US3779931A - Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners - Google Patents

Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners Download PDF

Info

Publication number
US3779931A
US3779931A US00184213A US3779931DA US3779931A US 3779931 A US3779931 A US 3779931A US 00184213 A US00184213 A US 00184213A US 3779931D A US3779931D A US 3779931DA US 3779931 A US3779931 A US 3779931A
Authority
US
United States
Prior art keywords
percent
acid
weight
activator
bleaching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00184213A
Other languages
English (en)
Inventor
H Rhld
D Jung
W Fries
H Bloching
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Application granted granted Critical
Publication of US3779931A publication Critical patent/US3779931A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • 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 invention relates to activator-containing compositions for the preparation of cold-bleaching liquors
  • 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:
  • 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.
  • 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
  • At least one optical brightener of the following types: 4,4'-bis-(azolyl)-stilbene-2,2-disulfonic acids, stilbyl-naphthotriazoles,
  • optical brighteners insofar as they are acids, particularly sulfonic acids, are also present in the form of their salts.
  • the brighteners named under (b) may be utilized singularly or in combination.
  • 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.
  • 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.
  • 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:
  • phosphoric acid esters 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").
  • phosphoric acid esters a acyl radicals of the activators" are liberated as carboxylic acids.
  • 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
  • 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,
  • 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.
  • 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.
  • 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:
  • washing agent ingredients may be present in such soaking agents, such as antimicrobial acting compounds, soil suspension agents, enzymes, perfumes, dyes, etc.
  • 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:
  • 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:
  • 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,
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • peroxyhydrates such as the peroxyhydrates of ortho-, pyroor polyphosphates, especially of the tripolyphosphates, as well as the carbonates.
  • 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.
  • 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.
  • 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.
  • substituents are, for example, chloroalkyl having 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, and p-methoxyphenyl,
  • compounds with a melting point of at least 70C, preferably at least 100C and especially at least 150C are specially suitable.
  • 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).
  • N-diacylated amines of the formula I in which X represents a residue R or one of the residues la, lb,
  • 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.
  • 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.
  • 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.
  • 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.
  • acylated glycolurils are j. N,N'-diacyl-sulfurylamides of f l VII], i suitable: di-(chloracetyl)-diacetyl-glycoluril (m.p.
  • 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).
  • 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.
  • N,N'-diethyl-N,N'-dipropionyll sulfurylamide (m.p. 9597C) may be mentioned as examples.
  • 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
  • the activators may be provided with a coating of substances which are inert towards the activators. This To these belong: I,3 diformy
  • 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).
  • 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.
  • 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.
  • 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).
  • optical brighteners to be used 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 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.
  • other sequestering agents may be used, insofar as their sequestering power, particularly for copper, is not substantially below that of the named compounds.
  • 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.
  • the following enumeration of the synthetic tensides, optionally contained in the products of the invention are to be considered.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • alkene 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • non-ionic surface-active compounds here called non-ionics
  • non-ionics 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.
  • 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.
  • propylene or butylene glycol ether residues or polyether chains may be present in or at the ends of these polyether residues.
  • 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.
  • Ucon-Fluid some of which are still water-soluble
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • foam stabilizers 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.
  • 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.
  • 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,
  • alkali metal salts 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,
  • YL (5H H(
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the products according to the invention may also contain antimicrobial substances.
  • the 2-hydroxy-2', 4,4'-trichloro-diphenylether has been proven good.
  • 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
  • HPK-sulfonate of HT-sulfonate
  • HPK-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.
  • 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
  • ATMP nitrilotriacetic acid
  • ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid
  • diethylenetriaminepentaacetic acid hydroxyethanediphosphonic acid or aminotrimethylene phosphonic acid, respectively.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • composition of claim 3 wherein said percompound yielding H,O in aqueous solution is a water soluble perborate.
  • 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.
  • 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 ethoxy
  • 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
  • n is an integer from to 10.
  • 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
  • halogen represents a member selected from the group consisting of CN, SO l-l and SO,NHR, R, a: a i a: s

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US00184213A 1970-12-10 1971-09-27 Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners Expired - Lifetime US3779931A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19702060762 DE2060762A1 (de) 1970-12-10 1970-12-10 Mittel zur Herstellung von Kaltbleichflotten,insbesondere von kaltbleichwirksamen Waschlaugen
DE2134691A DE2134691A1 (de) 1970-12-10 1971-07-12 Mittel zur herstellung von kaltbleichflotten, insbesondere von kaltbleichwirksamen waschlaugen

Publications (1)

Publication Number Publication Date
US3779931A true US3779931A (en) 1973-12-18

Family

ID=25760165

Family Applications (1)

Application Number Title Priority Date Filing Date
US00184213A Expired - Lifetime US3779931A (en) 1970-12-10 1971-09-27 Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners

Country Status (10)

Country Link
US (1) US3779931A (enrdf_load_stackoverflow)
AT (1) ATA1058471A (enrdf_load_stackoverflow)
BE (1) BE776404A (enrdf_load_stackoverflow)
BR (1) BR7105949D0 (enrdf_load_stackoverflow)
CA (1) CA992264A (enrdf_load_stackoverflow)
DE (2) DE2060762A1 (enrdf_load_stackoverflow)
FR (1) FR2117998B1 (enrdf_load_stackoverflow)
GB (1) GB1354583A (enrdf_load_stackoverflow)
IT (1) IT943719B (enrdf_load_stackoverflow)
NL (1) NL7112033A (enrdf_load_stackoverflow)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3945936A (en) * 1974-01-29 1976-03-23 The Procter & Gamble Company Bleaching article
US3975153A (en) * 1975-08-25 1976-08-17 Fmc Corporation Activation of peroxygen bleaches using isophorone enol acetates and isophorone oximinoacetate
US4014871A (en) * 1974-08-14 1977-03-29 Ciba-Geigy Corporation Stilbene compounds
US4028263A (en) * 1973-08-24 1977-06-07 Colgate-Palmolive Company Bleaching and brightening detergent composition
US4087369A (en) * 1976-11-08 1978-05-02 The Procter & Gamble Company Peroxybleach activated detergent composition
US4105399A (en) * 1973-09-05 1978-08-08 Ciba-Geigy Corporation Optically brightening with a synergistic mixture
US4111826A (en) * 1975-11-03 1978-09-05 Lever Brothers Company Bleaching assistants
US4123376A (en) * 1973-08-24 1978-10-31 Colgate-Palmolive Company Peroxymonosulfate-base bleaching and bleaching detergent compositions
US4177347A (en) * 1974-06-12 1979-12-04 Ciba-Geigy Corporation Distilbenyl-oxdiazoles
US4225452A (en) * 1978-09-27 1980-09-30 Lever Brothers Company Bleaching and cleaning composition
US4276188A (en) * 1974-06-12 1981-06-30 Ciba-Geigy Corporation Process for manufacturing 2-stilbenyl-1,2,3-triazoles and new 2-stilbenyl-1,2,3-triazoles
US4300897A (en) * 1973-08-24 1981-11-17 Colgate-Palmolive Company Method for bleaching with peroxymonosulfate-based compositions
US4422950A (en) * 1980-12-09 1983-12-27 Lever Brothers Company Bleach activator granules and preparation thereof
US4430244A (en) 1982-03-04 1984-02-07 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
US4460485A (en) * 1983-07-15 1984-07-17 Lever Brothers Company Polyester fabric conditioning and whitening composition
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5035825A (en) * 1987-11-26 1991-07-30 Ciba-Geigy Corporation Stable bleaching detergents containing stilbene fluorescent whitening agents
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5118436A (en) * 1989-12-15 1992-06-02 Kao Corporation Liquid oxygenic bleaching composition
US5124480A (en) * 1989-10-10 1992-06-23 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5183584A (en) * 1989-10-10 1993-02-02 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
US5273896A (en) * 1989-10-13 1993-12-28 Novo Nordisk A/S Hemopeptide having peroxidase activity for bleaching dyes
US5560749A (en) * 1995-06-06 1996-10-01 Lever Brothers Company, Division Of Conopco, Inc. Polymeric bleach precursors and methods of bleaching substrates
US5747438A (en) * 1993-11-03 1998-05-05 The Procter & Gamble Company Machine dishwashing detergent containing coated percarbonate and an acidification agent to provide delayed lowered pH
US6117357A (en) * 1996-07-29 2000-09-12 The Procter & Gamble Company Unsymmetrical acyclic imide bleach activators and compositions employing the same
US6585933B1 (en) 1999-05-03 2003-07-01 Betzdearborn, Inc. Method and composition for inhibiting corrosion in aqueous systems
WO2003093565A3 (de) * 2002-05-03 2004-03-04 Basf Ag Verfahren zum aufhellen von textilen materialien
US20040180803A1 (en) * 2001-08-02 2004-09-16 Sarah Dixon Laundry detergent compositions
US20060246383A1 (en) * 2005-04-29 2006-11-02 Kai-Kong Iu Amphoteric stilbene composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA851897B (en) * 1984-04-02 1986-10-29 Colgate Palmolive Co Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1059601B (de) * 1957-01-10 1959-06-18 Unilever Nv Reinigungsmittel
US3284462A (en) * 1963-11-25 1966-11-08 Ciba Ltd 2-aroxazolyl-5-aryl-thiophene compounds
US3630921A (en) * 1968-12-03 1971-12-28 Henkel & Cie Gmbh Scouring agents with a bleaching and disinfecting action
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US3650962A (en) * 1968-12-21 1972-03-21 Henkel & Cie Gmbh Washing bleaching and cleansing agents containing poly-(n-acetic acid)-ethyleneimines
US3655569A (en) * 1968-08-08 1972-04-11 Mo Och Domsjoe Ab Detergent compositions containing a sequestrant and optionally a bleaching agent having a reduced tendency to attack copper, zinc and aluminum
US3663444A (en) * 1969-05-02 1972-05-16 Henkel & Cie Gmbh Washing and cleansing agents with polyamides having improved dirtcarrying capacity

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1059601B (de) * 1957-01-10 1959-06-18 Unilever Nv Reinigungsmittel
US3284462A (en) * 1963-11-25 1966-11-08 Ciba Ltd 2-aroxazolyl-5-aryl-thiophene compounds
US3637339A (en) * 1968-03-07 1972-01-25 Frederick William Gray Stain removal
US3655569A (en) * 1968-08-08 1972-04-11 Mo Och Domsjoe Ab Detergent compositions containing a sequestrant and optionally a bleaching agent having a reduced tendency to attack copper, zinc and aluminum
US3630921A (en) * 1968-12-03 1971-12-28 Henkel & Cie Gmbh Scouring agents with a bleaching and disinfecting action
US3650962A (en) * 1968-12-21 1972-03-21 Henkel & Cie Gmbh Washing bleaching and cleansing agents containing poly-(n-acetic acid)-ethyleneimines
US3663444A (en) * 1969-05-02 1972-05-16 Henkel & Cie Gmbh Washing and cleansing agents with polyamides having improved dirtcarrying capacity

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028263A (en) * 1973-08-24 1977-06-07 Colgate-Palmolive Company Bleaching and brightening detergent composition
US4300897A (en) * 1973-08-24 1981-11-17 Colgate-Palmolive Company Method for bleaching with peroxymonosulfate-based compositions
US4123376A (en) * 1973-08-24 1978-10-31 Colgate-Palmolive Company Peroxymonosulfate-base bleaching and bleaching detergent compositions
US4105399A (en) * 1973-09-05 1978-08-08 Ciba-Geigy Corporation Optically brightening with a synergistic mixture
US3945936A (en) * 1974-01-29 1976-03-23 The Procter & Gamble Company Bleaching article
US4276188A (en) * 1974-06-12 1981-06-30 Ciba-Geigy Corporation Process for manufacturing 2-stilbenyl-1,2,3-triazoles and new 2-stilbenyl-1,2,3-triazoles
US4177347A (en) * 1974-06-12 1979-12-04 Ciba-Geigy Corporation Distilbenyl-oxdiazoles
US4014871A (en) * 1974-08-14 1977-03-29 Ciba-Geigy Corporation Stilbene compounds
US3975153A (en) * 1975-08-25 1976-08-17 Fmc Corporation Activation of peroxygen bleaches using isophorone enol acetates and isophorone oximinoacetate
US4111826A (en) * 1975-11-03 1978-09-05 Lever Brothers Company Bleaching assistants
US4087369A (en) * 1976-11-08 1978-05-02 The Procter & Gamble Company Peroxybleach activated detergent composition
US4225452A (en) * 1978-09-27 1980-09-30 Lever Brothers Company Bleaching and cleaning composition
US4422950A (en) * 1980-12-09 1983-12-27 Lever Brothers Company Bleach activator granules and preparation thereof
US4430244A (en) 1982-03-04 1984-02-07 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
US4460485A (en) * 1983-07-15 1984-07-17 Lever Brothers Company Polyester fabric conditioning and whitening composition
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5035825A (en) * 1987-11-26 1991-07-30 Ciba-Geigy Corporation Stable bleaching detergents containing stilbene fluorescent whitening agents
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
US5124480A (en) * 1989-10-10 1992-06-23 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5183584A (en) * 1989-10-10 1993-02-02 Monsanto Company Peroxygen bleach activators and bleaching compositions
US5605832A (en) * 1989-10-13 1997-02-25 Novo Nordisk A/S Dye transfer inhibition
US5273896A (en) * 1989-10-13 1993-12-28 Novo Nordisk A/S Hemopeptide having peroxidase activity for bleaching dyes
US5855621A (en) * 1989-10-13 1999-01-05 Novo Nordisk A/S Dye transfer inhibition
US5700770A (en) * 1989-10-13 1997-12-23 Novo Nordisk A/S Dye transfer inhibition and novel peroxidase
US5118436A (en) * 1989-12-15 1992-06-02 Kao Corporation Liquid oxygenic bleaching composition
USRE35000E (en) * 1989-12-15 1995-07-25 Muneo Aoyagi Liquid oxygenic bleaching composition
US5747438A (en) * 1993-11-03 1998-05-05 The Procter & Gamble Company Machine dishwashing detergent containing coated percarbonate and an acidification agent to provide delayed lowered pH
US5560749A (en) * 1995-06-06 1996-10-01 Lever Brothers Company, Division Of Conopco, Inc. Polymeric bleach precursors and methods of bleaching substrates
US6117357A (en) * 1996-07-29 2000-09-12 The Procter & Gamble Company Unsymmetrical acyclic imide bleach activators and compositions employing the same
US6585933B1 (en) 1999-05-03 2003-07-01 Betzdearborn, Inc. Method and composition for inhibiting corrosion in aqueous systems
US20040180803A1 (en) * 2001-08-02 2004-09-16 Sarah Dixon Laundry detergent compositions
WO2003093565A3 (de) * 2002-05-03 2004-03-04 Basf Ag Verfahren zum aufhellen von textilen materialien
US20050235429A1 (en) * 2002-05-03 2005-10-27 Basf Aktiengessellschaft Method for brightening textile materials
CN1333129C (zh) * 2002-05-03 2007-08-22 巴斯福股份公司 纺织材料的增白方法
US20060246383A1 (en) * 2005-04-29 2006-11-02 Kai-Kong Iu Amphoteric stilbene composition
US20080290320A1 (en) * 2005-04-29 2008-11-27 Kai Kong Iu Amphoteric stilbene composition
US7789917B2 (en) 2005-04-29 2010-09-07 Hewlett-Packard Development Company, L.P. Amphoteric stilbene composition

Also Published As

Publication number Publication date
DE2060762A1 (de) 1972-06-22
CA992264A (en) 1976-07-06
BR7105949D0 (pt) 1973-04-12
FR2117998A1 (enrdf_load_stackoverflow) 1972-07-28
FR2117998B1 (enrdf_load_stackoverflow) 1974-04-05
IT943719B (it) 1973-04-10
ATA1058471A (de) 1975-03-15
NL7112033A (enrdf_load_stackoverflow) 1972-06-13
GB1354583A (en) 1974-06-05
DE2134691A1 (de) 1973-02-08
BE776404A (fr) 1972-06-08

Similar Documents

Publication Publication Date Title
US3779931A (en) Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners
US3775332A (en) Method of activating per-compounds and solid activated per-compound compositions
US3965024A (en) Washing agent compositions and washing assistant composition containing phosphonopolycarboxylate sequestering agents
US3789002A (en) Solid, pulverulent to granular compositions containing bleaching activators
US3676340A (en) Combinations of detergents with controlled foaming properties and washing agents containing them
EP0086511B1 (en) Oxygen-bleach-containing liquid detergent compositions
US3850832A (en) Washing, rinsing and cleansing agent compositions containing furan-maleic anhydride copolymer sequestering agents
US3650962A (en) Washing bleaching and cleansing agents containing poly-(n-acetic acid)-ethyleneimines
CA2056938A1 (en) Bleach/builder precursors
EP0293040A1 (en) Liquid detergent containing solid peroxygen bleach
US4110242A (en) Compositions and method for activating oxygen utilizing N-acylated uracils and benzouracils
SU446974A1 (ru) Моющее средство
US5250212A (en) Liquid detergent containing solid peroxygen bleach and solvent system comprising water and lower aliphatic monoalcohol
US3625904A (en) Washing agents, washing adjuvants and cleaning agents containing antimicrobial substances
EP0036691B1 (en) Bleaching detergent compositions
US3725289A (en) Stain removing composition
US4115309A (en) Compositions and method for activating oxygen utilizing cyclic ester-anhydrides of α-hydroxycarboxylic acids
US3700600A (en) Process of preparing pulverulent to granular perborate containing washing compositions
US3753914A (en) Synergistic bleaching textile treating compositions with an antimicrobial action
US3785984A (en) Compositions for the preparation of cold-bleaching liquors,particularly active washing liquors
US3630921A (en) Scouring agents with a bleaching and disinfecting action
US3708427A (en) Washing and cleansing compositions
US3844951A (en) Detergent compositions containing a textile softener
JPH0525770A (ja) 漂白方法及び漂白組成物
GB2110259A (en) Peroxyacid bleaching and laundering composition