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WO1994028105A1 - Composes de blanchiment comprenant des adjuvants de blanchiment a base de n-acyl caprolactame et a base de sulfonate d'alcanoyloxybenzene - Google Patents

Composes de blanchiment comprenant des adjuvants de blanchiment a base de n-acyl caprolactame et a base de sulfonate d'alcanoyloxybenzene Download PDF

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Publication number
WO1994028105A1
WO1994028105A1 PCT/US1994/005371 US9405371W WO9428105A1 WO 1994028105 A1 WO1994028105 A1 WO 1994028105A1 US 9405371 W US9405371 W US 9405371W WO 9428105 A1 WO9428105 A1 WO 9428105A1
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WIPO (PCT)
Prior art keywords
caprolactam
weight
acyl
bleaching
bleach activator
Prior art date
Application number
PCT/US1994/005371
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English (en)
Inventor
Alan David Willey
Michael Eugene Burns
Jerome Howard Collins
Original Assignee
The Procter & Gamble Company
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Filing date
Publication date
Priority claimed from US08/226,915 external-priority patent/US5405412A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP7500720A priority Critical patent/JPH08510779A/ja
Priority to AU68334/94A priority patent/AU6833494A/en
Priority to CA002162362A priority patent/CA2162362C/fr
Publication of WO1994028105A1 publication Critical patent/WO1994028105A1/fr

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    • 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

Definitions

  • the present invention relates to laundry detergents and automatic dishwashing compositions with activated bleaching systems which are effective under mixed soil conditions, especially mixtures of hydrophobic and hydrophilic soils and stains.
  • peroxygen bleaches are effective for stain and/or soil removal from fabrics, but that such bleaches are temperature dependent. At a laundry liquor temperature of 60 C, peroxygen bleaches are only partially effective. As the laundry liquor temperature is lowered below 60°C, peroxygen bleaches become relatively ineffective. As a consequence, there has been a substantial amount of industrial research to develop bleaching systems which contain an activator that renders peroxygen bleaches effective at laundry liquor temperatures below 60°C.
  • TAED tetraacetyl ethylene diamine
  • NOBS nonanoyloxy-benzenesulfonate
  • activators which generally comprise long chain alkyl moieties
  • the class of bleach activators derived from hydrophilic N-acyl caprolactams performs very well when combined with the cleaning performance of hydrophobic alkanoyloxybenzenesulfonate and has the added benefit of being relatively inexpensive to manufacture. Accordingly, the present invention solves the long-standing need for an inexpensive bleaching system which performs efficiently and effectively at low temperatures and under mixed soil load conditions, especially mixtures of hydrophobic and hydrophilic soils.
  • the present invention relates to bleaching systems and methods which employ them for cleaning fabrics under mixed soil load conditions.
  • Said bleaching system comprises : a) at least about 0.1%, preferably from about 1% to about 75%, by weight, of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution; b) at least about 0.1%, preferably from about 0.1% to about 50%, by weight, of one or more hydrophilic N-acyl caprolactam bleach activators; and c) at least about 0.1%, preferably from about 0.1% to about 50%, by weight, of a hydrophobic alkanoyloxybenzenesul- fonate bleach activator.
  • alkanoyl moieties of said alkanoyloxybenzene- sulfonate bleach activators contain from about 8 to about 12 carbon atoms, preferably from about 8 to about 11 carbons.
  • Highly preferred moieties are members selected from the group consisting of octanoyl, nonanoyl, decanoyl, dodecanoyl, 3,5,5-trimethylhexa- noyl,
  • acyl moieties of said N-acyl caprolactam bleach activators have the formula R -CO- wherein R is H or an alkyl, aryl, alkaryl, or alkoxyaryl group containing from about 1 to about 6 carbon atoms.
  • R is a member selected from the group' consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl substituents.
  • the peroxygen bleaching compound can be any peroxide source, and is preferably a member selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, sodium peroxide and mixtures thereof.
  • Highly preferred peroxygen bleaching compounds are selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and mixtures thereof
  • the most highly preferred peroxygen bleaching compound is sodium percar- bonate.
  • the invention also encompasses detergent compositions in granular, paste, liquid, or bar form which comprise the aforesaid bleaching system together with detersive ingredients which are present in the composition at the levels indicated hereinafter.
  • the bleaching method herein is preferably conducted with agitation of the fabrics with an aqueous liquor containing the aforesaid compositions at levels from about 50 ppm to about 27,500 ppm, and is especially adapted for conditions in which the fabrics are soiled with both hydrophobic and hydrophilic soils.
  • the method can be carried out at any desired washing temperature, even at temperatures below about 60°C, and is readily conducted at temperatures in the range of from about 5°C to about 45°C.
  • the method can be conducted conveniently using a composition which is in bar form, but can also be conducted using granules, flakes, powders, pastes, and the like.
  • the aqueous laundry liquor typically comprises at least about 300 ppm of conventional detergent ingredients, as well as at least about 25 ppm of the bleaching compound and at least about 25 ppm of the mixture of bleach activators.
  • the liquor comprises from about 900 ppm to about 20,000 ppm of conventional detergent ingredients, from about 100 ppm to about 25,000 ppm of the bleaching compound and from about 100 ppm to about 2,500 ppm of the bleach activators.
  • the conventional detergent ingredients and bleaching system will typically be combined into a detergent composition such as a granular laundry detergent or laundry detergent bar.
  • the conventional detergent ingredients employed in said method and in the compositions herein comprise from about 1% to about 99.8%, preferably from about 5% to about 80%, of a detersive surfactant.
  • the detergent ingredients comprise from about 5% to about 80% of a detergent builder.
  • Other optional detersive adjuncts can also be included in such compositions at conventional usage levels.
  • the bleaching system employed in the present invention provides effective and efficient surface bleaching of fabrics which thereby removes stains and/or soils from the fabrics.
  • the bleaching system is particularly efficient at cleaning a mixture of soil loads, especially mixtures of hydrophobic and hydrophilic soils.
  • Hydrophobic soils are generally associated with lipid and protein-based soils and stains, such as body soils, blood, etc., but are also efifective on so-called "dingy soils”. Dingy soils are those that build up on textiles after numerous cycles of usage and washing, and result in a gray or yellow tint on white fabrics.
  • Hydrophilic soils include food and beverage stains.
  • the bleaching mechanism and, in particular, the surface bleaching mechanism are not completely understood.
  • the N-acyl bleach activator undergoes nucleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleaching compound, to form a peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis.
  • perhydrolysis the reaction is commonly referred to as perhydrolysis.
  • the N-acyl and alkanoyloxybenzenesulfonate bleach activators within this invention can render peroxygen bleaches more efficient even at laundry liquor temperatures wherein bleach activators are not necessary to activate the bleach, i.e., above about 60 C. Therefore, with bleach systems of the invention, less peroxygen bleach is required to achieve the same level of surface bleaching performance as is obtained with the peroxygen bleach alone.
  • the components of the bleaching system herein comprise the bleach activator and the peroxide source, as described hereinafter.
  • bleach activators of type b) employed in the present invention are hydrophilic
  • R is H or an alkyl, aryl, alkaryl, or alkoxyaryl group containing from about 1 to about 6 carbon atoms.
  • Caprolactam activators wherein the R moiety contains from about 1 to about 6 carbon atoms provide hydrophilic bleaching which affords beverage and food stain removal.
  • Benzoyl caprolactam i.e., wherein R is a phenyl substituent, has now been found to be unique among the bleach activator compounds, inasmuch as it appears to exhibit both hydrophobic and hydrophilic bleaching activity.
  • This hydrophobic/hydrophilic bleaching capability makes benzoyl caprolactam the activator of choice for the formulator who is seeking broad spectrum bleaching activity, and wishes to use a single caprolactam activator for hydrophilic cleaning and for additional hydrophobic performance in combination with the alkanoyloxybenzenesulfonate activator.
  • Highly preferred hydrophilic N-acyl caprolactams are selected from the group consisting of for yl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam, pentanoyl caprolactam, hexanoyl caprolactam, and benzoyl caprolactam.
  • N-acyl caprolactams are well known in the art.
  • Example I included below, illustrates a preferred laboratory synthesis. Contrary to the teachings of U.S. Pat. 4,545,784, cited above, the bleach activator is preferably not absorbed onto the peroxygen bleaching compound. To do so in the presence of other organic detersive ingredients could cause safety problems.
  • the bleach activators of type c) employed in the present invention are alkanoyloxybenzenesulfonates of the formula:
  • R -C(O)- contains from about 8 to about 12, preferably from about 8 to about 11, carbon atoms and M is a suitable cation, such as an alkali metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred
  • Highly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from the group consisting of nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzene- sulfonate, 2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate, decanoyl- oxybenzenesulfonate, dodecanoyloxybenzenesulfonate, and mixtures thereof.
  • the bleaching system comprises at least about 0.1%, preferably from about 0.1% to about 30%, more preferably from about 1% to about 30%, most preferably from about 3% to about 25%, by weight, of type b) and type c) bleach activators.
  • washing solutions wherein the pH of such solution is between about 8.5 and 10.5, preferably between 9.5 and 10.5, in order to facilitate the perhydrolysis reaction.
  • pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching systems herein.
  • the Peroxygen Bleaching Compound The peroxygen bleaching compounds useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
  • Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate peroxyhydrate, -urea peroxy- hydrate, sodium peroxide, and sodium percarbonate. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium percarbonate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhanced surface bleaching performance. Highly preferred percarbonate can be in uncoated or coated' form.
  • the average particle size of uncoated percarbonate ranges from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate and sulphate, silicate, borosilicate, or fatty carboxylic acids.
  • the bleaching system comprises at least about 0.1%, preferably from about 1% to about 75%, more preferably from about 3% to about 40%, most preferably from about 3% to about 25%, by weight, of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution.
  • the weight ratio of bleach activator to peroxygen bleaching compound in the bleaching system typically ranges from about 2: 1 to 1:5. In preferred embodiments, the ratio ranges from about 1 : 1 to about 1:3.
  • bleach activator/bleaching compound systems herein are useful per se as bleaches. However, such bleaching systems are especially useful in compositions which can comprise various detersive adjuncts such as surfactants, builders, enzymes, and the like as disclosed hereinafter.
  • the amount of detersive surfactant included in the fully-formulated detergent compositions afforded by the present invention can vary from about 1% to about 99.8%, by weight of the detergent ingredients, depending upon the pa ⁇ icular surfactants used and the effects desired.
  • the detersive surfactants comprise from about 5% to about
  • the detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also be used.
  • Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants.
  • Nonlimiting examples of surfactants useful herein include the conventional C, j -C,g alkyl benzene sulfonates and primary, secondary, and random alkyl sulfates, the C jQ -C j g alkyl alkoxy sulfates, the C, Q -C jg alkyl polyglycosides and their corresponding suifated polyglycosides, C ]2 -C j g alpha-sulfonated fatty acid esters, C, 2 -C,g alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C, --C, g betaines and suffobetaines ("sultaines”), C, Q -C j g amine oxides, and the like.
  • Other conventional useful surfactants are listed in standard texts.
  • adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:
  • R 1 (I) R 2 -C-N-Z wherein: R is H, C,-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C, -C ⁇ alkyl, more preferably C , or C 2 alkyl, most preferably C . alkyl (i.e., methyl); and R is a C 5 -C 32 hydrocarbyl moiety, preferably straight chain C -C.
  • g alkyl or alkenyl more preferably straight chain Cg-C , ⁇ alkyl or alkenyl, most preferably straight chain C, , -C j 9 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the -CH(CH 2 OH)-(CHOH) n l -CH 2 n is an integer from 1 to 5, inclusive, and R 1 is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH ⁇ CHOH ⁇ -C ⁇ OH.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,
  • R is preferably methyl or hydroxyalkyl. If lower sudsing is desired, R is preferably C--C 8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethyl hexyl.
  • R -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Optional detergent ingredients employed in the present invention contain inorganic and/or organic detergent builders to assist in mineral hardness control. If used, these builders comprise from about 5% to about 80% by weight of the detergent compositions.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates
  • silicate builders are the alkali metal silicates, particularly those having a
  • SiO ⁇ :Na ⁇ O ratio in the range 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially preferred layered silicate builder.
  • Carbonate builders especially a finely ground calcium carbonate with surface area greater than 10 m /g, are preferred builders that can be used in granular compositions
  • the density of such alkali metal carbonate built detergents can be in the range of 450-850 g/1 with the moisture content preferably below 4%.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are especially useful in the present invention.
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are preferred polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1,1- -diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the conventional detergent ingredients employed herein can be selected from typical detergent composition components such as detersive surfactants and detergent builders.
  • the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
  • Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al.
  • Adjuncts which can also be included in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to about 20% of the detergent ingredients, preferably from about 0.5% to about 10%), include enzymes, especially proteases, lipases and cellulases, color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solvents, solubilizing agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components static control agents, etc.
  • enzymes especially proteases, lipases and cellulases, color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical bright
  • Bleach systems optionally, but preferably, will also comprise a chelant which not only enhances bleach stability by scavenging heavy metal ions which tend to decompose bleaches, but also assists in the removal of polyphenolic stains such as tea stains, and the like.
  • a chelant including the aminophosphonates, available as DEQUEST from Monsanto, the nitrilotriacetates, the hydroxyethyl-ethylenediamine triacetates, and the like, are known for such use.
  • Preferred biodegradable, non-phosphorus chelants include ethylenediamine disuccinate ("EDDS"; see U.S.
  • the detergent compositions employed herein can comprise, in addition to the bleaching system of the present invention, one or more other conventional bleaching agents, activators, or stabilizers which are not rendered ineffective from interaction with the nucleophilic and body soils.
  • the formulator will ensure that the bleach compounds used are compatible with the detergent formulation. Conventional tests, such as tests of bleach activity on storage in the presence of the separate or fully-formulated ingredients, can be used for this purpose.
  • optional bleach activators for incorporation in this invention include, hydrophobic N-acyl caprolactam bleach activators wherein the acyl moiety contains from 6 to 12 carbon atoms, the benzoxazin-type bleaching activators disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990, and the bleach agents and activators disclosed in U.S. Patent 4,634,551, Burns et al, issued Jan. 6, 1987.
  • Such bleaching compounds and agents can be optionally included in detergent compositions in their conventional art-established levels of use, generally from 0% to about 15%, by weight of detergent composition.
  • the solid is triturated with 200 ml of boiling methanol. After cooling, the solid is collected by filtration, washed with 100 ml of methanol, and dried under vacuum. NMR and cationic titration analyses shows the resulting nonanoyloxybenzenesulfonate, sodium salt (0.15 moles) to be over 98% pure.
  • a granular detergent composition is prepared comprising the following ingredients.
  • Aqueous crutcher mixes of heat and alkali stable components of the detergent compositions are prepared and spray-dried.
  • the other ingredients are admixed so that the detergent composition contains the ingredients tabulated at the levels shown.
  • the detergent granules with bleaching system are added together with a 6 lb. (2.7 kg) load of fabrics to a Sears KENMORE washing machine. Actual weights of detergent and ester compositions are taken to provide a 1000 ppm concentration of the detergent composition in the 17 gallon (65 1) water-fill machine.
  • the water used has 7 grains/gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition of the detergent composition.
  • the fabrics are laundered at 35°C (95°F) for a full cycle (12 rnin.) and rinsed at 21°C (70°F).
  • test swatches are dried in a dryer. Tristimulus meter readings (L,a,b) are then determined for each test swatch. Whiteness performance in terms of Hunter Whiteness Values (W) is then calculated according to the following equation:
  • a granular detergent composition comprising the following ingredients.
  • Aqueous crutcher mixes of heat and alkali stable components of the detergent compositions are prepared and spray-dried.
  • the other ingredients are admixed so that the detergent composition contains the ingredients tabulated at the levels shown.
  • the detergent granules with bleaching system are added together with a 2.7 kg (6 lb.) load of fabrics to an automatic washing machine. Actual weights of detergent and ester compositions are taken to provide a 5000 ppm concentration of the detergent composition in the 17 liter (4.5 gallon) water-fill machine.
  • the water used has 7 grains/ gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5' after) addition of the detergent composition.
  • the fabrics are laundered at 40°C (104°F) for a full cycle (40 rnin.) and rinsed at 21°C (70°F).
  • the test swatches are dried in a dryer
  • Tristimulus meter readings (L,a,b) are then determined for each test swatch.
  • Whiteness performance in terms of Hunter Whiteness Values (W) is then calculated according to the following equation.
  • EXAMPLE V A laundry bar suitable for hand-washing soiled fabrics is prepared comprising the following ingredients.
  • the detergent laundry bars are processed in conventional soap or detergent bar making equipment as commonly used in the art. Testing is conducted following the methods used in Example IV. In the test, fabrics exposed to the bleaching system display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a laundry bar is prepared by a procedure identical to that of Example V, with the two exceptions that 20% of a 1 : 1 : 1 mixture of pentanoyl caprolactam, hexanoyl caprolactam, and benzoyl caprolactam is substituted for the benzoyl caprolactam bleach activator, and the level of sodium percarbonate is increased to 20%.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • EXAMPLE V ⁇ A laundry bar is prepared by a procedure identical to that of Example V, with the single exception that 15% of a 1 : 1 mixture of acetyl caprolactam and benzoyl caprolactam is substituted for the benzoyl caprolactam bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a laundry bar is prepared by a procedure identical to that of Example V, with the exceptions that 6% of a 1:1 mixture of benzoyl caprolactam and a benzoxazin-type bleach activator, as disclosed in U.S. Pat. 4,966,723, is substituted for the benzoyl caprolactam bleach activator and an equivalent amount of 2-ethylhexanoyloxybenzenesulfonate is substituted for the nonanoyloxybenzene sulfonate bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a bleaching system is prepared comprising the following ingredients.
  • Example V Testing is conducted following the methods used in Example V with the single exception that the an equivalent amount of the above bleaching system is substituted for the detergent composition used in Example V.
  • fabrics exposed to the bleaching system display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • compositions and processes of the present invention are especially useful in conventional fabric laundering operations, it is to be understood that they are also useful in cleaning system which involves low waterfabric ratios.
  • One such system is disclosed in U.S. Patent 4,489,455, Spendel, issued Dec. 25, 1984, which involves a washing machine apparatus which contacts fabrics with wash water containing detersive ingredients using a low water: fabric ratio rather than the conventional method of immersing fabrics in an aqueous bath.
  • the compositions herein provide excellent bleaching performance in such mechanical systems.
  • the ratio of water fabric ranges from about 0.5: 1 to about 6: 1 (liters of waterkg of fabric).
  • the bleach activator is preferably not absorbed onto the peroxygen bleaching compound. To do so in the presence of other organic detersive ingredients could cause safety problems. It has now been discovered that the caprolactam bleach activators of this invention can be dry-mixed with peroxygen " bleaching compounds, especially perborate, and thereby avoid potential safety problems.
  • Nonanoyloxybenzenesulfonate 5 Sodium perborate tetrahydrate 10
  • the detergent laundry bars are processed in conventional soap or detergent bar making equipment as commonly used in the art with the bleaching activator dry-mixed with the perborate bleaching compound and not affixed to the surface of the perborate. Testing is conducted following the methods used in Example IV. In the test, fabrics exposed to the bleaching system display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • EXAMPLE Xm A laundry bar is prepared by a procedure identical to that of Example XII, with the single exception that an equivalent amount of 2-ethyloxybenzenesulfonate is substituted for the nonanoyloxy benzenesulfonate bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a laundry bar is prepared by a procedure identical to that of Example XII, with the exceptions that 6% of a 1:1 mixture of benzoyl caprolactam and hexanoyl caprolactam is substituted for the benzoyl caprolactam bleach activator and 6% of a 1:1 mixture of dodecanoyloxybenzenesulfonate and decanoyloxybenzenesulfonate is substituted for the nonanoyloxybenzenesulfonate bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • EXAMPLE XV A laundry bar is prepared by a procedure identical to that of Example XII, with the single exception that 10% of a 1 : 1 mixture of benzoyl caprolactam and a benzoxazin-type bleach activator, as disclosed in U.S. Pat. 4,966,723, is substituted for the benzoyl caprolactam bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • EXAMPLE XVI A laundry bar is prepared by a procedure identical to that of Example XII, with the single exception that 6% of a 1: 1 mixture of benzoyl caprolactam and a bleach activator, as disclosed in U.S. Pat. 4,634,551, cited above, is substituted for the benzoyl caprolactam bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a granular detergent composition comprising the following ini
  • Aqueous crutcher mixes of heat and alkali stable components of the detergent compositions are prepared and spray-dried.
  • the other ingredients are dry-mixed so that the detergent composition contains the ingredients tabulated at the levels shown.
  • EXAMPLE XVIII A granular detergent composition is prepared by a procedure identical to that of Example XVH, with the single exception that 15% of a 1 : 1 mixture of benzoyl caprolactam and hexanoyl caprolactam is substituted for the hexanoyl caprolactam bleach activator. The laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention. EXAMPLE XIX
  • a granular detergent composition is prepared by a procedure identical to that of Example XVIII, with the single exception that 6% of a 1: 1 mixture of benzoyl caprolactam and a benzoxazin-type bleach activator, as disclosed in U.S. Pat. 4,966,723, is substituted for the hexanoyl caprolactam bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a granular detergent composition is prepared by a procedure identical to that of Example XVIII, with the single exception that 6% of a 1 : 1 : 1 mixture of octanoyloxybenxenesulfonate, decanoyloxybenzenesulfonate and a benzoxazin-type bleach activator, as disclosed in U.S. Pat. 4,634,551, cited above, is substituted for the nonanoyloxybenezenesulfonate bleach activator.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a particularly preferred embodiment of this invention is a 1:2.2:7.7 molar ratio of
  • N-acyl caprolactam to alkanoyloxybenzenesulfonate to peroxygen bleaching compound.
  • This mixed caprolactam alkanoyloxybenzenesulfonate bleaching composition delivers stronger than expected performance on hydrophobic stains and hydrophilic stains and on dingy clean up.
  • EXAMPLE XXI A laundry bar is prepared by a procedure identical to that of Example V, with the exceptions that the level of benzoyl caprolactam is 0.85%, the level of nonanoyloxy- benzenesulfonate bleach activator is 3% and sodium percarbonate is substituted with 3% perborate.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • EXAMPLE XXII A granular laundry detergent is prepared by a procedure identical to that of Example HI, with the exceptions that the level of benzoyl caprolactam is 0.85%, the level of nonanoyloxybenzenesulfonate bleach activator is 3% and sodium percarbonate is substituted with 3% perborate.
  • the laundering method of Example III is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • a granular laundry detergent is prepared by a procedure identical to that of Example IV, with the exceptions that the level of benzoyl caprolactam is 0.85%, the level of nonanoyloxybenzenesulfonate bleach activator is 3% and sodium percarbonate is substituted with 3% perborate.
  • the laundering method of Example IV is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention
  • EXAMPLE XXIV A laundry bar is prepared by a procedure identical to that of Example XI, with the exceptions that the level of benzoyl caprolactam is 0.85%, the level of nonanoyloxybenzenesulfonate bleach activator is 3% and the level of sodium perborate tetrahydrate is 3%. The laundering method of Example XI is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • Example XVII with the exceptions that the level of nonanoyloxybenzenesulfonate bleach activator is 3%, the level of sodium perborate tetrahydrate is 3%, and the hexanoyl caprolactam is substituted with 0.85% benzoyl caprolactam.
  • the laundering method of Example XVII is repeated. In the test, all fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the bleaching system of the invention.
  • the bleaching systems herein can be employed under any circumstance where improved oxygen bleaching is desired.
  • the technology of this invention may be used, for example, to remove stains and cleans dishes, to bleach paper pulp, to bleach hair, to cleanse and sanitize prosthetic devices such as dentures, in dentifrice compositions to clean teeth and kill oral bacteria, and in any other circumstances where bleaching is advantageous to the user.
  • EXAMPLE XXVI A granular automatic dishwashing detergent composition wherein stain removal and cleaning benefits are achieved is prepared comprising the following ingredients.
  • Nonionic surfactant2 2.00 2.00 2.00
  • compositions of the present invention are as follows
  • Automatic dishwashing compositions may be in granular, tablet, bar, or rinse aid form.
  • Methods of making granules, tablets, bars, or rinse aids are known in the art. See, for instance, U.S. Pat. Serial Nos. 08/106,022, 08/147,222, 08/147,224, 08/147,219, 08/052,860, 07/867,941.

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Abstract

L'invention se rapporte à des détergents pour lessives et à des compositions de produits de nettoyage pour lave-vaisselle, avec systèmes de blanchiment activés, qui sont efficaces dans des conditions où l'origine des taches est mixte, en particulier dans des cas où des taches et souillures hydrophobes et hydrophiles sont mélangées. Les adjuvants de blanchiment préférés sont à base de N-acyl caprolactame et à base de sulfonate de nonanoyloxybenzène.
PCT/US1994/005371 1993-05-20 1994-05-12 Composes de blanchiment comprenant des adjuvants de blanchiment a base de n-acyl caprolactame et a base de sulfonate d'alcanoyloxybenzene WO1994028105A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7500720A JPH08510779A (ja) 1993-05-20 1994-05-12 Ｎ−アシルカプロラクタム漂白活性剤とアルカノイルオキシベンゼンスルホネート漂白活性剤とを含む漂白コンパウンド
AU68334/94A AU6833494A (en) 1993-05-20 1994-05-12 Bleaching compounds comprising n-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
CA002162362A CA2162362C (fr) 1993-05-20 1994-05-12 Composes de blanchiment renfermant des activateurs de blanchiment a base de caprolactame n-acyle et de sulfonate d'alcanoyloxybenzene

Applications Claiming Priority (4)

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US6462793A 1993-05-20 1993-05-20
US08/064,627 1993-05-20
US08/226,915 1994-04-13
US08/226,915 US5405412A (en) 1994-04-13 1994-04-13 Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators

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WO1994028105A1 true WO1994028105A1 (fr) 1994-12-08

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672749A1 (fr) * 1994-03-17 1995-09-20 The Procter & Gamble Company Compositions de blanchiment
WO1996016155A1 (fr) * 1994-11-18 1996-05-30 The Procter & Gamble Company Compositions de blanchiment et additifs de blanchiment comprenant des activateurs de blanchiment efficaces a des concentrations basses de perhydroxyle
DE19549358A1 (de) * 1995-03-24 1996-09-26 Degussa Aktivatorzusammensetzungen für Peroxoverbindungen und sie enthaltende Mittel
WO1996036686A1 (fr) * 1995-05-17 1996-11-21 Basf Aktiengesellschaft Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques
EP0677576A3 (fr) * 1994-04-13 1997-11-05 The Procter & Gamble Company Compositions détergente pour le lavage automatique de la vaisselle contenant des activateurs de blanchiment
EP0829533A1 (fr) * 1996-09-13 1998-03-18 The Procter & Gamble Company Compositions de blanchiment peroxygenées contenant l'acide aminotri(methylènephosphonique) (ATMP), pour le prétraitement de linge
US5755992A (en) * 1994-04-13 1998-05-26 The Procter & Gamble Company Detergents containing a surfactant and a delayed release peroxyacid bleach system
JP2014227444A (ja) * 2013-05-20 2014-12-08 ライオン株式会社 食器洗い機用洗浄剤
US11932833B2 (en) 2021-02-18 2024-03-19 The Clorox Company Stable activated peroxide sanitizing liquid compositions without added phosphorous compounds or cationic surfactants

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2388924A1 (fr) * 1977-04-29 1978-11-24 Bosch Siemens Hausgeraete Procede de lavage, produits lessiviels utilises et machine a laver automatique pour la mise en oeuvre dudit procede de lavage
EP0122763A2 (fr) * 1983-04-14 1984-10-24 Interox Chemicals Limited Compositions de blanchiment
EP0204116A1 (fr) * 1983-02-23 1986-12-10 The Procter & Gamble Company Détergents de blanchiment liquides contenant des acides peroxycarboxyliques-précurseurs non-linéaires aliphatiques et composition pour leur utilisation dans les détergents
EP0283252A1 (fr) * 1987-03-17 1988-09-21 The Procter & Gamble Company Compositions de blanchiment
EP0399584A2 (fr) * 1989-05-10 1990-11-28 Unilever N.V. Activation du blanchiment et compositions à cet effet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2388924A1 (fr) * 1977-04-29 1978-11-24 Bosch Siemens Hausgeraete Procede de lavage, produits lessiviels utilises et machine a laver automatique pour la mise en oeuvre dudit procede de lavage
EP0204116A1 (fr) * 1983-02-23 1986-12-10 The Procter & Gamble Company Détergents de blanchiment liquides contenant des acides peroxycarboxyliques-précurseurs non-linéaires aliphatiques et composition pour leur utilisation dans les détergents
EP0122763A2 (fr) * 1983-04-14 1984-10-24 Interox Chemicals Limited Compositions de blanchiment
EP0283252A1 (fr) * 1987-03-17 1988-09-21 The Procter & Gamble Company Compositions de blanchiment
EP0399584A2 (fr) * 1989-05-10 1990-11-28 Unilever N.V. Activation du blanchiment et compositions à cet effet

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672749A1 (fr) * 1994-03-17 1995-09-20 The Procter & Gamble Company Compositions de blanchiment
EP0677576A3 (fr) * 1994-04-13 1997-11-05 The Procter & Gamble Company Compositions détergente pour le lavage automatique de la vaisselle contenant des activateurs de blanchiment
US5755992A (en) * 1994-04-13 1998-05-26 The Procter & Gamble Company Detergents containing a surfactant and a delayed release peroxyacid bleach system
WO1996016155A1 (fr) * 1994-11-18 1996-05-30 The Procter & Gamble Company Compositions de blanchiment et additifs de blanchiment comprenant des activateurs de blanchiment efficaces a des concentrations basses de perhydroxyle
DE19549358A1 (de) * 1995-03-24 1996-09-26 Degussa Aktivatorzusammensetzungen für Peroxoverbindungen und sie enthaltende Mittel
WO1996036686A1 (fr) * 1995-05-17 1996-11-21 Basf Aktiengesellschaft Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques
US5972237A (en) * 1995-05-17 1999-10-26 Basf Aktiengesellschaft Use of heterocyclic compounds as activators for inorganic peroxy compounds
EP0829533A1 (fr) * 1996-09-13 1998-03-18 The Procter & Gamble Company Compositions de blanchiment peroxygenées contenant l'acide aminotri(methylènephosphonique) (ATMP), pour le prétraitement de linge
JP2014227444A (ja) * 2013-05-20 2014-12-08 ライオン株式会社 食器洗い機用洗浄剤
US11932833B2 (en) 2021-02-18 2024-03-19 The Clorox Company Stable activated peroxide sanitizing liquid compositions without added phosphorous compounds or cationic surfactants

Also Published As

Publication number Publication date
CA2162362C (fr) 1999-07-27
AU6833494A (en) 1994-12-20
JPH08510779A (ja) 1996-11-12
CA2162362A1 (fr) 1994-12-08

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