US3741903A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
US3741903A
US3741903A US00206143A US3741903DA US3741903A US 3741903 A US3741903 A US 3741903A US 00206143 A US00206143 A US 00206143A US 3741903D A US3741903D A US 3741903DA US 3741903 A US3741903 A US 3741903A
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detergent composition
detergent
sodium
percent
composition according
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J Evans
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Lever Brothers Co
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Lever Brothers Co
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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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • a detergent composition of the low temperature bleaching type comprises an inorganic persalt, for ex- 30 Foreign Anna/ion p i D g. ample sodium perborate, an inorganic peracid precur- Dec 12 1968 Great Britain 59 272/68 example thyme r amine, a cotton substantive fluorescent agent of the 4,- 52 us. c1 252/95 252/39 252/99 4Ksym-"iazinylammwilbene'z'z"disulphmate 260/248' type and not more than 0.001 per cent of a triazine de- 51 Int. Cl 01 M 7/52 rival spedfied The have a 58 Field of Search 252/95, 99, 89; decreased endmy dim! and storage.
  • This invention relates to fabric-washing detergent compositions, and in particular it relates to so-called low-temperature bleaching detergent compositions of the type functioning by the generation in aqueous solution during use of organic peracids, for example peracetic acid, perbenzoic acid or substituted perbenzoic acids.
  • Low-temperature bleaching detergent compositions essentially comprise inorganic persalts and organic compounds reactive at relatively low temperatures, for example 20 to 60 C, with the persalts, or with hydrogen peroxide liberated by the persalts, to form organic peracids.
  • organic peracid precursors such organic compounds are referred to as organic peracid precursors.
  • organic peracid precursors were added to conventional detergent compositions of the type discussed above. However, it was noted that discoloration and mal-odor were produced in such compositions during storage. These compositions contained many other ingredients, but as there had been no serious instability problems with such compositions prior to the addition of the organic peracid precursor it was assumed that it was the organic precursor that was resulting in the poor storage propsrties. Attempts were made to improve the storage properties by altering the nature of the organic peracid precursors, but these attempts were unsuccessful and as a result it was not possible to produce commercially acceptable effective low-temperature bleaching detergent compositions. The public was, therefore, denied the advantages that such compositions would otherwise have provided.
  • a detergent composition consists essentially of:
  • At least one cotton-substantive fluorescent agent which is a derivative of 4,4'-di(symtriazinylamino)stilb'ene-2,2-disulphonic acid or of a salt thereof;
  • R is a hydroxy group or a halogen atom
  • R is a hydroxy group or the group NR,R each of R, and R being a hydrogen atom, or an alkyl, substituted alkyl, aryl or substituted aryl group, or R and R, being combined in a heterocyclic ring, and
  • R is an alkyl, substituted alkyl, aryl or substituted aryl group.
  • R is a hydroxy group or a chlorine atom.
  • R is selected from the group consisting of hydroxy, dimethylamino, N-methylethylamino, monoethylamino, diethylamino, l-methyl-2- hydroxy)ethylamino, amilino, p-chloranilino and mor pholino groups.
  • R is a methyl, phenyl or mono-sulphonated phenyl group.
  • inorganic persalt sodium perborate, which is used as the monohydratc or tetrahydrate, but other inorganic persalts, for example percarbonates, perpyrophosphates and persilicates may alternatively be used.
  • percarbonates, perpyrophosphates and persilicates may alternatively be used.
  • the organic peracid precursors are typically compounds containing one or more acyl groups which are susceptible to perhydrolysis. Acetyl and benzoyl radicals are preferred, generating peracetic and perbenzoic acid, respectively.
  • the perhydrolysis should be sufficiently fast and the organic peracid precursor sufficiently watersoluble for the organic peracid to be formed in a reasonable time. Moreover, the perhydrolysis must predominate over the competing hydrolysis reaction and the organic peracid formed must be sufficiently stable for the desired bleaching to occur under the laundering conditions employed.
  • organic peracid precursors which may be mentioned by way of example are esters such as sodium acetoxybenzene sulphonate and chloracetoxy salicylic acid, acyl-substituted cyanurates such as triacetylcyanurate, amides, particularly acetylated alkyl amines such as N,N,N',N-tetracetyl ethylenediamine, N-acyl azoles such as N-acetyl imidazole and N-benzoyl imidazole, acylated barbitones, hydantoins and glycolurils such as N,N'-diacetyl barbitone, N,N'-diacetyl-5,5- dimethylhydantoin and N,N,N,N'-tetracetyl glycoluril, respectively.
  • esters such as sodium acetoxybenzene sulphonate and chloracetoxy salicylic acid
  • the amounts of the inorganic persalt and the organic peracid precursor are both generally within the range of from about 5 to percent by weight in the detergent compositions.
  • the ratio of the inorganic persalt to the organic peracid precursor can vary, depending on the number of reactive acyl radicals per molecule of the organic peracid precursor, but generally the amounts of the two components are of the same order.
  • the cotton-substantive fluorescent agents which are used in the low-temperature bleaching detergent compositions of the invention are well-known, and many such fluorescent agents are available commercially. Specific fluorescent agents which may be mentioned by way of example are:
  • fluorescent agents are supplied and used in detergent compositions in the form of their alkali-metal salts, for example the sodium salts.
  • detergent compositions may of course contain other types of fluorescent agent which may be either cotton or nylon-substantive, for example pyrazoline fluorescent agents.
  • the total amount of fluorescent agent or agents used in a detergent composition is generally from about 0.1 to 2 percent by weight.
  • the triazine impurities are apparently formed during the preparation of the commercially-available fluorescent agents, and, if present in too high a concentration in the fluorescent agent, render the unpurified fluorescent agent unsatisfactory for use in a low-temperature bleaching detergent composition.
  • a test for determining whether or not a fluorescent agent incorporates triazine impurities to an excessive extent is described be low.
  • a detergent base powder had added to it 10 percent by weight of sodium perborate, 8 percent by weight of N,N,N,N'-tetraacetyl ethylenediamine and 2 percent by weight of the fluorescent agent.
  • the ingredients are well mixed and then placed in a bottle which is put into an oven maintained at 60 C. The bottle is periodically examined for the color and odor of its contents. The development of a detectable discoloration or foul odor within a period of 24 hours indicates that the fluorescent agent used contains too high an amount of triazine impurities.
  • An ideal detergent base powder for use in this test is described in Example 1 below.
  • a fluorescent agent when tested as described above gives only a slight discoloration or foul odor by the end of the period of storage of the powder at 60 C, it may still be possible to use the fluorescent agent without purification in low-temperature bleaching detergent compositions of the present invention, but at a lower concentration than the 2 percent level used in the test.
  • a fluorescent agent used in a com position at the 2 percent level may include minor amounts of up to about 0.05 percent by weight of the triazine impurities, without the level of the impurities in the composition (ie 0.00l percent) being excessive.
  • a fluorescent agent comprising, say, 0.2 percent by weight of the triazine impurities could only be used in a composition to an extent of about 0.5 percent by weight in order to avoid exceeding the same level of impurities in the composition.
  • the maximum permitted concentration of the triazine impurities in the lowtemperature bleaching detergent compositions of the invention is about 0.001 percent by weight, as 1 have found that more than this amount of such impurities is unacceptable.
  • a method which may be used for the purification of a fluorescent agent containing an unacceptably high level of triazine impurities is described below.
  • Method for the purification of a fluorescent agent A sample of the fluorescent agent is added to boiling water to which a minimum amount of ethanol is added in order to dissolve substantially all of the sample. The solution thus formed is cooled to about 60-65 C whereupon less soluble impurities in the fluorescent agent are precipitated and are removed from the solution by filtration. The filtrate is then cooled to room temperature to precipitate the fluorescent agent which is itself removed by filtration and subsequently dried. Other more soluble impurities in the fluorescent agent are left in the filtrate. Using this purification process it is possible in most cases to recover at least about percent by weight of the fluorescent agent incorporated in the original sample. Alternatively, chromatographic techniques may be used for the purification of the fluorescent agents, if desired.
  • triazine impurities which may be mentioned as causing discoloration and/or mal-odors are 2-anilinc-4,6-hydroxytriazine, 2-anilino-4- morpholino-6-hydroxytriazine, 2,4-di(ethylamino)-6- hydroxytriazine, and similar compounds containing halogen atoms, usually chlorine, instead of the hydroxy groups, to which they are readily hydrolyzed.
  • Further compounds contain two triazine rings of formula (I) in which the groups R, are conjoined in a 4,4'-substituted stilbene-2,2'-disulphonic acid (or salt) group.
  • a detergent composition of the invention may advantageously incorporate one or more metallic catalysts which promote the organic peracid bleaching effect.
  • metallic catalysts take the form of organic complexes with transition metals, such as cobalt, for example the cobalt chelates of pyridine 2-carboxylic acid and l,l0-phenan-throline.
  • Any metallic catalyst used is normally present in very small amounts, and a level of a metallic catalyst in a detergent composition such that a concentration of the metallic catalyst in a wash liquor of about 1 to 5 X 10 mole per liter is generally satisfactory.
  • the stain removal performance of a detergent composition of the invention may also be improved by incorporating therein enzymes, which may be proteolytic or amylolytic in nature.
  • the preferred enzyme is a'proteolytic enzyme (protease) obtained from b subrilis.
  • proteolytic enzymes are incorporated into detergent com positions in amounts such that the detergent compositions have enzymic activities in the range of from 10 to 10 maltose units per kilogram, when amylolytic enzymes are used and from 5 to 20 Anson units per gram when proteolytic enzymes are used.
  • a detergent composition of the invention will contain at least one detergent-active compound.
  • the detergent-active content of the detergent composition will generally be from about 5 to about 30 percent, and preferably from about 10 to about 25 percent, by weight of the detergent composition.
  • the nature of the detergent-active compound or compounds in the detergent composition is not an essential feature of the invention: any of the detergent-active compounds conventionally incorporated in or proposed for use in detergent compositions may be used, and those skilled in the art of formulating detergent compositions will be familiar with these detergent-active compounds and the various amounts and combinations in which they may advantageously be used.
  • the detergent-active compound or compounds may be anionic, nonionic or amphoteric in character.
  • Typical anionic detergent-active compounds are water-soluble or water-dispersible salts of various organic acids.
  • the cations of such salts are generally alkalimetals, such as sodium and, less preferably, potassium, but other cations, such as ammonium and substituted ammonium, can be used if desired.
  • alkyl benzene sulphonic acids the alkyl chains of which contain from about eight to about 20 carbon atoms, such as p-dodecyl benzene sulphonic acid and linear alkyl (C benzene sulphonic acid; the mixtures of sulphonic acids obtained by reacting linear and branched olefins, particularly linear cracked-wax or Ziegler alpha-olefins, containing from about eight to about 22 carbon atoms, with sulphur trioxide; alkyl sulphonic acids obtained by reacting alkanes containing from about eight to about 22 carbon atoms with sulphur dioxide/oxygen or sulphur dioxide/chlorine (followed by hydrolysis in the latter case), or by the addition of bisulphite to olefins, particularly linear cracked-wax or Ziegler alpha-olefins, containing from about eight to about 22 carbon atoms; alkyl
  • nonionic detergent-active compounds are: condensates of alkyl-phenols having an alkyl group (derived, for example, from polymerized propylene, diisobutylene, octene, dodecene or nonene) containing from about six to 12 carbon atoms in either a straight chain or branched chain configuration, with about to 25 moles of ethylene oxide per mole of alkylphenol; condensates containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide with the reaction produce of ethylenediamine and excess propylene oxide; condensates of linear or branched-chain aliphatic alcohols containing from eight to 18 carbon atoms with ethylene oxide, eg a coconut alcohol-ethylene oxide condensate containing about 6 to 30 moles of ethylene oxide per mole of coconut alcohol; long-chain tertiary amine oxides corresponding to the general formula
  • amphoteric detergent-active compounds are: derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group, such as sodium-3-dodecylaminopropionate, sodium-3-dodecylaminopropanesulphonate and sodium N-2-hydroxydodecyl-N- methyl-taurate; and derivatives of aliphatic quaternary ammonium compounds, sulphonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substitutents contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group, such as 3-(N,N-dimethyl-N-hexadecylammonium) propane-l-sulphonate be
  • detergentactive compounds commonly used in the art are given in 'Surface Active Agents, Volume I by Schwartz and Perry (lnterscience 1949) and Surface Active Agents, Volume II" by Schwartz, Perry and Berch (lnterscience 1958), the disclosures of which are included by reference herein.
  • a detergent composition of the invention will also include one or more detergency builders.
  • the total amount of detergency builders in a detergent composition of the invention will be from about 5 to about percent by weight of the detergent composition.
  • Many detergency builders are known, and those skilled in the art of formulating fabric-washing detergent com ositions will be familiar with these materials.
  • detergency builders examples include sodium tripolyphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium ethanel-hydroxy-l,l-diphosphonate; sodium carbonate; sodium silicate; sodium citrate; sodium oxydiacetate; sodium nitrilotriacetate; sodium ethylenediaminetetraacetate; sodium salts of long-chain dicarboxylic acids, for instance straight chain (C to C succinic acids and malonic acids; sodium salts of alphasulphonated long-chain monocarboxylic acids; sodium salts of polycarboxylic acids; ie acids derived from the polymerization or copolymerization of unsaturated carboxylic acids and unsaturated carboxy acid anhydrides such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of these acids, and also from the copolymerization of the above acids and anhydrides
  • a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such conventional ingredients are usually employed therein.
  • additional ingredients are lather boosters, such as coconut mono-ethanolamide and palm kernel monoethanolamide; lather controllers; inorganic salts such as sodium sulphate and magnesium sulphate; chlorine-releasing bleaching agents such as trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates; antiredeposition agents, such as sodium carboxymethylcellulose; and, usually present only in minor amounts, perfumes, colorants, fluorescers, corrosion inhibitors and germicides.
  • a detergent composition of the invention can be prepared using any of the conventional manufacturing techniques commonly used or proposed for the preparation of detergent compositions, such as slurry-making followed by spray-drying or spray-cooling, and subsequent dry-dosing of sensitive ingredients not suitable for incorporation prior to the drying step.
  • the inorganic persalts and organic peracid precursors, and enzymes and metallic chelate catalysts are examples of such sensitive ingredients.
  • Other conventional techniques such as noodling, granulation, and mixing by fluidization in a fluidized bed, may be utilized as and when necessary. Such techniques are familiar to those skilled in the art of detergent composition manufacture.
  • a detergent composition of the invention may be prepared in any of the common physical forms associated with detergent compositions, such as powders, flakes, granules, noodles, cakes, bars and, in some cases, liquids.
  • ingredient I Sodium alltylbenzene sulphonate (prepared by the sulphonation 14 of DOB/055 alkylbenzene) Sodium toluene sulphonate 1
  • coconut monoethanolamide 2 Alkaline sodium silicate l
  • Sodium carboxymethylcellulose l0.$ Sodium sulphate 13
  • Sodium tripolyphosphate 35
  • the powder was then placed in a sealed bottle and stored at 60 C. It was inspected at minute intervals for color and odor development.
  • NHPh which has a molecular weight of 279 and a calculated elemental analysis of: C 64.5%, H 4.7%, N 25.1%. 2,4- dianilino-triazin-e-one may also exist in the enol form (IV).
  • the synthesized 2,4-dianilino-triazin-6-one When incorporated into a sample of the base detergent powder and subjected to the same storage conditions, the synthesized 2,4-dianilino-triazin-6-one produced the same deleterious storage properties, thus confirming the nature of the impurity present in the commercially-available fluorescent agent.
  • a detergent base powder was prepared by conventional slurry-making and spray-drying techniques. Proportions of sodium perborate and N,N,N',N'- tetraacetyl ethylenediamine were than added to the base powder to give a detergent powder having the following formulation:
  • the fluorescent agents used were as follows:
  • Example Changes on storage at C 2 None (unpurified Pink/smell within 20 minutes 3 (purified) None (unpurified) Very slight yellow/smell within 20 minutes 4 (purified) None (unpurified) Turned yellow in 20 minutes, and to pink in 50 minutes with a bad smell 5 (purified) None (unpurified) Turned green in 30 minutes with a bad smell 6 (purified) None (unpurified) Turned yellow in 35 minutes, and
  • Fluorescent agent rum 4,4'-di(2",4 "-dianilinotriszin- 6-ylamino)-stilbene-2,2'- disulphonste 8 Disodium 4,4'-di(2-anilino-4"- morpholinotriazin-6"- ylamino )-stilbene-2,2'- disulphonate Example The following results were obtained:
  • a detergent composition consisting essentially of:
  • a detergent-active compound selected from the group consisting of anionic, nonionic and amphoteric detergent-active compounds
  • At least one cotton-substantive fluorescent agent selected from the group consisting of:
  • N,N,N,N-tetraacetyl ethylene diamine N-acetyl imidazole, N-benzoyl imidazole, N,N'-diacetyl barbitone, N,N'-diacetyl-S,S-dimethylhydantoin and N,N,N',N- tetraacetyl glycoluril.
  • a detergent composition according to claim 1, wherein said detergent-active compound is from about 5 to about 30 percent by weight of said detergent composition.
  • a detergent composition according to claim 1, wherein said organic peracid precursor is from about 5 to about 20 percent by weight of said detergent composition.
  • a detergent composition according to claim 1 which additionally incorporates a cobalt chelate of 1,10-phenanthroline.
  • a detergent composition according to claim 1 which additionally incorporates a protease enzyme in an amount of from 5 to 20 Anson units per kilogram. i i l t

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
US00206143A 1968-12-12 1971-12-08 Detergent compositions Expired - Lifetime US3741903A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB59272/68A GB1286459A (en) 1968-12-12 1968-12-12 Detergent compositions

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US3741903A true US3741903A (en) 1973-06-26

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US (1) US3741903A (fr)
AT (1) AT319440B (fr)
BE (1) BE743005A (fr)
BR (1) BR6914952D0 (fr)
CA (1) CA936113A (fr)
CH (1) CH536355A (fr)
DE (1) DE1961775B2 (fr)
DK (1) DK128325B (fr)
ES (1) ES374457A1 (fr)
FI (1) FI50995C (fr)
FR (1) FR2025990A1 (fr)
GB (1) GB1286459A (fr)
IE (1) IE33871B1 (fr)
LU (1) LU60008A1 (fr)
NL (1) NL158218B (fr)
SE (1) SE347993B (fr)
ZA (1) ZA698588B (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907698A (en) * 1973-03-21 1975-09-23 American Cyanamid Co Bridged halotriazine compounds as bleach activators
US3940340A (en) * 1973-01-12 1976-02-24 Hoechst Aktiengesellschaft Peracylated polyamines compatible with optical brighteners as activators for inorganic peroxo compounds
US3947374A (en) * 1973-03-21 1976-03-30 American Cyanamid Company Substituted halotriazines as peroxygen bleach activators
DE2741671A1 (de) * 1976-09-20 1978-03-23 Procter & Gamble Europ Granulares waschmittel
US4112226A (en) * 1975-10-24 1978-09-05 Lever Brothers Company Process for removing non-fluorescent triazine derivative impurities from fluorescent agents
US4430236A (en) 1981-06-22 1984-02-07 Texize, Division Of Mortonthiokol Liquid detergent composition containing bleach
US4591450A (en) * 1984-03-22 1986-05-27 Mira Lanza S.P.A. Process for the preparation of a bleaching activator in granular form
US5035825A (en) * 1987-11-26 1991-07-30 Ciba-Geigy Corporation Stable bleaching detergents containing stilbene fluorescent whitening agents
US5230820A (en) * 1987-11-23 1993-07-27 Ciba-Geigy Corporation Storage-stable bleaching detergents containing bis-benzofuranyl fluoescent whitening agents
US5326491A (en) * 1989-04-28 1994-07-05 Ciba-Geigy Corporation Detergents containing certain sulfonated dibenzofuranylbiphenyls
US5449477A (en) * 1991-12-19 1995-09-12 Ciba-Geigy Corporation Bleach dispersion of long shelf life
US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
US5703030A (en) * 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5705464A (en) * 1995-06-16 1998-01-06 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt catalysts
US5767055A (en) * 1996-02-23 1998-06-16 The Clorox Company Apparatus for surface cleaning
US5939373A (en) * 1995-12-20 1999-08-17 The Procter & Gamble Company Phosphate-built automatic dishwashing composition comprising catalysts
US20120165407A1 (en) * 2010-12-28 2012-06-28 Amit Gupta Strategy for on-site in situ generation of oxidizing compounds and application of the oxidizing compound for microbial control

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5122984B2 (fr) * 1972-07-29 1976-07-14
GB2330588B (en) * 1997-10-24 1999-08-18 Cheng Wen Lin Multipurpose cleaning agent
ITMI20112003A1 (it) 2011-11-04 2013-05-05 3V Sigma Spa Composizioni di agenti sbiancanti fluorescenti

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US2975139A (en) * 1956-10-02 1961-03-14 Fmc Corp Laundering method and composition therefor
US2992186A (en) * 1955-10-03 1961-07-11 Henkel Helios Ab Detergent compositions
US3163606A (en) * 1959-06-19 1964-12-29 Konink Ind Mij Vorheen Noury & Textile bleaching composition
US3177148A (en) * 1958-05-09 1965-04-06 Lever Brothers Ltd Bleaching processes and compositions
US3519379A (en) * 1967-04-28 1970-07-07 Procter & Gamble Soaking and laundering process
US3522634A (en) * 1967-11-28 1970-08-04 Burlington Industries Inc System for converting continuous filament tow into staple sliver

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2992186A (en) * 1955-10-03 1961-07-11 Henkel Helios Ab Detergent compositions
US2975139A (en) * 1956-10-02 1961-03-14 Fmc Corp Laundering method and composition therefor
US3177148A (en) * 1958-05-09 1965-04-06 Lever Brothers Ltd Bleaching processes and compositions
US3163606A (en) * 1959-06-19 1964-12-29 Konink Ind Mij Vorheen Noury & Textile bleaching composition
US3519379A (en) * 1967-04-28 1970-07-07 Procter & Gamble Soaking and laundering process
US3522634A (en) * 1967-11-28 1970-08-04 Burlington Industries Inc System for converting continuous filament tow into staple sliver

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3940340A (en) * 1973-01-12 1976-02-24 Hoechst Aktiengesellschaft Peracylated polyamines compatible with optical brighteners as activators for inorganic peroxo compounds
US3907698A (en) * 1973-03-21 1975-09-23 American Cyanamid Co Bridged halotriazine compounds as bleach activators
US3947374A (en) * 1973-03-21 1976-03-30 American Cyanamid Company Substituted halotriazines as peroxygen bleach activators
US4112226A (en) * 1975-10-24 1978-09-05 Lever Brothers Company Process for removing non-fluorescent triazine derivative impurities from fluorescent agents
DE2741671A1 (de) * 1976-09-20 1978-03-23 Procter & Gamble Europ Granulares waschmittel
US4430236A (en) 1981-06-22 1984-02-07 Texize, Division Of Mortonthiokol Liquid detergent composition containing bleach
US4591450A (en) * 1984-03-22 1986-05-27 Mira Lanza S.P.A. Process for the preparation of a bleaching activator in granular form
US5230820A (en) * 1987-11-23 1993-07-27 Ciba-Geigy Corporation Storage-stable bleaching detergents containing bis-benzofuranyl fluoescent whitening agents
US5035825A (en) * 1987-11-26 1991-07-30 Ciba-Geigy Corporation Stable bleaching detergents containing stilbene fluorescent whitening agents
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Also Published As

Publication number Publication date
NL158218B (nl) 1978-10-16
FI50995C (fi) 1976-09-10
BE743005A (fr) 1970-06-11
CH1839869A4 (fr) 1973-06-15
BR6914952D0 (pt) 1973-05-17
ZA698588B (en) 1971-07-28
GB1286459A (en) 1972-08-23
FR2025990A1 (fr) 1970-09-11
IE33871B1 (en) 1974-11-27
DE1961775B2 (de) 1974-09-12
DK128325B (da) 1974-04-08
DE1961775A1 (de) 1970-07-02
CA936113A (en) 1973-10-30
AT319440B (de) 1974-12-27
NL6918638A (fr) 1970-06-16
IE33871L (en) 1970-06-12
CH536355A (de) 1973-06-15
SE347993B (fr) 1972-08-21
LU60008A1 (fr) 1970-06-15
ES374457A1 (es) 1972-03-01
FI50995B (fr) 1976-05-31

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