WO1997001624A1 - Compositions de blanchiment peroxygenees comprenant un agent de protection des tissus - Google Patents

Compositions de blanchiment peroxygenees comprenant un agent de protection des tissus Download PDF

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Publication number
WO1997001624A1
WO1997001624A1 PCT/US1996/010938 US9610938W WO9701624A1 WO 1997001624 A1 WO1997001624 A1 WO 1997001624A1 US 9610938 W US9610938 W US 9610938W WO 9701624 A1 WO9701624 A1 WO 9701624A1
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WO
WIPO (PCT)
Prior art keywords
fabric
compositions
acid
composition
protection agent
Prior art date
Application number
PCT/US1996/010938
Other languages
English (en)
Inventor
Kevin Lee Kott
Patti Jean Kellett
Valentina Masotti
Stefano Scialla
Alan David Willey
Original Assignee
The Procter & Gamble Company
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
Priority claimed from US08/663,501 external-priority patent/US5759439A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP96923463A priority Critical patent/EP0836639A1/fr
Priority to BR9608668A priority patent/BR9608668A/pt
Priority to SK1745-97A priority patent/SK174597A3/sk
Priority to AU63966/96A priority patent/AU711809B2/en
Priority to JP9504549A priority patent/JPH11508627A/ja
Priority to MX9800201A priority patent/MX9800201A/es
Publication of WO1997001624A1 publication Critical patent/WO1997001624A1/fr

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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
    • C11D3/3947—Liquid compositions
    • 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
    • C11D3/395—Bleaching agents
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/24—Organic compounds containing halogen
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • the present invention relates to aqueous bleach-containing compositions suitable for use as pretreater and to a pretreatment process whereby fabric safety and/or color safety is improved.
  • the bleaching compositions are preferably acidic and comprise peroxygen bleach, preferably hydrogen peroxide or a source thereof, and a fabric protection agent.
  • Bleaching compositions have been extensively described in laundry applications as laundry detergents, laundry additives or even laundry pretreaters.
  • bleach-containing compositions in laundry pretreatment applications to boost the removal of encrusted stains/soils and "problem" stains, such as grease, coffee, tea, grass, mud/clay-containing soils, which are otherwise particularly difficult to remove by typical machine washing.
  • a drawback associated with such bleach-containing compositions is that said compositions may damage fabrics, resulting in dye damage and/or loss of tensile strength of the fabric fibers, especially when used in pretreatment applications under stressed conditions, e.g. when applied directly onto the fabric and left to act on said fabric for prolonged periods of time before washing said fabrics, especially when the fabric to be treated is contaminated with metal ions such as copper, iron, manganese, or chromium.
  • the peroxygen bleach can be responsible for the dye and fabric damage associated with these bleaching compositions. It is further believed that these metal ions on the surface of the fabrics, especially on cellulosic fabrics, catalyze the decomposition of peroxygen bleaches like hydrogen peroxide. Thus, the accelerated decomposition of the peroxygen bleach can result in fabric and/or dye damage.
  • compositions When said compositions are applied directly to fabrics, the different components in said compositions diffuse or migrate, possibly at different rates, through the fabric fibers. This is also true for the peroxygen bleach component o bleaching compositions designed for the pretreatment of fabrics.
  • a solution to the damage resulting from pretreating fabrics with bleaching compositions comprising peroxygen bleach is provided by adding certain fabric protection agents which act to reduce fabric and/or dye damage.
  • These fabric protection agents have been found to considerably reduce the damage associated with the treatment of fabrics with peroxygen bleach-containing compositions, especially those fabrics which are contaminated with metal ions.
  • Suitable fabric protection agents are characterized by sufficiently high stability constants for metal ions, such as copper or iron, to prevent, slow, and/or minimize, the metal ion catalyzed decomposition of the peroxygen bleach.
  • the fabric protection agent should have sufficiently high mobility to ensure that the fabric protection agents migrates along with the peroxygen bleach as the bleach spreads or migrates throughout the fabric fibers upon the application of the bleaching composition onto the fabric.
  • the present invention solves the long-standing need for an effective, dye-safe bleaching composition suitable for use as a pretreater which does not promote damage to fabrics.
  • the compositions ofthe present invention provide excellent performance when used in other applications apart from laundry pretreater application, such as in other laundry applications, as a laundry detergent or laundry additive, or even in hard surface cleaning applications, or in carpet cleaning applications.
  • EP-629,691A discloses emulsions of nonionic surfactants comr rising a silicone compound, and as optional ingredients, hydrogen peroxide, or a water soluble source thereof.
  • EP-629.690A discloses emulsions of nonionic surfactants comprising a terephthalate-based polymer, and as optional ingredients, hydrogen peroxide, or a water soluble source thereof.
  • EP-209,228B discloses compositions comprising a peroxide source like hydrogen peroxide.
  • EP-209,228B discloses that the hydrogen peroxide-containing compositions may be used as pre- spotters. See also U.S. Pat. No. 4,891,147, issued Jan. 2, 1990, and U.S. Pat. No. 5,019,289, issued May 28, 1991.
  • the present invention encompasses an aqueous composition
  • a peroxygen bleach such as hydrogen peroxide or a source thereof, and a fabric protection agent
  • the minimum concentration, C, of the fabric protection agent, measured as a weight percentage of said liquid bleaching composition is calculated by the following formula: ⁇ [C]* [stability constant for Cu2 + ] ⁇ > 2.5.
  • the fabric protection agents have a ratio of stability constant for copper(2+) to stability constant for calcium(2+) of at least about 2:1.
  • the present invention further encompasses a process of pretreating soiled fabrics with a liquid, aqueous composition comprising a peroxygen bleach and a fabric protection agent having a mobility factor higher than 0.7, when measured as defined herein, said process comprising the steps of applying said composition, preferably in its neat form, onto the fabric and allowing said composition to remain in contact with said fabric, preferably without leaving said composition to dry on the fabric, before said fabric is washed.
  • the aqueous composition is applied to soiled fabrics before said fabrics are washed, whereby the loss of tensile strength in said fabric is reduced as compared to fabrics which have been treated with similar peroxygen bleaching compositions, but without the fabric protection agents of this invention.
  • the aqueous composition is applied to colored/dyed fabrics before said fabrics are washed, whereby dye damage of said fabric is reduced and whereby the loss of tensile strength in said fabric is reduced as compared to fabrics which have been treated with similar peroxygen bleaching compositions but without the fabric protection agents of this invention.
  • pretreat soiled fabrics it is to be understood that the aqueous composition is applied in its neat form onto the soiled fabric and left to act on said fabric before said fabric is washed. Alternatively, the aqueous composition may be applied to the fabric substrate along with enough water to wet the fabric.
  • the present aqueous compositions have a pH offrom greater than 0 to about 6 and a viscosity of 50 cps, or greater, preferably from about 50 to about 2000 cps, at 20°C when measured with a Brookfield viscometer at 50 rpm with a spindle n°3.
  • the present invention encompasses an aqueous composition comprising a peroxygen bleach, such as -aydifgen peroxide or a source thereof, and a fabric protection agent.
  • a peroxygen bleach such as -aydifgen peroxide or a source thereof
  • a fabric protection agent such as a peroxygen bleach, such as -aydifgen peroxide or a source thereof.
  • Suitable fabric protection agents are characterized by sufficiently high stability constants for metal ions, such as copper or iron, to prevent the metal ion catalyzed decomposition of the peroxygen bleach. Moreover, the fabric protection agent should have sufficiently high mobility to ensure that the fabric protection agents migrates along with the peroxygen bleach as the bleach spreads or migrates throughout the fabric fibers upon the application of the bleaching composition onto the fabric.
  • a mobility factor defined hereinbelow
  • the fabric protection agents have a ratio of stability constant for copper(2+) to stability constant for calcium(2+) of at least about 3:1, more preferably at least about 4:1.
  • Stability constants are further defined in and procedures for the experimental determination of are included in Martell, A. E.; Smith, R. M. Critical Stability Constants, Plenum Press: New York, 1974; Volume 1, and references cited therein.
  • stability constant herein is meant log K values also designated as "log K- " as defined in Martell, cited above.
  • Fabric protection agents herein preferably comprise at least two moieties capable of chelating or binding metal ions, such as carboxylic, amino (primary, secondary, or tertiary), amido, hydroxy moieties, and mixtures thereof.
  • carboxylic means either carboxylic acid or the unprotonated carboxylate.
  • Highly preferred fabric protection agents of this invention can be selected from the group consisting of glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, aspartic acid, glutamic acid, malonic acid, the corresponding conjugate base salts (i.e., monosodium glutamate), and mixtures thereof. Structures for these compounds are:
  • fabric protection agents which have a ratio of stability constants for copper(2+) to calcium(2+) at least about 4:1 include those agents selected from the group consisting of glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, glutamic acid, aspartic acid, the corresponding conjugate base salts (i.e., monosodium glutamate), and mixtures thereof.
  • these fabric protection agents are thos selected from the group consisting of salicylic acid and its derivatives, including 5 sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, the correspondin conjugate base salts, and mixtures thereof.
  • the minimum concentration of the fabric protection agents in the bleachin composition can be calculated from the formula: (CXstability constant for Cu- ⁇ "1" ) 2.5, more preferably > 5, where C is the weight percent of fabric protection agent i the bleaching composition. In any case, the concentration of the fabric protectio agent should be less than about 50% of the total bleaching composition. As a example, if the stability constant for Cu--- + for a particular fabric protection agent is 3 the concentration can be calculated by (C)(3) > 2.5, or C is 0.83% of the tota bleaching composition.
  • a preferred range of fabric protection agent will comprise fro about 0.3% to about 3%, more preferably from about 1% to about 1.5%, by weight o the total bleaching composition.
  • compositions according to the present invention are aqueous liquid cleaning compositions.
  • Said aqueous compositions should be formulated in the acidic pH, preferably at a pH offrom greater than 0 to about 6 and more preferably at a pH offrom 3 to 5.
  • Formulating the compositions ofthe present invention in the acidic pH range contributes to the stability of said compositions.
  • the pH of the compositions ofthe present invention can be adjusted by using organic or inorganic acids or bases.
  • fabric damage herein is meant the degree of tensile strength loss of a fabric. Tensile strength loss may be measured by employing the Tensile Strength Loss Test, as can be seen in Example II hereinafter.
  • Mobility Factor is a measure of the fabric protection agent's ability to migrate on a cellulose substrate and is experimentally determined in a thin layer chromatography test.
  • the thin layer chromatography test is conducted as follows. A sample ofthe fabric protection agent candidate to be measured is spotted onto a Baker-flex Cellulose F indicating thin layer chromatography plate using a capillary applicator and subsequently developed in an enclosed chamber using 0.001 N aqueous acetic acid.ethanol (50:50 mixture) as the elutant. After drying, the plates are visualized under UV/vis light or exposure to iodine vapor.
  • the "mobility factor” as used herein is thus defined as the retention factor (R ⁇ , commonly recognized by those skilled in the art as the distance in which the sample moved divided by the distance in which the solvent front moved on the thin layer chromatography plate.
  • the mobility factor equal to the retention factor, ranges from 0 to 1, with 1 being the highest mobility.
  • the fabric protection agents of this invention possess excellent mobility on cellulose, as measured by this mobility test.
  • the highly preferred fabric protection agents herein have a mobility factor of 0.9 or above.
  • Peroxygen Bleach An essential element of the compositions of the present invention is peroxygen bleach.
  • a preferred peroxygen bleach herein is hydrogen peroxide or a water soluble source thereof or mixtures thereof. Hydrogen peroxide is most preferred. Indeed, the presence of peroxygen bleach, preferably hydrogen peroxide, provides strong cleaning benefits which are particularly noticeable in laundry applications.
  • a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include sodium carbonate peroxyhydrate or equivalent percarbonate salts, persilicate, perborates, e.g., sodium perborate (any hydrate but preferably the mono- or tetra- hydrate), sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and mixtures thereof.
  • Alternative peroxygen sources include persulfates such as monopersulfate, peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalatic acid, perbenzoic and alkylperbenzoic acids, and mixtures thereof.
  • an "effective amount" of a peroxygen bleach is any amount capable of measurably improving soil/stain removal from the soiled fabric substrate compared to a peroxygen bleach-free composition when the soiled substrate is washed by the consumer in the presence of alkali.
  • the compositions of the present invention comprise from 0.5% to 20% by weight of the total composition of said peroxygen bleach, preferably from 2% to 15% and most preferably from 1% to 6%.
  • bleach activator it is meant herein a compound which reacts with hydrogen peroxide to form a peracid.
  • the peracid thus formed constitutes the activated bleach.
  • Particularly preferred is acetyl triethyl citrate.
  • Said bleach activators, if present, will typically comprise from about 0.5% to about 20%, preferably from 2% to 10%, most preferably from 3% to 7%, by weight ofthe total composition.
  • Bleach activators suitable herein are any known activators typified by NOBS (nonanoyl oxybenzenesulfonate), TAED (tetraacetylethylenediamine), or ATC (acetyl triethyl citrate). Numerous other bleach activators are known. See for example activators referenced in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. See also U.S. 4,634,551 for other typical conventional bleach activators.
  • amido-derived bleach activators of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R2C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R- ⁇ - is an alkylene containing from 1 to about 6 carbon atoms, R $ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • bleach activators ofthe above formulae include (6-oct- anamidocaproyl)-oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
  • Another class of bleach activators comprises the benzoxazin- type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990.
  • Still another class of bleach activators includes acyl lactam activators such as substituted and unsubstituted benzoyl caprolactam, t-butyl-benzoylcaprolactam, n- octanoyl caprolactam, 3,5,5-trimethylhexanoyI caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam, t-butyl-benzoylvalerolactam and mixtures thereof.
  • acyl lactam activators such as substituted and unsubstituted benzoyl caprolactam, t-butyl-benzoylcaprolactam, n- o
  • Preferred bleach activators useful herein include those selected from the group consisting of acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, n- octanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and mixtures thereof.
  • Particularly preferred are the bleach activators which are liquid or oil at room temperature.
  • liquid bleach activators are acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, and mixtures thereof.
  • the present compositions can optionally comprise aryl benzoates, such as phenyl benzoate.
  • compositions described herein may also be used as a laundry detergent or as a laundry detergent booster and as a household cleaner in the bathroom or in the kitchen, for the cleaning of dishes or for the cleaning of carpets.
  • compositions according to the present invention may remain in contact with the fabric, typically for a period of 1 minute to 24 hours, preferably 1 minute to 1 hour, and more preferably 5 minutes to 30 minutes, or so as to avoid drying of the composition on the fabric.
  • the compositions according to the present invention may be rubbed and/or brushed, for example, by means of a sponge or a brush or simply by rubbing two pieces of fabric each against the other.
  • washing it is to be understood herein to simply rinse the fabrics with water, or the fabrics may be washed with conventional compositions comprising at least one surface active agent, this by the means of a washing machine or simply by hand.
  • compositions described herein are applied onto the fabrics to be pre-treated without undergoing any dilution, i.e. they are applied in the form described herein.
  • aqueous bleaching compositions typically will also comprise other optional conventional ingredients to improve or modify performance. Typical, non-limiting examples of such ingredients are disclosed hereinafter for the convenience of the formulator.
  • Organic Stabilizers may also optionally contain organic stabilizers for improving the chemical stability of the composition, provided that such materials are compatible or suitably formulated.
  • Organic stabilizers can be selected from the following group: monophenols such as 2,6-di-/er/-butylphenol or 2,6-di-/ert-butyl-4-methylphenol; diphenols such as 2,2'-methylenebis(4-methyl-6-terf- butylphenol) or 4,4'-methylenebis(2,6-di-ter/-butylphenol); polyphenols such as 1,3,5- trimethyl-2,4,6-tris(3',5 , -di-tert-butyl-4-hydroxybenzyl)benzene; hydroquinones such as 2,5-di-terf-amylhydroquinone or tert-butylhydroquinone; aromatic amines such as N- phenyl-N'-(l,3-dimethylbutyl)- ?
  • Organic stabilizers are typically used in the present compositions at levels from 0.01% to 5.0%, more preferably from 0.1% to 0.5%.
  • the peroxygen bleach-containing compositions according to the present invention may further comprise from 0.5% to 5%, preferably from 2% to 4% by weight ofthe total composition of an alcohol according to the formula HO - CRTt" - OH, wherein R' and R" are independently H or a C 2 -C ⁇ 0 hydrocarbon chain and/or cycle.
  • Preferred alcohol according to that formula is propanediol.
  • inorganic Stabilizers examples include sodium stannate and various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.
  • surfactants are useful herein for their usual cleaning power and may be included in preferred embodiments of the instant compositions at the usual detergent-useful levels. Generally, surfactants will comprise from about 0.1% to about 50%, preferably from about 1% to about 30%, more preferably from about 5% to about 25%, by weight ofthe liquid bleaching compositions herein.
  • Nonlimiting examples of surfactants useful herein include the conventional Cl l-Cl8 alkylbenzene sulfonates ("LAS") and primary, branched-chain and random C10-C2O alkyl sulfates (“AS"); the C ⁇ Q-C ⁇ 8 secondary alkyl sulfates of the formula CH 3 (CH 2 ) ⁇ (C ⁇ OS ⁇ 3 ⁇ M + )CH3 and CH 3 (CH 2 )y(CHOSO3 " M + )CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium; unsaturated sulfates such as oleyl sulfate; the ⁇ Q-C ⁇ alkyl alkoxy sulfates (“AExS”) especially those wherein x is from 1 to about 7; CJO-CIS alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates);
  • Detersive surfactants may be mixed in varying proportions for improved surfactancy as is well-known in the art.
  • conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg- Cj2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylate/ propoxylates), C12- 18 betaines and sulfobetaines ("sultaines”), C10-C18 amine oxides, and the like, can also be included in the cleaning compositions,
  • AE alkyl ethoxylates
  • sulfobetaines especially ethoxylates and mixed ethoxylate/ propoxylates
  • C10-C18 amine oxides especially C10-C18 amine oxides, and the like.
  • the CJO-CIS N-alkyl polyhydroxy fatty acid amides can also
  • Typical examples include the Cj2-Cl8 N-methylglucamides. See WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-ClS N" (3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C 10-C2O conventional soaps may also be employed. If high sudsing is desired, the branched-chain Cjo-Ci6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. High performance compositions typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not excluded.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt or "overbased". When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the 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.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
  • Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance due to their availability from renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C12-C18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing in laundry compositions, which may need to be taken into account by the formulator.
  • phosphorus-based builders can be used, and especially in hand- laundering operations, 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 though such materials are more commonly used in a low-level mode as chelants or stabilizers.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified -2 by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates.
  • compositions herein may also optionally contain a transition-metal selective sequestrants or "chelating agents", e.g., iron and/or copper and/or manganese chelating agents, provided that such materials are compatible or suitably formulated.
  • chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic chelating agents, and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron, copper and manganese ions from washing solutions by formation of soluble chelates; other benefits include inorganic film prevention or scale inhibition.
  • Commercial chelating agents for use herein include the DEQUEST® series, and chelants from Monsanto, DuPont, and Nalco, Inc.
  • Aminocarboxylates use ul as optional chelating agents are further illustrated by ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof.
  • chelant mixtures may be used for a combination of functions, such as multiple transition-metal control, long-term product stabilization, and/or control of precipitated transition metal oxides and/or hydroxides.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • a highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.
  • Another preferred chelator for use herein is ofthe formula:
  • Ri, R2, R3, and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO , -C(O)R ⁇ and -SO R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R5, Rg, R7, and Rs are independently selected from the group consisting of -H and alkyl.
  • Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include the ethylenediaminetetrakis (methylenephosphonates) and the diethylenetriaminepentakis
  • aminophosphonates Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • chelating agents or transition-metal-selective sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight ofthe compositions herein.
  • Enzymes - Enzymes can be included in the instant compositions for a wide variety of fabric laundering or other cleaning pu ⁇ oses, including removal of protein- based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be inco ⁇ orated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders, etc.. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • the enzymes useful herein may optionally be coated for protection in the aqueous formulation.
  • Enzymes are normally inco ⁇ orated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. Another suitable protease is obtained from a strain oi Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S as ESPERASE®. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76 in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +107 and +123 in Bacillus amyloliquefaciens subtilisin as described in the patent applications of A. Baeck, CK. Ghosh, P.P. Greycar, R.R. Bott and L.J.
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo Industries.
  • Cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB- A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® (Novo) is especially useful.
  • Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization offrom 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especiaUy for such components having about 20 to 30 oxypropylene units, at least about 50%
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 1 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2) n OCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C ⁇ -C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C ⁇ -C ⁇ vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end- capped oligomeric esters of U.S.
  • Patent 4,721,580 issued January 26, 1988 to Gosselink
  • block polyester oligomeric compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy- 1,2- propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio offrom about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)- ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • compositions of the present invention can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics ofthe compositions. Such materials are further illustrated in U.S. Pat. No. 3,936,537, Baskerville et al.
  • Adjuncts which can also be included in compositions ofthe 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 other active ingredients such as dispersant polymers from BASF Co ⁇ .
  • anti-tarnish and/or anti-corrosion agents include dyes, fillers, optical brighteners, germicides, hydrotropes, enzyme stabilizing agents, perfumes, solubilizing agents, clay soil removal/anti-redeposition agents, carriers, processing aids, pigments, solvents, fabric softeners, static control agents, etc.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one dyed surface to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N ⁇ O group can be represented by the following general structures:
  • Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N ⁇ O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI”) are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113. "Modern Methods of Polymer Characterization", the disclosures ofwhich are inco ⁇ orated herein by reference.)
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, inco ⁇ orated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • Suds Boosters If high sudsing is desired, suds boosters such as C ⁇ o _ Cl6 alkanolamides can be inco ⁇ orated into the compositions, typically at 1%-10% levels.
  • the C10-C- monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, for example, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • Brightener Any optical brighteners, fluorescent whitening agents or other brightening or whitening agents known in the art can be inco ⁇ orated in the instant compositions when they are designed for fabric treatment or laundering, at levels typically from about 0.05% to about 1.2%, by weight, ofthe detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocyclic brighteners, this list being illustrative and non-limiting. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2- (4-styryl- ⁇ henyl)-2H-naphthol[ 1 ,2-d]triazoles; 4,4'-bis- ( 1 ,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-benzimidazol-2- yl)ethylene; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-napth-[l,2-d]oxazole; and 2- (stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are typically preferred herein.
  • Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients into a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT® D10, Degussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • compositions herein can contain other fluids as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% ofsuch carriers.
  • Bleach catalysts may additionally inco ⁇ orate a catalyst or accelerator to further improve bleaching or soil removal. Any suitable bleach catalyst can be used.
  • the composition will typically deliver a concentration of from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 50 ppm, or less, ofthe catalyst species in the wash liquor.
  • Typical bleach catalysts comprise a transition-metal complex, for example one wherein the metal co-ordinating ligands are quite resistant to labilization and which does not deposit metal oxides or hydroxides to any appreciable extent under the typically alkaline conditions of washing.
  • Such catalysts include manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S. 5,114,606; and EP Nos.
  • catalysts include Mn ⁇ i2( ⁇ -O) 1 ( ⁇ -OAc)2(TACN)2(ClO 4 )2 ) MnIV 4 ( ⁇ -O) 6 (TACN)4(ClO 4 )4,
  • Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • Transition metals may be precomplexed or complexed in-situ with suitable donor ligands selected in function of the choice of metal, its oxidation state and the denticity ofthe ligands.
  • suitable donor ligands selected in function of the choice of metal, its oxidation state and the denticity ofthe ligands.
  • Other complexes which may be included herein are those of U.S. Application Ser. No. 08/210,186, filed March 17, 1994.
  • Pretreater Formulation - The preferred compositions of the present invention have a viscosity 50 cps or greater at 20°C when measured with a Brookfield viscometer at 50 ⁇ m with a spindle n°3, more preferably of from about 50 to about 2000 cps, and still more preferably of from about 200 to about 1500 cps.
  • Any surfactant system or polymeric thickener known in the art to increase the viscosity of a composition can be used to achieve the preferred viscosity.
  • the surfactants suitable to be used herein may be thickening surfactants such as nonionic, anionic, cationic, zwitterionic and/or amphotheric surfactants.
  • the bleaching composition herein comprise water in any amount up to about 95% by weight of the total composition.
  • the compositions herein will comprise from about 5% to about 95%, more preferably from about 10% to about 90%, by weight ofthe bleaching composition, of water.
  • peroxygen bleach-containing compositions according to the present invention f rther comprise an optional bleach activator
  • the composition When formulated as a microemulsion, the composition comprises the bleach activator in a matrix of water, the peroxygen bleach, and hydrophilic anionic and nonionic surfactants.
  • Suitable anionic surfactants herein include the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
  • Suitable nonionic surfactants for use in the microemulsions herein include the hydrophilic nonionic surfactants as defined hereinafter for the emulsions according to the present invention.
  • the composition When formulated as an emulsion, the composition comprises at least a hydrophilic surfactant having an HLB (hydrophilic-lipophilic balance) above 10 and at least a hydrophobic surfactant having an HLB up to 9, wherein said bleach activator is emulsified by said surfactants.
  • HLB hydrophilic-lipophilic balance
  • the two different surfactants in order to form emulsions which are stable must have different HLB values, and preferably the difference in value ofthe HLBs of said two surfactants is at least 1, preferably at least 3. In other words, by appropriately combining at least two of said surfactants with different HLBs in water, stable emulsions will be formed, i.e.
  • the emulsions which do not substantially separate into distinct layers, upon standing for at least two weeks at 50 °C.
  • the emulsions comprise from about 2 % to about 50%, by weight of the total composition, of said hydrophilic and hydrophobic surfactants, preferably from about 5% to about 40%, and more preferably from about 8% to about 30%.
  • the emulsions comprise at least about 0.1%, preferably at least 3%, more preferably at least 5%, by weight of the total emulsion, of one or more hydrophobic surfactant and at least about 0.1%, preferably at least 3%, more preferably at least 5%, by weight of the total emulsion, of one or more hydrophilic surfactant.
  • hydrophobic nonionic surfactants and hydrophilic nonionic surfactants.
  • Said hydrophobic nonionic surfactants to be used herein have an HLB up to 9, preferably below 9, more preferably below 8 and said hydrophilic surfactants have an HLB above 10, preferably above 11, more preferably above 12.
  • Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and or propoxylates. A variety of alkoxylated fatty alcohols are commercially available which have very different HLB values.
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with, for instance, an HLB of 6, such as a Dobanol® 23-2 and a hydrophilic nonionic surfactant with, for instance, an HLB of 15, such as a Dobanol® 91-10.
  • Dobanol® are commercially available nonionic surfactants available from Shell Co ⁇ .
  • Lutensol® are commercially available nonionic surfactants available from BASF Co ⁇ .
  • the peroxygen bleach-containing compositions according to the present invention may further comprise an amine oxide surfactant according to the formula R ⁇ R ⁇ O, wherein each of R 1 , R 2 and R 3 is independently a C 6 -C 30 , preferably a C 1 0-C30- most preferably a C ⁇ 2 -C*6 hydrocarbon chain. It has been further observed that in a pretreatment process, the presence of said amine oxide further improves the cleaning performance on particulate and/or greasy stains. It is believed that this improvement in cleaning performance is matrix independent. To obtain either of these benefits, amine oxides, if present, should be present in amounts ranging from 0.1% to 10 % by weight ofthe total composition, preferably from 1.5% to 3%.
  • Articles of Manufacture - Preferred articles include the compositions herein that are suitable for use in the processes described herein, in a package that can provide direct application of said compositions onto soiled fabrics.
  • the composition is packaged in a pliable container fitted with an applicator cap.
  • Suitable containers include those that permit application directly onto soiled fabric by squeezing or pouring the compositions through the applicator cap.
  • Such containers include those described in U. S. Pat. 4,107,067.
  • Appropriate applicator caps include, but are not limited to, fountain type nozzles, brush applicators, roller ball applicators, and flip-top caps.
  • the containers useful for the processes described herein contain from about 4 ounces to about 32 ounces, preferably from about 4 ounces to about 24 ounces, ofthe compositions described herein.
  • the following examples illustrate the compositions of this invention, but are not intended to be limiting thereof. All materials in the Examples satisfy the functional limitations herein.
  • BHT 2 0.05 0.05 .
  • Composition I comprises hydrogen peroxide and is free of a fabric protection agent.
  • Compositions II to V contain a fabric protection agent which are representative ofthe present invention.
  • compositions in Example I differ only in the identity of the fabric protection agent.
  • this formulation is used as the basic peroxygen bleaching composition to which the subject fabric protection agent is added.
  • the tensile strength loss measured above for the test composition is expressed as a percentage and is obtained by dividing the tensile strength of a reference cotton ribbon, i.e. a ribbon which has not been treated with a bleaching composition, by the tensile strength ofthe test ribbon pretreated by the test composition. Results are as follows:
  • compositions according to the present invention comprising a peroxygen bleach and a fabric protection agent as compared to the use of the same bleaching composition but without a fabric protection agent (composition I).
  • the tensile strength loss is reduced when pretreating fabrics with compositions according to the present invention (see compositions II to VI), even upon a prolonged contact time, i.e., 24 hours and in presence of a high concentration of copper on the surface of said fabrics, i.e., 30 ppm per gram of cotton fabric.
  • composition 2 A B C D Composition 2 A B C D
  • Salicylic acid 1 1.5 — —
  • Salicylic acid 1 1.5 — —
  • the tensile strength loss is reduced when pretreating fabrics with Compositions A to D of this example, even upon a prolonged contact time, i.e., 24 hours, and in the presence of a high concentration of copper on the surface ofthe fabrics, i.e., 30 ppm per gram of cotton fabric.
  • compositions A to D on colored fabrics in the same manner as above, no dye change and/or discoloration is observed.

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  • 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)
  • Health & Medical Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
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Abstract

La présente invention a pour objet des compositions acides aqueuses comprenant un agent de blanchiment peroxygéné et un agent spécifique de protection des tissus. Elle concerne en outre un procédé qui consiste à appliquer aux tissus à laver un traitement préalable destiné à réduire la perte de leur résistance à la traction ainsi que les dégâts qu'ils pourraient subir en termes de couleur/teinture.
PCT/US1996/010938 1995-06-27 1996-06-26 Compositions de blanchiment peroxygenees comprenant un agent de protection des tissus WO1997001624A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP96923463A EP0836639A1 (fr) 1995-06-27 1996-06-26 Compositions de blanchiment peroxygenees comprenant un agent de protection des tissus
BR9608668A BR9608668A (pt) 1995-06-27 1996-06-26 Composições alvejantes de peroxigênio compreendendo um agente de proteção de tecido
SK1745-97A SK174597A3 (en) 1995-06-27 1996-06-26 Peroxygen bleaching compositions comprising a fabric protection agent
AU63966/96A AU711809B2 (en) 1995-06-27 1996-06-26 Peroxygen bleaching compositions comprising a fabric protection agent
JP9504549A JPH11508627A (ja) 1995-06-27 1996-06-26 布帛保護剤を含む過酸素漂白組成物
MX9800201A MX9800201A (es) 1995-06-27 1996-06-26 Composiciones blanqueadoras peroxigenadas que comprenden un agente de proteccion de telas.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US55795P 1995-06-27 1995-06-27
US08/663,501 1996-06-14
US08/663,501 US5759439A (en) 1996-06-14 1996-06-14 Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
US60/000,557 1996-06-14

Publications (1)

Publication Number Publication Date
WO1997001624A1 true WO1997001624A1 (fr) 1997-01-16

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EP (1) EP0836639A1 (fr)
JP (1) JPH11508627A (fr)
KR (1) KR19990028486A (fr)
CN (1) CN1193992A (fr)
AU (1) AU711809B2 (fr)
BR (1) BR9608668A (fr)
CA (1) CA2225177A1 (fr)
CZ (1) CZ408797A3 (fr)
HU (1) HUP9901912A3 (fr)
MX (1) MX9800201A (fr)
PL (1) PL324407A1 (fr)
RU (1) RU2167923C2 (fr)
SK (1) SK174597A3 (fr)
TR (1) TR199701703T1 (fr)
WO (1) WO1997001624A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1126012A1 (fr) * 2000-02-17 2001-08-22 Bode Chemie GmbH & Co. Systèmes détergents et désinfectants pour instruments médicaux

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101831472B1 (ko) * 2010-06-28 2018-02-22 바스프 에스이 금속 비함유 표백 조성물
JP5923109B2 (ja) * 2010-12-13 2016-05-24 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 漂白触媒

Citations (6)

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Publication number Priority date Publication date Assignee Title
EP0013886A1 (fr) * 1979-01-22 1980-08-06 S.C. Johnson & Son, Inc. Composition de blanchiment contenant du peroxyde d'hydrogène
JPS55142100A (en) * 1979-04-23 1980-11-06 Kao Corp Bleaching agent composition
JPS5760000A (en) * 1980-09-29 1982-04-10 Showa Denko Kk Bleaching agent composition
EP0351772A2 (fr) * 1988-07-19 1990-01-24 HENKEL CORPORATION (a Delaware corp.) Peroxyde d'hydrogène stabilisé
EP0476257A1 (fr) * 1990-09-15 1992-03-25 Hüls Aktiengesellschaft Acides amino-dicarboxyliques et leurs dérivés comme stabilisants pour le blanchiment à l'oxygène du linge lors du lavage
JPH04345695A (ja) * 1991-05-24 1992-12-01 Kao Corp 液体漂白剤組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013886A1 (fr) * 1979-01-22 1980-08-06 S.C. Johnson & Son, Inc. Composition de blanchiment contenant du peroxyde d'hydrogène
JPS55142100A (en) * 1979-04-23 1980-11-06 Kao Corp Bleaching agent composition
JPS5760000A (en) * 1980-09-29 1982-04-10 Showa Denko Kk Bleaching agent composition
EP0351772A2 (fr) * 1988-07-19 1990-01-24 HENKEL CORPORATION (a Delaware corp.) Peroxyde d'hydrogène stabilisé
EP0476257A1 (fr) * 1990-09-15 1992-03-25 Hüls Aktiengesellschaft Acides amino-dicarboxyliques et leurs dérivés comme stabilisants pour le blanchiment à l'oxygène du linge lors du lavage
JPH04345695A (ja) * 1991-05-24 1992-12-01 Kao Corp 液体漂白剤組成物

Non-Patent Citations (3)

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Title
DATABASE WPI Section Ch Week 8051, Derwent World Patents Index; Class A97, AN 80-91264C, XP002015666 *
DATABASE WPI Section Ch Week 8220, Derwent World Patents Index; Class D25, AN 82-40499E, XP002015665 *
DATABASE WPI Section Ch Week 9302, Derwent World Patents Index; Class D25, AN 93-015396, XP002015664 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1126012A1 (fr) * 2000-02-17 2001-08-22 Bode Chemie GmbH & Co. Systèmes détergents et désinfectants pour instruments médicaux

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CZ408797A3 (cs) 1998-06-17
PL324407A1 (en) 1998-05-25
HUP9901912A2 (hu) 1999-11-29
CA2225177A1 (fr) 1997-01-16
RU2167923C2 (ru) 2001-05-27
CN1193992A (zh) 1998-09-23
EP0836639A1 (fr) 1998-04-22
TR199701703T1 (xx) 1998-06-22
AU6396696A (en) 1997-01-30
SK174597A3 (en) 1998-10-07
HUP9901912A3 (en) 2000-02-28
AU711809B2 (en) 1999-10-21
KR19990028486A (ko) 1999-04-15
JPH11508627A (ja) 1999-07-27
MX9800201A (es) 1998-04-30
BR9608668A (pt) 1999-05-04

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