|Publication number||US3779931 A|
|Publication date||Dec 18, 1973|
|Filing date||Sep 27, 1971|
|Priority date||Dec 10, 1970|
|Also published as||CA992264A, CA992264A1, DE2060762A1, DE2134691A1|
|Publication number||US 3779931 A, US 3779931A, US-A-3779931, US3779931 A, US3779931A|
|Inventors||Bloching H, Fries W, Jung D, Rhld H|
|Original Assignee||Henkel & Cie Gmbh|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (7), Referenced by (37), Classifications (15)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent [191 Fries et a].
COMPOSITIONS USEFUL IN THE AQUEOUS COLD-BLEACHING OF TEXTILES INCLUDING OPTICAL BRIGHTENERS  Inventors: Walter Fries, Erkrath-Unterbach;
Helmut Bloching, Monheim-Baumberg; Hilden Rhld, Monheim-Baumberg; Dieter Jung, Monheim-Baumberg, all of Germany  Assignee: I'lenkel & Cie GmbH,
Dusseldorf-Holthausen, Germany  Filed: Sept. 27, 1971 2! Appl. N03 184,213
 Foreign Application Priority Data Dec. 10, 1970 Germany 2060762 July 12, 1971 Germany 2134691  US. Cl 252/99, 8/1 1 l, 252/89, 252/95, 252/102, 260/248 R  Int. Cl Clld 7/54  Field of Search 252/99, 95, 102, 252/89; 260/248 R  References Cited UNITED STATES PATENTS 3,637,339 l/l972 Gray 252/95 X 3,663,444 5/1972 SchmadeL... 252/99 3,630,921 12/1971 Disch et a1. 252/95 3,655,569 4/1972 Hellsten et al 252/99 3,650,962 3/1972 Werdehausen et al. 252/102 3,284,462 1 H1966 Liechti et a1 252/99 X FOREIGN PATENTS OR APPLICATIONS 1.059.601 l/1958 Germany 252/102 Primary Examiner-Mayer Weinblatt Attorney-Hammond & Littell [5 7] 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 O, in aqueous solution and (ii) wmmflqy lk flfl qwnILQJD. the gmunmee afii tin m fl Nra xLane. gaexlesq ppunds 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-2,2f-disulfonic acids, stilbylnaphthotriazoles, bis-(benzoxazolyl)-derivatives, 2- benzoxazo1yl-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.
8 Claims, No Drawings COMPOSITIONS USEFUL IN THE AQUEOUS COLD-BLEACI'IING OF TEXTILES INCLUDING OPTICAL BRIGHTENERS 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 80C to 100C.
It has also been proposed to use organic compounds that belong to certain types of N-acyl or O-acyl com pounds, 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 to 70C, preferably 30 to 60C, 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 ing 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)- sti1bene-2,2-disulfonic acids, stilbyl-naphthotriazoles, bis-(benzoxazolyl)-derivatives, 2-benzoxazolyl-4,5- naphthothiophene, diphenyldistyryl 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) watersoluble 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.
sentially of (a) from 95 to 99.99 percent by weight of a mixture of (i) a percompound yielding H,O, 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, stilbylnaphthotriazoles, bis-(benzoxazolyl)-derivatives, 2- benzoxazolyl-4,5-naphthothiophene, diphenyldistyryl 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 11,0, in aqueous solution and (ii) an activator for active oxygen selected from the group consisting of N-acyl and O-acyl compounds hav- These agents are characterized in that they contain:
3 to 100 percent, preferably 5 to percent, by weight of a bleaching component, consisting of: a. 99.99 to percent, preferably 99.98 to 97.5 percent, by weight of a percompound, yielding H,O, in aqueous solution, as well as an N-acyl or O-acyl compound, serving as activator for I-I,O,, 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,
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 20to 70C, preferably 30 to 60C, on the basis of the bleaching activation, a degree of whiteness is attained such as can only be attained at temperatures of 70 to 100C, preferably 80 to 95C 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:
to 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-, pyroor 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 percent, preferably 10 to 70 percent, by
weight of the above described bleaching component, consisting of percompound, activator and brightener, 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,
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, nonsequestering 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:
to 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 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 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 70C, 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 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,
I 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 O, in aqueous solution, sodium perborate tetrahydrate (NaBO,-H O,-3H,O) is of special practical importance. Partly or completely dehydrated perborates, i.e., up to NaBO,.H O,, may be used in its place. Borates such as mam-H 0, described in German Pat. No. 901,287 and US. Pat. No. 2,491,789, in which the ratio M 03 0, is less than 0.5 :1 and preferably lies in the region of 0.4 to 0.15:1, while the ratio H O zNa 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-, pyroor 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 watersoluble 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 (MgOzSiO 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 watersoluble 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," l-l,O,. 3H,O (4 mMol/liter) and 2.5 gm/liter of Na O-,'10 H O, are heated to 60C, 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 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 5 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 l 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 alkoxy groups, halogen atoms, nitro or nitrile groups; when Ris an aromatic residue it may be chloroand/or nitrosubstituted, especially m-chloro or mor p-nitrosubstituted. 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 70C, preferably at least 100C and especially at least 150C, 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 (l) 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 la, lb,
R c 0 CO-RIS NX -CHr-N R|:-C 0 C O-Ru C O-Rn C O-Rn -CH:CH;N N\
(1b) (IQ) From this class of compounds, N,N,N',N-tetraacetylmethylenediamine (melting point 92-95C), N,N,N,N'- tetraacetylethylenediamine, N,N-diacetylaniline and N,N-diacetyl-ptoluidine are named as examples.
b. N-alkyl-N-sulfonyl-carbonamides of formula ll, in which R,;, preferably signifies a C alkyl residue.
OC-Ru Rn-N 8 Activators of this type are, for example, N-methyl-N- mesylacetylamide (melting point 73-79C). N-methyl-N-mesyl-benzoylamide (m.p.
ll6-l l8.5C), nitrobenzoylamide (m.p. methyl-N-mesyl-p-methoxybenzoylamide ll7l l7.5C).
c. N-acylhydantoins of formula III, in which at least one of the residues X and X represent an RCO- residue, while the other may also represent a residue R or a carboxymethyl or a lower alkoxycarbonylmethyl residue; Y and Y represent hydrogen or alkyl residues with l to 2 carbon atoms.
N-methyl-N-mesyl-pl59-l60C) and N- C ii (III) Suitable compounds are, for example, l,3-diacetyl- 5,5- dimethylhydantoin, 1,3-dipropionylhydantoin (m.p. 104.5to 106C) and 3-benzoylhydantoin-lacetic acid ethyl ester.
d. Cyclic Nacylhydrazides of formula W, 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.
A suitable compound is, for example, mono-acetylmaleic acid hydrazide.
e. Triacyl-cyanurates of formula VI R or R to give a succinyl or phthalyl residue and n signifies a whole number from O to 2.
Activators of this type are, for example, Obenzoyl- N,N-succinyl-hydroxylamine (m.p. l37l39C), O-acetyl-N,N-succinyl-hydroxylamine (mp. 13 2l 34C), O-p-methoxybenzoyLN,N-succinylhydroxylamine (m.p. l42-l45C), O-p- Tetraacylated glycolurils and especially tetraacetylnitrobenzoyl-N,N-succinyl-hydroxylamine (m.p. glycoluril (m.p. 233-240C) are preferably used. 2l2 215C) and O,N,N-triacetyl-hydroxylamine. In addition. the following acylated glycolurils are j. N,N'-diacyl-sulfurylamides of f l VII], i suitable: di-(chloracetyl)-diacetyl-glycoluril (m.p.
which R, and R preferably represent C alkyl 5 267-269C). r pr pi nyl-g y l ri -P- residues or aryl residues such as phenyl, while R l44l46C). m t y -3. ,6-tria etylglycoluril and R preferably represent C alkyl residues, es- -P- 7921 dlacetyldipfoplonylglycol"Til pecially C alkyl residues. (m.p. l44-l46C) and diacetyl-dibenzoylglycoluril (m.p. 244249C). The acylated glycolurils are not only of special practical impor- N-SO -N tance on account of their excellent properties as R co (vm) activators, but owing to their high melting point they are very suitable for the preparation of pulver- N,N-dimethyl-N,N'-diacetyl-sulfurylamide (m.p. ulent products which are stable on storage.
58 to 60C) and N,N'-diethyl-N,N'-dipropionyll sulfurylamide (m.p. 9597C) may be mentioned as examples.
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 k. l,3-Diacyl-4,5-diacyloxy-lmidazolidmes of forper gram-atom of active oxygen are sufi'icient. If the mula m whlch represents hydrogen or greatest possible activation of the active oxygen is re- Rand and represent hydrogen or quired, the addition of activator can be increased up to OCRn 4 mols, preferably up to 3 mols. However, it is preferred to work with 0.3 to 2 mols of activator per gramatom of the active oxygen. These amounts can, of
XPCH H O C course be varied according to the activity of the particm ular activator used.
The activators may be provided with a coating of substances which are inert towards the activators. This To these belong: I,3 diformy| 4,5 diaccwxy prevents a contact of the activators with the strongly imidazolidine 16004655: C), l3 diacety} alkaline-reacting alkali metal silicates, according to the 4,5-diacetoxyimidazolidine (m.p. 139-140.5c above defimtlom and P y Wlth the Perwmpounds,
O -Rn (1x) l,3-diacetyl-4,5-dipropionyloxy-imidazolidi e which contributes to the stability in storage of the prod- (m'p 5 37 ucts of the invention. Acylaled SlycOluTlls of the general formula The optical brighteners utilized in the compositions Whlch X101 represents the resldue R of the invention are those of the 4,4'-bis-(azolyl)- Rurco xm stilbene-2,2'-disulfonic acid type (I), the stilbyl- 1 naphthotriazole type (ll), the bis-(benzoxazolyl)- C o derivative type (1"), the 2-benzoxazolyl-4,S-naphthol 40 thiophene type (IV), and the diphenyldistyryl type (V). These optical brighteners are compounds of the formu- Riwo O-R10I (X): lae selected from the group consisting of Azolyl CH=CH azolyl l R1 ll1 \N v N i N W R5 0 0 Rs Wm s and o (v) CH=CH- -c H=C H and A represents a member selected from the group consisting of hydrogen and SO H, R represents a member selected from the group consisting of hydrogen and alkyl having 1 to carbon atoms, R represents a member selected from the group consisting of hydrogen and halogen, R, represents a member selected from the group consisting of CN, SO H and SO NHR, R represents a bivalent linkage selected from the group consisting of --CH==CH,
X represents a member selected from the group consisting of -NH-, S, and O, R represents a member selected from the group consisting of hydrogen, alkyl having 1 to 5 carbon atoms and phenyl, R and R, 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,H, SO,CL and SO,N R,,R,, and R and R, 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-Z-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-(S-phenyl-pyrazol-Z-yl)-stilbene-2,2'-disulfonic acid and its sodium salt, 4-(4,5naphthotriazol-2-yl) stilbene-Z-sulfonic acid and its sodium salt, 4-(4,5 naphthotriazol-Z-yl)-4'-chlorostilbene-Z-sulfonic acid and its sodium salt, 4-(4,5-naphthotriazol-2-yl)- stilbene-Z-sulfamide, 2,5-bis-(benzoxazol-2-yl thiophene, l,2-bis-(S-methyI-benzoxazol-Z-yl ethylene, 4,4'-bis-(S-phenyl-benzoxazol-Z-yl)-stilbene, 2-benzoxazolyl-4,5naphthothioprene, 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 l to IV in the compositions of the invention may be optionally replaced wholly or in part with the diphenyldistyryl compounds of the formula where each of the radicals R or R may represent a hydrogen atom or a sulfonic acid radical. Like the radicals R and R also the radicals R and R may be identical or different. R and R are phenyl radicals or substituted phenyl radicals, where as substituents the following atoms or atom groups are possible: alkyl, hydroxyalkyl, or alkoxy radicals with l 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 l 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 or R 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 and R may preferably represent the radicals sulfamidophenyl (C,H SO -NH,) and morpholinosulfophenyl (C H -SO,NC H 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 l 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, l,2- and l,8-naphthotriazoles, nitrobenzotriazole, tetrazole, S-aminotetrazole, alkylene-5,5- ditetrazole, 5-alkylenetetrazoles, S-dialkylaminotetrazoles, and 5alkyl-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 aminotriethylidene-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-, pyroor 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 orthophosphoric acid also partial esters of anhydric acids of phosphorus are formed, particularly of the pyroand polyphosphoric acids, where, however, the esters of ortho-phosphoric acid, optionally also the esters of orthoand 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 A-O o l o-H V A-O wherein A is a member selected from the group consisting of hydrogen and with the proviso that one A may be hydrogen, R, is a member selected from the group consisting of hydrogen and methyl, R, is a fatty alcohol residue having from 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-, dior triethanolamine salts.
The salts of orthophosphoric acid diesters of ethoxyl ated 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 heatdried, that are not changed by water and/or heat, and the other ingredients are admixed with the thusobtained 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 y p UBic 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 esterlike 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 l 8, 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 alkylben zenes 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 and preferably C1248 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 a-sulfo-fatty acids, and aalts of esters of these acids with monoor 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 sulfomonoor di-carboxylie 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 olefins. Sulfated fatty acid alkylolamides or fatty acid monoglycerides, and sulfated alkoxylation products of alkylphenols (C 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 amidelike 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 whic e 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 nonionics may contain per molecule 4 to 100, preferably 6 to 40 and especially 8 to 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-m I e 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 monoor 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 propaneor 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 65C, but at higher temperatures to l00C) 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 l 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 (I), (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 l8 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 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, nonsurface-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 monoand/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 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 ID 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 paraffms or halogenated paraff'ms with melting points below 100C, aliphatic C to C 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-, dior tri-alkali metal orthophosphates, dior 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-, tolueneor 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. Copolymerizates 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
polyamine-N-polycarboxylic acids and other known organic complex-forming substances, while com binationsof different complex-forming substances may also be used. Diand poly-phosphonic acids of the following constitutions also belong to the other known complexforming substances:
YL (5H H(|) XL Y 0H 1 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 l to 4 carbon atoms and Z represents OH, NH, or NXR. For a practical application above all the following compounds are considered: methylene-diphosphonic acid, l-hydroxyethanel l -diphosphonic acid, 1- aminoethane- 1 l -diphosphonic acid, amino-tri- (methylene-phosphonic acid), methylaminoor 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. Watersoluble 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 polyarnides 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 val ues 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 70C.
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-, pyroor 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, nonionic, 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 en zymic substances in the nonionic 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 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 lE/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 oflipases, 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. l-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 ftlr Physiologiche Chemie," Vol. 1923), pp. 1 10-1 17; R. Boissonas, Helvetica Chimica Acta, Vol. 31
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 1 rt l3,"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 par- 21 affins with 12 to 16 carbon atoms by the sulfoxidation method.
HPK-sulfonate" of HT-sulfonate" are the sulfonates in the a-position, obtained from the methyl esters of a hardened palm kernel fatty acid or a hardened tallow fatty acid by sulfonation with S0,.
Olefin sulfonate" is a sulfonate obtained from mixtures of olefins with 12 to 18 carbon atoms by sulfonating with S0, 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 aor from non-terminal olefins.
RA-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.
A E0", KA E0" or Fs-amide 8 E0 are the addition products of ethylene oxide (E0) to technical oleyl alcohol (0A) 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 E0 12 PO" is a non-ionic obtained by re action of 1 mol ofKA 9 E0 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.
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. nonsurface-active foam inhibitors can be used. for exam ple, 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, parafiin 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,-H,O, or Na 80," H20g'3 H20.
TAGU is tetraacetylglycoluril.
The products described in the examples contained the following optical brighteners:
Brightener l The sodium salt of the 4,4'-bis-(4-phenyl-vic-tri-azol- 2-yl)-stilbene- 2,2'-disulfonic acid of the formula Brightener lll 2,5-bis-( benzoxazol-Z-yl)-thiophene Brightener IV l,2-bis-( 5-methylbenzoxazol-2-yl)-ethylene Brightener V 2-benzoxa2o1y1-4,S-naphthothiophene Napbthyl Brightener Vla The sodium salt of a diphenyl-distyryl-disulfonic acid VNBOI OzNa Brightener Vlb The sodium salt of a chloro-diphenyl-distyrylmonosulfonic acid of the structure:
dichloro-diphenyl-distyryl of the structure:
Brightener VIc Ingredients of the preparaation Perborute TAGU KA-EO-Phosphate TA-EO-Phosphate EDTA ATMP BENZOTRIAZOLE NaJHO,
Na CO, Brightener Vla Brightener Vlb Brightencr Vlc Ingredients of the preparation Perborate TAG U KA-EO-Phosphate EDTA DETPA Methylbenzotriazole 1 ,8 Naphto- Ingredients of the preparation Perborate TAGU KA-EO-Phosphate TA-EO-Phosphate EDTA ATMP Benzotriazole NaJ O, Na,CO; Brightener 1 Brightencr 11 Brightener I11 Brightener IV Brightener V Ingredients of the preparation Perborate TAGU KA-EO-Phosphate EDTA DETPA Methylbenzotriazole 1.8-N11phthotriuole Brightener I Brightener II Brightener I11 Brightener IV Brightener V TABLE II I: by weight of ingredients in example B1 B2 83 41.0 36.1 41.0 (U 23.0 19.7 21.3
TABLE 111 k by weight of ingredients in example B6 B7 88 43.5 44.8 38.0 23.3 46.3 22.8
triazole Na P,O, Na,CO, Brightener VIa Brightener Vlb Brightener VIC TABLE IV I by weight of ingredients in example B1 1 B12 B13 41.0 36.1 41.0 23.0 19.7 21.3
TABLE V k by weight of ingredients in example B16 B17 B18 43.5 44.8 38.0 23.3 46.3 22.8
B14 B15 42.6 38.1 [ml (ml 43.5 16.5
B19 820 47.1 32.2 (m) 10.1 24.8 23.6 3.5 (T) The composition of some washing agents, according to the invention are described in Examples W1 to W20 in Tables VII to IX.
Ingredients of the preparation ABS HPK-Sulfonate Olefinsulfonate Soap B Soap D KA-EO-Phosphate TA-EO-Phosphate 0A 10 E0 KA 20 E0 KA 9 E0 12 PO Fs-amide+ 8 E0 Foam inhibitor t z m Na,0.3.3SiO, Na,CO;,
Mg S10, Perborate TAGU Benzotriazole Brightener I Brightener II Brightener I11 Brightener IV Brightener V Residue Water TABLE VI 1: by weight of ingredients in example W1 W2 W2 6.1 4.9 1.2
' Ingredients of the preparation ABS Alkanesulfonate l-lT-Sulfonate KA-Sulfate TA-sulfate KA-EO-Sulfate Soap C KA-EO-Phosphate A 10 E0 KA 9 E0 12 PO Clrboxybetaine Sult'obetaine Foam Inhibitor NIIPIO 1e Na,0.3,3 S10, Na,CO, Na,SO
CMC NTA EDTA DETP HEDP ATMP MgSiO, Perborate TAGU Methylbenzotriazole 1,8-Naphthotriazole Brightener I Brightener l1 Brightener lll Brightener 1V Brightener V Residue Water Ingredients of the prepara' tion ABS l-ll'K-Sulfonate Olefinsulfonate Soap B Soap D KA-EO-Phosphate TA-EO-Phosphate 0A 10 E0 KA 20 E0 Fs-amide 8 E0 Foam inhibitor Na,P,O,. Na,0.3.3 SiO, Na,CO,
MgSiO, Perborate TAGU Benzotriazole Brightener Vla Brightener Vlb Brightencr Vlc Residue Water Ingredients of the preparation ABS Alkanesulfonate HT-Suli'onale KA-Sulfate TA-Sulfate KA-EO-Sulfate Soap C KA-EO-Phosphate 0A 10 E0 KA 9 E0 25 TABLE V11 by weight of ingredients in example W6 W7 W8 5.3 5.0 2.9
TABLE V111 L by weight of ingredient-I in example W11 W12 W13 6.1 4.9 1.2
TABLE 1X by weight of ingredients in example W16 W17 W18 12 P0 1.8 Carboxybetainc 0.5 Sultobetaine 0.7 06
Foam inhibitor 0.5 0.5 0.6 0.4 Na,P,O,. 32.6 34.2 41.1 36.1 Na,0.3,3 SiO, 5.5 3.4 4.0 4.5 Na,CO, 14.8 16.2 14.1 Na,SO. 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, 2.5 2.0 Perborlte 19.0 14.0 10.0 14.0 15.6
(m) (m) (m) TAGU 10.2 14.0 6.0 3.0 15.6 Methylbenzotriazole 0.2
LS-Naphthotriazole 0.2 Brightener Vla 0.2 0.5 0.1 Brightener Vlb 0.05 0.15 0.1 Brightener Vlc 0.13 0.15 0.28 0.1
Residue Water 1f 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 pl-l-value is somewhat lowered by the carboxylic acid formed from the activator. Since above all in white linen a lowering of the pl-l-value is not advisable, the products of the invention may contain alkaline-reacting salts, as required for the neutralization of the carboxylic acids formed.
11', 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, diacetyldibenzoyl-glycoluril, diacetylaniline, diacetyltoluidine, diacetyl-dimethyl-hydantoin, tetraacetylmethylenediamine 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 Wl 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.
N/ Q -N/ N/ W R and 1. A bleaching component composition useful in an aqueous cold-bleaching treatment consisting essentially of (a) from 95 to 99.9 percent by weight ofa mixture of (i) a water-soluble inorganic percompound yielding H O, in aqueous solution and (ii) an activator for active oxygen having the formula wherein R R and R represent a member selected from the group consisting of alkyl having l to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, phenyl, and phenylalkyl having 7 to 8 carbon atoms and X represents a member selected from the group consisting of R and R -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 Azolylher selected from the group consisting of hydrogen and halogen, R, represents a member selected from the group consisting of CN, SO,H and SO,NHR, FL represents a bivalent linkage selected from the group consisting of CH=CH-,
CH=CH, Gabonand R R and R and R, 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 watersoluble 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,O 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)
Re A A B1 wherein azolyl represents an azole structure of the 55 from 0 to 20% by weight of water-soluble salts of parformula selected from the group consisting of A represents a member selected from the group consisting of hydrogen and SO H, R represents a member selected from the group consisting of hydrogen and alkyl having l to 5 carbon atoms, R represents a memtial 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 watersoluble salts of partial esters has the formula tially of the steps of adding to an aqueous solution con- 29 30 wherein A is a member selected from the group consistrepresents a bivalent linkage selected from the group ing of hydrogen and consisting of CH=CH'.
with the proviso that one A may be hydrogen, R is a member selected from the group consisting of hydrogen and methyl, R, is a fatty alcohol moiety having from 10 to 22 carbon atoms, and n is an integer from to 10. l
7. The composition of claim 1 wherein said activator for active oxyten is a member selected from the group consisting of tetraacetylglycoluril, tetrapropionyl- TCH=(IIHOTR= Q Q Q a CH=CH-, CH=CH and glycoluril, methyltriacetylglycoluril and diacetyldiben- X represents a membel' Selected from the group zoylglycoluriL sisting of -NH-, S, and -O, R, represents a 8. A process for the stabilization of optical brightenmember Selected from the group consisting of y ers against deterioration in aqueous solutions in the g lkyl having 1 t0 5 Carbon oms and phenyl, R. presence of copper ions and H,0, which consists essenand R, represent members selected from the group consisting of phenyl and phenyl substituted with at least taining (1) small amounts of copper ions, (2) an effec-' one substituent selected from the group consisting of tive amount for optical brightening for textiles of an opalkyl having 1 to 4 carbon atoms, hydroxyalkyl having tical brightener having a formula selected from the 2 to 5 carbon atoms, alkoxy having 1 to 5 carbon group consisting of atoms, chloro, CN, COOH, SO l-l, CO,Cl and SO,N
CH=CH CH=CH W+.m A
wherein azolyl represents an azole structure of the for- R,,R,, and R and R, are members selected from the mula selected from the group consisting of 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- N N N soluble salts, and (3) an effective amount for bleaching A of a water-soluble inorganic percompound yielding N and H O, in aqueous solution, an amount of an activator for R said inorganic percompounds selected from the group N N consisting of N-acyl and O-acyl compounds having 2 to 7' i r v M 9 carbon atoms in the acyl said activator having an ac- A re resents a m m cted from the rou conp 6 bet sele g p tivatmg action of at least 3 In the Per-Acid Formation sisting of hydrogen and SOSH R represents a member test said percompound and said activator having presselected from the group consisting of hydrogen and ent in such ratio that from 0.01 to 4 mols of said activaalkyl having 1 to 5 carbon atoms, R represents a memtor are present for each gram-atom of active oxygen in ber selected from the group consrstmgof hydrogen and said inorganic percompound.
halogen, R, represents a member selected from the group consisting of CN, SO l-l and SO,NHR, R, a: a i a: s
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|U.S. Classification||8/648, 252/301.22, 510/307, 548/260, 252/186.39, 8/111, 548/255, 548/219|
|International Classification||C11D3/42, C11D3/40, C11D3/39|
|Cooperative Classification||C11D3/3917, C11D3/42|
|European Classification||C11D3/42, C11D3/39B2D6|