABLE I
No. of Carbon Atoms % Wt. of Fatty Acid Constituent in the Fatty
Acid in the Soap B C D G .ltoreq. C.sub.10 2 2 4 1 C.sub.12 19 21
16 6 C.sub.14 8 6 10 5 C.sub.16 4 16 25 28 C.sub.18 22 33 45 60
C.sub.20 8 4 C.sub.22 37 18
__________________________________________________________________________
Iodine value of the fatty acid mixture 4 8 6 4
If the Soaps B, C and D in the formulations given below are
replaced by the same quantity of the Soap G, washing compositions
are obtained in which the foaming is somewhat less strongly
inhibited than the corresponding composition with the soaps B and C
but more strongly than with the soap D.
Together with these soaps or in place of them, non-surface-active
foam inhibitors can be used, for example, a mixture of about 45
percent of a di(alkylamino)-monochlorotriazine and about 55 percent
of a N,N', N"-trialkylmelamine. In all these triazine derivatives
the alkyl residue may be present as mixtures of homologs with 8 to
18 carbon atoms. The monochlorotriazine derivative or
trialkylmelamine can also be used with a similar result. Provided
the described washing compositions contain synthetic sulfates of
sulfonates together with soap, the other non-surface-active foam
inhibitors mentioned in the description can be used, as for
example, paraffin oil or paraffin. It is advisable to incorporate
the non-surface-active foam inhibitor used separately in the
washing composition, for example, dissolved in a suitable organic
solvent or sprayed in the molten state on the moving powder by
means of a nozzle.
"Perborate (mono)" or "perborate (tetra)" are a perborate
monohydrate or perborate tetrahydrate of the approximate
compositions NaBO.sub.2.sup.. H.sub.2 O.sub.2 or Na BO.sub.2.sup..
H.sub.2 O.sub.2.sup.. 3 H.sub.2 O.
"TAGU" is tetraacetylglycoluril.
The products described in the examples contained the following
optical brighteners:
Brightener I
The sodium salt of the
4,4'-bis-(4-phenyl-vic-tri-azol-2-yl)-stilbene- 2,2'-disulfonic
acid of the formula ##SPC17##
Brightener II
The sodium salt of the 4-(4,5-naphthotriazol-2-yl-)
stilbene-2-sulfonic acid. ##SPC18##
Brightener III
2,5-bis-(benzoxazol-2-yl)-thiophene ##SPC19##
Brightener IV
1,2-bis-(5-methylbenzoxazol-2-yl)-ethylene ##SPC20##
Brightener V
2-benzoxazolyl-4,5-naphthothiophene ##SPC21##
Brightener VIa
The sodium salt of a diphenyl-distyryl-disulfonic acid
##SPC22##
Brightener VIb
The sodium salt of a chloro-diphenyl-distyryl-monosulfonic acid of
the structure: ##SPC23##
Brightener VIc
dichloro-diphenyl-distyryl of the structure: ##SPC24##
The composition of some of the bleaching agents, according to the
invention, which may be preferably used in the textile industry or
in commercial laundries as a bleaching component, are described in
Examples B1 to B20 in Tables II to V.
TABLE II
Ingredients of % by weight of ingredients the prepara- in example
tion B1 B2 B3 B4 B5 Perborate 41.0 36.1 41.0 42.6 38.1 (t) (t) (m)
(m) (m) TAGU 23.0 19.7 21.3 43.5 16.5 KA-EO-Phosphate 5.8
TA-EO-Phosphate 12.0 EDTA 2.0 2.0 0.2 ATMP 1.6 Benzotriazole 0.1
Na.sub.4 P.sub.2 O.sub.7 23.1 21.4 Na.sub.2 CO.sub.3 33.2 12.6 34.6
13.4 11.8 Brightener I 0.8 Brightener II 1.0 Brightener III 0.2
Brightener IV 0.3 Brightener V 0.2
table iii
ingredients of % by weight of ingredients the prepara- in example
tion B6 B7 B8 B9 B10 Perborate 43.5 44.8 38.0 47.1 32.2 (t) (m) (m)
(m) (m) TAGU 23.3 46.3 22.8 10.1 24.8 KA-EO-Phosphate 23.6 3.5 (T)
(D) EDTA 0.7 DETPA 0.5 Methylbenzo- triazole 0.7 1.8-Naphtho-
triazole 0.7 Na.sub.4 P.sub.2 O.sub.7 10.8 11.8 4.5 Na.sub.2
CO.sub.3 32.5 7.45 26.45 6.15 34.0 Brightener I 0.6 0.4 0.7
Brightener II 0.8 0.5 Brightener III 0.1 0.2 Brightener IV 0.05
Brightener V 0.1 0.15 0.05 0.1
table iv
ingredients of % by weight of ingredients the prepara- in example
ation B11 B12 B13 B14 B15 Perborate 41.0 36.1 41.0 42.6 38.1 (t)
(t) (m) (m) (m) TAGU 23.0 19.7 21.3 43.5 16.5 KA-EO-Phosphate 5.8
TA-EO-Phosphate 12.0 EDTA 2.0 2.9 0.2 ATMP 1.6 BENZOTRIAZOLE 0.1
Na.sub.4 P.sub.2 O.sub.7 23.1 21.4 Na.sub.2 CO.sub.3 33.2 12.6 34.6
13.4 11.8 Brightener VIa 0.8 0.5 0.6 Brightener VIb 1.0 0.5
Brightener VIc 0.4 0.4
TABLE V
Ingredients of % by weight of ingredients the prepar- in example
ation B16 B17 B18 B19 B20 Perborate 43.5 44.8 38.0 47.1 32.2 (t)
(m) (m) (m) (m) TAGU 23.3 46.3 22.8 10.1 24.8 KA-EO-Phosphate 23.6
3.5 (T) (D) EDTA 0.7 DETPA 0.5 Methylbenzo- triazole 0.7
1,8-Naphto- triazole 0.7 Na.sub.4 P.sub.2 O.sub.7 10.8 11.8 4.5
Na.sub.2 CO.sub.3 32.5 7.45 26.45 6.15 34.0 Brightener VIa 0.2
Brightener VIb 0.3 0.05 Brightener VIc 1.1 0.7 0.7 0.3
The composition of some washing agents, according to the invention
are described in Examples W1 to W20 in Tables VII to IX.
TABLE VI
Ingredients of % by weight of ingredients the prepara- in example
tion W1 W2 W2 W4 W5 ABS 6.1 4.9 5.1 HPK-Sulfonate 1.2
Olefinsulfonate 1.5 Soap B 3.6 3.1 Soap D 4.1 KA-EO-Phosphate 4.0
TA-EO-Phosphate 5.0 OA + 10 EO 2.0 1.2 1.9 KA + 20 EO 7.0 KA + 9 EO
+ 12 PO 2.0 6.6 Fs-amide+ 8 EO 3.1 Foam inhibitor 0.2 Na.sub.5
P.sub.3 O.sub.10 31.0 36.5 38.5 30.2 40.2 Na.sub.2 0.3.3SiO.sub.2
5.4 1.5 4.8 2.9 4.5 Na.sub.2 CO.sub.3 14.4 14.2 8.2 18.7 5.0
Na.sub.2 SO.sub.4 0.3 0.3 3.4 0.5 NTA EDTA 0.2 0.5 0.1 HEDP ATMP
1.1 CMC 0.6 1.0 0.3 0.5 1.5 Mg SiO.sub.3 1.1 2.4 2.2 1.0 1.0 1.0
Perborate 21.4 25.0 17.4 16.3 16.0 (t) (t) (m) (m) (m) TAGU 11.8
7.7 9.0 15.0 0.7 Benzotriazole 0.1 Brightener I 0.2 0.3 0.2
Brightener II 0.3 0.20 Brightener III 0.15 0.05 Brightener IV 0.08
Brightener V 0.1 0.08 Residue Water
TABLE VII
Ingredients of % by weight of ingredients the prepara- in example
tion W6 W7 W8 W9 W10 ABS 5.3 5.0 Alkanesulfonate 2.9 HT-Sulfonate
5.0 7.1 KA-Sulfate 1.4 1.2 TA-sulfate 0.5 0.3 KA-EO-Sulfate 1.5 5.0
Soap C 7.6 6.2 KA-EO-Phosphate 7.0 1.5 OA + 10 EO 5.0 2.5 KA + 9 EO
+ 1.8 12 PO 1.8 Carboxybetaine 0.5 Sulfobetaine 0.7 0.6 Foam
Inhibitor 0.5 0.5 0.6 0.4 Na.sub.5 P.sub.3 O.sub.10 32.6 34.2 41.1
36.1 Na.sub.2 0.3,3 SiO.sub.2 5.5 3.4 4.0 4.5 Na.sub.2 CO.sub.3
14.8 16.2 14.1 Na.sub.2 SO.sub.4 0.4 0.2 2.5 0.4 CMC 1.6 1.3 1.7
1.0 NTA 15.0 15.0 EDTA 0.2 DETP 0.2 HEDP 14.0 4.0 7.0 9.0 ATMP 0.2
MgSiO.sub.3 2.5 2.0 Perborate 19.0 14.0 10.0 14.0 15.6 (t) (m) (m)
(m) (m) TAGU 10.2 14.0 6.0 3.0 15.6 Methylbenzo- 0.2 triazole
1,8-Naphtho- 0.2 triazole Brightener I 0.31 0.25 Brightener II 0.35
0.29 Brightener III 0.12 0.009 Brightener IV 0.16 Brightener V 0.13
0.03 Residue Water
TABLE VIII
Ingredients of % by weight of ingredients the prepara- in example
tion W11 W12 W13 W14 W15 ABS 6.1 4.9 5.1 HPK-Sulfonate 1.2
Olefinsulfonate 1.5 Soap B 3.6 3.1 Soap D 4.1 KA-EO-Phosphate 4.0
TA-EO-Phosphate 5.0 OA + 10 EO 2.0 1.2 1.9 KA + 20 EO 7.0 KA +9 EO
+ 12 PO 2.0 6.6 Fs-amide + 8 EO 3.1 Foam inhibitor 0.2 Na.sub.5
P.sub.3 O.sub.10 31.0 36.5 38.5 30.2 40.2 Na.sub.2 0.3,3 SiO.sub.2
5.4 1.5 4.8 2.9 4.5 Na.sub.2 CO.sub.3 14.4 14.2 8.2 18.7 5.0
Na.sub.2 SO.sub.4 0.3 0.3 3.4 0.5 NTA EDTA 0.2 0.5 0.1 HEDP ATMP
1.1 CMC 0.6 1.0 0.3 0.5 1.5 MgSiO.sub.3 1.1 2.4 2.2 1.0 1.0
Perborate 21.4 25.0 17.4 16.3 16.0 (t) (t) (m) (m) (m) TAGU 11.8
7.7 9.0 15.0 0.7 Benzotriazole 0.1 Brightener VIa 0.2 0.2
Brightener VIb 0.1 0.5 0.1 Brightener VIc 0.3 0.2 Residue Water
TABLE IX
Ingredients of % by weight of ingredients the prepara- in example
tion W16 W17 W18 W19 W20 ABS 5.3 5.0 Alkanesulfonate 2.9
HT-Sulfonate 5.0 7.1 KA-Sulfate 1.4 1.2 TA-Sulfate 0.5 0.3
KA-EO-Sulfate 1.5 5.0 Soap C 7.6 6.2 KA-EO-Phosphate 7.0 1.5 OA +
10 EO 5.0 2.5 KA + 9 EO + 12 PO 1.8 Carboxybetaine 0.5 Sulfobetaine
0.7 0.6 Foam inhibitor 0.5 0.5 0.6 0.4 Na.sub.5 P.sub.3 O.sub.10
32.6 34.2 41.1 36.1 Na.sub.2 0.3,3 SiO.sub.2 5.5 3.4 4.0 4.5
Na.sub.2 CO.sub.3 14.8 16.2 14.1 Na.sub.2 SO.sub.4 0.4 0.2 2.5 0.4
CMC 1.6 1.3 1.7 1.0 NTA 15.0 15.0 EDTA 0.2 DETP 0.2 HEDP 14.0 4.0
7.0 9.0 ATMP 0.2 MgSiO.sub.3 2.5 2.0 Perborate 19.0 14.0 10.0 14.0
15.6 (t) (m) (m) (m) (m) TAGU 10.2 14.0 6.0 3.0 15.6 Methylbenzo-
triazole 0.2 1,8-Naphtho- triazole 0.2 Brightener VIa 0.2 0.5 0.1
Brightener VIb 0.05 0.15 0.1 Brightener VIc 0.13 0.15 0.28 0.1
Residue Water
If textiles of cotton or polyamide are washed or bleached with the
use of the bleaching and washing agents, described in the examples,
an excellent degree of whiteness is attained even below the boiling
temperature. This represents the prerequisite for a satisfactory
effect of the optical brighteners. The optical brighteners, to be
utilized, according to the invention, are not damaged, although
with other optical brightener types, a damage by percompounds and
activators occurs. This advantage of the product of the invention
is particularly observed, when there are traces of heavy metals in
the treatment liquors and/or if the liquors were prepared some time
before the addition of the textile goods to be treated. The
described advantages are present also if the pH-value is somewhat
lowered by the carboxylic acid formed from the activator. Since
above all in white linen a lowering of the pH-value is not
advisable, the products of the invention may contain
alkaline-reacting salts, as required for the neutralization of the
carboxylic acids formed.
If, in the agents of the Examples B1 to B20 and W1 to W20, the
tetraacetylglycoluril contained therein is replaced by the
corresponding amounts of tetrapropionylglycoluril,
methyl-triacetyl-glycoluril, diacetyl-dibenzoyl-glycoluril,
diacetylaniline, diacetyltoluidine, diacetyl-dimethyl-hydantoin,
tetraacetyl-methylenediamine or tetraacetyl-ethylene-diamine,
similar results are obtained. However, the perborate is better
activated by the acylated glycolurils than by the other
activators.
The products, according to the above Examples B1 to B20 or W1 to
W20 contain, in some instances, a deficiency in amounts of
activator; that is, not all of the active oxygen contained in the
perborate, is activated. Work with such preparations is then
advantageous, if the effect of the activators is to be utilized at
lower temperatures, in order to continue the bleaching at higher
temperatures with the active oxygen still present. In such a
procedure the amount of activator may be reduced, for instance, up
to 5 percent of the carrier of active oxygen present.
The preceding examples are illustrative of the practice of the
invention. It is to be understood, however, that other expedients
known to those skilled in the art, or disclosed herein, may be
employed without departing from the spirit of the invention or the
scope of the appended claims.
* * * * *