KR19990087531A - Laundry pretreatment method and bleaching composition - Google Patents

Abstract

The present invention relates to a method for pretreatment of a contaminated fabric with a liquid composition comprising a peroxygen bleach and a contaminant dispersant selected from the group consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers and mixtures thereof. It is about. The present invention is also formulated as an emulsion or microemulsion and comprises a contaminant dispersant selected from the group consisting of peroxygen bleach, surfactants and ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers and mixtures thereof. Also disclosed are compositions suitable for pretreatment of contaminated fabrics.

Description

Laundry pretreatment method and bleaching composition

A wide variety of cleaning compositions are described in the art that are particularly suitable for pretreating fabrics.

For example, European Patent No. 598,170 describes certain types of aqueous emulsions of nonionic surfactant systems which further comprise hydrogen peroxide or its water-soluble source and liquid bleach activator, or certain other hydrophobic components that need to be separated from said hydrogen peroxide. Cleaning compositions are disclosed.

European patent application 95203330.6 discloses a specific type of cleaning composition which is an aqueous microemulsion of a bleach activator in a matrix comprising water, hydrogen peroxide and a hydrophilic surfactant system.

However, such emulsions or microemulsions, including peroxygen bleach and bleach activators, are particularly suitable for laundry pretreatment for different kinds of fabrics, for example cotton and / or synthetic fabrics (eg polyester / polyamides). When used, they have the drawback that they do not deliver the efficacy to satisfactorily meet consumer needs for all types of stains, including grease stains, enzymatic stains, mud / clay stains as well as bleachable stains. Indeed, there is still room for further improvement in stain removal as well as in the bleaching-containing composition when the fabric is pretreated with such a bleach-containing composition.

It is therefore an object of the present invention to provide improved stain removal for a wide range of stains as well as improved bleaching capacity, especially when applied to at least a portion of the fabric under washing pretreatment conditions, ie prior to washing the fabric.

In addition, another problem associated with such emulsions and / or microemulsions, especially those containing relatively high concentrations, for example at least about 8% of surfactants, is that the main viscosity is increased, making the distribution of the emulsions / microemulsions difficult, and thus consumer perspectives. That makes it unacceptable.

Accordingly, another object of the present invention is to provide a liquid emulsion or microemulsion containing a peroxygen bleach and a surfactant, which can conveniently adjust the viscosity while maintaining a suitable physical stability.

With the present invention, using a liquid composition comprising a peroxygen bleach and a contaminant dispersant selected from the group consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers, and mixtures thereof, described below. It has been found that improved stain removal is obtained by pretreatment of contaminated fabrics. Indeed, the addition of such contaminant dispersants into a liquid composition comprising a peroxygen bleach, and optionally a bleach activator, results in grease stains, enzymes under pretreatment conditions as compared to the stain removal capability provided by the same composition without such contaminant dispersants. Provides improved stain removal for various types of stains, including sex stains, clay / mud stains, and more. It has also been surprisingly found that liquid compositions comprising both peroxygen bleach and the fouling dispersant provide improved bleaching efficacy when compared to the same composition without the fouling dispersant when the fabric is pretreated with the same. . Thus, it has been found that the addition of a single compound, ie, such a contaminant dispersant, in a peroxygen bleach-containing composition provides both improved stain removal and improved bleaching ability. Moreover, it has been found that improved stain removal for various stains is maintained even for long term storage of peroxygen bleach-containing compositions. Thus, it is speculated that oxidized forms of contaminating suspending agents that may form in the presence of peroxygen bleach under long storage times and / or elevated temperatures still provide improved stain removal for various types of stains. Thus, in a broad aspect, the present invention provides a method of applying a liquid composition comprising 0.01% to 15% by weight of peroxygen bleach, and a contaminant dispersant, in a pure form on at least a portion of a fabric, optionally the composition. And bleaching the fabric with the composition, the method comprising maintaining a contact with the fabric and washing the fabric.

Also selected from the group consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers or mixtures thereof in liquid compositions formulated as emulsions or microemulsions comprising peroxygen bleach and surfactants. The addition of the dispersant has been found to reduce the viscosity of the composition, whatever the viscosity prior to adding the contaminating dispersant. Indeed, the advantage of the compositions of the present invention formulated as emulsions or microemulsions is that they provide improved stain removal and improved bleaching capabilities while providing acceptable viscosity without the need to add viscosity modifiers. In other words, the present invention provides improved overall staining at reduced cost, i.e. at reduced cost without adding specific viscosity modifiers that increase the price of the formulation and increase the volume of the composition without contributing to the bleaching / cleaning ability of the composition. It may be formulated into emulsions or microemulsions with removal / bleaching capabilities and the desired physical properties.

Another advantage of the present invention is that a stable liquid emulsion or microemulsion is provided that is suitable for use by the consumer in the most convenient way over an extended period of time.

Another advantage of the compositions according to the invention formulated as emulsions or microemulsions is also excellent cleaning when these compositions are used as laundry detergents or laundry additives in applications other than laundry pretreatments, for example in other laundry applications. / Bleaching power.

European patent application 95870079.1 discloses a laundry composition suitable for pretreatment of a fabric comprising a polyamine and a peroxygen bleach. However, no ethoxylated amines, ethoxylated polyamines or ethoxylated amine polymers are disclosed.

US patent application Ser. No. 08 / 663,501 discloses certain components such as certain chelating agents, peroxygen bleaches, and polymeric fouling release agents such as bleach activators, sulfonated polyethoxy / propoxy end-protected ester oligomers. Exclusive pretreatment compositions are disclosed. However, no ethoxylated amines, ethoxylated polyamines or ethoxylated amine polymers are disclosed.

EP 271,312 discloses a laundry composition comprising a peroxy acid bleach and a contaminating release agent such as polymers comprising alkyl and hydroxyalkyl ethers of cellulose, ethylene terephthalate and polyethylene oxide terephthalate. However, no ethoxylated amines, ethoxylated polyamines or ethoxylated amine polymers are disclosed.

International Publication No. WO96 / 12004 discloses laundry compositions comprising lipophilic enzymes and primary and / or tertiary amines. Such compositions provide improved cleaning of grease / oil phase contamination and stains, especially when used in pretreatment laundry methods for cleaning textiles contaminated with grease stains. Exemplary compositions include ethoxylated (15-18) tetraethylenepentaamine but no bleach.

EP 112,593 discloses a detergent composition (pH = 6 to 8.5) comprising an ethoxylated mono- or diamine, ethoxylated amine polymer as clay decontamination / antideposition agent. The composition can be used for laundry pretreatment applications. Peroxygen bleach is not disclosed at all.

Summary of the Invention

The present invention provides 0.01 to 15% by weight of peroxygen bleach of the total composition and (1) an ethoxylated monoamine of formula (1), (2) an ethoxylated diamine of formula (2), (3) or (4) , In a pure form, a liquid composition comprising a contaminant dispersant selected from the group consisting of (3) an ethoxylated polyamine of formula (5), (4) an ethoxylated amine polymer of formula (6), and (5) mixtures thereof A method of bleaching said fabric with said composition comprising applying onto at least a portion of said fabric and then washing said fabric:

(XL) -N- (R ² ) ₂

(XL-) ₂ -NR ¹ -N- (R ² ) ₂

In the above formulas,

A ¹ is

ego;

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl;

R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C ₂ -C ₃ oxy having 2 to 20 oxyalkylene units which do not form an ON bond Alkylene residues;

R ² is each C ₁ -C ₄ alkyl or hydroxyalkyl;

The residues -LX, or two R ² together form a residue-(CH ₂ ) _r -A ^2- (CH ₂ ) _s- ;

A ² is -O- or -CH _2- ;

r is 1 or 2;

s is 1 or 2;

r + s is 3 or 4;

X is a nonionic group, an anionic group or a mixture thereof;

R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having a p-substituted moiety;

R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, or C ₂ -C ₃ with 2 to 20 oxyalkylene units which do not form OO or ON bonds; Oxyalkylene moiety;

L is a hydrophilic chain containing a polyoxyalkylene moiety-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]-;

R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene;

m and n are numbers such that the residues-(CH ₂ CH ₂ O) _n -occupy at least 50% by weight of the polyoxyalkylene residues; For said monoamine, m is 0-4 and n is 12 or more; For the diamines, m is from 0 to 3, n is R ¹ is C ₂ -C ₃ alkylene, hydroxy alkylene or alkenylene which has 6 or more and R ¹ is C ₂ -C ₃ alkylene, hydroxy when If not oxyalkylene or alkenylene it is 3 or more; For the polyamine and amine polymer, m is 0 to 10 and n is at least 3;

p is 3 to 8;

q is 1 or 0;

t is 1 or 0, provided that t is 1 when q is 1;

w is 1 or 0;

x + y + z is at least 2;

y + z is two or more.

The present invention provides a pretreatment of a fabric comprising peroxygen bleach, a surfactant and a contaminant dispersant selected from the group consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers or mixtures thereof as defined above. And liquid compositions formulated into emulsions or microemulsions.

The present invention relates to bleaching compositions and methods of pretreatment of fabrics which are particularly suitable for use as a pretreatment agent.

Laundry pretreatment method

In a broad embodiment, the present invention is directed to a method of pretreating a fabric with a liquid composition comprising a contaminant dispersant as defined herein and from 0.01% to 15% by weight of peroxygen bleach.

The term " pretreatment of fabric " refers to the process of bleaching a fabric according to the invention, as described below, applying the liquid composition of the invention to at least a portion of the contaminated fabric in pure form and optionally washing the contaminated fabric. Prior to doing so typically means to remain on the fabric for 1 minute to several hours.

Indeed, the present invention prior to washing contaminated fabric as compared to the stain removal capabilities provided when using the same composition without the contaminant dispersant by adding the contaminant dispersant in a liquid composition comprising peroxygen bleach as described above. It is based on the finding that improved stain removal is obtained when the contaminated fabric is pretreated with the composition.

The term "stain removal performance" refers herein to stain removal for a variety of stains / contaminations such as grease / oil stains, and / or enzymatic stains and / or mud / clay stains, as well as bleachable stains. do.

The term " greasy / oily stain " is used herein to refer to grease characteristics that can be found on fabrics such as dirty motor oils, mineral oils, make-ups, lipsticks, vegetable oils, spaghetti sauces, mayonnaise and the like. Means certain contaminations and stains.

Examples of bleachable stains include tea, coffee and wine. Examples of enzymatic stains include grass, chocolate and blood.

The stain removal ability of certain compositions on contaminated fabrics under pretreatment conditions can be assessed by the following test methods. The composition according to the invention is first applied to a contaminated portion of the fabric and left to react for about 1 to about 10 minutes, typically 5 minutes, and then the pretreated fabric is used to bleach the fabric at 30 to 70 ° C. The washing is carried out according to the usual washing conditions using a conventional washing composition for a sufficient time. For example, representative soiled fabrics used in such stain removal test methods, such as clay, chocolate, spaghetti sauce, on two different substrates / fabrics, for example cotton (CW120) and polycotton (PCW28), Dirty motor oil, make-up, tea, coffee, and blood-contaminated fabrics can be purchased from the EMC (Empirical Manufacturing Company) of Cincinnati, Ohio.

The stain removal ability can then be evaluated by side-by-side comparison of the contaminated fabric pretreated with the composition according to the invention and a control, for example a contaminated fabric pretreated with the same composition without the contaminating dispersant according to the invention. The visual grade can be used to determine the difference in panel score units (psu) in the range 0-4.

Accordingly, the present invention applies a liquid composition comprising 0.01% to 15% by weight of peroxygen bleach and a contaminant dispersant as defined herein, in at least a portion of the fabric, in a pure form, wherein the composition is dried. And bleaching the fabric with the composition, the method comprising maintaining the composition in contact with the fabric so as not to leave on the fabric and then washing the fabric.

The composition can typically remain in contact with the fabric for 1 minute to several hours, preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes, most preferably 2 minutes to 10 minutes. Optionally, if the fabric is contaminated with encrusted stains / contamination that are relatively difficult to remove, for example, using a sponge or brush or facing the fabric in two pieces, the composition is strongly and weakly rubbed / rubbed or brushed can do.

The term "washing" is to be understood herein as simply washing the fabric with water or washing the fabric with a conventional composition comprising a washing machine or simply one or more surfactants by hand.

The term "neat form" means the pretreatment of a fabric by applying it directly onto the fabric without special dilution of the liquid composition, for example by applying the liquid composition according to the invention as described herein. do.

According to the method of pretreatment of the contaminated fabric of the present invention, the liquid composition used in the method should preferably be kept dry on the fabric. Indeed, moisture evaporation has been found to increase the concentration of free radicals on the surface of the fabric and consequently increase the rate of the chain reaction. It is also presumed that the auto-oxidation reaction occurs as the moisture evaporates when the liquid composition is kept dry on the fabric. The auto-oxidation reaction contributes to the production of peroxy-radicals which can cause collar damage and / or fabric damage. Therefore, in the fabric bleaching method according to the present invention, the liquid bleaching composition used according to the present invention is dried on the fabric so that it does not deviate, thereby making the pretreatment operation using the liquid bleaching composition more stable.

The composition used according to the invention comprises as an essential element peroxygen bleach or mixtures thereof.

Peroxygen bleach used in the present invention is a specific peroxygen bleach that is well known to those skilled in the art. Such peroxygen bleaches include hydrogen peroxide or a water soluble source thereof, or mixtures thereof. Indeed, the presence of peroxygen bleach contributes to the excellent cleaning and bleaching benefits of the compositions used according to the invention. As used herein, the term "hydrogen peroxide source" refers to a particular compound that produces perhydroxyl ions when the compound is in contact with water.

Examples of water-soluble sources of hydrogen peroxide suitable for use in the present invention include persulfates such as percarbonates, persilicates, monopersulfates, perborates, peroxy acids such as diperoxydodecanedioic acid (DPDA), magnesium phthalate, perlaurate Acids, perbenzoic acids and alkylperbenzoic acids, hydroperoxides, diacyl peroxides and mixtures thereof. Preferred peroxygen bleaches for use in the present invention are hydrogen peroxide, hydroperoxide and / or aliphatic diacyl peroxide.

Preferred hydroperoxides for use in the present invention include tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, Tert-amyl hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide. These hydroperoxides have the advantage of being particularly stable in fabrics and colors while providing excellent bleaching capabilities.

Preferred aliphatic diacyl peroxides for use in the present invention are dilauryl peroxide, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof. These diacyl peroxides offer the advantage of being particularly stable in fabrics and colors while providing excellent bleaching capabilities.

The compositions used according to the invention comprise 0.01 to 15% by weight, preferably 0.1 to 12% by weight, more preferably 0.5 to 10% by weight, most preferably 2 to 8% by weight, based on the total weight of such compositions Peroxygen bleach or mixtures thereof.

The composition used according to the invention comprises as essential elements a contaminant dispersant selected from the group consisting of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers and mixtures thereof as defined above. Indeed, the presence of such contaminant dispersants contributes to the excellent cleaning and bleaching benefits of the compositions used according to the invention.

In the above-mentioned formula of the contaminant dispersant used in the present invention, R ¹ is , Fantasy , Or most preferably linear Can be. In the case of ethoxylated diamines and amine polymers R ¹ is preferably C ₂ -C ₆ alkylene. In the case of ethoxylated diamines, the minimum degree of ethoxylation required for suitable decontamination / antideposition properties is reduced to C ₂ -C ₃ alkylene (ethylene, propylene) to hexamethylene. However, for ethoxylated amine polymers, in particular high molecular weight ethoxylated polyalkyleneamines and polyalkyleneimines, R ¹ is preferably C ₂ -C ₃ alkylene (ethylene, propylene), with ethylene being most preferred. Each R ² is preferably residue-LX.

In the above formula, the hydrophilic chain L generally consists of the polyoxyalkylene moiety-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]-. The residues-(R ⁵ O) _m -and-(CH ₂ CH ₂ O) _n -of the polyoxyalkylene moiety are mixed together or preferably-(R ⁵ O) _m -and-(CH ₂ CH ₂ O) _n -may form a block of residues. R ⁵ is preferably C ₃ H ₆ (propylene). In the case of ethoxylated polyamines and amine polymers, m is preferably from 0 to 5. For all ethoxylated amines of the invention, m is most preferably 0, ie the polyoxyalkylene moiety consists entirely of the residue-(CH ₂ CH ₂ O) _n- . The residue-(CH ₂ CH ₂ O) _n -preferably accounts for at least 85% by weight of the polyoxyalkylene moiety, most preferably 100% by weight.

In the above formula, X may be a miscible nonionic group, anionic group or a mixture thereof. Examples of suitable nonionic groups include C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups, preferably acetate or methyl ethers; Hydrogen (H); Or mixtures thereof. Particularly preferred nonionic group is H. With regard to anionic groups, PO ₃ ^-2 and SO ₃ ^- are suitable. Particularly preferred anionic groups are SO ₃ ⁻ . It has been found that the percentage of anionic groups to nonionic groups may be important for the decontamination / antideposition properties provided by the ethoxylated amines. Mixtures of 0-30% anionic groups and 70-100% nonionic groups provide the desired properties. Mixtures of 5 to 10% anionic groups and 90 to 95% nonionic groups provide the most desirable properties. Generally, a mixture of 0-80% anionic groups and 20-100% nonionic groups provides suitable decontamination / antideposition properties.

Preferred ethoxylated mono- and diamines have the formula:

Where

X and n are as defined above;

a is 0 or 1;

b is 0-4.

For preferred ethoxylated monoamines (a = 0), n is at least 15, typically in the range of 15 to 35. For preferred ethoxylated diamines (a = 1), n is at least 12, typically in the range of 12 to 42.

A process for preparing ethoxylated amines is disclosed in European Patent No. 112,593.

In the above formula for ethoxylated polyamines, R ³ (linear, branched or cyclic) is preferably a substituted C ₃ -C ₆ alkyl, hydroxyalkyl or aryl group; A ¹ is preferred

Makes ego; n is preferably at least 12, typically 12 to 42; p is preferably 3 to 6. When R ³ is a substituted aryl or alkaryl group, q is preferably 1 and R ⁴ is preferably C ₂ -C ₃ alkylene. When R ³ is an alkyl, hydroxy alkyl or alkenyl group and q is 0, R ¹ is preferably a C ₂ -C ₃ oxyalkylene moiety; When q is 1, R ⁴ is preferably C ₂ -C ₃ alkylene.

Such ethoxylated polyamines can be derived from polyamino amides such as:

Such polyamines may also be derived from polyaminopropylene oxide derivatives such as

Where

c is a number of 2-20, respectively.

Preferred ethoxylated amine polymers are ethoxylated C ₂ -C ₃ polyalkyleneamines and polyalkyleneimines. Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are ethoxylated polyethyleneamines (PEA's) and polyethyleneimines (PEI's). Such preferred compounds include units having the formula:

Where

X, w, x, y, z and n are as defined above.

Prior to ethoxylation, the PEAs used to prepare the compounds of the present invention have the formula:

Wherein x + y + z is 2 to 9, y + z is 2 to 9 and w is 0 or 1 (molecular weight 100 to 400).

Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For preferred PEAs, y + z is 3 to 7 (molecular weight 140 to 310), most preferably 3 to 4 (molecular weight 140 to 200). Such PEA's can be obtained by reacting ammonia and ethylene dichloride followed by fractional distillation. Typical PEA's obtained are triethylenetetraamine (TETA) and tetraethylenepentaamine (TEPA). In the case of amines above pentaamine, ie hexaamines, heptaamines, octaamines and possibly nonaamines, the totally derived mixture does not appear to be separated by distillation, and other substances such as cyclic amines, in particular piperazine, It may include. There may also be cyclic amines having side chains in which nitrogen atoms are present. See US Pat. No. 2,792,372, issued to Dickinson on May 14, 1957, which describes a process for the manufacture of PEAs.

The minimum degree of ethoxylation required for the desired decontamination / antideposition ability may depend on the number of units in the PEA. When y + z is 2 or 3, n is preferably about 6 or more. When y + z is 4 to 9, a suitable advantage is achieved when n is 3 or more. For most preferred ethoxylated PEAs, n is at least 12, with a typical range of 12 to 42.

The PEIs used to prepare the compounds of the present invention have a molecular weight of at least 440 prior to ethoxylation, which represents at least 10 units. Preferred PEIs used to prepare such compounds have a molecular weight of 600 to 1800. The polymer backbone of such PEIs can be represented by the formula:

H ₂ N-[CH ₂ CH ₂ N] _x- [CH ₂ CH ₂ NH] _y- [CH ₂ CH ₂ NH ₂ ] _z

Wherein the sum of x, y, and z represents a sufficient number to obtain a polymer having the molecular weight defined above.

Linear polymer backbones are possible, but side chains may also appear. The relative proportions of primary, secondary and tertiary amines present in the polymer can vary depending on the method of preparation. The degree of dispersion of the amine groups are typically a _{30% -CH 2 CH 2 -NH 2} , -CH 2 CH 2 -NH is 40%, and -CH ₂ CH ₂ -N <30%.

Each hydrogen atom attached to each nitrogen atom of PEI represents an active site for subsequent ethoxylation. Such PEIs can be prepared by polymerizing ethyleneimine in the presence of a catalyst such as, for example, carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid or acetic acid. Specific methods for making PEIs are disclosed in the following documents: U.S. Patent No. 2,182,306, issued to Ulrich et al. On December 5, 1939, to Maile et al. On May 8, 1962. US Patent No. 3,033,746, US Patent No. 2,208,095 to Esselmann et al. On July 16, 1940, US Patent No. 2,806,839 to Crowther et al. On September 17, 1957. And US Patent No. 2,553,696 to Wilson et al. On May 21, 1951.

As defined in the above formula, n is at least 3 for ethoxylated PEIs. However, it should be noted that as the molecular weight of PEI increases, in particular, well above 1800, the minimum degree of ethoxylation required for proper decontamination / antideposition is increased. In addition, as the molecular weight of PEI increases, the degree of ethoxylation for the preferred compound also increases. For PEIs having a molecular weight of 600 or more, n is preferably in the range of 12 or more, typically 12 to 42. For PEIs having a molecular weight of at least 1800, n is preferably in the range of at least 24, typically in the range from 24 to 42.

Typically, the compositions used according to the invention comprise from 0.01 to 20% by weight, preferably from 0.2 to 4% by weight and most preferably from 0.5 to 2% by weight of oil dispersants or mixtures thereof, based on the total weight of the composition. do.

The liquid composition used according to the method of the invention is preferably an aqueous composition. The composition used in the process of the present invention has a pH of 0-6, preferably 1-5, more preferably 2-5, most preferably 3-5. Acidic compositions are preferred herein for reasons of stability.

The compositions used according to the invention are prepared with bleach activators, surfactants, fragrances, brighteners, chelating agents, radical scavengers, stabilizers, fouling suspending agents, dye transfer agents, solvents, dyes, other amines or mixtures thereof. And may contain any of the same ingredients. Preferred optional components are described in more detail below.

Composition

The present invention is also formulated as an emulsion or microemulsion, comprising a contaminant dispersant selected from the group consisting of peroxygen bleach, ethoxylated monoamine, ethoxylated diamine, ethoxylated polyamine, ethoxylated amine polymer, and mixtures thereof, and a surfactant. And a liquid composition suitable for pretreating the fabric.

By adding such contaminant dispersants into liquid compositions comprising peroxygen bleach, surfactants and formulated as emulsions or microemulsions, not only improved bleaching ability but the desired viscosity are obtained, as well as grease stains, enzymatic properties, especially under pretreatment conditions. Improved stain removal is achieved for various stains, including stains, clay / mud stains.

According to the present invention, the contaminant dispersant according to the present invention is formulated into an emulsion or a microemulsion while maintaining a suitable viscosity whatever the viscosity before adding the contaminant dispersant in the composition comprising a peroxygen bleach and a surfactant. It has been found that it is easily processed in the composition, that is, the viscosity of the composition decreases.

Certain surfactants or mixtures thereof, such as anionic, nonionic, cationic, amphoteric, zwitterionic surfactants, or mixtures thereof, which are well known to those skilled in the art, may range from 0.01 to 50% by weight, based on the total weight of the composition. It is suitable for use in the compositions of the present invention formulated as emulsions or fine emulsions, preferably at a level of 1 to 30% by weight, more preferably 2 to 20% by weight. Preferably, a surfactant system comprising at least one hydrophilic surfactant and at least one hydrophobic surfactant is used in the composition according to the invention. In order to form a stable emulsion or microemulsion, the two surfactants preferably have different HLB values (hydrophilic lipophilic equilibrium), and the difference in HLB values of the two surfactants is typically at least one, preferably Is 2 or more, most preferably 3 or more.

The term "hydrophobic surfactant" in the present invention means a surfactant or mixtures thereof having an HLB value of 10 or less, preferably less than 10, more preferably less than 9. Indeed, the hydrophobic surfactants used in the present invention have excellent grease cutting properties, ie the hydrophobic surfactants have a solvent effect that contributes to the removal of hydrophobic contamination.

The term "hydrophilic surfactant" means herein a surfactant or mixtures thereof having an HLB value of at least 10, preferably at least 10.5, more preferably at least 11.

Typically, the compositions according to the invention formulated as emulsions or microemulsions comprise from 1 to 50% by weight, more preferably from 5 to 40% by weight and most preferably from 8 to 30% by weight, based on the total weight of the composition. Hydrophilic and hydrophobic surfactants. Preferred compositions according to the invention comprise at least 0.01% by weight, preferably at least 2% by weight, more preferably at least 4% by weight of hydrophobic surfactants or mixtures thereof and at least 0.01% by weight, preferably based on the total weight of the composition At least 2% by weight, more preferably at least 4% by weight, of hydrophobic surfactants or mixtures thereof.

Thus, particularly preferred surfactants used in the compositions according to the invention are nonionic surfactants. Indeed, suitable nonionic surfactants for use in the present invention are, for example, alkoxylated fatty alcohols, with fatty alcohol ethoxylates and / or propoxylates being preferred. Indeed, a wide variety of such alkoxylated fatty alcohols with very different HLB values (hydrophilic / lipophilic equilibrium) are commercially available. The HLB value of such alkoxylated nonionic surfactants essentially depends on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have high alkoxylation and short chain fatty alcohols, while hydrophobic surfactants tend to have low alkoxylation and long chain fatty alcohols. Many surfactants, including non-ionic surfactants, are available with a surfactant catalog where their individual HLB values are recorded.

Preferred chemistry methods for preparing nonionic surfactants for use in the present invention include condensation of the corresponding alcohols and alkylene oxides in the desired proportions. Such methods are well known to those skilled in the art and have been described extensively in the art. Alternatively, a wide variety of alkoxylated alcohols suitable for use herein are commercially available from various suppliers.

Preferred hydrophobic nonionic surfactants for use in the compositions according to the invention have an HLB value of 10 or less and have the formula RO- (C₂H₄O)_n(C₃H₆O)_mAs a surfactant having H, wherein R is C₆To C₂₂Alkyl chain or C₆To C₂₈It is an alkyl benzene chain, n + m is 0.5-5, n is 0-5, m is 0-5, Preferably n + m is 0.5-4.5, n and m are 0-4.5. Preferred R chains for use in the present invention are C₈To C₂₂Alkyl chains. Accordingly, suitable hydrophobic nonionic surfactants for use in the present invention are dobanol®. 91-2.5 (HLB = 8.1; R is C₉And C₁₁A mixture of alkyl chains, n is 2.5 and m is 0), or Lutensol® TO3 (HLB = 8; R is C₁₃And C₁₅A mixture of alkyl chains, n is 3, m is 0, or tergitol® 25L3 (HLB = 7.7; R is C₁₃To C₁₅In the range of the alkyl chain length, n is 3 and m is 0), or dobanol 23-3 (HLB = 8.1; R is C₁₂And C₁₃A mixture of alkyl chains, n is 3, m is 0, or dobanol 23-2 (HLB = 6.2; R is C₁₂And C₁₃Alkyl chains, n is 2, m is 0), or mixtures thereof. Preferred in the present invention is dobanol 23-3, dobanol 23-2, lutensol TO3 or mixtures thereof. Such dobanol Surfactants are commercially available from SHELL. Lutensol Surfactants are commercially available from BASF, Tergitol Surfactants are commercially available from UNION CARBIDE. Other hydrophobic nonionic surfactants suitable for use in the present invention are unalkoxy surfactants, an example of which is dobanol 23 (HLB <3).

Preferred hydrophilic nonionic surfactants for use in the compositions according to the invention have an HLB value of at least 10 and have the formula RO- (C₂H₄O)_n(C₃H₆O)_mAs a surfactant having H, wherein R is C₆To C₂₂Alkyl chain or C₆To C₂₈It is an alkyl benzene chain, n + m is 5-11, n is 0-11, m is 0-11, Preferably n + m is 6-10, n and m are 0-10. Throughout this specification, n and m refer to the average of degrees of ethoxylation / propoxylation. Preferred R chains for use in the present invention are C₈To C₂₂Alkyl chains. Thus, suitable hydrophilic nonionic surfactants for use in the present invention are dobanol 23-6.5 (HLB = 11.9; R is C₁₂And C₁₃A mixture of alkyl chains, n is 6.5 and m is 0), or dobanol 25-7 (HLB = 12; R is C₁₂To C₁₅A mixture of alkyl chains, n is 7 and m is 0), or dobanol 45-7 (HLB = 11.6; R is C₁₄And C₁₅A mixture of alkyl chains, n is 7 and m is 0), or dobanol 91-5 (HLB = 11.6; R is C₉To C₁₁A mixture of alkyl chains, n is 5 and m is 0), or dobanol 91-6 (HLB = 12.5; R is C₉To C₁₁A mixture of alkyl chains, n is 6 and m is 0), or dobanol 91-8 (HLB = 13.7; R is C₉To C₁₁A mixture of alkyl chains, n is 8 and m is 0), or dobanol 91-10 (HLB = 14.2; R is C₉To C₁₁Alkyl chains, n is 10, m is 0), or mixtures thereof. Preferred in the present invention is dobanol 91-10, Dobanol 45-7, dobanol 23-6.5 or mixtures thereof. Such dobanol Surfactants are commercially available from SHELL.

Apart from the hydrophilic nonionic surfactants, other hydrophilic surfactants such as polyhydroxy fatty acid amide surfactants or mixtures thereof may also be used in the compositions of the present invention:

R ² -C (O) -N (R ¹ ) -Z

Wherein R ¹ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, and R ² is C ₅ -C ₃₁ hydrocarbyl Z is a polyhydroxyhydrocarbyl or alkoxylated derivative thereof having a linear hydrocarbyl chain having three or more hydroxyls directly linked to the chain.

Preferably, R ¹ is C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably methyl and R ² is straight C ₇ -C ₁₉ alkyl or alkenyl, preferably straight C ₉ -C ₁₈ alkyl or alkenyl, more preferably straight C ₁₁ -C ₁₈ alkyl or alkenyl, most preferably straight C ₁₁ -C ₁₄ alkyl or alkenyl, or mixtures thereof. Z will preferably be derived from reducing sugars in a reductive amination reaction, more preferably Z is glycidyl. Examples of suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As the raw material, not only the individual sugars mentioned above but also high content dextrose corn syrup, high content fructose corn syrup and high content maltose corn syrup can be used. From this corn syrup a mixture of sugar components for Z can be obtained. It should be understood that other suitable raw materials are not excluded. Z is preferably -CH _2- (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH)-(CHOH) _n-1 -CH ₂ OH, CH _2- (CHOH) _2- (CHOR ') ( CHOH) -CH ₂ OH (wherein n is each an integer of 3 to 5 and R 'is H or a cyclic or aliphatic monosaccharide) and their alkoxylated derivatives will be selected from the group consisting of. Most preferred are glycidyl, in which n is 4, in particular -CH _2- (CHOH) ₄ -CH ₂ OH.

In the formula R ² -C (O) —N (R ¹ ) —Z, R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2 -Hydroxy ethyl, or N-2-hydroxy propyl. R ² -C (O) -N <may be, for example, cokeamide, stearamide, oleamide, lauamide, myristamide, capricamide, palmitamide, tallowamide and the like. Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymaltyl, 1-deoxylactyl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotrio Tityl and the like.

Polyhydroxy fatty acid amide surfactants suitable for use in the present invention may be those sold under the trade name HOE® by Hoechst.

Methods of making polyhydroxy fatty acid amide surfactants are known in the art. Generally, such polyhydroxy fatty acid amide surfactants react alkyl amines with reducing sugars under reducing amination reaction conditions to form the corresponding N-alkyl polyhydroxyamines, followed by the N- in the condensation / amidation reaction step. Alkyl polyhydroxyamines can be prepared by reacting with fatty aliphatic esters or triglycerides to form N-alkyl, N-polyhydroxy fatty acid amide products. Methods for preparing compositions containing polyhydroxy fatty acid amides are described, for example, in British Patent Specification No. 809,060, issued February 18, 1959, to Thomas Hedley & Co., Ltd., all incorporated herein by reference. ), Dated December 20, 1960. egg. U.S. Patent No. 2,965,576 to E. R. Wilson, Anthony M. on March 8, 1955. U. S. Patent No. 2,703, 798 to Anthony M. Schwartz, U. S. Patent No. 1,985, 424 to Piggott, issued December 25, 1934, and WO 92/06070.

Other hydrophilic surfactants suitable for use in the compositions of the present invention are, for example, anionic surfactants and mixtures thereof.

Examples of suitable anionic surfactants for use in the compositions of the present invention are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably C ₁₀ -C Alkyl or hydroxyalkyl having ₂₀ alkyl components, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation such as an alkali metal cation (eg sodium, potassium, lithium) ) Or ammonium or substituted ammonium (eg, methyl-, dimethyl-, and trimethyl ammonium cations, and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations and ethylamine, diethylamine, triethylamine And quaternary ammonium cations derived from alkylamines such as mixtures thereof. Typically, alkyl chains of C ₁₂ -C ₁₆ are preferred for low washing temperatures (eg, below about 50 ° C.) and C ₁₆ -C for higher washing temperatures (eg, above about 50 ° C.). Preference is given to alkyl chains of ₁₈ .

Other anionic surfactants suitable for use in the present invention are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, wherein R is an alkyl or hydroxyalkyl group having a C ₁₀ -C ₂₄ alkyl component, Preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is at least 0, typically about 0.5 To between about 6 and more preferably between about 0.5 to about 3, M is H or a cation such as a metal cation (eg sodium, potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted Ammonium cation. In addition to alkyl ethoxylated sulfates, alkyl propoxylated sulfates can also be considered in the present invention. Specific examples of substituted ammonium cations derive from methyl-, dimethyl-, trimethyl-ammonium, and alkanolamines such as tetramethylammonium, dimethyl piperidinium and ethylamine, diethylamine, triethylamine and mixtures thereof Quaternary ammonium cations such as cations. Exemplary surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E (1.0) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate (C _12- C ₁₈ E (2.25) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate (C ₁₂ -C ₁₈ E (3.0) M) and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₈ E (4.0) M), where M is conveniently selected from sodium and potassium.

Other anionic surfactants useful for cleaning purposes may also be used. Examples of such surfactants include salts of soaps (eg, substituted ammonium salts such as sodium, potassium, ammonium, and mono-, di- and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, for example prepared by sulfonation of pyrolysis products of alkaline earth metal citrate as described in British Patent No. 1,082,179 Sulfonated polycarboxylic acids, C ₈ -C ₂₄ alkylpolyglycol ether sulfate (containing up to 10 ethylene oxide residues); Alkyl ester sulfonates such as C ₁₄ -C ₁₆ methyl ester sulfonates; Acetyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate such as acyl isethionate, N-acyl taurate, alkyl succinate and sulfosuccinate , Monoesters of sulfosuccinates (particularly saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (particularly saturated and unsaturated C ₆ -C ₁₄ diesters), sulfates of alkylpolyglucosides Sulfates of alkylpolysaccharides (nonionic unsulfated compounds are described below), branched primary alkyl sulfates, formula RO (CH ₂ CH ₂ O) _k CH ₂ COO-M ⁺ , where R is Alkyl polyethoxy carboxylates such as C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10, M is a soluble salt-forming cation). Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from deoiling. Further examples are given in "Surface Active Agents and Detergents", Vol. I and II by Schwartz, Perry and Berch. Various such surfactants are generally disclosed in US Pat. No. 3,929,678, issued December 30, 1975 to Laughlin, et al. At Column 23, line 58 through Column 29, line 23.

Other anionic surfactants suitable for use in the present invention are acyl sacosinates or mixtures thereof, for example in acid and / or salt form, preferably long chain acyl sacosinates having the formula:

Wherein M is hydrogen or a cationic moiety and R is an alkyl group having 11 to 15, preferably 11 to 13 carbon atoms.

Preferred M are hydrogen and alkali metal salts, in particular sodium and potassium salts. The acyl sacosinates are derived from natural fatty acids and the amino acid sacosine (N-methyl glycine). They are suitable for use as aqueous solutions of their salts or as powders in acid form. The acyl sacosinates, derivatives of natural fatty acids, can be rapidly and completely biodegradable and have good skin compatibility.

Thus, particularly preferred long chain acyl sacosinates for use in the present invention are C ₁₂ acyl sacosinates (ie acyl sacosinates of the above formula where M is hydrogen and R is an alkyl group having 11 carbon atoms) and C ₁₄ Acyl sacosinates (ie acyl sacosinates of the above formula wherein M is hydrogen and R is an alkyl group having 13 carbon atoms). For example, C ₁₂ acyl sacosinate is commercially available as Hamposyl L-30 (R) from Hampshire. For example, C ₁₄ acyl sacosinate is commercially available from Hampshire as Hamposil M-30®.

It has been observed that even more improved stain removal is achieved using surfactant systems further comprising polyhydroxy fatty acid surfactants and / or alkyl ethoxylated sulfates as well as hydrophilic nonionic surfactants and hydrophobic nonionic surfactants.

The bleaching composition of the present invention is according to the formula R1R2R3NO, wherein R1, R2 and R3 are each independently C ₁ -C _30, preferably C ₁ -C ₂₀ , most preferably C ₁ -C ₁₆ hydrocarbon chains It may further comprise an amine oxide surfactant.

In an embodiment of the present invention formulated as an emulsion, the composition of the present invention is aqueous. In the centrifugation test, the emulsion was observed to show no phase separation after 15 minutes at 6000 rpm. In microscopic examination, the emulsion appeared as droplet dispersion in the matrix.

In embodiments of the present invention formulated with microemulsions, the compositions of the present invention are visually transparent in the absence of opacifiers and dyes. In the centrifugation test, the emulsion was observed to show no phase separation after 15 minutes at 6000 rpm. In microscopic examination, the emulsion appeared as droplet dispersion in the matrix. The inventors have found that the particles typically have a particle diameter of 3 microns or less, preferably less than 2 microns. In a preferred embodiment of the emulsion of the invention wherein the emulsion further comprises a non-water soluble component for emulsifying, such as the bleach activator described below, the emulsification system satisfies Equation 1:

Wherein the sum of weight% A and weight% B is 100%, HLB (X) refers to the HLB of the component to be emulsified if there are several components to emulsify and X is the component of each component to be emulsified (the Weight average based on%), where HLB (A) refers to the HLB of a hydrophilic surfactant or mixture thereof, and HLB (B) refers to the HLB of a hydrophobic surfactant or mixture thereof.

In a particularly preferred embodiment of the emulsion of the present invention in which the emulsion may further comprise a bleach activator such as acetyl triethyl citrate, suitable surfactant systems include hydrophobic nonionic surfactants having an HLB value of 6 such as dobanol 23-2 and Hydrophilic nonionic surfactants having an HLB value of 15 such as dobanol 91-10. Other suitable nonionic surfactant systems include, for example, dobanol 23-6.5 (HLB = about 12) and dobanol 23 (HLB = less than 6) or dobanol 45-7 (HLB = 11.6) and dobanol 23-3 ( HLB = 8.1).

Bleaching compositions of the invention formulated in the form of emulsions or microemulsions are chemically stable. The term "chemically stable" means that the composition of the present invention comprising peroxygen bleach does not lose more than 10% of the effective oxygen within two weeks at 50 ° C. The concentration of active oxygen can be measured by chemical titration methods known in the art such as iodine titration, permanganic acid titration and cerium titration. Criteria for selecting such methods and appropriate methods are described, for example, in "Hydrogen Peroxide", W. C. Schumb, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970]. Alternatively, the stability of the composition may be assessed by a bulging test method.

Thus, the bleaching composition of the present invention can be packaged in any deformable container / bottle without affecting the stability of the container / bottle containing the composition for a long time.

Liquid compositions of the invention formulated as emulsions or microemulsions are typically aqueous and have an acidic pH range of 6 or less, preferably 1 to 5, more preferably 2 to 5, most preferably 3 to 5 Formulated as 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 acid or an inorganic acid.

Random ingredient

The compositions of the present invention may further comprise optional ingredients such as bleach activators, stabilizers, chelating agents, radical scavengers, extenders, fouling suspending agents, dye transfer agents, solvents, brighteners, fragrances, or dyes or mixtures thereof. Can be.

As an optional but highly preferred component, the compositions of the present invention comprise a bleach activator or mixtures thereof. The term "bleach activator" refers to a compound that reacts with hydrogen peroxide to form peracids. Thus, the peracid formed constitutes an activated bleach. Particularly suitable bleach activators for use in the present invention are hydrophobic bleach activators, ie, bleach activators that are substantially and not continuously miscible with water. Typically, such hydrophobic bleach activators have a secondary HLB value of less than 11, preferably less than 10. Secondary HLB values are known in the art and are described, for example, in "Emulsions theory and practice" by P. Becher, Reinhold, New York, 1957, or "Emulsion science" by P. Sherman, Academic Press, London, 1969].

Suitable bleach activators for use in the present invention are those belonging to the ester, amide, imide or anhydride classes. Examples of suitable compounds of this type are disclosed in British Patent Nos. 1,586,769 and 2,143,231. Examples of such compounds suitable for use in the present invention are tetraacetyl ethylene diamine (TAED), sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate, for example diperoxy dode as described in US Pat. No. 4,818,425. Cannoic acid and nonylamide and nonanoyloxybenzenesulfonate (NOBS) of peroxyadipic acid described in US Pat. No. 4,259,201. Substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecanoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam Also suitable are N-acyl caprolactams selected from the group consisting of butanoyl caprolactam, pentanoyl caprolactam or mixtures thereof. A particular class of bleach activators of interest is disclosed in European Patent No. 624,154, particularly preferred is acetyl triethyl citrate (ATC). Acetyl triethyl citrate is advantageous in that it is substantially decomposed into citric acid and alcohol to be environmentally friendly. In addition, acetyl triethyl citrate has good hydrolytic stability in the product upon storage and is therefore an effective bleach activator. Finally, acetyl triethyl citrate gives the composition a good enhanced dose.

The composition according to the invention comprises from 0.01 to 20% by weight, preferably from 1 to 10% by weight and more preferably from 3 to 7% by weight of said bleach activator or mixtures thereof, based on the total weight of the composition.

Chelating agents suitable for use in the present invention include phosphonate chelating agents, amino carboxylate chelating agents, multifunctional-substituted aromatic chelating agents, and also mixtures of glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, and mixtures thereof. A chelating agent selected from a crowd of chelating agents. Chelating agents used are typically present in amounts of 0.001 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the composition.

Suitable phosphonate chelating agents for use in the present invention are, for example, amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonate, ethylene diamine tetra Amino phosphonate compounds, including methylene phosphonate and diethylene triamine pentamethylene phosphonate, as well as etidronic acid. The phosphonate compounds may be present as salts of different cations in acid form or for some or all of these acid functionalities. Preferred amino phosphonate chelating agents for use in the present invention is diethylene triamine pentamethylene phosphonate. Such phosphonate chelating agents are commercially available from Monsanto under the tradename DEQUEST®.

Most preferred phosphonate chelating agent for use in the present invention is aminotri (methylene phosphonic acid), referred to as ATMP. Indeed, the addition of ATMP, i.e., a compound of the formula below, into the liquid composition of the present invention significantly reduces the frost that occurs when pretreating fabrics, especially fabrics containing copper, iron, chromium and manganese, with a peroxygen bleach-containing composition. It turns out that:

Multifunctional-substituted aromatic chelators may also be useful in the compositions of the present invention (US Pat. No. 3,812,044, issued to Connor on May 21, 1974). Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, for example 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use in the present invention are ethylene diamine N, N'-disuccinic acid, or alkali or alkaline earth metals, ammonium or substituted ammonium salts thereof, or mixtures thereof. Ethylenediamine N, N'-disuccinic acid, especially its (S, S) isomers, is described extensively in US Pat. No. 4,704,233, issued November 3, 1987 to Hartman and Perkins. Ethylenediamine N, N'-disuccinic acid is commercially available, for example, under the name ssEDDS ^R from Palmer Research Laboratories.

Examples of preferred amino carboxylates for use in the present invention include ethylene diamine tetraacetate, diethylene triamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetate, nitrilo triacetate, ethylenediamine tetrapropionate, Propylene diamine triacetic acid (PDTA) and methyl glycine diacetic acid (MGDA) in the form of triethylenetetraaminehexaacetate, ethanol-diglycin, acid form or its alkali metal, ammonium and substituted ammonium salts. Particularly suitable amino carboxylates for use in the present invention are diethylene triamine pentaacetic acid, such as propylene diamine tetraacetic acid (PDTA) and methyl glycine diacetic acid, which are chiffins available from BASF under the trade name Trilon FS®. MGDA).

Another chelating agent preferred for use in the present invention is a compound having the formula:

Where

R_One, R₂, R₂, R₄ Are independently -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO₂, -C (O) R 'and -SO₂R "is selected from the crowd consisting of;

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;

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

Particularly preferred chelating agents for use in the present invention are ATMP, diethylene triamine methylene phosphonate, ethylene N, N'-disuccinic acid, diethylene triamine pentaacetate, glycine salicylic acid, aspartic acid, glutamic acid, malonic acid or these Is a mixture of and ATMP is most preferred.

Suitable radical scavengers for use in the present invention are well-known substituted mono and dihydroxy benzenes and analogs thereof, alkyl and aryl carboxylates and mixtures thereof. Examples of such radical scavengers preferred for use in the present invention include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tertiary -Butyl-hydroxy anisole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane , n-propyl-gallate or mixtures thereof, most preferred is di-tert-butyl hydroxy toluene. When used, radical scavengers are typically present in amounts ranging from 0.001 to 2% by weight, preferably 0.001 to 0.5% by weight, based on the total weight of the composition.

The presence of chelating agents, in particular ATMP and / or radical scavengers, contributes to the stability profile of the present compositions suitable for pretreatment of the fabric for long contact times prior to washing the contaminated and colored fabric.

The composition of the present invention may further comprise up to 20% by weight, preferably 2 to 10% by weight of the solvent or mixtures thereof, based on the total weight of the composition. More particularly, the addition of a solvent system comprising at least one hydrophobic solvent and at least one hydrophilic solvent in the liquid composition according to the invention further contributes to the advantages of the composition, namely grease stains, enzymatic stains as well as bleachable stains. It has been found that the overall stain removal ability for various types of stains is improved.

Examples of suitable hydrophobic solvents for use in the present invention include terpenes such as mono- and acyclic monoterpenes, especially terpenes of hydrocarbons including terpinene, terpinolene, limonene and pinene and mixtures thereof. Very preferred materials of this type are d-limonene, dipentene, alpha-pinene and / or beta-pinene. Other hydrophobic solvents include all types of paraffins, linear or nonlinear, containing 2 to 20, preferably 4 to 10, more preferably 6 to 8 carbon atoms. Octane is preferable in the present invention. Another hydrophobic solvent suitable for use in the present invention is benzyl alcohol. Particularly preferred hydrophobic solvents for use in the present invention are limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol or mixtures thereof.

Examples of suitable hydrophilic solvents for use in the present invention include methoxy propanol, ethoxy propanol, propoxy propanol, alkoxylated aliphatic alcohols such as butoxy propanol, alkoxylated glycols such as ethoxy-ethoxy-ethanol, ethanol, propanol And aliphatic or aromatic alcohols such as glycols such as propanediol or mixtures thereof.

Certain polymeric fouling release agents known to those skilled in the art can optionally be used in the compositions and methods of the present invention. Polymeric fouling release agents serve as anchors for hydrophilic segments by hydrophilizing the surfaces of hydrophobic fibers such as polyester and nylon, and by being deposited on hydrophobic fibers and attached to the fibers through cleaning and cleaning cycles. It is characterized by having all of the hydrophobic segments.

Polymeric fouling release agents useful in the present invention are in particular (a) (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein the hydrophilic segments Does not include certain oxypropylene units unless they are bonded to adjacent residues at each end by ether linkages), or (iii) oxyalkylene units comprising oxyethylene and 1 to about 30 oxypropylene units Wherein the mixture contains a sufficient amount of oxyethylene units so that the hydrophilic component has a hydrophilicity large enough to increase the hydrophilicity of the fiber surface when contaminating release agents are deposited on conventional polyester synthetic fiber surfaces. Wherein the hydrophilic segment preferably comprises at least about 25% oxyethylene units More preferably at least one nonionic hydrophilic component consisting essentially of at least about 50% oxyethylene units, especially for those components having about 20 to 30 oxypropylene units, or (b) (i) C ₃ oxyalkylene terephthalate segment (when the hydrophobic component also includes oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate unit is about 2: 1 or less), (ii) C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene segments or mixtures thereof, (iii) poly (vinyl ester) segments having a degree of polymerization of two or more, preferably polyvinyl acetate, or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents or mixtures therein, wherein the substituents are C ₁ -C ₄ alkyl ethers or C ₄ hydroxyalkyl ethers Le cellulose derivatives, or in the form of mixtures therein, and since these cellulose derivatives are amphoteric, they are deposited on conventional polyester synthetic fiber surfaces to increase fiber surface hydrophilicity when attached to such conventional synthetic fiber surfaces. Has a level of C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units sufficient to maintain a sufficient level of hydroxyl), or such contamination with a combination of components (a) and (b) above It is a release agent.

Typically, the polyoxyethylene segments of component (a) (i) will have a degree of polymerization of about 1 to about 200, preferably 3 to about 150, more preferably 6 to about 100, although higher levels may be used. will be. Suitable oxy C ₄ -C ₆ alkylene hydrophobic segments include the formula MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O—, which is disclosed in US Pat. No. 4,721,580, issued January 26, 1988 to Gosselink. , M is sodium, n is an integer from 4 to 6), and may be end-caps of polymeric contaminant release agents.

Polymeric fouling release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, ethylene terephthalate or propylene terephthalate and copolymer blocks of polyethylene oxide or polypropylene oxide terephthalate and the like. Such release agents are commercially available and include, for example, hydroxy ethers of cellulose such as METHOCEL (Dow). Examples of cellulose contaminating release agents used in the present invention also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose. See US Pat. No. 4,000,093 to Nicole et al., Dec. 28, 1976.

Contaminant release agents characterized by poly (vinyl ester) hydrophobic segments include, for example, poly (vinyl esters) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones, for example C ₁ -C ₆ vinyl esters, Preferably a graft copolymer of poly (vinyl acetate). See European Patent Application No. 0,219,048, published by Kurd et al. On April 22, 1987. Commercially available contaminant release agents of this kind are SOKALAN type materials sold by BASF, Germany, for example Sokalan HI-22 (HP-22).

One type of preferred contaminant release agent is a copolymer with random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of such polymeric fouling release agents range from about 25,000 to about 55,000. See US Pat. No. 3,959,230, issued May 25, 1976 and US Pat. No. 3,893,929, issued July 8, 1975.

Another preferred polymeric fouling release agent contains together 10 to 15 weight percent ethylene terephthalate units and 90 to 80 weight percent polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 300 to 5,000. It is a polymer having repeating units of ethylene terephthalate units. Examples of such polymers include ZELCON 5126 (available from DuPont) and MILEASE T (commercially available from ICI), which are commercially available materials. See US Pat. No. 4,702,857, issued to Gosélink on October 27, 1987.

Another preferred polymeric fouling release agent is the sulfonation product of an almost linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeating units and terminal residues covalently attached to the backbone. These contaminant release agents were released on 6 November 1990. second. J. J. Scheibel and Lee. blood. It is described in detail in US Pat. No. 4,968,451 to Goselink. Other suitable polymer line contamination release agents are, for example, terephthalate polyesters disclosed in U.S. Patent No. 4,711,730 issued to Gocelink et al., December 8, 1987, and U.S. Patent No. 4,721,580 issued to Goselink, January 26, 1988. Anionic end-protected oligomeric esters disclosed herein, and block polyester oligomeric compounds disclosed in US Pat. No. 4,702,857 to Goselink, issued October 27, 1987.

In addition, examples of preferred polymeric fouling release agents are the contamination of US Pat. No. 4,877,896 to Maldonado et al. On October 31, 1989, which discloses anionic, in particular sulfoaroyl, end-protected terephthalate esters. It is a release agent.

Another preferred contaminant release agent is an oligomer 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 end-cap. Particularly preferred contaminant release agents of this type are about 1 sulfoisophthaloyl units, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units and two sodium 2 in a ratio of about 1.7 to about 1.8. End-cap units of-(2-hydroxyethoxy) -ethanesulfonate. The fouling release agent also preferably comprises from about 0.5 to about 20 weight percent of an oligomer of crystalline-reducing stabilizer, selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof. See US Pat. No. 5,415,807, issued to Gosélink et al. On May 16, 1995.

When used, contaminant release agents will generally comprise from about 0.01 to about 10.0 weight percent, typically from about 0.1 to about 5 weight percent, preferably from about 0.2 to about 3.0 weight percent of the detergent composition.

The compositions of the present invention may also comprise one or more substances effective to inhibit the transfer of dye from one dyed surface to another during the cleaning process. Generally, such dye transfer inhibitors include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof. Included. When used, such dye transfer inhibitors typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2% by weight of the composition.

More specifically, preferred polyamine N-oxide polymers for use in the present invention have the structure RA _x -P, wherein P may be bonded to an NO group, or the NO group may form part of a polymerizable unit, or The NO group is a polymerizable unit which can be bonded to both units, A is one of the structures -NC (O)-, -C (O) O-, -S-, -O-, -N =; Is 0 or 1; R is a unit having an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or cycloaliphatic group or combination thereof in which the NO group may be bonded or NO group forms part of these groups) It contains. Preferred polyamine N-oxides are compounds in which R is a heterocycle group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

N-O groups can be represented by the formula:

Where

R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocycle or cycloaliphatic groups or combinations thereof;

x, y and z are 0 or 1;

The nitrogen of the N—O group may be attached to or form part of the group mentioned above.

The amine oxide units of the polyamine N-oxides have a pKa value of less than 10, preferably less than 7, more preferably less than 6.

Certain polymer backbones may be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibition. Suitable polymer backbones are, for example, polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. Such polymers are random or block copolymers in which one monomer type is an amine N-oxide and the other polymer type is an N-oxide. Amine N-oxide polymers typically have a ratio of amine: amine N-oxides of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can vary depending on the degree of copolymerization or the appropriate degree of N-oxidation. Polyamine oxides can be obtained with the desired degree of polymerization. Typically, the average molecular weight of such polymers is in the range of 500 to 1,000,000, more preferably 1,000 to 500,000, most preferably 5,000 to 100,000. This preferred class of materials may be referred to as "PVNO". Preferred polyamine N-oxides useful in the detergent compositions of the present invention are poly (4-vinylpyridine-N-oxides) having an average molecular weight of about 50,000 and an amine: amine N-oxide ratio of about 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (called "PVPVI") are also preferred for use in the present invention. PVPVI preferably has an average molecular weight in the range of 5,000 to 1,000,000, more preferably in the range of 5,000 to 200,000 and most preferably in the range of 10,000 to 20,000. (Average molecular weight range is determined by light scattering methods as described in Barth, et al., Chemical Analysis, Vol 113, "Modern Methods of Polymer Characterizayion", which is incorporated herein by reference.) PVPVI copolymers are typically Molar ratio of N-vinylimidazole: N-vinylpyrrolidone in the range of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. Have Such copolymers may be linear or branched.

The compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000. PVP is known to experts in the field of detergents, see for example European Patent Nos. 262,897 and 256,696, which are hereby incorporated by reference. Compositions containing PVP may also contain polyethylene glycol (“PEG”) having an average molecular weight of about 500 to 100,000, preferably about 1,000 to about 10,000. The ratio of PEG: PVP on a ppm delivered in wash solution is about 2: 1 to about 50: 1, more preferably about 3: 1 to about 10: 1.

If a lot of foam is required, foam amplifying agents such as C ₁₀ -C ₁₆ alkanolamides may be incorporated into the composition, typically at a concentration of 1 to 10%. Representative classes of such foam amplifiers exemplify C ₁₀ -C ₁₄ monoethanol and diethanol amides. If necessary, soluble magnesium salts such as MgCl ₂ , MgSO _4, etc. may be added at concentrations of, for example, 0.1 to 2% to provide additional foam and improve grease removal capability.

When designed for textile treatment or laundry use, any particular brightener, fluorescent brightener or other brightener known in the art is typically used at a concentration of about 0.05 to about 1.2 weight percent of the detergent composition. It can be incorporated into. Any commercially available brightener that may be useful in the present invention is a derivative of stilbene, pyrazoline, comarin, carboxylic acid, methocyanine, dibenzothiophene-5,5-dioxide, azole, 5- and 6- Circular ring heterocycle brighteners may be included but are not limited to these. 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).

Specific examples of optional brighteners useful in the compositions of the present invention are those shown in US Pat. No. 4,790,856, issued December 13, 1988 to Wixon. These brighteners include the PHORWHITE family of brighteners available from Verona. Other brighteners disclosed in this patent are, for example, Tinopal UNPA, Tinopal CBS and Tinopal 5BM sold by 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 aminocomarin. Examples of such brighteners include 4-methyl-7-diethyl-amino comarin; 1,2-bis (benzimidazol-2-yl) ethylene; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphth- [1,2-d] oxazole; And 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole. See US Pat. No. 3,646,015, issued February 29, 1972 to Hamilton. Typically anionic brighteners are preferred.

Preferred uses of the compositions described herein are laundry pretreatments as mentioned above, but the compositions of the present invention can also be used as laundry detergents or laundry detergent amplifiers and household cleaners in bathrooms or kitchens.

Compositions of the invention suitable for treating fabrics can be packaged in a variety of containers including conventional bottles, bottles mounted on rolls, sponges, brushes or sprayers.

The invention will be further illustrated by the following examples.

The following compositions were prepared by mixing the ingredients mentioned in the following table in the proportions mentioned in the list:

When the contaminated fabric is pretreated using certain of the compositions I to VI as described above, for example, the composition is allowed to act on the fabric for about 5 minutes of contact time and then the fabric is washed with water or For example, Tide (registered trademark) diluted to a concentration of 1 to 400 times. When washed with conventional detergent compositions such as powders, clays, dirty motor oils, make-ups, grease / oil stains such as lipsticks, carotenoid-like stains such as spaghetti sauces, bleachable stains and pastes such as tea, blood and Excellent stain removal was demonstrated for various stains, including the same enzymatic stain.

Claims (13)

0.01-15% by weight of peroxygen bleach of the total composition, and (1) an ethoxylated monoamine of formula (1), (2) an ethoxylated diamine of formula (2), (3) or (4), ( 3) A liquid composition comprising a contaminant dispersant selected from the group consisting of an ethoxylated polyamine of formula (5), (4) an ethoxylated amine polymer of formula (6), and (5) a mixture thereof: Applying to at least a portion, and then washing the treated fabric, bleaching the fabric with the liquid composition: Formula 1 (XL) -N- (R ² ) ₂ Formula 2 Formula 3 Formula 4 (XL-) ₂ -NR ¹ -N- (R ² ) ₂ Formula 5 Formula 6 Where A ¹ is ego; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C ₂ -C ₃ oxy having 2 to 20 oxyalkylene units which do not form an ON bond Alkylene residues; R ² is each C ₁ -C ₄ alkyl or hydroxyalkyl; The residues -LX, or two R ² together form a residue-(CH ₂ ) _r -A ^2- (CH ₂ ) _s- ; A ² is -O- or -CH _2- ; r is 1 or 2; s is 1 or 2; r + s is 3 or 4; X is a nonionic group, an anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having a p-substituted moiety; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, or C ₂ -C ₃ with 2 to 20 oxyalkylene units which do not form OO or ON bonds; Oxyalkylene moiety; L is a hydrophilic chain containing a polyoxyalkylene moiety-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]-; R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene; m and n are numbers such that the residues-(CH ₂ CH ₂ O) _n -occupy at least 50% by weight of the polyoxyalkylene residues; For said monoamine, m is 0-4 and n is 12 or more; For the diamines, m is from 0 to 3, n is R ¹ is C ₂ -C ₃ alkylene, hydroxy alkylene or alkenylene which has 6 or more and R ¹ is C ₂ -C ₃ alkylene, hydroxy when If not oxyalkylene or alkenylene it is 3 or more; For the polyamine and amine polymer, m is 0 to 10 and n is at least 3; p is 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; y + z is two or more. The method of claim 1, Maintaining the liquid composition in contact with the fabric for 1 minute to 1 hour, preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and then washing the fabric. Formulated in emulsion or microemulsion, peroxygen bleach, surfactant, and (1) ethoxylated monoamine of formula (1), (2) ethoxylation of formula (2), (3) or (4) Pretreatment of a fabric comprising a contaminant dispersant selected from the group consisting of diamine, (3) an ethoxylated polyamine of formula (5), (4) an ethoxylated amine polymer of formula (6) and (5) mixtures thereof Suitable Liquid Bleaching Compositions: Formula 1 (XL) -N- (R ² ) ₂ Formula 2 Formula 3 Formula 4 (XL-) ₂ -NR ¹ -N- (R ² ) ₂ Formula 5 Formula 6 In the above formulas, A ¹ is ego; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C ₂ -C ₃ oxy having 2 to 20 oxyalkylene units which do not form an ON bond Alkylene residues; R ² is each C ₁ -C ₄ alkyl or hydroxyalkyl; The residues -LX, or two R ² together form a residue-(CH ₂ ) _r -A ^2- (CH ₂ ) _s- ; A ² is -O- or -CH _2- ; r is 1 or 2; s is 1 or 2; r + s is 3 or 4; X is a nonionic group, an anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having a p-substituted moiety; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, or C ₂ -C ₃ with 2 to 20 oxyalkylene units which do not form OO or ON bonds; Oxyalkylene moiety; L is a hydrophilic chain containing a polyoxyalkylene moiety-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]-; R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene; m and n are numbers such that the residues-(CH ₂ CH ₂ O) _n -make up at least 50% by weight of the polyoxyalkylene residues; For said monoamine, m is 0-4 and n is 12 or more; For the diamines, m is from 0 to 3, n is R ¹ is C ₂ -C ₃ alkylene, hydroxy alkylene or alkenylene which has 6 or more and R ¹ is C ₂ -C ₃ alkylene, hydroxy when If not oxyalkylene or alkenylene it is 3 or more; For the polyamine and amine polymer, m is 0 to 10 and n is at least 3; p is 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; y + z is two or more. The method according to any one of claims 1 to 3, Peroxy bleach is a water-soluble source of hydrogen peroxide or preferably selected from the group consisting of percarbonates, persilicates, persulfates, perborates, peroxy acids, hydroperoxides, diacyl peroxides and mixtures thereof, preferably Is hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide, 2,5-dimethyl-hexane-2,5-dihydroperoxide, dilauroyl peroxide, didecanoyl peroxide, dimyristoyl peroxide, or a mixture thereof. The method according to any one of claims 1 to 4, The composition comprises from 0.01 to 15% by weight, preferably from 0.1 to 12% by weight, more preferably from 0.5 to 10% by weight, most preferably from 2 to 8% by weight of peroxygen bleach or mixtures thereof. Or the way. The method according to any one of claims 1 to 5, The contaminant dispersant is a composition wherein R ¹ is C ₂ -C ₃ alkylene, preferably ethylene, L is all composed of residues-(CH ₂ CH ₂ O) _n -and n is an ethoxylated amine polymer having at least 12 or Way. The method of claim 6, The composition or method wherein the ethoxylated amine polymer is an ethoxylated polyethyleneamine having a molecular weight of 140 to 310 prior to the ethoxylation reaction. The method of claim 6, The composition or method wherein the ethoxylated amine polymer is an ethoxylated polyethyleneimine having a molecular weight of 600 to 1800 prior to the ethoxylation reaction. The method according to any one of claims 1 to 8, The composition comprising from 0.01 to 20%, preferably from 0.1 to 10%, more preferably from 0.2 to 4% and most preferably from 0.5 to 2% by weight of a contaminating dispersant or mixture thereof Way. The method according to any one of claims 1 to 9, The composition or method preferably further comprises 0.01 to 20%, more preferably 1 to 10% and most preferably 3 to 7% by weight of the bleach activator of the total composition. The method of claim 10, Bleach activators include acetyl triethyl citrate, tetraacetyl ethylene diamine, sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate, diperoxy dodecanoic acid, nonylamide of peroxyadipic acid, n-nonanoyloxy Benzenesulfonate, N-acyl caprolactam, substituted and unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam , Acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam, pentanoyl caprolactam and mixtures thereof, wherein the composition or method is preferably acetyl triethyl citrate. The method according to any one of claims 1 to 11, The composition or method wherein the composition is aqueous and has a pH of 6 or less, preferably 1 to 5, more preferably 2 to 5, most preferably 3 to 5. The method according to any one of claims 3 to 12, The composition has one or more hydrophobic surfactants or mixtures thereof having an HLB value of 10 or less, preferably less than 10, more preferably less than 9, and a HLB value of 10 or more, preferably 10.5 or more, more preferably 11 or more. A composition comprising one or more hydrophilic surfactants or mixtures thereof.