AU757788B2 - Sequesterants as hypochlorite bleach enhancers - Google Patents

Description

-SEQUESTERANTS AS HYPOCHLORITE BLEACH ENHANCERS FIELD OF THE INVENTION The present invention generally relates to liquid bleach compositions useful i treating fabrics and particularly relates to hypochlorite bleachcontaining aqueous cleaning compositions comprising sequestering agents as whitening and fabric strength enhancers.

BACKGROUND OF THE INVENTION The quality of raw water and finished (treated) water varies considerably throughout the world. For instance, the types and levels of trace metals found in water from household taps can vary significantly from one country to another. The presence of certain trace metals often reduces the effectiveness of laundering aids and causes fabric damage.

Hypochlorite liquid bleaches have found wide commercial acceptance and are commonly used in a variety of household cleaning and laundering 15 products. The effectiveness of hypochlorite bleach compositions is usually not adversely affected by trace metals found in water used in laundering.

However, it has been found that the presence of iron and manganese metal ions in water used in laundering causes fabrics to yellow and deteriorate. This phenomenon is particularly pronounced when the bleaching composition is not used in combination with a laundry detergent.

In WO 96/00188 it was speculated that the presence of metal impurities in the washing environment catalyzed the attack of hypochlorous acid on fabrics with the generation of yellow oxidized species. It was believed that the metal ions are adsorbed on fabrics as colored species and catalyzed the degradation of the brighteners absorbed on fabrics. Furthermore. it was said that the metal ions stabilized colored pigments of enzymatic stains, such as blood and grass.

that caused such stains to "set". Finally, it was said that the metal ions catalyzed the depolymerization of cotton fibers which leads to reduced tensile strength of the fabrics thereby reducing fabric resistance.

To counter the deleterious effects caused by the presence of heavy metal ions in hypochlorite-containing cleaning compositions, the art has suggested the employment of various agents to improve fabric whiteness and integrity. These agents, for example, include periodate, silicates, and pyridine with carboxylic acid substituents. See, for example, WO 96/00188, and EP 0653482. and EP 10 0653483.

:While some of these complexing agents have demonstrated hypochlorite bleach enhancement in terms of fabric whitening and safety, they are not satisfactory for a number of reasons. First, these prior art complexing agents are expensive to use. Second, some of these complexing agents do not mitigate the dingying effect of hypochlorite on fabrics washed in water containing significant levels of iron and/or manganese ions.

SUMMARY OF THE INVENTION The present invention is based in part on the discovery of a series of sequestering agents for use as a whitening and fabric strength enhancer for aqueous hypochlorite bleach compositions. It was found that the sequesterants when used with hypochlorite in the presence of heavy metal ions, particularly iron and/or manganese ions, provide significantly improved whitening. It is expected that the sequesterants will also provide fabric protection. The sequesterants comprise polycarboxylates. Most preferably, the sequesterant is selected from polyacrylic acid, a polyacrylic acid derivative, a copolymer of acrylic acid or methacrylic acid and a comonomer which is maleic acid or maleic anhydride and mixtures thereof. Adjuvants such as sodium hydroxide.

sodium carbonate, fluorescent whiting agents, fragrances dyes, and thickening agents can also be employed in conjunction with the sequesterants.

In one aspect, the invention is directed to a method for laundering fabrics with improved whitening and reduced fabric damage, said method comprising: s a) providing, in a wash liquor containing at least about 40 ppb of iron cations or (ii) at least about 10 ppb of manganese cations, or (iii) the cations of both (i) and and a fabric piece; and b) adding prior to, contemporaneously with, or after, the step of providing said fabric piece to said wash liquor a liquid aqueous hypochlorite composition which comprises from about 4 to 15% by weight of an alkali metal hypochlorite and an effective amount of a non-crosslinked polyacrylic acid polymer or a copolymer of acrylic acid and maleic acid, said polymer or copolymer having a molecular weight of about 1,000 to about 70,000 daltons to mitigate attack of said cations on said fabric; said hypochlorite composition further comprising an effective amount of buffer to achieve a pH of the 15 composition of greater than about In a further aspect, the invention is directed to a wash liquor containing at S* least about 40 ppb of iron cations or (ii) at least about 10 ppb of manganese cations, or (iii) the cations of both and said wash liquor further comprising: a) at least one fabric piece which has a tendency to be attacked by said 20 cations in said wash liquor, and b) a liquid hypochlorite composition which includes from about 4 to by weight of an alkali metal hypochlorite and an effective amount of a non-crosslinked polyacrylic acid polymer or a copolymer of acrylic acid and maleic acid, said polymer or copolymer having a molecular weight of about 1,000 to about 70,000 daltons to mitigate attack of said cations on said fabric; said hypochlorite composition further comprising an effective amount of buffer to achieve a pH of the composition of greater than about Preferably, the polymer or copolymer, also referred to herein as "sequesterant" or "sequestering agent", comprises at least about 0.1 ppm by weight of said wash liquor.

Preferably, the hypochlorite composition is an alkali metal hypochlorite.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 and 2 are graphs showing the effect of polyacrylate level on yellowing of cotton fabric by hypochlorite bleaching compositions in washes containing soil and

S

T metals.

[R:\LIBZ]05811.doc:lam Figure 3 is a graph showing the effect of soil on the performance of polyacrylate on yellowing of cotton fabric by metal-hypochlorite washes.

Figure 4 is a graph showing the effect of polycarboxylate molecular weight on the yellowing of cotton fabric by hypochlorite-metal washes.

Figure 5 is a graph showing the effect of hardness on the performance of polyacrylate in hypochlorite metal washes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Sequestering agents for use in the present invention are selected from noncrosslinked polyacrylic acid polymers and copolymers of acrylic acid and maleic acid.

Although the scope of the invention is not to be limited by any particularly theory, it is believed that hypochlorite bleach accelerates a chemical reaction analogous to the one that forms rust when iron ions are present. It is believed that the carboxyl groups in these •polymer sequestering agents are able to shield the Mn and Fe cations from :1 5 hypochlorite ions, and/or disperse the oxidized forms of the metals in solution and thereby prevent them from depositing onto fabrics.

It has been demonstrated that the yellowing effect of hypochlorite and the accompanying fabric damage occur when the level of iron ions in the wash liquor is about ppb or higher or when the level of manganese ions is about 20 ppb or higher. It is 20 expected that the yellow effect and fabric damage will occur when the iron ion concentration is about 40-50 ppb or the manganese ion concentration is about 10-15 ppb.

It is expected that the sequestering agents described herein will be effective when the wash liquor comprises about 40 ppb or higher of iron ions and/or about 10 ppb or higher :of manganese ions. It has been further demonstrated that ferrous ions cause approximately the same level of yellowing and damage to fabric as ferric ions, therefore, iron ions shall refer to either ferrous ions, ferric ions, or a mixture of both. Manganese ions are generally Mn(II). The concentration of sequestering agents should be sufficient to mitigate the dingying effect of hypochlorite on fabric, particularly white fabric, and to prevent or reduce the level of fabric damage when the fabric is washed in water containing iron and/or manganese ions present at these concentration level(s).

Sequestering agents described herein are particularly suited when the wash liquor contains both iron and manganese ions. Preferably, the concentration of the sequestering agents in the wash liquor is from about 0.1 ppm to about 200 ppm, more preferably from about 0.2 ppm to about 80 ppm and most preferably about 0.4 ppm to Sabout 20 ppm all measured on a weight basis. A higher sequestering agent concentration [R:\LIBZ]0581 .doc:lam is preferably used when higher level(s) of iron and/or manganese ions are present. Thus, the amount of sequestering agent employed in the wash liquor can be formulated in accordance with the level of iron and/or manganese ions found in the water source of a particular location or region. Furthermore, the sequestering agent can be added as a separate additive to the wash liquor comprising a hypochlorite bleach. Preferably hypochlorite bleach compositions are formulated to include requisite amounts of the sequestering agent.

The sequestering agents can be employed in aqueous hypochlorite bleach compositions containing an alkali metal hypochlorite, most preferably sodium hypochlorite. Hypochlorite bleaching compositions are described, for instance, in U.S.

Patent No. 5,080,826 which is incorporated herein. The hypochlorite bleach composition (without said sequestering agents) is typically commercially available as an aqueous solution comprising about a 1-15%, preferably about a solution of sodium hypochlorite in water, with various amounts of sodium hydroxide, sodium chloride and 15 other by-products of the manufacturing process present. (All percentages herein are on a weight basis unless stated otherwise). When the hypochlorite bleach composition is formulated with a sequestering agent, the composition preferably comprises about 0.0015% to about more preferably about 0.0015% to about and most preferably about 0.0025% to about 0.5% of said sequestering agent.

The hypochlorite bleach composition may, if desired, also contain additional components such as buffers, primary cleansing agents (surfactants), builders, fluorescent whitening agents, fragrances, pigments, dyes and thickening agents. Buffers preferably comprise one or more ofpH adjusting [R:\LIBZ]0581 .doc:lam 0 0 .0HSPGEI.NEN0NL LF LN 0000 [RALIBZ]058 II .doc: lam THIS PAGE IS INTENTIONALY LEFT BLANK [R:\LIBZ]058 I doc:Iam agent effective to adjust or to maintain the pH of a solution wash liquor) in which the hypochlorite bleach composition is added to a pH greater than about 10. Suitable pH adjusting agents, are well known to the art and include.

for example, carbonates, borates, phosphates, silicates, and bicarbonates.

Although one or more adjuvants may be incorporated, the hypochlorite bleach composition with the sequestering agent is particularly suited when the wash liquor does not include any laundry detergent such as, for example, TIDE" by Procter Gamble, Cincinnati OH, and WISK" and SURF" by Lever Brothers.

N.Y. By "laundry detergent" is meant a composition that contains both 0 surfactants and builders and preferably various adjuvant components.

Representative fluorescent whitening agents include naphtholtriazol stilbene and distyryl biphenyl fluorescent whitening agents sold by the Ciba- Geigy Corporation under the names TINOPAL® RBS and TINOPAL® CBS-X.

respectively, and the stilbene materials also marketed by Ciba-Geigy under the name TINOPAL® 5BMX. Other useful whiteners are disclosed in U.S. Patent No. 3,393,153 and further useful whiteners are disclosed in ASTM publication D-553A, List of Fluorescent Whitening Agents for the Soap and Detergent Industry, which disclosures are incorporated herein.

Representative surfactants include conventional anionic, cationic, nonionic. ampholytic and zwitterionic surfactant materials as are described in the art. Examples of suitable surfactants for use in these formulations may be found in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition.

volume 22, pages 247-387 (1983) and McCutcheon's Detergents and Emulsifiers. North American Edition (1983). These two disclosures are incorporated herein by reference. One generally preferred group of surfactants are the nonionic surfactants such as are described at pages 360-377 of Kirk- Othmer. Nonionic materials include alcohol ethoxylates, alkyl phenol e(hoxylates. carboxylic acid esters, glycerol esters. polyoxyethylene esters.

anhydrosorbitol esters, ethoxylated anhydrosorbitol esters, ethoxylates of natural fats, oils and waxes, glycol esters of fatty acids, carboxylic amides, diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, polyalkylene oxide block copolymers, poly(oxyethylene-cooxypropylene) nonionic surfactants and the like. A wide range of such materials are available commercially, including the Shell Chemical NEODOLS®, the Union Carbide TERGITOLS®, the ICI TWEEN® series, and the SPAN® series and the like. Preferably. surfactants range from 0 to about 5% by weight of the inventive composition.

*o 10 Fragrances are usually blends of volatile oils that are composed of organic compounds such as esters, aldehydes, ketones or mixtures thereof.

Such fragrances are usually proprietary materials commercially available from such manufacturers as Quest, International Flavors and Fragrances. Givaudan and Firmenich, Inc. E.xmples of fragrances which may be suitable for use in the present invention may be found in Laufer et al., U.S. Pat. No. 3,876,551, and Boden et al, U.S. Pat. No. 4,390,448, which are incorporated herein.

Stable fragranced hypochlorite bleaching compositions are described, for example, in U.S. Patent No. 5,080,826.

Fillers or bulking agents may also be included in the bleaching compositions of the invention. A preferred filler salt is an alkali metal sulfate or an alkali chloride, such as potassium or sodium sulfate, the latter being especially preferred.

EXPERIMENTAL

Ex. 1. Sequestering Agent as a Whitening Enhancer To demonstrate the effectiveness of the inventive sequestering agents.

unbrightened. white cotton swatches were prewashed for 20 minutes in water containing 900 ppb Fe(II) and 300 ppb Mn(II) and various NaOCI bleach formulations in a U.S. Testing TERG-O-TOMETER bath that was maintained at a temperature of about 100 °F (37.8 0 The wash liquor comprised water with a hardness of 100 ppm of 3:1 (Ca:Mg) hardness and 1.5 mM bicarbonate.

(These levels are referred to herein as the baseline hardness and bicarbonate levels.) Enough of each bleach formulation (or bleach product) was added to the wash liquor to provide 200 ppm available chlorine. The enhancer refers to the additive (wt present in the bleach formulation prior to dilution in the wash liquor. Whiteness was determined by making pre-wash and post-wash 10 reflectance measurements on a Hunter Colorimeter without an ultraviolet filter. AW is a standard measure of whiteness derived from the colorimeter.

The more positive the number, the whiter the material. The results are tabulated in Tables 1 and 2.

TABLE 1 Bleach Enhancer in Product AW 1. A None -13.18 2. B None -11.15 3. C None -5.76 4. B 4.0% NaOH -10.44 5. B 1.8% Na 2

CO

3 -8.18 6. B 4.0% NaOH 1.8% NaCO 3 -10.33 7. B 4.0% NaOH 1.8% NaCO, 1% -10.98 Dipicolinic acid 8. B 1% KI -3.78 9. B 1% Picolinic Acid N-oxide -9.83 10. B 1% Trisodium Phosphate -2.93 LSD 2.39 TABLE 2 Bleach Enhancer in Product

AW

1. B None -13.70 2. B 2% of actives of SOKOLAN CP7" -1.15 3. B 2% of actives of ACUSOL 445N" -0.88 4. B 2% of actives of ACUSOL 479N -2.79 B 2% of actives of ACUSOL 505N T -3.21 6. C None -255 LSD 3.09 10 Bleach comprises aqueous 5.25% NaOCI solution which is available as CLOROX® LIQUID BLEACH from Clorox Co., Oakland. Calif.

Bleach comprises aqueous 5.25% NaOC1 solution with 0.65% NaOH.

Bleach comprises 5.8% NaCCI, 5.37% NaC1, 1.38% NaOH. 1.28% Na,CO 3 0.47% NaCIO,, and 0.86% NaO(SiO,) 2 ACUSOL 445N is polyacrylic acid. Na salt (MW 4,500). ACUSOL 479N is acrylic acid/maleic acid copolymer, Na salt (MW 70,000), ACUSOL 505N is acrylic acid/maleic acid copolymer. Na salt (MW 40,000) all from Rohm and Haas Co., SOKALAN CP7 is acrylic acid/maleic acid copolymer, Na salt (MW 50,000) from BASF Corp.

20 LSD is the least significant difference at a 95% confidence level.

The results in Table 1 demonstrate that formulation 3 which contains silicates reduced the adverse effects of hypochlorite slightly whereas increasing the alkalinity, in formulations 4-6, or adding dipicolinic acid or picolinic acid N-oxide, in formulations 7 and 9, respectively, had little effect. Increased alkalinity does improve the shelf stability of hypochlorite in the presence of the polycarboxylate sequestering agent, thus, preferably, the pH of hypochlorite bleaching compositions comprising the sequestering agents should have a pH of at least about 10. Formulations 8 and 9 reduced the adverse effects of hypochlorite significantly. Finally, the results in Table 2 further demonstrate that the presence of the inventive sequestering agents significantly reduced the deleterious effects of hypochlorite bleach.

-12- Examples 2-4 For Examples 2-4, unbrightened, white cotton swatches were washed in a commercial washer for 20 minutes in warm water (about 88°F (31"C) 105"F (40.6 0 having the baseline hardness and bicarbonate levels with no detergent present. The amount of each bleach product provided 200 ppm available chlorine. All samples were also rinsed at 68 °F (20"C) under the normal U.S. rinse cycles comprising presoak. agitation, and drainage.

Thereafter, the fabric was dried for 30 minutes in a dryer. Metals levels were 900 ppb Fe(III) and 300 ppb Mn(II). One soiled pillow case was used to add 10 soil. The polyacrylate sequestering agent usc.d was ACUSOL 445 N" (average MW 4500 daltons). Whiteness was determined by making pre-wash and postwash reflectance measurements on a Hunter Colorimeter without a uv filter. In each case, the AW and number of LSD units from unwashed cotton fabric were measured.

15 For Examples 2-7 herein, Bleach Product comprised an aqueous 5.25% NaOCI solution available as CLOROX 1 LIQUID BLEACH" from Clorox Co.. Oakland. Calif.. and Bleach Product comprised an aqueous 5.25% NaOCI and 0.65% NaOH solution.

Ex. 2. Effect of Sequesterine Agent Concentration on Whitening Ability Cotton swatches were washed in wash liquors each containing a different amount of the sequestering agent. Specifically. Bleach Product A (5.25% NaOCI) was formulated to contain varying amounts to of the polyacrylate. Each formulation was added to the washer at the presoak cycle.

The results are shown in Fig. I which is a graph of number of least significant difference units from unwashed cotton tAW) vs. the weight percent of active polymer added to Bleach Product A. As a comparison, the same wash -13using Bleach Product A, produced ALSD value of 0.53 when the water contained no Fe or Mn ions and no soil. The results suggest that hypochlorite bleach formulations containing about 0.02 sequestering agent produced good whitening enhancement when both soil and Fe and Mn metal ions are present.

However, above about 0.02 there is not a significant improvement in whitening whereas below about 0.02% there is a significant reduction.

Ex. 3. Effect of Sequestering Agent on Whitening Ability Essentially the same experiment as in Example 2 was conducted except that the weight percent of active polymer added ranged from 0.0 to 0.10%.

10 Sufficient amounts of samples were used in order to bring the available chlorine level up to 200 ppm. The results are shown in Fig. 2 which is a graph of number of LSD units from unwashed cotton (AW) vs. the weight percent of active polymer added to Bleach Product A. As a comparison, the same wash using Bleach Product A produced ALSD value of 0.52, when the water So: 15 contained no Fe or Mn ions and no soil. The results confirm that when the wash liquor contains significant levels of Fe (III) and Mn(II) ions, hypocihlorite bleach formulations containing about 0.02 sequestering metal is preferred to produce good whitening enhancement.

Ex. 4. Effect of Soil on Sequestering Agent Performance Cotton swatches were washed in wash liquors each comprising Bleach Products A or B, each containing varying amounts of the polyacrylate sequestering agent. Further each wash liquor comprised metal ions, (2) soil, or both metal ions and soil. The results are shown in Fig. 3 which is a graph of number of LSD units from unwashed cotton (1W) for the different wash liquor compositions. The results suggest that the extra sodium hydroxide in Bleach Product B (5.25% NaOCI and 0.65% NaOH' appears to provide a small consistently present, but not always statistically significant) increase in the whitening performance at low polycarboxylate polymer concentrations.

The hydroxide may neutralize some additional carboxylic acid sites on the polymer thereby providing more metal binding sites. In addition, in conjunction with Fig. 1, the data suggest that if 0.02% polycarboxylate is used, the presence of soil in the wash has little effect on the whitening performance of polymers in metal ion containing hypochlorite washes.

Examples 5 and 6 For Examples 5 and 6, cotton swatches were washed in a TERG-O- 10 TOMETER for 20 minutes in 100 *F (37.8 0 C) water with the baseline hardness and bicarbonate levels with no detergent present. The amount of each Bleach Product used provided 200 ppm available chlorine. All samples were rinsed in room temperature water and then dried for 30 minutes in a dryer. Metals levels were 900 ppb Fe(III) and 300 ppb Mn(II). No soil was added.

15 Whiteness was determined by making pre-wash and post-wash reflectance -measurements on a Hunter Colorimeter without a uv filter. In each case, the AW and number of LSD units from unwashed cotton were measured.

Ex. 5. Effect of Polycarboxylate Molecular Weight on Whitening Ability Cotton swatches were washed in wash liquors each comprising Bleach Product A or B and each containing either 0.05 or 2 of a sequestering agent selected from ACUSOL 445N polyacrylic acid, Na salt (MW 4,500), ACUSOL 479N acrylic acid/maleic acid copolymer, Na salt (MW 70,000), ACUSOL 505N acrylic acid/maleic acid copolymer. Na salt (MW 40,000) and SOKALAN CP7 acrylic acidimaleic acid copolymer, Na salt (MW 50,000). The results are shown in Fig. 4 which is a graph of number of LSD units from unwashed cotton (AW) for the different wash liquor compositions.

As a comparison, cotton swatches were also washed using Bleach Product A or B with no sequestering agents and the data are labeled as bars 1 and 2, respectively, in Fig. 4. The results suggest that variation of polymer chain length between 4.5k to 70k daltons has little effect on performance, and that substitution of another sequesterant of differing claim length should produce substantially equally good results.

Ex. 6. Effect of Hardness on Sequestering Agent Performance Cotton swatches were washed in wash liquors each comprising Bleach 10 Product A and having baseline or high hardness and either 0.001 0.01%, 0.05%, or 2 of a sequestering agent. ACUSOL 445N High hardness is 250 ppm of 2:1 (Ca:Mg) hardness and 3.0 mM bicarbonate.

Baseline hardness is 100 ppm of 3:1 (Ca:Mg) hardness and 1.5 mM bicarbonate. The results are shown in Fig. 5 which is a graph of number of 15 LSD units from unwashed cotton (AW) for the different wash liquor compositions. The results demonstrate that hardness does not effect polyacrylate performance in metal-hypochlorite washes.

Ex. 7. Effect of Sequestering Agent on Different Fabric Materials Cotton, polycotton, polyester, and nylon swatches were washed in wash liquor comprising: different Mn and Fe ion levels. (ii) Bleach Product A(5.25% NaOCI solution), and (iii) presence (PC) and absence (no PC) of a 0.01 w/w% of a sequestering agent, namely. ACUSOL 445N polyacrylic acid, Na salt (MW 4,500) in said Bleach Product. The swatches were washed in a TERG-O-TOMETER for 20 minutes in 100 'F (37.8*C) water with -16standard hardness and bicarbonate levels with no detergent present. The amount of each bleach product used provided 200 ppm available chlorine. All samples were rinsed under room temperature water and then dried for minutes in a dryer. No soil was added. Whiteness was determined by making pre-wash and post-wash reflectance measurements on a Hunter Colorimeter without a uv filter. In each case, the AW and number of LSD units from unwashed cotton were measured and calculated. The results are shown in Table 3 which indicate for each wash the number of AW units from unwashed cotton (AW) for the different wash liquor compositions and the calculated LSD for 10 each fabric. A is the difference between AWpc and AWNoc.

Metal ions ppb Mn, 120 ppb Fe ppb, Mn. 60 ppb Fe 40 ppl) M~n No metals added Cotton NoPC PC -1.2 0.9 -0.6 1.1 0.1 1.3 0.8 1.4

LSD

A

2.1 1.7 1.2 0.6 1.6 Table 3 Polycotton NoPC PC -1.1 1.0 -0.4 1.4 -0.4 1.1 0.0 0.9 LSDf Polyester NoPC PC -1.4 0.5 -0.9 0.2 -1.0 1.0 0.2 0.4

LSD

A

1.9 1 .1 2.0 0.3 1.2 NoPC -0.3 -0.3 -0.7 -0.2 Nylon

PC

0.2 0.4 0.6

LSD

-18- The data demonstrate that yellowing of fabric is appreciable when the level of iron ions is about 60 ppb in the wash liquor or when the manganese ions is about 20 ppb and that a polycarboxylate hypochlorite formulation can provide improved whitening at these metal levels.

Although only preferred embodiments of the invention are specifically disclosed and described above, it will be appreciated that many modifications and variations of the present invention are possible in light of the above teachings and witin the purview of the appended claims without departing from the spirit and intended scope of the invention.

*e

Claims (14)

1. A method for laundering fabrics with improved whitening and reduced fabric damage, said method comprising: a) providing, in a wash liquor containing at least about 40 ppb of iron cations or (ii) at least about 10 ppb of manganese cations, or (iii) the cations of both (i) and and a fabric piece; and b) adding prior to, contemporaneously with, or after, the step of providing said fabric piece to said wash liquor a liquid aqueous hypochlorite composition which comprises from about 4 to 15% by weight of an alkali metal hypochlorite and an effective o0 amount of a non-crosslinked polyacrylic acid polymer or a copolymer of acrylic acid and maleic acid, said polymer or copolymer having a molecular weight of about 1,000 to about 70,000 daltons to mitigate attack of said cations on said fabric; said hypochlorite composition further comprising an effective amount of buffer to achieve a pH of the composition of greater than about is 2. The method of claim 1 wherein the polymer or copolymer comprises at least 0.1 ppm by weight of said wash liquor. *i 3. The method of claim 1 or claim 2 wherein said polymer or copolymer comprises from about 0.0015% to about 5% by weight of said hypochlorite composition.

4. The method of any one of claims 1-3 wherein said fabric piece is 20 manufactured from cotton, polycotton, polyester, nylon materials and combinations thereof.

5. The method of any one of claims 1-4 wherein said hypochlorite composition additionally comprises at least one additional adjunct selected from the group consisting of buffers, builders, fluorescent whitening agents, pigments, dyes and thickening agents.

6. The method of any one of clams 1-4 wherein said hypochlorite composition further comprises a surfactant.

7. The method of any one of claims 1-6 wherein the wash liquor does not include a laundry detergent.

8. The method of any one of claims 1-7 wherein the said alkali metal hypochlorite is sodium hypochlorite which comprises about 4% to 8% of said composition.

9. A wash liquor containing at least about 40 ppb of iron cations or (ii) T at least about 10 ppb of manganese cations, or (iii) the cations of both and said 3 wash liquor further comprising: [R:\LIBZ]05811.doc:lam a) at least one fabric piece which has a tendency to be attacked by said cations in said wash liquor, and b) a liquid hypochlorite composition which includes from about 4 to by weight of an alkali metal hypochlorite and an effective amount of a non-crosslinked polyacrylic acid polymer or a copolymer of acrylic acid and maleic acid, said polymer or copolymer having a molecular weight of about 1,000 to about 70,000 daltons to mitigate attack of said cations on said fabric; said hypochlorite composition further comprising an effective amount of buffer to achieve a pH of the composition of greater than about The wash liquor of claim 9 wherein the polymer or copolymer o0 comprises at least 0.1 ppm by weight of said wash liquor.

11. The wash liquor of claim 9 or claim 10 wherein said fabric piece is manufactured from cotton, polycotton, polyester, nylon materials and combinations thereof

12. The wash liquor of any one of claims 9-11 wherein said polymer or 15 copolymer comprises from about 0.0015% to about 5% of said hypochlorite composition.

13. The wash liquor of any one of claims 9-12 wherein said hypochlorite composition additionally comprises at least one additional adjunct selected from the group consisting of buffers, builders, fluorescent whitening agents, pigments, dyes and thickening agents. 20 14. The wash liquor of any one of claims 9-12 wherein said hypochlorite composition further comprises a surfactant.

15. The wash liquor of any one of claims 9-14 wherein the wash liquor does not include a laundry detergent.

16. The wash liquor of any one of claims 9-15 wherein the said alkali metal hypochlorite is sodium hypochlorite which comprises about 4% to 8% of said composition.

17. A method for laundering fabrics, according to claim 1, substantially as hereinbefore described with reference to any one of the Examples.

18. A wash liquor according to claim 9, substantially as hereinbefore described with reference to any one of the Examples. Dated 21 October, 2002 ST The Clorox Company Patent Attorneys for the Applicant/Nominated Person oF SPRUSON FERGUSON [R:\LIBZ]05811.doc:lam