KR19990028486A - Oxygen bleaching compositions comprising fabric protectants - Google Patents

Abstract

The present invention relates to an aqueous acidic composition comprising an over-oxygen bleaching agent and a specific fabric protector. The present invention also relates to a method of pretreating a contaminated fabric to reduce the loss of tensile strength of the fabric and to reduce damage to the fabric color / dye.

Description

Oxygen bleaching compositions comprising fabric protectants

Bleaching compositions have been extensively disclosed in laundry applications such as laundry detergents, laundry additives, or even laundry pretreatments.

Indeed, the use of such bleach-containing compositions for washing pretreatment purposes is particularly advantageous because of the presence of stains / contaminants, and also of contaminants containing grease, coffee, tea, grass, clay / clay that are otherwise difficult to remove by typical machine washing Promoting the removal of the same "problematic" stain. However, a disadvantage associated with such a bleaching agent containing composition is that the fabric to be treated is contaminated with metal ions, such as copper, iron, manganese or chromium, which is applied directly to the fabric and remains on the fabric for a long time before washing the fabric When used in pretreatment applications under stress conditions, such compositions can damage the fabric and lead to dye damage and / or loss of tensile strength of the fabric fibers. Although not theoretically proven, over oxygen bleaching agents can cause dye and fabric damage associated with such bleaching compositions. These metal ions on the fabric, especially on the cellulosic fabric surface, also promote decomposition of peroxy bleach, such as hydrogen peroxide. Thus, increased degradation of over-oxygen bleaching agents can damage fabrics and / or dyes.

When such compositions are applied directly to the fabric, the different components in the composition are dispersed or otherwise transferred through the fabric fibers, possibly at different rates. This is especially the case with the bleaching component of the bleaching composition designed for pretreatment of the fabric.

The solution to damage caused by pretreatment of the fabric with a bleaching composition comprising an oxygen bleach is to add a specific fabric protector which acts to reduce fabric and / or dye damage. Such fabric protectants have been found to significantly reduce the damage associated with treating fabrics, particularly fabrics contaminated with metal ions, using compositions containing oxygen and bleach. Suitable fabric protectants are characterized by very high stabilization constants for metal ions, such as copper or iron, to inhibit, slow down, and / or minimize metal ion catalytic cracking of peroxy bleach. The fabric protector should also have high mobility to move the fabric protector and the oxygen bleaching agent together as the bleach agent disperses or migrates through the fabric fibers when the bleach composition is applied to the fabric.

Thus, the present invention solves the need for long-standing, effective, dye-safe bleaching compositions suitable for use as pretreatment agents that do not promote fabric damage. The compositions of the present invention also provide excellent performance when used in other applications separate from laundry pretreatment applications, such as laundry detergents or laundry additives, or even in hard surface cleaning applications or carpet cleaning applications.

And oxygen-based bleach-containing compositions have been widely disclosed in the art. For example, EP-629,691A discloses a silicone compound, and a nonionic surfactant emulsion comprising hydrogen peroxide as an optional component or a water-soluble source thereof. EP-629,690A discloses a terephthalate-based polymer and a nonionic surfactant emulsion comprising hydrogen peroxide or a water-soluble source thereof as an optional component. EP-209,228B discloses a composition comprising a peroxide source such as hydrogen peroxide. EP-209,228B discloses a hydrogen peroxide-containing composition which can be used as a pre-stain remover. See also U.S. Patent No. 4,891,147, issued January 2, 1990, and U.S. Patent No. 5,019,289, issued May 28, 1994.

SUMMARY OF THE INVENTION

The invention includes an aqueous composition containing the oxygen-based bleaching agent, and a fabric protective agent such as hydrogen peroxide or a source, wherein the fabric protective agent has a transfer coefficient of 0.7 or more as defined below, a fabric protectant is logK for Cu ²⁺ Has a stabilization constant of 3 or more. The minimum concentration (C) of the fabric protector, measured in weight percent of such liquid bleaching composition, is also calculated by the following equation:

{[C] * [Stabilization constant for Cu ²⁺ ]} ≥ 2.5.

Preferably, the fabric protector has a stabilization constant for Cu ²⁺ to a stabilization constant for Ca ²⁺ of at least about 2: 1.

The present invention also encompasses a method of pretreating a fabric contaminated with a liquid aqueous composition comprising an overbased oxygen bleaching agent and a fabric protector having a coefficient of motion greater than or equal to 0.7 as determined herein, To the fabric, and allowing the composition to contact the fabric such that the composition does not dry on the fabric, preferably before washing the fabric.

In another method, the aqueous composition is applied to the contaminated fabric prior to washing the fabric, whereby the loss of tensile strength of such fabric is reduced when compared to a fabric treated with a similar peroxy bleaching composition without the fabric protector of the present invention.

In another method, the aqueous composition is applied to the stained / dyed fabric prior to washing the fabric, thereby reducing dye damage to the fabric, thereby reducing the tensile strength loss of the fabric in such fabric, And is reduced when compared to fabrics treated with similar and oxygen based bleaching compositions.

A " pretreated contaminated fabric " is understood to mean that the aqueous composition is applied to the soiled fabric in its sole form and left to act on the fabric prior to washing the fabric. Alternatively, the aqueous composition may be applied to the fabric substrate with sufficient water to wet the fabric.

In a preferred embodiment, the aqueous compositions of the present invention have a viscosity of from 0 to about 6, and a viscosity of at least 50 cps, preferably from about 50 to about 2000 cps at 20 캜, as measured by a Brookfield viscometer at 50 rpm at spindle n ° 3 .

All percentages, ratios, and proportions herein are by weight unless otherwise stated. All references cited are incorporated herein by reference.

The present invention relates to a composition comprising an aqueous bleaching agent suitable for use as a pretreatment agent, and to a pretreatment method which improves fabric safety and / or color stability. The bleaching composition is preferably acidic and comprises an over-oxygen bleaching agent, preferably hydrogen peroxide or a source thereof, and a fabric protector.

The present invention relates to an aqueous composition comprising an over-oxygen bleaching agent, such as hydrogen peroxide or a source thereof, and a fabric protector. Such fabric protectants have been found to significantly reduce the damage associated with processing fabrics contaminated with metal ions, such as copper, iron, chromium and manganese, with compositions containing oxygen and bleach. Suitable fabric protectants are characterized by sufficiently high stabilization constants for metal ions such as copper or iron to inhibit metal ion catalytic cracking of the peroxy bleach. The fabric protector should also have high mobility to move the fabric protector and the oxygen bleaching agent together as the bleach agent disperses or migrates through the fabric fibers when the bleach composition is applied to the fabric.

The fabric protective agent of the present invention is characterized by having a migration coefficient (as defined below) of at least 0.7, preferably at least about 0.8, more preferably at least about 0.9. Such a fabric protector also has a stabilization constant for Cu ²⁺ at log C of at least 3, more preferably at least 6, even more preferably at least 9 at a temperature of 25 ° C and an ionic strength of 0.1. In addition, such a fabric protector has a stabilization constant for Fe ³⁺ at a temperature of 25 ° C and an ionic strength of 0.1, with a log K of preferably at least 6, more preferably at least 9, even more preferably at least 12. In a more preferred embodiment, the fabric protector has a stabilization constant for Cu ²⁺ to a stabilization constant for Ca ^{2+ of} at least about 3: 1, more preferably at least about 4: 1. Stabilization constants are also found in Martell, AE, Smith, RM Critical Stability Constants, Plenum Press: New York, 1974; Volume 1] and methods for experimental determination included in the references mentioned herein. The " stabilization constant " referred to herein as log K is named " log K ₁ "

The fabric protectants herein preferably comprise residues capable of chelating or bonding metal ions such as two or more carboxylates, amino (primary, secondary or tertiary), amido, hydroxy moieties and mixtures thereof . Those skilled in the art will recognize that " carboxylyl " refers to either a carboxylic acid or an unprotonated carboxylate. More preferred fabric protectants of the present invention are those which contain a combination of glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, aspartic acid, glutamic acid, malonic acid, the corresponding conjugate salts (ie, monosodium glutamate) ≪ / RTI > The structures of these compounds are as follows:

In a highly preferred embodiment of the invention, the fabric protector with a ratio of stabilization constants of Cu ²⁺ to Ca ²⁺ of at least about 4: 1 is glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, A reagent selected from the group consisting of glutamic acid, aspartic acid, the corresponding conjugate salt (i.e., monosodium glutamate), and mixtures thereof.

Particularly preferred embodiments of these fabric protectants are those selected from the group consisting of salicylic acid, and derivatives of salicylic acid, including 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, .

The minimum concentration of fabric protector in the bleaching composition can be calculated from Equation 1:

Equation 1

(C) * (stabilization constant for Cu ²⁺ ) ≥ 2.5, more preferably ≥5.

Where C is the weight percent of the fabric protector in the bleaching composition.

In any case, the fabric protector should be less than about 50% of the total bleaching composition. By way of example, if the stabilization constant for Cu ²⁺ is 3 for a particular fabric protector, the concentration can be calculated as (C) (3) ≥ 2.5, or C is 0.83% of the total bleaching composition.

In any case, the preferred range of fabric protector constitutes from about 0.3 to about 3 weight percent, more preferably from about 1 to about 1.5 weight percent, of the total bleaching composition.

The composition according to the invention is an aqueous liquid cleaning composition. Such aqueous compositions should be formulated at an acidic pH, preferably at a pH of from 0 to about 6, more preferably at a pH of from 3 to 5. The formulation of the composition of the present invention in the acidic pH range contributes to the stability of the composition. The pH of the composition of the present invention can be adjusted using an organic or inorganic acid or base.

The "fabric damage" herein means the degree of loss of tensile strength of the fabric. Tensile strength loss can be measured using the tensile strength loss test as described in Example II below.

Movement coefficient

The migration coefficient is a measure of the ability of the fabric protector to migrate on the cellulose substrate and is determined experimentally in thin layer chromatography tests. The thin layer chromatography test is carried out as follows. A sample of the fabric protector to be measured was spotted on a thin layer chromatography plate with Baker-flex Cellulose F 'using a capillary applicator and 0.001 N aqueous acetic acid: ethanol (50:50 mixture) as eluent To develop in a closed chamber. After drying, the plate is visualized under UV / visible light or exposed to iodine vapor. As used herein, " migration coefficient " is defined as the retention coefficient (R _f ) that is commonly recognized in the art as the distance traveled by the sample on a thin layer chromatography plate divided by the distance traveled by the forward line of the solvent.

Therefore, the movement coefficient equal to the retention coefficient is 0 to 1, and 1 is the maximum movement. The fabric protector of the present invention has excellent mobility on cellulose as measured in this mobility test. Indeed, the most preferred fabric protectants herein have a migration coefficient of 0.9 or greater.

This thin layer chromatography method is well known in the art and is disclosed in the Examples of Touchstone, J.C., Practice of Thin Layer Chromatography, 3rd edition, John Wiley & Sons: New York, 1992.

And oxygen bleach

The essential components of the composition of the present invention are peroxy bleach. Preferred peroxy bleaching agents herein are hydrogen peroxide or an aqueous source thereof or mixtures thereof. Hydrogen peroxide is most preferred. Indeed, the presence of over-oxygen, preferably hydrogen peroxide bleach, provides a strong cleaning benefit that is particularly perceived in laundry applications. A hydrogen peroxide source as used herein means any compound capable of producing hydrogen peroxide when contacted with water.

Suitable aqueous sources of hydrogen peroxide for use herein include sodium carbonate peroxyhydrate or equivalent percarbonate salts, fosylates, perborates such as sodium perborate (any hydrate possible but preferably mono- or tetrahydrate ), Sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, and mixtures thereof. Other peroxide sources include peroxides such as persulfates such as monopersulfate, diperoxydodecanedic acid (DPDA), magnesium perphthalic acid, perbenzoic acid and alkyl perbenzoic acid, and mixtures thereof.

And " effective amount " of an oxygen bleaching agent may be any amount that allows the consumer to wash the contaminated substrate in the presence of an alkali and to remove any contaminants / stains on the contaminated fabric substrate as compared to a composition without oxygen bleach It is a quantity. Typically the compositions of the present invention comprise from 0.5 to 20%, preferably from 2 to 15%, and most preferably from 1 to 6% by weight of the total composition of peroxy bleach.

Optional bleach activator

The oxygen and oxygen containing compositions herein optionally but preferably also comprise a bleach activator. The bleaching activator herein means a compound which reacts with hydrogen peroxide to form a peracid. The acid thus formed constitutes the activated bleaching agent. Acetyl triethyl citrate is particularly preferred. When present, such bleach activators typically constitute from about 0.5 to about 20%, preferably from 2 to 10%, most preferably from 3 to 7% by weight of the total composition.

Suitable bleach activators herein are any known activators which are formulated by NOBS (nonanoyloxybenzenesulfonate), TAED (tetraacetylethylenediamine) or ATC (acetyltriethyl citrate). A number of other bleach activators are known. See, for example, U.S. Patent No. 4,915,854 issued April 10, 1990 to Mao et al., And U.S. Patent No. 4,412,934. See also U.S. Patent No. 4,634,551 for other typical conventional bleach activators. The general formula ^{R 1 N (R 5) C} (O) R 2 C (O) L or ^{R 1 C (O) N (} R 5) R 2 C (O) L ( wherein R ¹ is from about 6 to about 12 carbon atoms, R ² is alkylene having 1 to about 6 carbon atoms, R ⁵ is H or alkyl, aryl or alkaryl having about 1 to about 10 carbon atoms, and L is any suitable leaving group. Are also known. Another example of a bleach activator of the above formula is (6-octanamidocaproyl) -oxybenzenesulfonate, (6-noanamidocaproyl) oxybenzenesulfonate as disclosed in U.S. Patent No. 4,634,551 6-decanamidocaproyl) -oxybenzenesulfonate and mixtures thereof. Another group of bleach activators include benzo-phthalate activators as disclosed in U.S. Patent No. 4,966,723, issued October 30, 1990 to Hodge et al. Another group of bleach activators are substituted and unsubstituted benzoyl caprolactam, t-butyl-benzoyl caprolactam, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, Nonyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, t -Butyl-benzoylvalerolactam, and mixtures thereof.

Preferred bleach activators used herein include, but are not limited to, acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, n-octanoyl valerol But are not limited to, those selected from the group consisting of lactam, 3,5,5-trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and mixtures thereof . Particularly preferred are bleach activators which are liquid or oil at room temperature. Examples of liquid bleaching activators are acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, and mixtures thereof. The composition may optionally comprise an aryl benzoate such as phenyl benzoate.

Pretreatment process

Although the preferred embodiment of the composition disclosed herein is a pretreatment for laundering, the composition according to the present invention may be used as a laundry detergent or laundry detergent enhancer and as a household cleaner in a bathroom or kitchen to clean the dish or clean the carpet.

The composition may be in contact with the fabric for typically from 1 minute to 24 hours, preferably from 1 minute to 1 hour, more preferably from 5 minutes to 30 minutes, or may remain in the fabric to avoid drying of the composition have. Optionally, if the fabric is contaminated with relatively stubborn stains / contaminants to otherwise remove, the composition according to the invention may be rubbed / rubbed or brushed with a sponge or brush, or simply rubbed against two pieces of fabric .

As used herein, " laundry " can be understood simply as washing the fabric with water, or the fabric is washed with a conventional composition comprising at least one surfactant, which uses a washing machine or a hand.

&Quot; Single Form " is understood to mean that the compositions disclosed herein are not diluted, i.e. used in a pretreated fabric used in the form disclosed herein.

Conventional miscellaneous ingredients for cleaning compositions

The aqueous bleaching compositions herein may also typically include other optional conventional ingredients for improving or modifying performance. Typically, non-limiting examples of such ingredients are disclosed below for convenience of formulator.

Organic stabilizer

The compositions herein may also contain organic stabilizers to improve the chemical stability of the compositions, as long as they are compatible or suitably compounded. Organic stabilizers can be selected from the following group: monophenols such as 2,6-di-t-butylphenol or 2,6-di-t-butyl-4-methylphenol; Diphenols such as 2,2'-methylenebis (4-methyl-6-t-butylphenol) or 4,4'-methylenebis (2,6-di-t-butylphenol); Polyphenols such as 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4-hydroxybenzyl) benzene; Hydroquinone such as 2,5-di-t-amylhydroquinone or t-butylhydroquinone; Aromatic amines such as N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine or N-phenyl- alpha -naphthylamine; Dihydroquinolines such as 2,24-trimethyl-1,2-dihydro-quinoline; Hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137 ) And mixtures thereof.

The organic stabilizer is typically used at a level of from 0.01 to 5.0%, more preferably from 0.1 to 0.5%.

The peroxy bleaching agent-containing composition according to the present invention may also contain 0.5 to 5% by weight, preferably 2 to 4% by weight of the total composition of the formula HO-CR'R " -OH wherein R 'and R " H or a C ₂ -C ₁₀ hydrocarbon chain and / or cycle. A preferred alcohol according to this general formula is propanediol.

Inorganic stabilizer

Examples of inorganic stabilizers include sodium stannate, and various alkali metal phosphates such as the known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate.

Detergent surfactant

Surfactants can be used in conventional tanning applications and are included in preferred embodiments of the compositions of the present invention at conventional detergent-use levels. In general, the surfactant will comprise from about 0.1 to about 50 weight percent, preferably from about 1 to about 30 weight percent, and more preferably from about 5 to about 25 weight percent of the liquid bleaching composition of the present invention.

Non-limiting examples of surfactants used herein include conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ("LAS") and primary branched chains and random C ₁₀ -C ₂₀ alkyl sulfates ("AS"); Formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) CH 3 and _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 ( wherein, x and (y + 1) is about 7 More preferably an integer of at least about 9, and M is a water soluble cation, especially sodium; C ₁₀ -C ₁₈ secondary alkyl sulfate; Unsaturated sulfates such as oleyl sulfate; C ₁₀ -C ₁₈ alkyl alkoxy sulfates ( "AE _x S", and particularly x is from 1 to about 7); C ₁₀ -C ₁₈ alkyl alkoxycarboxylates (especially EO 1-5 ethoxycarboxylates); C ₁₀ -C ₁₈ glycerol ether; C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides; And C ₁₂ -C ₁₈ alpha-sulfonated fatty acid esters. Detergent surfactants can be mixed at various ratios to improve surface activity as is known in the art. Also C ₁₂ -C ₁₈ alkyl ethoxylates including the ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (rate / propoxylate ethoxylates and mixed ethoxylates, especially the rate), the alkyl of the so-called narrow peak ( "(&Quot; AE ") in the composition, and the C ₁₂ -C ₁₈ betaine and sulfobetaine ("sultaine"), C ₁₀ -C ₁₈ amine oxides, May be included in the composition. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl or N-hexyl C ₁₂ -C ₁₈ glucamides may be used to reduce foaming. C ₁₀ -C ₂₀ Conventional soaps may also be used. If bubbling is desired, a branched C ₁₀ -C ₁₆ soap may be used. Mixtures of anionic and nonionic surfactants are particularly useful.

extender

Detergent extenders may optionally be included in the compositions herein to assist in controlling the mineral hardness. Inorganic and organic extenders can be used. Extender is typically used in fabric laundry compositions to assist in removing particulate contaminants.

The amount of extender may vary widely depending on the final purpose of the composition and the desired physical form. When present, the compositions typically comprise about 1% or more of an extender. High performance compositions typically comprise from about 10 to about 80 weight percent, more typically from about 15 to about 50 weight percent of detergent builder. However, it is not possible to exclude smaller or larger amounts of extender.

Suitable organic detergent extenders for purposes of the present invention include, but are not limited to, a wide range of polycarboxylate compounds. As used herein, " polycarboxylate " means a compound having a plurality, preferably three or more, carboxylate groups. The polycarboxylate bulking agent may be added to the composition in generally acidic form, but may be added in neutral salt or " overbased " form. When used in salt form, alkyllithium or alkanolammonium salts such as sodium, potassium and lithium are preferred.

Among the polycarboxylate bulking agents are a wide variety of useful materials. One important category of polycarboxylate bulking agents is disclosed in U.S. Patent No. 3,128,287, issued April 7, 1964 to Berg, and U.S. Patent No. 3,635,830, issued January 18, 1972 to Lamberti et al. , ≪ / RTI > including the oxysuccinate as disclosed in U.S. Pat. See also "TMS / TDS" extender of US Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, as disclosed in U.S. Patent Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid , Various alkylidium metals such as nitrilotriacetic acid, ammonium and substituted ammonium salts, polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid And water-soluble salts thereof.

Citrate extenders, such as citric acid and its water-soluble salts (especially sodium salts), are particularly important polycarboxylate extenders due to their availability and biodegradability from recycled sources. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Particularly suitable for the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds disclosed in U.S. Patent No. 4,566,984 issued to Bush on Jan. 28, Useful succinic acid bulking agents include C ₅ -C ₂₀ alkyl and alkenylsuccinic acid and salts thereof. Specific examples of succinate extenders include lauryl succinate, myristyl succinate, palmitylsuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinate is the preferred extender of this group and is disclosed in European Patent Application No. 86200690.5 / 0,200, 263, published November 5,1986.

Other suitable polycarboxylates are disclosed in U.S. Patent No. 4,144,226, issued March 13, 1979 to Crutchfield et al., And U.S. Patent No. 3,308,067, issued March 7, 1967 to Diehl. . See also U.S. Patent No. 3,723,322.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may be incorporated into the compositions alone or in combination with the aforementioned extenders, particularly citrate and / or succinate extenders, to provide additional extender activity. This use of fatty acids generally reduces the foam of the laundry composition, which needs to be taken into account by the formulator.

A phosphorus-based extender is used, and in the case of hand-washing, various alkali metal phosphates such as known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate may be used. Hydroxy-1,1-diphosphonate, and other known phosphonates (see, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148, 3,422,137) can be used, and these materials can more typically be used in low amounts as chelating agents or stabilizers.

The inorganic or phosphorus-containing detergent builder may be selected from the group consisting of polyphosphates (such as tripolyphosphate, pyrophosphate and glassy polymerizable meta-phosphate), phosphonates, fumaric acid, silicates, carbonates (including bicarbonates and sesquicarbonates) But are not limited to, alkali metal, ammonium and alkanoyl ammonium salts of sulfates and aluminosilicates.

Chelating agent

The compositions herein may also optionally contain a transition metal selective promoter or " chelating agent ", such as iron and / or copper and / or manganese chelating agents, provided that such materials are compatible or suitably compounded . Chelating agents suitable for use herein may be selected from the group consisting of amino carboxylates, phosphonates (especially aminophosphonates), polyfunctional-substituted aromatic chelating agents and mixtures thereof. Without being limited by theory, the benefits of these materials are partly due to their excellent ability to remove iron, copper and manganese ions from the wash liquor by forming soluble chelates, and other advantages include inorganic film prevention or scale inhibition . Commercially available chelating agents as used herein include the DEQUEST series of registered trademarks and the chelating agents of Monsanto, DuPont and Nalco, Inc.

Examples of aminocarboxylates useful as selective chelating agents also include ethylenediamine tetraacetate, N-hydroxyethylethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetraproprionate, triethylenetetraamine hexaacetate, diethylenetriamine Pentaacetate and ethanol diglycine, its alkyl-metal, ammonium and substituted ammonium salts. In general, the chelating agent mixture can be used for mixing functions such as multiple transition-metal control, long-term product stabilization and / or control of precipitated transition metal oxides and / or hydroxides.

Multifunctional substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent No. 3,812,044, issued May 21, 1974 to Connor et al. A preferred compound of this type in acid form is dihydroxydisulfobenzene such as 1,2-dihydroxy-3,5-disulfobenzene.

A highly preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate (" EDDS ") as disclosed in U.S. Patent No. 4,704,233, issued November 3, 1987 to Hartman and Perkins, , In particular the [S, S] isomers. Trisodium salts are preferred, but other forms such as magnesium salts may be used.

Another chelating agent that is preferred for use herein is a compound of formula 1:

In this formula,

R ₁ , R ₂ , R ₃ and R ₄ are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO ₂ , -C (O) R ' H, -OH, alkyl and are selected from alkoxy, aryl and aryloxy group consisting of a), and -SO ₂ R "(wherein, R" is a group consisting of is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy) Lt; / RTI >

R ₅ , R ₆ , R ₇ and R ₈ are independently selected from the group consisting of -H and alkyl.

Aminophosphonates are suitable for use as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is acceptable in the detergent composition and include ethylenediaminetetrakis (methylenephosphonate) and diethylenetriaminepentaquis Methylene phosphonate). Preferably, these aminophosphonates do not contain an alkyl or alkenyl group having about 6 carbon atoms or more.

If used, the chelating agent or transition metal-selective adsorbent preferably constitutes from about 0.001 to about 10% by weight of the composition, more preferably from about 0.05 to about 1% by weight.

enzyme

Enzymes may be included in the compositions of the invention for extensive cleaning of the fabric or for other cleaning purposes, including removal of proteinaceous, carbohydrate or triglyceride based stains, and for the prevention of fabric dye transfer and fabric restoration. Encompassed enzymes include proteases, amylases, lipases, cellulases and peroxidases, and mixtures thereof. Other types of enzymes may also be included. These can be of any suitable origin, such as plants, animals, bacteria, fungi and yeast origin. However, their selection is governed by a number of factors such as pH-activity and / or optimal stability, thermal stability, stability to active detergents, extenders and the like. In this regard, bacterial amylase and bacterial and fungal enzymes such as proteases and fungal cellulases are preferred. Enzymes useful herein can optionally be coated to be protected in aqueous formulations.

The enzyme is typically incorporated in an amount sufficient to provide less than about 5 mg active enzyme per gram of composition, more typically about 0.01 to about 3 mg active enzyme. In other words, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01% to 1%, of a commercially available enzyme preparation. Protease enzymes are generally present in such commercial preparations in an amount sufficient to provide from 0.005 to 0.1 ounce units (AU) per gram of composition.

Suitable examples of proteases include, but are not limited to, B. subtilis and rain. It is subtilisin obtained from a particular strain of B. licheniformis. Other suitable proteases are obtained in Bacillus strains, which have maximal activity in the pH range of 8-12 and are marketed under the registered trademark ESPERASE by Novo Industries A / S. The preparation of this enzyme and its analogous enzymes is disclosed in Novo UK Patent 1,243,784. Suitable proteolytic enzymes for removal of commercially available protein-based stains include the ALCALASE and SAVINASE registered trademarks of Novo Industries, A / S (Denmark), and the International Bio-Synthetics Incorporated Bio-Synthetics, Inc. (The Netherlands) under the registered trademark MAXATASE. Other proteases include protease A (see European Patent No. 130,756, published Jan. 9, 1985) and protease B (European Patent No. 87303761.8, filed April 24, 1987, and Bott et al (See European Patent 130,756, published Jan. 9, 1985, incorporated herein by reference).

A particularly preferred protease referred to as " protease D " is a carbonyl hydrolase enzyme variant having an amino acid sequence that is not found naturally, which is a variant of A. baeck, CK Ghosh, PP Greycar, US Patent No. 08 / 136,797 entitled " Protease-Containing Cleaning Compositions ", which is entitled " Bleaching Compositions Comprising Protease Enzymes ", by RR Bott and LJ Wilson, , +101, +103, +107 and +123 in Bacillus amyloliquefaciens subtilisin as disclosed in U.S. Patent No. 08 / 136,626 which is incorporated herein by reference. By substituting several amino acids for multiple amino acid residues at a position in the carbonyl hydrolase corresponding to the position of +76 along with the amino acid residue position, the precursor carbonylhydro La from zero are derived.

Amylase is commercially available, for example, as described in British Patent Specification No. 1,296,839 (Novo), α-amylase, RAPIDASE (International Bio-Cytotics Inc.) and TERMAMYL Industries).

Cellulases useful in the present invention include both bacterial or fungal cellulases. Preferably, they may have an optimum pH of from 5 to 9.5. Suitable cellulases are disclosed in U.S. Patent No. 4,435,307, issued March 6, 1984 to Barbesgoard et al., Which discloses the use of Humicola insolens and Humicola strain DSM 1800 or aero Discloses a fungal cellulase produced from Cellulase 212-producing fungi belonging to the genus Aeromonas, and a cellulase extracted from the liver pancreas of Dolabella Auricula Solander. Also disclosed in British Patent 2,075,028, British Patent 2,095,275 and German Patent 2,247,834. The registered trademark CAREZYME (Novo) is particularly useful.

Suitable lipase enzymes for detergent applications include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stultzeri ATCC 19.154 as disclosed in British Patent 1,372,034. Reference can also be made to the lipase of Japanese Patent No. 53,20487, which is publicly disclosed on February 24, 1978. This lipase is sold under the trade name Lipase P "Amano" from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, hereinafter referred to as "Amano-P". Other commercially available lipases are extracted from Chromobacter viscose, such as Chromobacter viscosum var. Lipolyticum NRRLB 3673, available from Toyo Jozo Co., Daigata, Japan. ≪ / RTI > Amino-CES, lipase; And US Biochemical Corp. of the United States and Chromobacter viscosum lipase from Disoynth Co. of the Netherlands and Lipase extracted from Pseudomonas gladioli . The registered trademark LIPOLASE enzyme, which is derived from Humicola lanuginosa and is available from Novo (see also EPO No. 341,947), is a preferred lipase for use herein.

Peroxidase enzymes may be used in admixture with oxygen sources such as percarbonates, perborates, persulfates, hydrogen peroxide, and the like. They are used for " solution bleaching " which inhibits transfer of dyes or pigments removed from the substrate during washing to other substrates in the wash liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidases, ligninases, and haloperoxidases such as chloro-and bromo-peroxidases. The peroxidase-containing detergent compositions are described, for example, in PCT International Patent Application No. WO 89/099813, published Nov. 19, 1989 by O. Kirk, assigned to Novo Industries, A / S Lt; / RTI >

A wide variety of enzyme materials and means for incorporating them in synthetic detergent compositions are also disclosed in U.S. Patent No. 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are also disclosed in U.S. Patent No. 4,101,457, issued July 18, 1978 to Place et al., And U.S. Patent No. 4,507,219, issued March 26, 1985 to Hughes. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. Patent No. 4,261,868, issued April 14, 1981 to Hora et al. Enzymes used in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are described, for example, in U.S. Patent No. 3,600,319, issued Aug. 17, 1971 to Gedge et al., And European Patent Publication No. 0 199 405, Venegas, Oct. 29, No. 86200586.5, which is hereby incorporated by reference. An enzyme stabilization system is also disclosed, for example, in U.S. Pat. No. 3,519,570.

Polymeric Pollutants Glass

Any polymeric contaminant free glass known to those skilled in the art can optionally be used in the compositions and methods of the present invention. Polymeric Contaminant Glasses are hydrophilic residues that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic residues that remain attached to the fiber until the washing and cleaning cycle is over and stick to the hydrophilic residue Lt; RTI ID = 0.0 > hydrophobic < / RTI > This allows the stains that occur after contaminated glass treatment to be more easily cleaned in subsequent washing processes.

(I) a polyoxyethylene residue having a degree of polymerization of at least 2, (ii) an oxypropylene or polyoxypropylene residue having a degree of polymerization of from 2 to 10, wherein such hydrophilic moieties are (Iii) a mixture of oxyalkylene units comprising from 1 to about 30 oxypropylene units and comprising oxyethylene, wherein the oxyalkylene units comprise from 1 to about 30 oxypropylene units and do not include any oxypropylene units unless bonded to adjacent residues at each end by an ether linkage; This mixture contains a sufficient amount of oxyethylene units such that when the contaminant glass is adhered on such a surface, the hydrophilic component has a hydrophilicity sufficiently large to increase the hydrophilicity of the conventional polyester synthetic fiber surface, Preferably at least about 25% oxyethylene units, more preferably from about 20 to about 30 oxyps At least one nonionic hydrophilic component consisting essentially of at least about 50% oxyethylene units in the case of a component having a triphenylene unit; or

(b) a polyoxyalkylene terephthalate component comprising (i) a C ₃ oxyalkylene terephthalate component wherein the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is about 2: 1 when the hydrophobic component also comprises oxyethylene terephthalate; (Ii) a C ₄ -C ₆ alkylene or oxyC ₄ -C ₆ alkylene residue or a mixture thereof, (iii) a poly (vinyl ester) residue having a degree of polymerization of at least about 2, preferably a polyvinyl Acetate, or (iv) a C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituent or mixture thereof, wherein such substituents are in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof And these cellulose derivatives are amphoteric so that they are attached to conventional polyester synthetic fiber surfaces and once attached to such conventional synthetic fiber surfaces, Hydroxy C ₁ -C enough to hold on to the lock increase fiber surface hydrophilicity ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units has a) at least one hydrophobic component comprising; or

(a) and (b).

Typically, the polyoxyethylene residue of (a) (i) has a degree of polymerization of from about 1 to about 200 (although higher levels may be used), preferably from 3 to about 150, more preferably from 6 to about 100 Lt; / RTI > Suitable oxy C ₄ -C ₆ alkylene hydrophobic moieties include, but are not limited to, MO ₃ S (CH ₂ ) n OCH ₂ CH ₂ O- (CH ₂ ) n OCH ₂ O, as disclosed in U.S. Patent No. 4,721,580 issued Jan. 26, 1988 to Gosselink. End cap of a polymeric contaminant glass, such as, but not limited to, sodium (where M is sodium and n is an integer from 4 to 6).

Polymeric contaminant glasses for use in the present invention also include cellulose ethers such as hydroxyether cellulosic polymers, copolymerized blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. Such a glass may be a commercially available one, and hydroxyethers of cellulose such as METOCEL (Dow) can be mentioned as an example. Cellulosic contaminant glasses useful herein are selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkylcellulose. See US Pat. No. 4,000,093, issued Dec. 28, 1976 to Nicol, ).

Examples of contaminating glasses characterized by poly (vinyl ester) hydrophobic moieties include graft copolymers of poly (vinyl esters) (e.g., C ₁ -C ₆ vinyl esters), preferably grafted on polyalkylene oxide (Polyvinyl acetate). European Patent Application No. 0219048 (Kud et al.), Published April 22, 1987, may be referred to. An example of this type of commercially available contaminating glass is SOKALAN based material (e.g. SOKALAN HP-22) available from BASF (Germany).

A preferred class of contaminating glasses is copolymers with random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of such polymeric contaminant glasses is from about 25000 to about 55000. See U.S. Patent No. 3,959,230, issued May 25, 1976 to Hays, and U.S. Patent No. 3,893,929, issued July 8, 1975, to Basadur.

Another preferred polymeric contaminant glass comprises 90 to 80% by weight of polyoxyethylene terephthalate units derived from polyoxyethylene glycols having an average molecular weight of 300 to 5000 and 10 to 15% by weight of ethylene terephthalate Of repeating units. Examples of such polymers are commercially available ZELCON 1526 (DuPont) and MILEASE T (Icyia). See U.S. Patent No. 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric contaminant glass is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal residue covalently attached to the backbone. Such contaminating glasses are described in detail in U.S. Patent No. 4,968,451, issued November 6, 1990 to J. J. Scheibel and E.P. Gosselink. An example of another suitable polymeric contaminant glass is disclosed in US Patent No. 4,711, 730, issued Dec. 8, 1987 to EP Gosselink, EP Gosselink, The anionic end-capped oligomeric esters described in U.S. Patent No. 4,721,580 to Gosselink and the block polyester oligomeric esters described in U.S. Patent No. 4,702,857, issued October 27, 1987 to EP Gosselink, / RTI >

Preferred contaminant glasses are also the contaminating glasses of U.S. Patent No. 4,877,896, issued October 31, 1987 to Maldonado, which describes anionic, especially sulfo mono-capped, terephthalate esters.

Still preferred contaminant glasses are oligomers having repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat unit forms the backbone of the oligomer and is preferably terminated with a modified isethionate endcap. Particularly preferred this type of contaminating glass comprises a sulfoisophthaloyl unit of about 1, a phthaloyl unit of 5, oxyethyleneoxy and oxy-1,2-propylenoxy units (ratio of about 1.7 to about 1.8) and sodium 2 - (2-hydroxyethoxy) -ethanesulfonate. ≪ / RTI > The contaminating glass also comprises from about 0.5% to about 20% (by oligomer weight) of a crystallization-reducing stabilizer, which is preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof do. See U.S. Patent No. 5,415,807, issued May 16, 1995 to Kose Links et al.

Contaminant glasses may comprise from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, and preferably from 0.2% to about 3.0%, by weight of the detergent composition, if such is useful.

Other ingredients

Detergent ingredients or adjuvants optionally included in the compositions of the present invention may include one or more of a substance that assists or enhances the cleaning performance, a substance that treats the substrate to be cleaned, or a substance that aesthetically enhances the composition. Such materials are also described in U.S. Patent No. 3,936,537 to Baskerville et al. Adjuvants that may be included in the compositions of the present invention may be dispersed in a dispersing polymer (BASF Corp. or Rohm < (R) >) in their conventional customary dosage range (generally 0 to about 20%, preferably about 0.5% to about 10% &Haas); A colorant, a solvent, a fabric softening agent, an antistatic agent, a coloring agent, a coloring inhibitor and / or a corrosion inhibitor, a dye, a filler, a polish agent, a bactericide, a hydrotrope, an enzyme stabilizer, a fragrance, a solubilizer, Other active ingredients may be included.

Dye transfer inhibitor

The compositions of the present invention may include one or more effective substances that prevent transfer of the dye from one dye face to another dye face during washing. Generally, such dye transfer inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof . If such dye transfer inhibitors are used, such dye transfer inhibitors will typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 5% 2% < / RTI > by weight.

More particularly, preferred polyamine N-oxide polymers for use herein are RA _x -P wherein P is a polymerizable unit to which an N? O group can be attached, an N? O group can form part of the polymerizable unit (O) -, -C (O) O-, -S-, -O-, -N = O-, or a polymerizable unit in which an N? O group is attached to two units, Wherein x is 0 or 1 and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or acyclic group or a mixture thereof wherein the nitrogen of the N-O group may be attached to the group And the N-O group is part of this group). Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine and derivatives thereof.

The N? O group can be represented by the following structure:

Wherein x, y and z are 0 or 1, and the nitrogen of the N → O group is attached to the group (s), wherein R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or acyclic groups or mixtures thereof, Or the N-O group is part of this group). The amine oxide unit of the polyamine N-oxide is pKa < 10, preferably pKa < 7, more preferably pKa < 6.

The polymer backbone can be used when the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. Examples of such polymers are random or block copolymers in which one monomer is an amine N-oxide and the other monomer is an N-oxide. Amine N-oxide polymers generally have a ratio of amine: amine N-oxide of 10: 1 to 1: 1000000. However, the number of amine oxide groups present in the polyamine oxide polymer depends on the copolymerization reaction or the degree of copolymerization of the N-oxides. Polyamine oxides can be obtained with almost any degree of polymerization. Typically, the average molecular weight is 500 to 1000000, more preferably 1000 to 500000, and most preferably 5000 to 100000. This preferred material class is referred to as " PVNO ". The most preferred polyamine N-oxide useful in the present detergent ancillary is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about one to four.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole (designated "PVPVI") are preferred in the present invention. Preferably, the PVPVI has an average molecular weight of 5000 to 1000000, more preferably 5000 to 20000 and most preferably 10000 to 20000 (average molecular weight is determined according to Barth et al., Chemical Analysis Vol 113, " Modern Methods of Polymer Characterization ", incorporated herein by reference). The PVPVI copolymers can be prepared by reacting N-vinylimidazole: N-vinylpyrrolidone in an amount of about 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: . Such copolymers can be linear or branched.

The composition of the present invention may also employ polyvinylpyrrolidone (" PVP ") having an average molecular weight of from about 5000 to about 400000, preferably from about 5000 to about 200000, and more preferably from 5000 to about 50000. PVP is also well known in the detergent art. See, for example, European Patent Application No. 262,897 and European Patent Application No. 256,696, which are incorporated herein by reference. The composition containing PVP may contain polyethylene glycol (" PEG ") having an average molecular weight of from about 500 to about 100,000, preferably from about 1000 to about 10000. Preferably, the ratio of PEG to PVP based on ppm dissolved in the wash solution is from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.

Foam promoter

If foam-rich is desired, a foam promoter such as a C ₁₀ -C ₁₆ alkanolamide may typically be incorporated into the composition in a 1% to 10% content. C ₁₀ -C ₁₄ monoethanol can be illustrated and diethanolamide as the foam promoter. It is also advantageous to use the foam promoter described above with a high sudsing surfactant such as amine oxides, betaines and sulphates. If necessary, a soluble magnesium salt such as MgCl ₂ , MgSO ₄ may be added in an amount of, for example, 0.1 to 2% in order to provide additional foam and improve grease removal performance.

Polish

If any brightener, fluorescent bleach or other brightener or bleach known in the art is intended for fabric treatment or washing, it may be present in the composition of the present invention at a level of from about 0.05% to about 1.2% by weight of the detergent composition herein &Lt; / RTI &gt; Commercially available polishes that may be used in the present invention include, but are not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinececene, dibenzothiophene-5,5-dioxide, azole, 5- and 6- Lt; RTI ID = 0.0 &gt; polystyrenes &lt; / RTI &gt; and these are merely exemplary and non-limiting. Examples of such brighteners are described in &quot; The Production and Application of Fluorescence Brightening Agents &quot;, M. Zahradink, Published by John Wiley &amp; Sons, New York (1982).

Specific examples of polishes useful in the present invention are described in U.S. Patent No. 4,790,856, issued December 13, 1988 to Wixon. Such brighteners include the PHORWHITE series available from Verona. Other polishes described for reference are Tinopal UNPA, Tinofal CBS and Tinofol 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD available from Hilton-Davis, Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazole; 4,4'-bis (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (styryl) bisphenyl; And aminocoumarin. Specific examples of such polishes include 4-methyl-7-diethyl-aminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naph- [l, 2-d] oxazole; And 2- (stilben-4-yl) -2H-naphtho- [l, 2-d] naphtho. See U.S. Patent No. 3,646,015, issued Feb. 29, 1972 to Hamiton. Anionic brighteners are typically preferred in the present invention.

Clone

Various detergent ingredients, which may be optionally employed in the present invention, can be further stabilized by absorbing the components into a porous hydrophobic substrate and coating the substrate with a hydrophobic coating agent. It is preferred that the detergent component is mixed with the surfactant before being absorbed into the porous substrate. In use, the detergent component can release the substrate to the aqueous wash liquor and perform the desired detergent function.

Gritty more detail these techniques, a porous hydrophobic silica (trade name for a commercially available from gussa Shipper naeteu (SIPERNAT ^R) D10] is the 3% to 5% C ₁₃ -C ₁₅ ethoxylated alcohol (EO 7) nonionic surfactant The enzyme / surfactant solution is 2.5 times the weight of the silica. The resulting powder is dispersed in the silicone oil under agitation (various silicones with a viscosity of 500 to 12500 The oil viscosity may be used.) The resulting silicone oil dispersion may be emulsified or otherwise added to the final detergent matrix. In this sense, the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, Components such as fabric conditioning agents and hydrolyzable surfactants can be protected for use in detergents including liquid laundry detergent compositions.

The compositions of the present invention may contain other fluids such as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for dissolving surfactants, and compounds containing from 2 to about 6 carbon atoms and containing from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1 , 2-propanediol) can also be used. The composition may contain from 5 to 90%, typically 10 to 50%, carrier.

Bleaching catalyst

If desired, the compositions of the present invention may additionally incorporate catalysts or promoters to further enhance bleaching or decontamination. Any suitable bleaching catalyst may be used. In a detergent composition used in a total amount of from about 1000 ppm to about 5000 ppm in water, the composition typically delivers a concentration of the catalyst component of from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to 50 ppm, to the wash liquor.

Typical bleach catalysts include transition metal complexes in which metal coordination ligands are resistant to instability and do not adhere metal oxides or hydroxides under typical alkaline washing conditions. Examples of such catalysts are described in U.S. Patent Nos. 5,246,621, 5,244,594, 5,194,416, 5,114,606 and EP 549,271A1, 549,272A1, 544,440A2 and 544,490A1 Based catalysts described in U.S. Patent No. 5,102,

Wherein the TACN is trimethyl-l, 4,7-triazacyclononane or its equivalent macrocycle, alternating metal coordination ligands and mononuclear complexes are possible, but mono-metallic and di- and multi-metallic complexes and iron Or complexes of alternating metals such as ruthenium are within the scope of the present invention. Examples of other metal bleaching catalysts are those described in U.S. Patent No. 4,430,243 and U.S. Patent No. 5,114,611. For the use of manganese with various complex ligands to improve bleachability, U.S. Patent Nos. 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084 Reported.

The transition metal may be pre-complexed or complexed in situ with a suitable donor ligand selected according to the choice of the metal, its oxidation state and the density of the ligand. Other complexes that may be included in the present invention are those described in U.S. Patent Application Serial No. 08 / 210,186, filed March 17, 1994.

Pretreatment agent

The preferred compositions of the present invention have a viscosity of at least 50 cps at 20 캜, preferably from about 50 to about 2000 cps, and most preferably from about 200 to 1500 cps, as measured by a Brookfield viscometer at 50 rpm on a spindle n ° 3. Any surfactant system or polymer thickener known in the art for increasing the viscosity of the composition can be used to obtain the desired viscosity. Thus, surfactants suitable for use in the present invention are increasing surfactants such as nonionic, anionic, cationic, zwitterionic and / or amphoteric surfactants.

The bleaching composition herein may contain up to about 95% by weight of water, based on total composition. Preferably, the composition herein may contain from about 5 wt% to about 95 wt%, more preferably from about 10 wt% to about 90 wt% water, based on the bleaching composition.

When the over-oxygen bleaching composition according to the present invention further comprises any bleaching activator, it is preferable to blend the composition as a micro emulsion or a stable emulsion.

When the composition is formulated with a microemulsion, the composition comprises a bleach activator in a water matrix, an oxygen bleach, and a hydrophilic anionic and a nonionic surfactant. Suitable anionic surfactants herein are alkyl benzene sulfonates, alkyl sulphates, alkyl alkoxylated sulphates, and mixtures thereof. Suitable nonionic surfactants for use in the microemulsions herein are hydrophilic nonionic surfactants, as defined in the following emulsions, according to the invention.

When the composition is formulated as an emulsion, the composition comprises a hydrophilic surfactant having an HLB (hydrophilicity-lipophilic balance) of at least 10 and a hydrophobic surfactant having an HLB of at least 9, wherein the bleach activator comprises And can be emulsified by a surfactant. In order to form a stable emulsion, the two different surfactants must have different HLB values, and preferably the difference in the HLB values of the two surfactants is at least 1, preferably at least 3. In other words, by properly mixing two or more surfactants with different HLB values in water, they will form emulsions, such as emulsions, which do not undergo substantially distinct delamination when left at 50 ° C for at least two weeks. The emulsion comprises from about 2 to 50 wt% (preferably from 5 to about 40 wt%, more preferably from about 8 to about 30 wt%) of a hydrophilic and hydrophobic surfactant, based on the total composition. The emulsion may comprise at least about 0.1% by weight, preferably at least about 3% by weight, more preferably at least about 5% by weight, based on the total emulsion, of at least one hydrophobic surfactant and at least about 0.1% At least about 3% by weight, more preferably at least about 5% by weight of at least one hydrophilic surfactant. Hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are suitable for use in the present invention. The hydrophobic nonionic surfactant used in the present invention has an HLB of 9 or less, preferably 9 or less, more preferably 8 or less, and the hydrophilic surfactant has 10 or more, preferably 11 or more, HLB of 12 or more. Examples of suitable nonionic surfactants for use in the present invention are alkoxylated fatty acid alcohols, preferably fatty acid alcohol ethoxylates and / or propoxylates. The various alkoxylated fatty acid alcohols are commercially available with very different HLB values. For a further discussion of the theory of HLB and the application of HLB to emulsion formation, see Encyclopedia of Emulsion Technology, Becher, P., Ed .; Marcel Dekker, Inc .: New York, 1985; Vol. 1 and 2].

For embodiments of particularly preferred emulsions comprising acetyl triethyl citrate as a bleaching activator if present, suitable nonionic surfactant systems are hydrophobic surfactants having an HLB of 6, such as, for example, Dobanol ^R 23-2 Nonionic surfactants and hydrophilic nonionic surfactants having an HLB of 15, such as, for example, Dovanol ^R 91-10. Other suitable nonionic surfactant systems include, for example, Dobanol ^R 23-6.5 (HLB of about 12) and Dobanol ^R 23 (HLB of less than 6) or Dobanol ^R 45-7 (HLB of 11.6) and Rutensol Lutensol ^R ) TO3 (HLB of 8). Dovanol ^R is a commercial nonionic surfactant commercially available from Shell Corp. Rutensol ^R is a commercial non-ionic surfactant commercially available from BASF Corp.

The peroxy bleaching agent-containing composition according to the present invention comprises an amine oxide surfactant having the structure R ¹ R ² R ³ NO wherein R ¹ , R ² , and R ³ are each C ₆ -C ₃₀ , C ₁₉ -C ₃₀ , most preferably C ₁₂ -C ₁₆ hydrocarbon chains. The presence of the amine oxide during the pretreatment process improves the cleaning performance against particle and / or greasy stains. This improvement in clean performance is considered to be independent of the matrix. If amine oxides are present to achieve these benefits, the amine oxides are present in amounts of from 0.1 to 11% by weight, preferably from 1.5 to 3% by weight of the total composition.

Manufactured products

A preferred product may include a composition suitable for use in the processes described herein in a package form that can be added directly to the contaminated fabric. Preferably the composition can be packaged in an elastic container with an application cap. An example of a suitable container is a container that can be squeezed or poured through the application cap and used directly on the poured and contaminated fabric. An example of such a container is the container described in U.S. Patent No. 4,107,067. Examples of suitable application caps are, but are not limited to, fractional nozzles, brush-type applications, roller ball applications, and flip-top caps. A container useful in the processes described herein contains from about 4 ounces to about 32 ounces, preferably from about 4 ounces to about 24 ounces of the composition of the present invention.

The following examples illustrate the compositions of the present invention and are not intended to limit the invention. In the examples all materials meet the functional limits.

Example I

The following compositions were prepared by mixing the components listed below in the following amounts (wt.% Unless otherwise noted).

Composition I II III IV V NaC ₁₀ -C ₁₈ alkyl sulfate 2 2 2 2 2 Dovanol ^R 45-7 8.6 8.6 8.6 8.6 8.6 Dovanol ^R 23-3 6.4 6.4 6.4 6.4 6.4 ATC 3.5 3.5 3.5 3.5 3.5 H ₂ O ₂ 6 6 6 6 6 BHT ² 0.05 0.05 0.05 0.05 0.05 Salicylic acid ¹ ... 1.5 ... ... ... Malonic acid ¹ ... ... 1.5 ... ... Glycine ¹ ... ... ... One ... Glutamic acid ¹ ... ... ... ... 1.5 Water and trace materials ^* Up to 100% H ₂ SO ₄ Up to pH 4 ¹ Fabric Protectant ^* Trace materials contain fragrance, dye, etc. ² -Butylated Hydroxytoluene

Composition I contains hydrogen peroxide and is free of fabric protector. Compositions II to V contain representative fabric protectants in the present invention.

The compositions in this Example I differ only in the type of fabric protectant. Thus, in order to compare the loss of tensile strength of the fabric treated with an overpotent bleaching composition containing an effective fabric protector, this formulation was used as a basic and oxygen bleaching composition with added fabric protector.

Example II

Tensile strength test method

The tensile strength loss of the fabric is measured by the following method:

A Krefeld face ribbon (size: 12.5 x 5 cm2) containing 30 ppm of copper (2+) per gram of cotton fabric was treated with 2 ml of the test composition according to Example I. The test composition was contacted with the ribbon for 24 hours. The ribbon was rinsed with water and the loss of tensile strength was measured with an INSTRON Model 4411. The degree of damage of the ribbon was evaluated by pulling the cotton ribbon until the cotton ribbon was broken. The force required to break the ribbon, i.e. the ultimate tensile strength, was measured with the Instron Model 4411 while the ribbon was wet. The smaller the force required to break the ribbon, the greater the damage to the fabric. Repeat 5 times for each test to obtain good reliability (standard deviation = 2-4 kg) for the results.

The loss of tensile strength with respect to the test composition is expressed as a percentage, which is obtained by dividing the tensile strength of the reference surface ribbon, that is, the untreated ribbon with the tensile strength of the test ribbon pretreated with the test composition.

Composition I II III IV V Tensile strength loss (%) 69 11 19 40 45 30 ppm of copper per gram of fabric, pretreatment for 24 hours

And an antioxidant bleaching agent and a fabric protective agent, an unexpected improvement in the loss of tensile strength is achieved compared to the composition (composition I), which uses the same bleaching composition but does not contain a fabric protective agent It is obvious from the result. (I. E., Copper concentration of 30 ppm per gram of cotton fabric) on the fabric surface, even during prolonged contact time (i. E., 24 hours) The loss of tensile strength was also reduced.

Example III

The following compositions were prepared by mixing the components listed below in the following amounts (wt.% Unless otherwise noted).

Composition 1 A B C D H ₂ O ₂ 6 6 6 6 ATC 3.5 3.5 3.5 3.5 NaC ₁₀ -C ₁₈ alkyl sulfate 2 2 2 2 Dovanol ^R 23-3 15 15 15 15 Glycine ¹ One ... ... ... Salicylic acid ¹ ... 1.5 ... ... Malonic acid ¹ ... ... 1.5 ... Glutamic acid ¹ ... ... ... 1.5 Water and trace materials ^* Up to 100% H ₂ SO ₄ Up to pH 4 ¹ Fabric Protector ^* Trace materials contain spices, dyes, etc.

Composition 2 A B C D H ₂ O ₂ 6 6 6 6 ATC 3.5 3.5 3.5 3.5 NaC ₁₀ -C ₁₈ alkyl sulfate 12 12 12 12 Dovanol ^R 23-3 12 12 12 12 Glycine ¹ One ... ... ... Salicylic acid ¹ ... 1.5 ... ... Malonic acid ¹ ... ... 1.5 ... Glutamic acid ¹ ... ... ... 1.5 Water and trace materials ^* Up to 100% H ₂ SO ₄ Up to pH 4 ¹ Fabric Protector ^* Trace materials contain spices, dyes, etc.

Composition 3 A B C D H ₂ O ₂ 7 7 7 7 NaC ₁₀ -C ₁₈ alkyl sulfate 2 2 2 2 Dovanol ^R 23-3 3 3 3 3 Glycine ¹ One ... ... ... Salicylic acid ¹ ... 1.5 ... ... Malonic acid ¹ ... ... 1.5 ... Glutamic acid ¹ ... ... ... 1.5 Water and trace materials ^* Up to 100% H ₂ SO ₄ Up to pH 4 ¹ Fabric Protector ^* Trace materials contain spices, dyes, etc.

The creped face ribbons were treated with compositions A through D in the same manner as described for the composition of Example I.

When pretreating the fabric with the compositions of this example (Compositions A through D), even during long contact times (i.e., 24 hours) and under high copper concentration on the fabric surface (i.e., 30 ppm copper concentration per gram of cotton fabric) The loss of tensile strength was reduced.

No change in dyeing and / or discoloration was observed when using the compositions (A to D) on a colored fabric in the same manner as above.

Claims (10)

An effective amount of fabric protector and peroxygen bleach having a migration coefficient of 0.7 or greater, Wherein the fabric protector has a stabilization constant for Cu ²⁺ with a log K of at least 3 and a concentration (C) calculated as weight percent of the liquid bleaching composition as calculated by the following equation: Equation 1 {[C] * [Stabilization constant for Cu ²⁺ ]} ≥ 2.5 The method according to claim 1, Wherein the fabric protector has a stabilization constant for copper (2+) to stabilization for calcium (2+) of at least 2: 1, preferably at least 4: 1. 3. The method according to claim 1 or 2, Wherein the fabric protector has a stabilization constant for Fe &lt; ^{3 + &} gt ;, wherein log K is greater than or equal to 6, preferably log K greater than or equal to 9. The method according to claim 1, 2, or 3, Wherein the fabric protector has a stabilization constant for Cu ²⁺ with a migration coefficient of at least 0.8, preferably at least 0.9, and a log K of at least 6, preferably at least 9. 5. The method according to any one of claims 1 to 4, Wherein the fabric protector has a stabilization constant for Fe &lt; ^{3 +} &gt; with a log K of 12 or greater and a stabilization constant for Cu &lt; ^{2 +} &gt; The method according to any one of claims 1 to 5, Wherein the fabric protector is selected from the group consisting of glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, aspartic acid, glutamic acid, malonic acid, conjugate base salts thereof, . 7. The method according to any one of claims 1 to 6, Wherein the over-oxygen bleaching agent is hydrogen peroxide or a water-soluble substance thereof and is present in an amount of from 0.5% to 20% by weight of the total composition. 8. The method according to any one of claims 1 to 7, Wherein the composition is selected from the group consisting of acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, n-octanoyl valerolactam, , Bleach activators that are preferably selected from the group consisting of 5-trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and mixtures thereof, And from 0.5% to 20% by weight of the composition. 8. A method of treating a contaminated fabric comprising applying an aqueous bleaching composition according to any one of claims 1 to 8 to a fabric and contacting the fabric with the fabric before washing the fabric, A method of pretreating an aqueous bleaching composition according to any one of the preceding claims. A product suitable for individual use in cleaning a contaminated fabric, comprising a container containing an aqueous bleaching composition according to any one of claims 1 to 8 and an applicator cap, suitable for applying the composition directly to the contaminated fabric