WO2005059075A1

WO2005059075A1 - Liquid bleaching composition in container

Info

Publication number: WO2005059075A1
Application number: PCT/EP2004/012246
Authority: WO
Inventors: Maartje Ouwendijk-Vijenhoek; Derdiyok Sonmezer; Simon Marinus Veerman
Original assignee: Hindustan Lever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2003-12-10
Filing date: 2004-10-28
Publication date: 2005-06-30
Anticipated expiration: 2006-06-10
Also published as: EP1694804A1; AR046744A1; GB0328631D0

Abstract

The present invention concerns the preservation of a catalyst in a liquid bleaching composition. The bleaching composition is substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system.

Description

LIQUID BLEACHING COMPOSITION IN CONTAINER

FIELD OF INVENTION

This invention relates to the enhancement of bleaching compositions that are substantially devoid of peroxyl species.

BACKGROUND OF INVENTION

The use of bleaching catalysts for stain removal has been developed over recent years. The recent discovery that some catalysts are capable of bleaching effectively in the absence of an added peroxyl source has recently become the focus of some interest, for example: O9965905; O0012667; O0012808; O0029537, and, O0060045.

The shelf life of a product may be regarded as the period of time over which the product may be stored whilst retaining its required quality. A satisfactory shelf life is in many instances a crucial factor for the success of a commercial product. A product with a short shelf life generally dictates that the product is made in small batches and is rapidly sold to the consumer. It is also a concern to the owners of a brand with a short shelf life that the consumer uses the product within the shelf life otherwise the consumer may be inclined to change to a similar product of another brand. In contrast a similar product with a long shelf life may be made in larger batches, held as stock for a longer period of time and the period of time that a consumer stores the product is not of a great concern to the owners of a particular brand.

It is an object of the present invention to provide an air bleaching composition that has improved storage properties .

SUMMARY OF INVENTION

We have found that the activity of a bleaching catalyst in a liquid formulation is reduced by exposure to

Ultraviolet (UV) irradiation. Ultraviolet radiation is found in irradiation from the Sun and artificial lights.

The present invention provides a liquid bleaching composition comprising:

(a) an organic substance which forms a complex with a transition metal for bleaching a substrate with atmospheric oxygen, the bleaching composition upon addition to an aqueous medium providing an aqueous bleaching medium substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system; and,

(b) the balance carriers and adjunct ingredients to 100 wt/wt % of the total bleaching composition,

wherein the liquid bleaching composition is stored in a container, the container absorbing incident UV irradiation and reducing the amount of UV irradiation passing through the container upon exposure of the container to the incident UV irradiation.

The term "substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system" should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species present as possible. It is preferred that the bleaching formulation contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof. In addition, it is preferred that the presence of alkyl hydroperoxides is kept to a minimum in a bleaching composition.

The present invention also extends to a commercial package together with instructions for its use.

DETAILED DESCRIPTION OF THE INVENTION

THE CONTAINER The container absorbs UV irradiation and reduces the incident UV irradiation on the container passing through to the contents held within. It is preferred that the container absorbs strongly in the range 220 to 400 nm, most preferably 290 to 320nm. The amount of UV irradiation in everyday situations will depend upon whether the irradiation is direct sunlight light from artificial lighting.

The container may have an amount of UV absorbent material incorporated into it such that the UV absorbent material is integral to the container. Alternatively, the container is sheathed or has a coating such that the sheath or coating absorbs incident UV irradiation.

It is preferred that the container is substantially uniform in its absorption of UV irradiation. That is to say, that there is no area of the container that permits UV irritation to pass through to the inner surface of the container as defined herein. In addition to the container it is preferred that any top that is used to cap/seal the container is also UV absorbent as defined herein.

Another approach to stabilising the liquid bleaching formulations is to incorporate a material that absorbs UV irradiation into the liquid per se. The presence of a fluorescent material in the liquid bleaching formulations provides a UV shield. A preferred material that absorbs UV irradiation is one that quenches in an intramolecular manner.

THE BLEACH CATALYST

The bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules (ligands) . The level of the catalyst in a commercial bleaching composition is from 0.0001 to 0.6 wt/wt %, preferably 0.001 to 0.15 wt/wt %, most preferably 0.01 to 0.1 wt/wt %. We have found that the level of catalyst is optimum between 0.03 to 0.09 wt/wt % in the commercial bleaching composition.

In typical washing compositions the level of the organic substance is such that the in-use level is from 0.05 μM to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 to 100 μM. Higher levels may be desired and applied in industrial textile bleaching processes. A mixture of different catalysts may be employed in the bleaching composition.

Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in: WO00/12667; EP 1008645; EP 1001009; EP 999050; WO-A-9534628; EP-A-458379; EP 0909809; United States Patent 4,728,455; WO98/39098; WO98/39406, W097/48787,

WO00/29537; WOOO/52124, and WO00/60045 the complexes and organic molecule (ligand) precursors of which are herein incorporated by reference. An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis (pyridin- 2-yl-methyl) -1, 1-bis (pyridin-2-yl) -1- aminoethane) .

The ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I- III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.

An example of a preferred catalyst is a monomer ligand or transition metal catalyst thereof of a ligand having the formula (I) :

wherein each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkyl0-, -NH-CO-H, -NH-C0-C1- C4-alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl; Rl and R2 are independently selected from: Cl-C4-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal;

R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, Cl-C8-alkyl-0-Cl-C8-alkyl, Cl-C8-alkyl-O-C6-C10- aryl, C6-C10-aryl, Cl-C8-hydroxyalkyl, and - (CH2 ) _nC (0) OR5 wherein R5 is independently selected from: hydrogen, Cl- C4-alkyl, n is from 0 to 4, and mixtures thereof; and, X is selected from C=0, -[C(R6)₂]_y- wherein Y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, Cl-C4-alkoxy and Cl-C4-alkyl. Preferably, at least one of Rl and R2 is the group containing the heteroatom. Most preferably at least one of Rl and R2 is pyridin-2-ylmethyl .

The transition metal complex preferably is of the general formula (Al) : [M_aL_kX_n]Y_m

in which: M represents a metal selected from Mn (II) - (III) - (IV)-(V), Cu(I)-(II)-(III), Fe (II) - (III) - (IV) - (V) , Co(I)-(II)-(III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)- (V), Mo(II)-(III)-(IV)-(V)-(VI) and W ( IV) - (V) - (VI ) , preferably from Fe (II) - (III) - (IV) - (V) ; L represents the ligand, preferably N,N-bis (pyridin- 2-yl-methyl) -1, 1-bis (pyridin-2-yl) -1-aminoethane, or its protonated or deprotonated analogue; X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner; Y represents any non-coordinated counter ion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10; m represents zero or an integer from 1 to 20.

BALANCE CARRIERS AND ADJUNCT INGREDIENTS

These are generally surfactants, builders, foam agents, anti-foam agents, solvents, and enzymes. The use and amounts of these components are such that the bleaching composition performs depending upon economics, environmental factors and use of the bleaching composition.

The air bleach catalyst may be used in a detergent composition specifically suited for stain bleaching purposes, and this constitutes a second aspect of the invention. To that extent, the composition comprises a surfactant and optionally other conventional detergent ingredients. The invention in its second aspect provides an enzymatic detergent composition which comprises from 0.1 - 50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost. The enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.

In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C₆~C₂₂ alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs-Ci8 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals con- taining from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs-Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C₉-C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl C₁0-C₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium C₁₁-C₁5 alkyl benzene sulphonates and sodium Cι₂-Cι₈ alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides . Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a Ciβ-Ciβ primary alcohol sulphate together with a Cι₂-Cι₅ primary alcohol 3-7 EO ethoxylate.

The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.

One skilled in the art will appreciate that some adventitious peroxyl species may be in the composition nevertheless it is most preferred that the bleaching composition of the present invention has less that 1%, preferably less than 0.1%, most preferably less than

0.01%, of a peroxyl species present. These adventitious peroxyl are predominantly alkyl hydroperoxides formed by autoxidation of the surfactants.

The composition may contain additional enzymes as found in WO01/00768 Al page 15, line 25 to page 19, line 29, - li ¬

the contents of which are herein incorporated by reference.

Builders, polymers and other enzymes as optional ingredients may also be present as found in WO0060045.

Suitable detergency builders as optional ingredients may also be present as found in WO0034427.

In the context of the present invention, bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate. Furthermore, in the context of the present invention bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light.

The present invention extends to both isotropic and complex liquid compositions and formulations a brief discussion of which follows. Some isotropic formulations are termed 'micro-emulsion' liquids that are clear and thermodynamically stable over a specified temperature range. The 'micro-emulsion' formulation may be water in oil, or oil in water emulsions. Some liquid formulations are macro-emulsions that are not clear and isotropic. Emulsions are considered meta-stable. Concentrated, clear compositions containing fabric softening actives have been disclosed in WO98/08924 and W098/4799, both Procter & Gamble. Such compositions comprise bio-degradable fabric conditioners. However, both disclose compositions comprising water miscible solvents that do not form water-in-oil micro-emulsions. Clear fabric conditioning compositions have also been disclosed in EP 730023 (Colgate Palmolive) , W096/19552 (Colgate Palmolive) , WO96/33800 (Witco Co.), WO97/03170 (Procter & Gamble), WO97/03172 (Procter & Gamble), WO97/03169 (Procter & Gamble), US 5492636 (Quest Int.) and US 5427697 (Procter & Gamble) . Liquid formulations of the present invention may contain for example; monoethoxy quats; AQAs and bis- AQAs; cationic amides; cationic esters; amino/diamino quats; glucamide; amine oxides; ethoxylated polyethyleneimines; enhancement polymers of the form linear amine based polymers, e.g. bis- hexamethylenetriamine; polyamines e.g. TETA, TEPA or PEI polymers.

The liquid may be contained within a sachet as found in WO02/068577. The sachet is a container within the context of the present invention.

It is most preferred that when the catalyst is in a liquid composition, the liquid composition has a pH of 7 or below. Experimental

The transition metal catalyst present in the liquid formulation was the iron chloride complex of dimethyl 2, -di- (2-pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7- diaza-bicyclo [3.3.1] nonan-9-one-l, 5-dicarboxylate [FeCl (N2Py3o) ] Cl which was prepared as described in WO0248301.

The activities of the liquid bleaching compositions were determined at 40 °C in a H202 containing NaH2P04.H20 pH7 buffer and Acid Blue 45 (CAS No. 2861-02-1) as substrate using the following protocol.

Samples of 70 mg liquid were diluted in 10.00 ml MilliQ water. We added 45 μl of this solution to an assay of 230 μL containing 20 mM H202, 75 μM Acid blue 45 and 54 mM NaH2P04.H20 pH7 buffer.

The solutions were mixed and pre incubated for 1 min at 40 °C. The changes in absorbance at 600 nm were measured for 8 min at 40 °C using a spectrophotometer . The absolute changes in absorbance were correlated to activities obtained with freshly prepared calibration samples. The measured activities were expressed as μMol/1.

Polyethylene teraphthalate = PET High density polyethylene = PEHD

The liquid bleaching composition were irradiated on a sun bed having the following measured properties: UV A= 2.7 mW/cm3 and UV B= 0.05 mW/cm3. UV-A is irradiation in the range 320-400 nm and UV-B is irradiation in the range 280 to 320 nm.

Table 1: The concentration bleach catalyst (μMol/1) in liquid A after irradiation in different types of bottles.

Bottle A: PEHD +/- Clariant Sarmastab UV 9M-B@ 2% UV absorber (ex Alpla)

Bottle B: PET 8 fl.Oz Resin 7352 +/- UV absorber 117880 (ex Owens Illinois)

Bottle C: PET 20 fl.Oz +/- UV absorber Clearshield UV 400M (5% T@390 nm) (ex Milliken)

Liquid A:

6 % LAS

6 % sLES 3 EO 6 % Nonionic 7 EO 0.016 % Proxel GXL 3.35 % sorbitol 2.30 % Borax.10 H20 4.75 % MPG 0.75 % NaOH 0.4 % Relase 16.0L EXI

Table 2: The concentration bleach catalyst (μMol/1) in liquid B after irradiation in different types of bottles.

Bottle A: PEHD +/- Clariant Sarmastab UV 9M-B0 2% UV absorber (ex Alpla)

Bottle B: PET 8 fl.Oz Resin 7352 +/- UV absorber 117880 (ex Owens Illinois)

Bottle C: PET 20 fl.Oz +/- UV absorber Clearshield UV 400M (5% T@390 nm) (ex Milliken) Liquid B: 6 % LAS 6 % sLES 3 EO 6 % Nonionic 7 EO 0.016 % Proxel GXL 3.35 % sorbitol 2.30 % Borax.10 H20 4.75 % MPG 0.75 % NaOH 0.5 % Prifac 7908

0.4 % Relase 16.0L EXI

Claims

We clai :

1. A liquid bleaching composition comprising: (a) an organic substance which forms a complex with a transition metal for bleaching a substrate with atmospheric oxygen, the bleaching composition upon addition to an aqueous medium providing an aqueous bleaching medium substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system; and,

(b) the balance carriers and adjunct ingredients to 100 wt/wt % of the total bleaching composition, wherein the liquid bleaching composition is stored in a container, the container absorbing incident UV irradiation and reducing the amount of UV irradiation passing through the container upon exposure of the container to the incident UV irradiation.

2. A bleaching composition comprising according to claim 1, wherein the UV filter is integral to the container.

3. A bleaching composition according to claims 1 or 2, wherein the UV filter is a coating applied to the container. A liquid bleaching composition according to claim 1, wherein the UV filter is a sheath surrounding the container.

A liquid bleaching composition according to claim 1, wherein the UV filter reduces the intensity of the UV passing through the container by at least 80 %.

A liquid bleaching composition according to claim 5, wherein the UV filter reduces the intensity of the UV passing through the container by at least 90 %.

A liquid bleaching composition according to claim 6, wherein the UV filter reduces the intensity of the UV passing through the container by at least 99 %.

A bleaching composition according to claim 7, wherein the container is opaque to UV-radiation.

A liquid bleaching composition according to any preceding claim, wherein the organic substance is of the form:

wherein each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH- CO-H, -NH-CO-Cl-C4-alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl; Rl and R2 are independently selected from: Cl-C4-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal; R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, Cl-C8-alkyl-0-Cl-C8-alkyl, Cl-C8-alkyl- O-C6-C10-aryl, C6-C10-aryl, Cl-C8-hydroxyalkyl, and -(CH2)_nC(0)OR5 wherein R5 is independently selected from: hydrogen, Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof; and, X is selected from C=0, -[C(R6)₂]_y- wherein Y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, Cl-C4-alkoxy and Cl-C4-alkyl.

10. A liquid bleaching composition according to claim 9, wherein at least one of Rl and R2 is the group containing the heteroatom.

11. A liquid bleaching composition according to claim 10, wherein least one of Rl and R2 is pyridin-2- ylmethyl .

12. A liquid bleaching composition according to claim 9, wherein Rl and R2 is methyl or benzyl.

3. A liquid bleaching composition according any one of claims 9 to 12, wherein X is C=0.