DE69633176T2 - Peroxygen bleach containing aminotri (methylenephosphonic acid) (ATMP), for pretreatment of tissues - Google Patents

Abstract

The present invention relates to aqueous, acidic compositions comprising a peroxygen bleach and amino tri(methylene phosphonic acid) (ATMP). The present invention further encompasses a process for pretreating soiled fabrics whereby the loss of tensile strength in said fabric is reduced and the color/dye damage of said fabric is reduced.

Description

technical area

The present invention relates to bleach-containing compositions, which are suitable for use as pretreatment, and a pretreatment process, through which the textile or fabric safety and / or color safety is improved. The liquid ones Compositions of the invention are also extremely stable, and the preferred Bleaching compositions herein are acidic.

Background of the invention

bleaching compositions were used in laundry applications as a laundry detergent, Laundry additives or even as a laundry washing pretreater extensively described.

In In fact, it is known such bleach-containing compositions in laundry pretreatment applications to use for the removal of encrusted stains / dirt and "problem" stains, like dope, Coffee, tea, grass, mud / clay-containing stains, which otherwise are extremely difficult to remove by means of a typical machine washing, to promote. However, there is one with such bleach-containing compositions associated disadvantage in that these compositions are the textiles to damage can, what in a dye damage and / or a loss of the tensile strength of the textile fibers, especially when under stress conditions in pretreatment applications be used, for. When applied directly to the tissue be and on the fabric for a long time to be left to work before the tissues are washed, especially if the tissue to be treated contains metal ions, such as copper, Contains iron, manganese or chromium. Without wishing to be bound by any theory it is assumed that a peroxygen bleach for the dye and textile damage, which is associated with these bleaching compositions, responsible can be. It is further believed that these metal ions on the surface textiles, especially on cellulose tissues, decomposition catalyze peroxygen bleaching, such as hydrogen peroxide. Thus, the decomposition of peroxygen bleach may result in damage to the Tissue and / or the dye result.

If these compositions are applied directly to the textiles, diffuse or migrate the different components in the compositions, possibly at different speeds, through the textile fibers. This is true as well the peroxygen bleaching component used for the pretreatment of textiles certain bleaching compositions.

It now becomes a solution that of the pretreatment of textiles with bleaching compositions which containing a peroxygen bleach, resulting from damage Addition of a specific textile protection provided, which effective in reducing textile and / or dye damage is. It has been found that this textile protective agent, aminotri (methylenephosphonic acid) - hereinafter referred to as ATMP - the with the treatment of textiles containing peroxygen bleach Compositions related damage, especially those Textiles which are contaminated with metal ions, significantly reduced.

Accordingly The present invention satisfies the long-felt need on an effective bleaching composition for use as a pretreater, the damage does not promote textiles, suitable is. About that In addition, the compositions of the present invention provide excellent performance, when used in other applications regardless of the laundry pretreatment application used, as in other laundry applications, as a laundry detergent or as a laundry detergent additive, or even in applications for cleaning hard surfaces or in Carpet cleaning applications.

In the compositions of the present invention which are liquid compositions represent ATMP continues to have the advantage of an exceptional chemical stability for the Peroxygen bleach available.

State of technology

Peroxygen bleach-containing compositions have been extensively described in the art. For example, the EP 629 691 A Emulsions of nonionic surfactants to comprising a silicone compound, and optionally hydrogen peroxide or a water-soluble source thereof. The EP 629 690 A discloses emulsions of nonionic surfactants comprising a terephthalate-based polymer and optionally hydrogen peroxide or a water-soluble source thereof. The EP 209 228 B discloses compositions comprising a peroxide source, such as hydrogen peroxide, and an aminopolyphosphonate, such as ATMP. The EP 209 228 B discloses that the hydrogen peroxide-containing compositions can be used as a stain pretreatment agent. See also U.S. Patent No. 4,891,147, issued January 2, 1990, and U.S. Patent No. 5,019,289, issued May 28, 1991. ATMP-containing compositions have been used in a laundry context in the U.S. Pat EP 517 605 describing DD 280 783 and DD 280 784. However, the compositions therein do not include peroxygen bleach. Chem. Abstracts 92: 112646w describe colorless bleaches containing Na-percarbonate and ATMP.

Summary the invention

The The present invention comprises an aqueous liquid composition comprising Hydrogen peroxide, ATMP and 0.5% to 20% by weight of the total composition a bleach activator. Preferred compositions are liquid aqueous compositions, which has a pH greater than 0 to 6 and a viscosity of 1 MPa · s or more, preferably from 50 to 2000 MPa · s, at 20 ° C as measured by a Brookfield viscometer at 50 rpm with a No. 3 spindle.

The The present invention further comprises a process for pretreatment of textiles with a liquid, aqueous A composition comprising a peroxygen bleach and ATMP, preferably in undiluted Form, on the textile and leaving the composition in contact with the textile, preferably without drying the Composition on the textile before washing the textile.

Under "Pretreatment of contaminated textiles " the application of the aqueous Composition in its undiluted Form on the soiled textile and leave to act on the textile before the textile is washed, understood. Alternatively, the aqueous Composition on the textile substrate together with for wetting enough water is applied to the textile.

All Percentages, ratios and parts herein are by weight of total liquid composition, unless otherwise stated.

detailed Description of the invention

The The present invention comprises a composition comprising a Contains peroxygen bleach and ATMP. It was found that ATMPs containing the treatment of textiles containing peroxygen bleach Compositions related damage, especially those Textiles containing metal ions such as copper, iron, chromium and manganese included, significantly reduced.

Textile retardants

When Textile protectants include the compositions herein ATMP, d. H. the compound of the formula:

Preferably the compositions herein comprise from 0.005% to 5.0% by weight, most preferably 0.01% to 1.0% by weight of the total bleaching composition to ATMP.

The compositions according to the present invention are aqueous liquid cleaning compositions. The aqueous compositions should be formulated at an acidic pH, preferably at a pH of greater than 0 to 6, and more preferably at a pH of from 3 to 5. The formulation of the compositions of the present invention in the acidic pH range contributes to the stability of the compositions. The pH of the compositions of the present invention can be adjusted by using tion of organic and inorganic acids or bases.

Tensile Test Method - By "fabric damage" herein is meant the degree of loss of the tensile strength of a fabric. The loss of fabric tensile strength can be determined as follows: Krefeld cotton tapes (12.5 x 5 cm ^{2 in} size) with a copper (2+) concentration of 30 ppm per gram of cotton are mixed with 2 ml of the test composition according to Example I. treated. The test composition is left in contact with the bands for 24 hours. The ribbons are then rinsed with water, and the loss of tensile strength is measured with an INSTRON ^®, model no. 4411th Damage to the cotton bands is determined by pulling the bands until they burst. The necessary to burst the bands force, that is the ultimate tensile stress (Ultimate Tensile Stess), is measured using an Instron ^® Model 4411, while the ribbons are wet. The lower the force needed to rupture the cotton bands, the more severe the damage caused in the fabrics. Good reliability (standard deviation = 2-4 kg) of the results is obtained when five repetitions are scheduled for each test.

Peroxygen bleach - An essential Element of the compositions of the present invention is the Peroxygen bleach, wherein the peroxygen bleach is hydrogen peroxide is. In fact, the presence of hydrogen peroxide mediates excellent cleaning benefits, especially in laundry applications are recognizable.

An "effective amount" of a peroxygen bleach is any one for measurable improvement of dirt / stain removal from the soiled textile substrates compared to pers oxygen bleach-free Compositions suitable amount when the soiled substrate is washed by the consumer in the presence of alkali. typically, For example, the compositions of the present invention comprise 0.5% by weight. up to 20% by weight of the total composition of peroxygen bleach, preferably from 1% to 15% by weight, and most preferably 2 wt .-% to 6 wt .-%.

Bleach activators - The peroxygen-containing Compositions herein further comprise a bleach activator. By bleach activator is meant herein a compound which reacted with hydrogen peroxide to form a peracid. The thus formed peracid represents the activated bleach. Particularly preferred is acetyl triethyl citrate. The bleach activator is in the composition herein in one Proportion of from 0.5% by weight to 20% by weight, preferably from 2% by weight to 10 wt%, most preferably from 3 wt% to 7 wt% of the total composition in front.

Suitable bleach activators herein are any known activators typified by NOBS (nonanoyloxybenzenesulfonate), TAED (tetraacetylethylenediamine) or ATC (acetyltriethyl citrate). A variety of other bleach activators are known. See, for example, the activators described in U.S. Patent 4,915,654, issued April 10, 1990 to Mao et al., And U.S. Patent 4,412,934. See also US 4,634,551 with regard to other typical conventional bleach activators. Also known are amido-derived bleach activators of the formulas:
R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L where R ^{1 is} an alkyl group containing from about 6 to about 12 carbon atoms R ² is alkylene containing from 1 to about 6 carbon atoms, R ^{5 is} H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. Further examples of bleach activators of the above formula include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof as described in U.S. Patent 4,634,551. Another class of bleach activators includes the benzoxazine-type activators described by Hodge et al. in U.S. Patent 4,966,723, issued October 30, 1990. Yet another class of bleach activators include acyl lactam activators such as substituted and unsubstituted benzoyl caprolactam, t-butyl benzoyl caprolactam, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3.5 , 5-trimethylhexanoylvalerolactam, t-butylbenzoylvalerolactam and mixtures thereof.

Preferred bleach activators useful herein include those selected from the group consisting of acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, n-octanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, Nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and mixtures thereof. Particularly preferred are the bleach activators, which are liquid at room temperature or an oil. Examples of liquid bleach activators are acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexa noylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, and mixtures thereof. The present compositions may optionally include aryl benzoates, such as phenyl benzoate.

Pretreatment process - though the preferred use of the compositions described herein the laundry washing pretreatment represents, can the compositions according to the present invention Invention as well as laundry detergent or as a laundry detergent booster and as a household cleaner in the bathroom or in the kitchen, for cleaning dishes or carpets are used.

The liquid Composition may be in contact with the textile, typically within a period of 1 minute to 24 hours, preferably from 1 minute to 1 hour, and more preferably 5 minutes to 30 minutes, or such that drying of the liquid composition on the textile is avoided, remain. Optionally, the liquid Compositions according to the present invention Invention when the textile is contaminated with encrusted stains / dirt are otherwise relatively difficult to remove, for example by means of a sponge or a brush or simply by rubbing of two parts of the textile rubbed against each other and / or brushed in become.

By "washing" herein is meant simple rinsing the textile with water or washing the textiles with conventional Compositions comprising at least one surfactant by means of a washing machine or just by hand understood.

By "in undiluted form" is meant herein that the liquid described herein Compositions on the pretreated textiles without any Kind of dilution be applied, d. H. they are applied as described herein.

Other conventional Ingredients for Cleaning Compositions - The Bleaching compositions herein typically also include others optional conventional Components for improving or modifying the performance. typical non-limiting examples of such ingredients will be given below described for the convenience of the formulator.

organic Stabilizers - The Compositions herein can be used optionally also organic stabilizers to improve the chemical stability of the composition, provided that such materials be formulated compatible or suitable. Organic stabilizers can be selected from the following group: monopenoles, such as 2,6-di-tert-butylphenol or 2,6-di-tert-butyl-4-methylphenol; Diphenols, such as 2,2'-methylenebis (4-methyl-6-tert-butylphenol) or 4,4'-methylenebis (2,6-di-tert-butylphenol); Polyphenols such as 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) benzene; Hydroquinones, such as 2,5-di-tert-amylhydroquinone or tert-butylhydroquinone; aromatic amines such as N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine or N-phenyl-α-naphthylamine; dihydroquinolines, such as 2,2,4-trimethyl-1,2-dihydroquinoline; Ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), as well as Mixtures thereof.

organic Stabilizers are typically used in the present invention at levels of from 0.01% to 5.0% by weight, more preferably from 0.05% by weight to 0.5% by weight.

The peroxygen bleach-containing compositions according to the present invention may further comprise from 0.5% to 5%, preferably from 2% to 4%, by weight of the total composition of an alcohol according to the formula -HO-CR'R ''-OH, wherein R' and R "independently represent H or a C ₂ -C ₁₀ hydrocarbon chain and / or a ring. A preferred alcohol according to this formula is propanediol.

inorganic Stabilizers - Examples for inorganic Stabilizers include sodium stannate and various alkali metal phosphates, like the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.

Detergents surfactants - surfactants are useful herein because of their usefulness Cleaning power usable and can in preferred embodiments of the present compositions in the usual detergents useful Be included. In general, surfactants include 0.1 Wt% to 50 wt%, preferably 1 wt% to 30 wt%, especially preferably from 5% to 25% by weight of the bleaching compositions herein.

Non-limiting examples of surfactants useful herein include the conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ( "LAS") and primary, branched-chain and random C ₁₀ -C ₂₀ alkyl sulfates ( "AS"); the secondary C ₁₀ -C ₁₈ alkyl sulfates of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ ) GH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) CH ₂ CH ₃ , wherein x and (y + 1) are integers of at least about 7, more preferably at least about 9, and M is a water-solubilizing cation, especially sodium; unsaturated sulfates, such as oleyl sulfate; the C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AE _x S"), especially those wherein x ranges from 1 to about 7; C ₁₀ -C ₁₈ alkyl alkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates); the C ₁₀ -C ₁₈ glycerol ethers; the C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides; and C ₁₂ -C ₁₈ alpha-sulfonated fatty acid esters. Detersive surfactants may be mixed in various proportions for improved surfactant activity as known in the art. Also optionally included in the compositions are conventional nonionic and amphoteric surfactants, such as the C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including the so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylate / propoxylates ), and C ₁₂ -C ₁₈ betaines and sulfobetaines ("sultaines"), C ₁₀ -C ₁₈ amine oxides and the like may also be included in the cleaning compositions. The C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ₁₂ -C ₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. The N-propyl through N-hexyl C ₁₂ -C ₁₈ glucamides can be used for low foaming. Conventional C ₁₀ -C ₂₀ soaps can also be used. If foaming is desired, the branched chain C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful.

Builder - Detergensbuilder can optionally included in the compositions herein, to support the regulation or control of the mineral hardness. inorganic as well as organic builders can be used. Builders are typically used in fabric washing compositions used to aid in the removal of particulate soil.

Of the Share of builders can be dependent the end use of the composition and its desired vary widely in physical or physical form. Provided When present, the compositions typically comprise at least 0.1% builder.

organic Detergent builders suitable for the purpose of the present invention are, but are not limited to, a broad one Variety of polycarboxylate compounds. As used herein "polycarboxylate" on compounds with a plurality of carboxylate groups, preferably with at least 3 carboxylates. Polycarboxylate builders can generally be incorporated into the Composition in acid form can be added, however they may also be added in the form of a neutralized salt or overbased. When used in salt form, alkali metal, such as sodium, potassium and lithium or alkanolammonium salts.

In The polycarboxylate builders include a variety of Categories more useful Materials. An important category of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinate, as in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972 becomes. See also "TMS / TDS" builder of the US patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable Etherpolycarboxylates also include cyclic compounds, in particular alicyclic compounds such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful Detergent builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and Carboxymethylbernsteinsäure, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, like nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and suitable salts thereof.

Citrate builders, z. Citric acid and suitable salts thereof (especially the sodium salt) are polycarboxylate builders of particular importance due to their availability from renewable sources and their biodegradability. Oxydisuccinates are just as special useful in such compositions and combinations.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984 issued on January 28, 1986 to Bush. Useful succinic acid builders include the C ₅ -C ₂₀ alkyl and alkenyl succinic acids and the salts thereof. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.

laurylsuccinates are the preferred builders of this group and are disclosed in the European patent application 86200690.5 / 0,200,263, published on November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 on March 13, 1979 to Crutchfield et al., and U.S. Patent 3,308,067 on the 7th of March 1967 to Diehl, described. See also U.S. Patent 3,723,322.

Fatty acids, e.g. C ₁₂ -C ₁₈ monocarboxylic acids may also be incorporated into the compositions alone or in combination with the above builders, especially the citrate and / or succinate builders, to provide additional builder activity. Such use of fatty acids generally results in a reduction of foaming in laundry compositions, which may be considered important by the formulator.

If Phosphorus-based builders can be used, and especially in the hand-laundry process, can the various alkali metal phosphates, such as the well-known sodium tripolyphosphates, Sodium pyrophosphate and sodium orthophosphate. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and others known in the art Phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used although such materials are conventional in low proportions as complexing agents or stabilizers be used.

inorganic or P-containing detergent builders, but without limited, alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, Pyrophosphates and the vitreous polymeric metaphosphates), phosphonates, phytic acid, Silicates, carbonates (including Bicarbonates and sesquicarbonates), sulfates and aluminosilicates.

Complexing Agents in Addition to ATMP - The compositions herein may also optionally contain transition metal-selective complexing agents or "chelating agents", e.g. Ferrous and / or copper and / or manganese complexing agents, provided that such materials can be formulated as compatible or suitable. Complexing agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic complexing agents, and mixtures thereof. Without wishing to be bound by any theory, it is believed that the benefit of these materials is in part due to their exceptional ability to remove iron, copper and manganese ions from the wash solutions by forming soluble chelates; Other advantages include the prevention of inorganic films or limestone inhibition. Commercial complexing agents for use the DEQUEST ^® series, as well as complexing agents herein comprise from Monsanto, DuPont, and Nalco, Inc.

aminocarboxylates, which are useful as optional complexing agents will continue to be by ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, Nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetramine hexaacetates, Diethylene triamine pentaacetates and ethane diglycines, alkali metal, Ammonium and substituted ammonium salts thereof clarified. in the general can Complexing agent mixtures for a combination of functions, such as the regulation of several transition metals, the long-term product stabilization and / or the regulation of precipitated transition metal oxides and / or hydroxides.

Polyfunctionally-substituted Aromatic complexing agents are also useful in the compositions here in. See U.S. Patent 3,812,044, issued May 21 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), particularly (but not limited to) the [S, S] isomer as disclosed in U.S. Patent 4,704,233, issued November 3, 1987 Harman and Perkins, is described. The Trisodium salt is preferred, although other forms, such as magnesium salts, may also be useful.

worin R₁, R₂, R₃ und R₄ unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus -H, Alkyl, Alkoxy, Aryl, Aryloxy, -Cl, -Br, -NO₂, -C(O)R' und -SO₂R''; worin R' ausgewählt ist aus der Gruppe, bestehend aus -H, OH, Alkyl, Alkoxy, Aryl und Aryloxy; R'' ausgewählt ist aus der Gruppe, bestehend aus Alkyl, Alkoxy, Aryl und Aryloxy; und R₅, R₆, R₇ und R₈ unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus -H und Alkyl.Another preferred complexing agent for use herein follows the formula:

wherein R ₁ , R ₂ , R ₃ and R _{4 are} independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO ₂ , -C (O) R ' and -SO ₂ R "'; wherein R 'is selected from the group consisting of -H, OH, alkyl, alkoxy, aryl and aryloxy; R '' is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy; and R ₅ , R ₆ , R ₇ and R _{8 are} independently selected from the group consisting of -H and alkyl.

Amino phosphonates are equally useful for use as a complexing agent in the compositions of the invention, provided that at least small amounts of total phosphorus in the detergent compositions are permitted, and include Ethylenediaminetetrakis (methylenephosphonates) and the diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates contain no alkyl or Alkenyl groups with more than about 6 carbon atoms.

Provided They include the chelating agents or the transition metal-selective complexing agents preferably from 0.001% by weight to 10% by weight, particularly preferably 0.05 From 1% to 1% by weight of the compositions herein.

polymers Protective Repellent - One any polymeric antisoiling agent that is familiar to those skilled in the art is known in the art, optionally in the compositions and methods of the present invention. polymers Stain repellents are provided by both hydrophilic segments Hydrophilization of the surface hydrophobic fibers, such as polyester and nylon, as well as through hydrophobic segments for settling on hydrophobic chamfers and adherent Stay on it until the completion of the washing and rinsing, whereby she as an anchor for serve the hydrophilic segments, characterized. This one can easier cleaning of stains after treatment with the soil repellent agent occur in later washing procedures.

The polymeric soil release agents useful herein include, in particular, those soil release agents comprising: (a) one or more nonionic hydrophilic components consisting essentially of (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 segment does not comprise oxypropylene units except when attached to adjacent units by ether linkages at each end, or (iii) a mixture of oxyalkylene units, which are oxyethylene and 1 to 30 Oxypropylene units, wherein the mixture contains a sufficient amount of oxyethylene units such that the hydrophilic component has sufficient hydrophilicity to increase the hydrophilicity of conventional synthetic polyester fiber surfaces by depositing the soil release agent on such surface; Preferably, segments comprise at least 25% oxyethylene units, and more preferably, especially for those components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) C ₃ oxyalkylene terephthalate segments, wherein, if the hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is 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 (preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv ) C ₁ -C ₄ alkyl ethers or C ₄ hydroxyalkyl ether substituents, or mixtures thereof, wherein the substituents are in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof, and wherein Cellulose derivatives are amphiphilic, thereby providing a sufficient proportion of C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units to settle on conventional synthetic polyester fiber surfaces and to retain sufficient The amount of hydroxylene, once deposited on such conventional synthetic fiber surfaces, for increasing fiber surface hydrophilicity, or with a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization of from 1 to about 200, although higher grades can be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable hydrophobic oxy-C ₄ -C ₆ alkylene segments include, but are not limited to, end caps of polymeric soil release agents such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, wherein M is sodium and n is an integer from 4 to 6, as described in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, are described.

Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate and propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL ^® (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose; See U.S. Patent 4,000,093, issued December 28, 1976 to Nicol et al.

Soil-repelling agents characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester), e.g. C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987, by Kud et al. Commercially available soil release agents of this kind include the SOKALAN ^® -type materials from such. B. SOKALAN HP-22 ^®, available from BASF (West Germany).

One Type of preferred soil-repelling agent is a copolymer with statistical blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See the US patent 3,959,230, issued May 25, 1976 to Hays, and the US Patent 3,893,929, issued July 8, 1975 to Basadur.

Another preferred polymeric soil release agent is a polyester having repeat units of ethylene terephthalate units containing 10 to 15 weight percent ethylene terephthalate units along with 90 to 80 weight percent polyoxyethylene terephthalate units derived from a 300 weight average molecular weight polyoxyethylene glycol up to 5,000. Examples of this polymer include the commercially available material ZELCON 5126 ^® (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

One Another preferred polymeric soil release agent is one sulfonated product of a substantially linear ester oligomer, comprising an oligomeric ester backbone from terephthaloyl and oxalkyleneoxy repeat units and terminal Units covalently bonded to the backbone. These Stain repellents are fully described in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink, described. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730 issued on December 8, 1987 to Gosselink et al., the anionic end-capped oligomeric esters of US Pat. No. 4,721,580, issued Dec. 26. January 1988 to Gosselink, and the oligomeric block polyester compounds U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

preferred polymeric soil release agents also close the soil release U.S. Patent 4,877,896, issued October 31, 1989 Maldonado et al., which include anionic, especially sulfoaroyl, end-capped terephthalate esters disclose.

Yet Another preferred soil release agent is an oligomer with repeating units of terephthaloyl units, sulfoisoterephthaloyl units, Oxyethyleneoxy and oxy-1,2-propylene units. The repeat units make up the backbone of the oligomer and are preferably terminated with modified isethionate endcapes. A particularly preferred soil release agent of this type comprises approximately a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two end-capping units of sodium 2- (2-hydroxyethoxy) ethanesulfonate. This soil release agent also comprises from 0.5% to 20% by weight. the oligomer of a crystallinity-reducing Stabilizer, preferably selected from the group consisting from xylenesulfonate, cumene sulfonate, toluenesulfonate, and mixtures from that. See the US patent No. 4,415,807, issued May 16, 1995 to Gosselink et al.

When used, the soil release agents generally comprise from 0.01% to 10% by weight of the detergent compositions herein, typically from 0.1% to 5% by weight, preferably 0.2 wt .-% to 3.0 wt .-%.

Other Ingredients - detergent ingredients and adjuvants optionally in the present compositions added are, can one or more materials to support or enhance the Cleaning performance, the treatment of the substrate to be cleaned or those which for improving the appearance of the compositions are included. Such materials are disclosed in U.S. Patent No. 3,936,537, Baskerville et al., further described. Aids, which also in the compositions of the present invention as conventionally established in the art Use levels (generally from 0% to 20% of the detergent ingredients, preferably from 0.5% to 10%), others include Active ingredients, such as dispersing polymers from BASF or from Rohm &Haas; misting and / or anti-corrosion agents, dyes, fillers, optical brighteners, Germicides, hydrotropes, enzyme stabilizing agents, fragrances, Solubilizer, clay soil removal / anti-redeposition agent, Carriers, Processing aids, pigments, solvents, fabric softeners, Static control, etc., a.

dye transfer Medium - The Compositions of the present invention may also include one or more Include materials which in the inhibition of transmission of dyes from a dyed surface to another while the cleaning process are effective. In general, such include farbstoffübertragungsinhibierenden Medium Polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, Peroxidases, as well as mixtures thereof. If used, include these agents typically 0.01% to 10% by weight of the composition, preferably 0.01% by weight to 5% by weight and particularly preferably 0.05% by weight to 2% by weight.

In particular, the polyamine N-oxide polymers which are preferred for use herein contain units having the following structural formula: RA _x -P; wherein P represents a polymerizable moiety to which an NO group may be attached, or wherein the NO group may form part of the polymerizable moiety, or wherein the NO group may be bonded to both moieties; A has one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R comprises aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the NO group may be attached or wherein the NO group may constitute part of these groups. Preferred polyamine N-oxides are those wherein R represents a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

worin R₁, R₂, R₃ aliphatische, aromatische, heterocyclische oder alicyclische Gruppen oder Kombinationen davon sind; x, y und z 0 oder 1 darstellen; und der Stickstoff der N-O-Gruppe an irgendeine der vorstehenden Gruppen gebunden sein kann oder einen Teil davon bilden kann. Die Aminoxid-Einheit der Polyamin-N-oxide besitzt einen pKa < 10, vorzugsweise einen pKa < 7, besonders bevorzugt einen pKa < 6.The NO group can be represented by the following general structures:

wherein R ₁ , R ₂ , R _{3 are} aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z represent 0 or 1; and the nitrogen of the NO group may be attached to or form part of any of the above groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably a pKa <7, more preferably a pKa <6.

One every polymer backbone may be used as long as the amine oxide polymer formed is water-soluble and dye transfer inhibiting Features. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyesters, polyamide, polyimides, Polyacrylates and mixtures thereof. These polymers include statistical or block copolymers wherein a monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a relationship from amine to amine N-oxide from 10: 1 to 1: 1,000,000. however may be the number of amine oxide groups present in the polyamine oxide polymer by suitable copolymerization or by a suitable degree of N-oxidation be varied. The polyamine oxides can be produced in almost all degrees of polymerization to be obtained. Typically, the average molecular weight is within the range of 500 to 1,000,000; particularly preferred from 1,000 to 500,000; most preferably from 5,000 to 100,000. This preferred class of materials may be referred to as "PVNO" become. The most preferred polyamine N-oxide used in the detergent compositions useful herein is poly (4-vinylpyridine-N-oxide), which has an average molecular weight of 50,000 and an amine too Amine N-oxide ratio of 1: 4.

copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (designated as a class "PVPVI") are also to Use herein preferred.

Prefers the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization ".) The PVPVI copolymers exhibit typically a molar ratio from N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched.

The Compositions of the present invention may also be a polyvinylpyrrolidone ("PVP") with a medium Molecular weight from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. The PVP's are the Person skilled in the field of detergents; see for example EP-A-262,897 and EP-A-256,696. The PVP-containing compositions may also be polyethylene glycol ("PEG") with a middle one Molecular weight of 500 to 100,000, preferably 1,000 to 10,000, included. Preferably, the ratio of PEG to PVP ranges to one ppm basis, which in washing solutions is released from 2: 1 to 50: 1, and more preferably from 3: 1 to 10: 1.

Foaming boosters - If high foaming is desired, suds boosters such as C ₁₀ -C ₁₆ alkanolamides can be incorporated into the compositions typically in proportions of 1% to 10%. The C ₁₀ -C ₁₄ monoethanol and diethanolamides are a typical class of such suds boosters. The use of such suds boosters with high sudsing auxiliary surfactants, such as the amine oxides, betaines and sultaines described above, is also advantageous. If desired, soluble magnesium salts such as MgCl ₂ , MgSO ₄ and the like can be added in levels of, for example, 0.1% to 2% to provide additional suds and to enhance lubricity removal performance.

Brightener - Any optical brighteners, fluorescent whiteners or other whitening agents or whitening Means known in the art can be used in the present compositions are incorporated when used for textile treatment or -wash are provided, in proportions of typically 0.05 wt .-% to 1.2% by weight of the detergent compositions herein. Commercial optical brighteners, which may be useful in the present invention can be found in Subgroups are classified which, albeit without necessarily to be limited to derivatives of stilbene, pyrazoline, coumarin, Carboxylic acids, Methine cyanines, dibenzothiophene-5,5-dioxide, azoles, heterocyclic Include brighteners with 5- and 6-membered rings, where this list is for clarification and by no means limiting. Examples such brighteners are in "The Production and Application of Fluorescent Brightening Agents ", M. Zahradnik, published by John Viley & Sons, New York (1982).

Specific examples of optical brighteners useful in the present compositions are those described in U.S. Patent 4,790,856, issued December 13, 1988 to Wixon. These brighteners include the PHORWHITE ^{® range} of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA ^®, Tinopal CBS and Tinopal ^® 5BM ^®, available from Ciba Geigy; Artic White CC and Artic White CWD ^{® ®,} available from Hilton-Davis, located in Italy; the 2- (4-styrylphenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1,2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 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 also U.S. Patent 3,646,015, issued to Hamilton on February 29, 1972. Anionic brighteners are typically preferred herein.

Bleach catalysts - if so he wishes can the compositions herein additionally a catalyst or accelerator for further improving the Bleaching or dirt removal included. Any suitable Bleach catalyst can be used. For those in a total proportion from 1,000 to 5,000 ppm of detergent compositions used in water the composition typically provides a concentration of approximately 0.1 ppm to 700 ppm, more preferably from 1 ppm to 50 ppm, or less of the catalyst species in the wash liquor.

Typical bleach catalysts include a transition metal complex, for example, one wherein the metal-coordinating ligands are quite stable to labilization, and which does not deposit metal oxides or hydroxides to any appreciable extent under typical alkaline washing conditions. Such catalysts include manganese-based catalysts disclosed in U.S. Patent 5,246,621; the US 5,244,594 ; the US 5,194,416 ; the US 5,114,606 ; and EP 549,271 A1, 549,272 A1, 544,440 A2 and 544,490 A1; preferred examples of these catalysts include Mn ^IV ₂ (μ-O) ₃ (TACN) ₃ - (PF ₆ ) ₂ , Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ (ClO ₄ ) ₂ , Mn ^IV 4 (μ-O) ₆ (TACN) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV 4- (μ-O) ₁ (μ-OAc) ₂ - (TACN) ₂ - (ClO ₄ ) ₃ , Mn ^IV - (TACN) - (OCH ₃ ) ₃ (PF ₆ ), as well as mixtures thereof, wherein TACN is trimethyl-1,4,7-triazacyclononane or an equivalent macrocycle; Thus, alternating metal coordinating ligands as well as mononuclear complexes are also possible, and monometallic as well as di- and polymetallic complexes and complexes with alternating metals, such as iron or ruthenium, all fall within the present scope. Other metal-based bleach catalysts include those disclosed in U.S. Patent 4,430,243 and U.S. Patent 5,114,611. The use of manganese with various complexing ligands to enhance bleaching is also disclosed in the following U.S. patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Transition metals can with suitable donor ligands, which with respect to the function of the selected metal, its oxidation state and denticity the ligands selected are precomplexed or complexed in situ. Other complexes, which are included herein are those of WO 95/25159, which the priority U.S. Application No. 08 / 210,186, filed March 17, 1994 claimed.

Pre-treatment preparation - The preferred Compositions of the present invention are liquid a viscosity of 1 MPa · s or more at 20 ° C, when using a Brookfield viscometer at 50 rpm with a Spindle No. 3 are measured, more preferably from 50 to 2,000 MPa · s and more preferably from 200 to 1,500 MPa · s. Any surfactant system or polymeric thickener, which in the prior art for increasing the viscosity A composition is known to achieve the preferred viscosity be used. Thus, you can the surfactants used herein thickening surfactants, such as nonionic, anionic, cationic, zwitterionic and / or amphoteric surfactants, be.

The liquid Bleaching composition herein includes water in any amount of up to 98% by weight of the total composition. Preferably include the compositions herein are from 5% to 98% by weight, more preferably From 10% to 95% by weight of the bleaching composition of water.

If the liquid ones Peroxygen bleach-containing compositions according to the present invention further comprising an optional bleach activator, it is highly desirable herein, the compositions either as a microemulsion or as a to formulate stable emulsion.

If it is formulated as a microemulsion comprises the composition the bleach activator in a matrix of water, peroxygen bleach and hydrophilic anionic and nonionic surfactants. suitable Anionic surfactants herein include the alkylbenzenesulfonates, alkyl sulfates, alkylalkoxylated sulfates, as well as mixtures thereof. Suitable nonionic Surfactants for use in the microemulsions herein include hydrophilic nonionic surfactants as described below for the emulsions according to the present Invention are defined.

When formulated as an emulsion, the composition comprises at least one hydrophilic surfactant having an HLB (hydrophilic-lipophilic balance) or equal to 10 and at least one hydrophobic surfactant having an HLB of up to 9, wherein the bleach activator is emulsified by these surfactants. The two different surfactants must have different HLB values in order to form stable emulsions, and preferably the difference in HLB values of these two surfactants is at least 1, preferably at least 3. In other words, by suitably combining at least two of the surfactants emulsions which are stable with different HLB values in water, ie emulsions which essentially do not separate into two separate layers on standing within at least two weeks at 40 ° C., preferably at 50 ° C. The emulsions comprise from 2% to 50% by weight of the total composition of the hydrophilic and hydrophobic surfactants, preferably from 5% to 40% and more preferably from 8% to 30% by weight. The emulsions comprise at least 0.1% by weight, preferably at least 3% by weight, more preferably at least 5% by weight of the total emulsion of one or more hydrophobic surfactants and at least 0.1% by weight, preferably at least 3% by weight. -%, particularly preferably at least 5 wt .-% of the total emulsion of one or more hydrophilic surfactants. Preferred for use herein are the hydrophobic nonionic surfactants and hydrophilic nonionic surfactants. These hydrophobic nonionic surfactants to be used herein have an HLB of up to 9, preferably below 9, more preferably below 8, and the hydrophilic surfactants have an HLB above 10, preferably above 11, more preferably above 12. Ge Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols, preferably fatty alcohol ethoxylates and / or propoxylates. A variety of alkoxylated fatty alcohols are commercially available which have extremely different HLB values. For a further discussion of HLB theory and its application to the formation of emulsions, reference is made to "Encylopedia of Emulsion Technology"; Becher, P .; Marcel Dekker, Inc .: New York, 1985, Volumes 1 and 2 and the references cited therein.

In a particularly preferred embodiment of the emulsion, it if is present, wherein the emulsions acetyl include as a bleach activator, an adequate nonionic surfactant system would a hydrophobic nonionic surfactant with for instance an HLB of 6, such as a Dobanol ^® 23-2 and a hydrophilic nonionic surfactant with for example, an HLB of 15, such as a Dobanol ^® 91-10 comprise. Other suitable nonionic surfactant systems comprise for example a Dobanol ^® 23-6.5 (HLB about 12) and a Dobanol ^® 23 (HLB below 6) or a Dobanol ^® 45-7 (HLB = 11.6) and Lutensol ^® TO3 (HLB = 8th). Dobanol ^® are commercially available nonionic surfactants available from Shell Corp. are available. Lutensol ^® are commercially available nonionic surfactants available from BASF Corp. are available.

The peroxygen bleach-containing compositions according to the present invention may further comprise an amine oxide surfactant according to the formula R1R2R3NO, wherein R1, R2 and R3 are each independently a C ₆ -C ₃₀ -, preferably a C ₁₀ -C ₃₀ -, preferably most represent a C ₁₂ -C ₁₆ hydrocarbon chain. It has further been found that in a pretreatment process, the presence of the amine oxide further improves the cleaning performance against particulate stains and / or smudges. It is believed that this improvement in cleaning performance is matrix-independent. To achieve one of these advantages, the amine oxides, if present, should be present in amounts ranging from 0.1% to 10% by weight of the total composition, preferably from 1.5% to 3% by weight. % exist.

The following examples illustrate the composition of the present invention but are not intended to be limiting thereof. All materials in the examples meet the functional limitations herein. Formulation I Na-alkyl sulfate 2.0 Dobanol ^® 45-7 6.5 Dobanol ^® 23-3 8.5 ATC 3.5 H ₂ O ₂ 4.0 BHT 0.05 ATMP 0.15 H ₂ SO ₄ up to pH 4 water Rest on 100% Formulation II Na-alkyl sulfate 12.0 Dobanol ^® 45-7 6.0 Dobanol ^® 23-6.5 6.0 ATC 3.5 H ₂ O ₂ 6.0 BHT 0.05 ATMP 0.15 propanediol 3.0 H ₂ SO ₄ up to pH 4 water Rest on 100%

Claims (8)

An aqueous liquid bleaching composition comprising an effective amount of a peroxygen bleaching agent, amino tri (methylene phosphonic acid) (ATMP) and 0.5 to 20% by weight of the total together a bleach activator wherein the peroxygen bleach is hydrogen peroxide. A composition according to claim 1, which has a pH from above 0 to 6 and a viscosity of 1 MPa · s or more, preferably 50 MPa · s up to 2000 MPa · s, at 20 ° C, measured with a Brookfield viscometer at 50 rpm with a Spindle No. 3, has. Composition according to at least one of the preceding Claims, comprising 0.005 to 5% by weight of the total composition of ATMP. Composition according to at least one of the preceding Claims, wherein the hydrogen peroxide in an amount of 0.5 to 20 wt .-% the total composition is present. A composition according to claim 4, wherein the bleach activator chosen from the group consisting of ATC, NOBS, n-octanoyl-caprolactam, 3,5,5-trimethylhexanoyl-caprolactam, Nonanoyl caprolactam, decanoyl caprolactam, n-octanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, Nonanoyl valerolactam and mixtures thereof. Composition according to claims 1 to 5, wherein the composition is formulated as a microemulsion of the bleach activator in one Matrix comprising water, the peroxygen bleach and a hydrophilic A surfactant system comprising an anionic and a nonionic surfactant. aqueous A bleaching composition according to claims 1-5, wherein the composition formulates is considered an aqueous one An emulsion comprising at least one hydrophilic surfactant having a HLB above 10 and at least one hydrophobic surfactant with a HLB up to 9, wherein the bleach activator emulsifies by the surfactants becomes. Process for pretreating soiled textiles having a composition according to at least one the claims 1-7, wherein the method includes the steps of applying the composition on the textile and the composition remaining in contact covered with the textile before the textile is washed.