RU2169806C2 - Peroxide bleaching compositions containing peroxide bleacher and aminotrimethylenephosphonic acid suitable for use as fabric pretreatment agent - Google Patents

Abstract

FIELD: textile industry. SUBSTANCE: composition contains effective amount of peroxide bleacher and aminotrimethylenephosphonic acid and has pH value between 0 and 6. EFFECT: reduced loss in rupture strength of fabric. 10 cl, 3 ex

Description

 The invention relates to compositions containing bleach suitable for use as a pretreatment agent, and to a pretreatment method by which the preservation of fabric and / or dye is increased. The liquid formulations of this invention are also extremely stable, and preferred whitening formulations are acidic.

 Bleaching compositions are widely described in washing applications as detergents for washing, additives for washing, or even as pretreatment agents before washing. Indeed, it is known to use such bleach-containing pre-treatment compositions before washing in order to accelerate the removal of surface stains / dirt and difficult to remove (“problem”) stains such as grease, coffee, tea, grass, dirt / soil containing clay, which are especially difficult otherwise removed with normal machine wash. However, a drawback associated with such formulations is that these formulations can damage the tissue, leading to damage to the dye and / or loss of tensile strength of the fabric fibers, especially if they are used for pretreatment under intense conditions, for example, when applied directly to fabrics and left to act on said fabric for extended periods of time before washing said fabrics, especially when the fabric to be treated contains metal ions, such as copper, zo, manganese or chromium. Without limitation by theory, it is believed that peroxide bleach may be responsible for damage to the dye and tissue associated with the use of these whitening compositions. In addition, it is believed that these metal ions on the surface of tissues, especially on cellulose tissues, catalyze the decomposition of peroxide bleaches, like hydrogen peroxide. Thus, decomposition of peroxide bleach can lead to damage to the fabric and / or dye.

 When these compositions are applied directly to the tissues, the various components of these compositions diffuse or migrate, possibly at different speeds, through the fibers of the tissues. This fact is also true in relation to the peroxide whitening component of the whitening compositions intended for tissue pretreatment.

 Currently, the solution to the problem of damage resulting from the pretreatment of fabrics with bleaching compositions containing peroxide bleach is provided by the addition of a specific tissue protecting agent that acts so that damage to the fabric and / or dye is reduced. It was found that this tissue protecting agent, aminotri (methylenephosphonic acid) - hereinafter ATMP - significantly reduces the damage associated with the processing of tissues containing peroxide bleach, especially if these tissues are contaminated with metal ions.

 Accordingly, the present invention solves the long-standing need for an effective whitening composition suitable for use as a pretreatment agent that does not contribute to tissue damage. In addition, the compositions of the present invention provide excellent characteristics when used for purposes other than use as a pretreatment agent for washing, such as in other washing applications, as a detergent for washing or as a washing aid, or even for cleaning hard surfaces, or for cleaning carpets.

 In the preferred formulations of this invention, which are liquid formulations, ATMP further provides the advantage of the exceptional chemical stability of the peroxide bleach.

 Formulations containing peroxide bleach are comprehensively described in the art. For example, EP-629691A describes emulsions of nonionic surfactants containing a silicone compound and, as optional ingredients, hydrogen peroxide or a water-soluble source thereof. EP-629690A describes emulsions of nonionic surfactants containing a terephthalate-based polymer and, optionally, hydrogen peroxide or a water-soluble source thereof. EP-209228B describes formulations containing a peroxide source similar to hydrogen peroxide. EP-209228B describes the possibility of using formulations containing hydrogen peroxide as stain removers in pretreatment. See also US patent N 4891147, issued January 2, 1990, and US patent N 5019289, issued May 28, 1991. Compositions containing ATMMP in relation to washing were described in EP 517605, DD 280783 and DD 280784, however, here the composition does not contain peroxide bleach.

The present invention encompasses a composition comprising peroxide bleach, such as hydrogen peroxide or a source thereof, and ATMP. Preferred formulations are liquid aqueous formulations which have a pH value from above 0 to about 6 and a viscosity of 1 cP or higher, preferably from about 50 to about 2000 cP, at 20 ^° C. as measured by a Brookfield viscometer at 50 rpm using spindle N 3.

 The present invention also encompasses a method for pretreating contaminated fabrics with a liquid aqueous composition comprising peroxide bleach and ATMP, preferably in a pure (undiluted) form, on the fabric and contacting said composition with said fabric, preferably preventing the composition from drying on the fabric before washing said tissue.

 By “pretreatment of contaminated tissues” it is to be understood that the aqueous composition is applied in its pure form to the contaminated tissue and left to affect said tissue before washing said tissue. Alternatively, the aqueous composition may be applied to the tissue substrate together with sufficient water to moisten the tissue.

 All percentages of the ratio and proportion are given here by weight of the total liquid composition, unless otherwise indicated. All cited documents are incorporated herein by reference.

 The present invention encompasses a composition comprising peroxide bleach and ATMP. Atmf has been found to significantly reduce the damage associated with treating fabrics containing peroxide bleach, especially if these fabrics contain metal ions such as copper, iron, chromium and manganese.

Предпочтительно составы по изобретению будут содержать от приблизительно 0,005% до приблизительно 5,0%, более предпочтительно от приблизительно 0,01 до приблизительно 1,0 мас.% АТМФ общей массы отбеливающего состава.Fabric Protecting Agent
As a tissue protective agent, the compositions of the invention contain ATMP, i.e. compound of the formula:

Preferably, the compositions of the invention will contain from about 0.005% to about 5.0%, more preferably from about 0.01 to about 1.0 wt.% ATMP, of the total weight of the whitening composition.

 Preferred formulations of the present invention are aqueous liquid cleansing compositions. These aqueous formulations should be prepared in an acidic pH range, preferably at pH values from above 0 to about 6, and more preferably at pH values of 3 to 5. The preparation of the present compositions in an acidic pH range contributes to the stability of said formulations. The pH of the compositions of the present invention can be established by the use of organic or inorganic acids or bases.

Tensile strength test procedure. The term "tissue damage" in the description means the degree of loss of tensile strength of the fabric. The loss of tensile strength of fabrics can be determined as follows: strips of Krefeld cotton fabric (sizes 12.5x5 cm ² ) containing a copper concentration (2+) of 30 ppm. (ppm) per gram of cotton, treated with 2 ml of the test composition according to Example 1. The test composition is left in contact with the strips for 24 hours. The strips are then rinsed with water and the tensile strength of the fabrics is measured using INSTRON, model N 4411. Damage to the cotton strips is evaluated by stretching these strips until they break. The force required to break the strip, i.e. ultimate tensile stress is measured on wet strips using INSTRON, model N 4411. The less the force required to break the cotton strips, the more severe the damage to the fabrics. Good results (standard deviation = 2-4 kg) are obtained by applying five repetitions for each test.

 Peroxide Bleach. An essential element of the compositions of the present invention is peroxide bleach. A preferred peroxide bleach is hydrogen peroxide or a water-soluble source thereof, or a mixture thereof. Most preferred is hydrogen peroxide. Indeed, the presence of a peroxide bleach, preferably hydrogen peroxide, provides great advantages in cleaning quality, which are especially noticeable in washing applications. As used herein, a “hydrogen peroxide source” refers to any compound that forms hydrogen peroxide by contacting said compound with water.

 Suitable water-soluble sources of hydrogen peroxide for use in the invention include sodium carbonate perhydrate or equivalent percarbonate salts, persilicate, perborates, for example sodium perborate (any hydrate, but preferably mono or tetrahydrate), sodium pyrophosphate perhydrate, urea perhydrate, sodium peroxide and mixtures thereof . Alternative sources of peroxide include persulfates, such as monopersulfate, peroxyacids, such as diperoxide dodecandioic acid (DPDC), magnesium perftalic acid, perbenzoic and alkyl perbenzoic acids, and mixtures thereof.

 An “effective amount” of peroxide bleach is any amount that can to some extent improve the removal of stains / stains of a contaminated tissue substrate compared to a non-peroxide bleach formulation when a consumer erases a contaminated substrate in the presence of alkali. Typically, the compositions of the present invention contain from 0.5 to 20 wt.% The specified peroxide bleach of the total weight of the composition, preferably from 1 to 15% and more preferably from 2 to 6%.

 Optional bleach activators. Peroxide-containing formulations may optionally, but preferably, additionally contain a bleach activator. By bleach activator is meant a compound that reacts with hydrogen peroxide to form an acidic acid. The acid thus formed is activated bleach. Especially preferred is acetyl triethyl citrate. Said bleach activators, if present, will usually comprise from about 0.5 to about 20 wt.%, Preferably from 2 to 10%, most preferably from 3 to 7% of the total composition.

Suitable bleach activators are any known activators represented by NOBS (nonanoyloxybenzenesulfonate), TAED (tetraacetylethylenediamine) or ATC (acetyl triethyl citrate). Many other bleach activators are known. See, for example, activators referred to in US Pat. No. 4,915,854, issued April 10, 1990, to Mao et al., And US Pat. No. 4,412,934. For other conventional bleach activators, see also US Pat. No. 4,634,551. Amide derivative bleach activators of the formula R ¹ N are also known. (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 an alkylene containing from 1 to about 6 carbon atoms, R ⁵ represents H or an alkyl, aryl or alkaryl, with ERZHAN from about 1 to about 10 carbon atoms, and L is any suitable leaving group. Other examples of bleach activators of the above formulas include (6-actinamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof, as described in US Pat. et ai. U.S. Patent 4,966,723, issued October 30, 1990. Another class of bleach activators includes acylactam activators such as substituted and unsubstituted benzoylcaprolactam, tert-butylbenzoylcaprolactam, n-octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprodeno-octaloalkeno-deca-alkaloacetamide 5-trimethylhexanoylvalerolactam, tert-butylbenzoylvalerolactam and mixtures thereof.

 Preferred bleach activators useful for the invention include activators selected from the group consisting of acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, 3,5-n-octanoylvalerola-octa-lanolamate 3,5, nitrobenzoylcaprolactam, nitrobenzoylvalerolactam and mixtures thereof. Particularly preferred are bleach activators that are liquid or oil at room temperature. Examples of liquid bleach activators are acetyl triethyl citrate, n-octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, and mixtures thereof. The compositions of the invention may optionally contain aryl benzoates, such as phenyl benzoate.

 The pre-processing method. Although the preferred use of the compositions described herein is pre-treatment before washing, the compositions of the present invention can also be used as detergent for washing or as a detergent enhancer for washing and as a home cleaning agent for the bathroom or for kitchens, for washing dishes or for cleaning carpets.

 Said liquid composition may remain in contact with the tissue typically for a period of from 1 minute to 24 hours, preferably from 1 minute to 1 hour, and more preferably from 5 minutes to 30 minutes, or so as to avoid drying of the liquid composition to the fabric. Optionally, when the fabric is contaminated with surface stains / dirt that would be relatively difficult to remove otherwise, the liquid formulations of the present invention can be rubbed and / or brushed, for example by means of a sponge or brush, or simply by rubbing two sections of fabric relative to each other.

 By “washing” is meant simply rinsing the fabrics in water, or the fabrics can be washed with traditional formulations containing at least one surfactant using a washing machine or simply by hand.

 The term "in its pure (undiluted) form" means that the liquid compositions disclosed in the description are applied to the fabrics to be pretreated without any dilution, i.e. they are applied as described here.

 Other traditional ingredients for cleaning products. The whitening compositions of the invention will usually also contain other optional traditional ingredients to improve or change characteristics. Typical non-limiting examples of such ingredients are described below for ease of presentation.

 Organic stabilizers. The compositions of the invention may also optionally contain organic stabilizers to improve the chemical stability of the composition, provided such compounds are compatible or properly formulated. Organic stabilizers can be selected from the following group: monophenols, 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, US patents 3159581; 3213030; 3422021; 3400148 and 3422137 ) and mixtures thereof.

 Typically, organic stabilizers are used in the present compositions in an amount of from 0.01 to 5.0%, more preferably from 0.05 to 0.5%.

The peroxide bleach compositions of the present invention may additionally contain from 0.5 to 5%, preferably from 2 to 4 wt.%, Of the total alcohol composition of the formula HO-CR′R ″ —OH, where R ″ and R ″ independently represent an H or C ₂ -C ₁₀ hydrocarbon chain and / or cycle. The preferred alcohol of this formula is propanediol.

 Inorganic stabilizers. Examples of inorganic stabilizers include sodium stannate and various alkali metal phosphates, such as well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.

 Detergent surfactants. Surfactants are useful because of their usual cleansing ability, and they can be included in preferred embodiments of the present compositions in conventional detergent-useful amounts. Typically, surfactants will comprise from about 0.1 to about 50%, preferably from about 1 to about 30%, more preferably from about 5 to about 25% by weight of the whitening compositions of the invention.

Non-limiting examples of useful surfactants include conventional C ₁₁ -C ₁₈ alkylbenzenesulfonates (LAS) and primary branched and disordered C ₁₀ -C ₂₀ alkyl sulfates (AS); C ₁₀ -C ₁₈ secondary alkyl sulfates of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ ) CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) CH ₂ CH ₃ , where x and (Y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, especially sodium; unsaturated sulfates such as oleyl sulfate; C ₁₀ -C ₁₈ alkyl alkoxysulfates (AE _x S), especially those where x is from 1 to about 7; C ₁₀ -C ₁₈ alkylalkoxycarboxylates (especially EO 1-5 ethoxycarboxylates); C ₁₀ -C ₁₈ glycerol esters; C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides; and C ₁₂ -C ₁₈ alpha sulfonated fatty acid esters. Detergent surfactants can be mixed in various proportions to increase surface activity, which is well known in the art. Also optionally included in the formulations are conventional nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates (AE), including so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylate / propoxylates) , C ₁₂ -C ₁₈ betaines and sulfobetaines (sultaines), C ₁₀ -C ₁₈ amine oxides and the like. Amides of C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acids may also be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamides. See WO 9206154. Other sugar derivative surfactants include N-alkoxypolyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. For low foaming, N-propyl- to N-hexyl-C ₁₂ -C ₁₈ glucamides can be used. C ₁₀ -C ₂₀ traditional soaps can also be used. If high foaming is desired, C ₁₀ -C ₁₆ branched chain soaps can be used. Especially useful are mixtures of anionic and nonionic surfactants.

 Modifying additives. Detergent modifiers may optionally be included in the compositions of the invention to help control mineral hardness. Inorganic as well as organic modifying additives may be used. Modifying additives are commonly used in fabric detergents to help remove particulate contaminants.

 The content of the modifying additive can vary widely depending on the end use of the composition and its desired physical condition. When present, the formulations will typically contain at least about 0.1% modifier.

 Organic modifying additives for detergents suitable for the purposes of the present invention include, but are not limited to, a wide range of polycarboxalate compounds. As used herein, the term "polycarboxylate" refers to compounds containing multiple carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate modifier can usually be added in acidic form, but can also be added in the form of a neutralized salt or in a “alkalized” form. If it is used in salt form, alkali metal salts such as sodium, potassium and lithium salts or alkanolammonium salts are preferred.

 Polycarboxylate modifiers include many classes of beneficial compounds. One important class of polycarboxylate modifying additives includes ether polycarboxylates, including oxydisuccinate, as described by Berg, US Patent 3,128,287, issued April 7, 1964, and Lamberti et al. US patent 3635830, issued January 18, 1972. See also “TMS / TDS” modifying additives from US Pat. No. 4,663,071 to Bush et al. May 5, 1987. Suitable ester polycarboxylates also include cyclic compounds, especially alicyclic compounds, such as those described in US Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

 Other useful detergent modifying additives include hydroxypolycarboxylate ethers, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxy succinic acid, salts of various alkali metals, ammonium and substituted ammonium and poly acids, such as nitrilotriacetic acid, as well as polycarboxylates, such as mellitic acid, succinic acid, hydroxy succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid ta, carboxymethyloxy succinic acid and their soluble salts.

 Citrate modifying additives, for example citric acid and its soluble salts (especially sodium salt), are particularly important polycarboxylate modifying additives due to the possibility of their production from renewable resources and the possibility of their biological destruction. Oxidisuccinates are also particularly useful in such formulations and combinations.

Also suitable for use in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and similar compounds described in US Pat. No. 4,566,984 to Bush, issued January 28, 1986. Useful succinic acid modifiers include C ₅ -C ₂₀ alkyl and alkenyl succinic acids and their salts. Specific examples of succinate modifying additives include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are the preferred modifiers of this group and are described in European Patent Application 86200690.5 / 0200263, published November 5, 1986.

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

Fatty acids, for example, C ₁₂ -C ₁₈ monocarboxylic acids, can also be included separately or in combination with the above modifying additives, especially with citrate and / or succinate modifying additives to provide additional activity of modifying additives. Such use of fatty acids will typically result in a reduction in foaming in the laundry detergents, which may need to be taken into account by the manufacturer of the composition.

 Where phosphorus-based modifiers can be used, and especially in handwash, phosphates of various alkali metals such as well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphate modifying agents such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates may also be used (see, for example, US Pat. Nos. 3,195,581; 3,230,030; 34,22021; 3,400,148 and 3,422,137), although these compounds are more widely used in low concentrations as chelating agents or stabilizers.

 Inorganic or P-containing detergent modifying additives include, but are not limited to, polyphosphate salts of alkali metals, ammonium and alkanolammonium (represented by tripolyphosphates, pyrophosphates and glass polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquioxides, sulfates and aluminosilicates.

 Chelating agents besides ATMF. The compositions described herein may also optionally contain substances that selectively enhance the yield of transition metals, or chelating agents, for example, chelating iron and / or copper and / or manganese compounds, provided that they are compatible or properly prepared. Chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, phosphonates (especially aminophosphonates), polysubstituted aromatic chelating agents, and mixtures thereof. Without any theoretical limitation, it is believed that the advantage of these compounds is the result of their exceptional ability to remove iron, copper and manganese ions from washing solutions by the formation of soluble chelate complexes; other benefits include preventing inorganic film formation or inhibiting scale formation. Commercial chelating agents for the application described herein include the DEQUESTR series and chelating agents from Monsanto, DuPont and Naico, Inc.

 The aminocarboxylates used as optional chelating agents are further represented by ethylenediamine tetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexaacetates, diethylene triamine pentaacetates, and ethanomelamide aminomel amine diamines. Typically, chelating mixtures can be used to combine functions, such as multiple control of transition metal contents, long-term stabilization of products, and / or control of precipitated transition metal oxides and / or hydroxides.

 Multifunctionally substituted aromatic chelating agents can also be used in the compositions described herein. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acidic form are dihydroxy disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

 An extremely preferred biodegradable chelator for the use described herein is ethylene diamindisuccinate (EDDS), especially (but not exclusively) the [S, S] isomer, which is described in US Pat. No. 4,704,233, issued November 3, 1987 to Hartman and Parkins. Trisodium salt is the preferred form, although other forms, such as magnesium salts, may also be used.

где R₁, R₂, R₃ и R₄ независимо выбраны из группы, содержащей -H, алкил, алкокси, арил, арилокси, -Cl, -Br, -NO₂, - C(O)R' и -SO₂R''; где R' выбирают из группы, содержащей -H, -ОН, алкил, алкокси, арил и арилокси; R'' выбирают из группы, содержащей алкил, алкокси, арил и арилокси; R₅, R₆ R₇ и R₈ независимо выбраны из группы, содержащей -H и алкил.Another preferred chelator for the use described herein is represented by the formula:

where 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 ''; where R 'is selected from the group consisting of —H, —OH, alkyl, alkoxy, aryl and aryloxy; R ″ is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy; R ₅ , R ₆ R ₇ and R _{8 are} independently selected from the group consisting of —H and alkyl.

 Aminophosphonates are also suitable for use as chelating agents in the compositions of this invention, if at least a low total phosphorus content in the washing compositions is acceptable, and include ethylene diamine tetrakis (methylene phosphonates) and diethylene triamine pentakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups containing more than about 6 carbon atoms. In the presence of chelating agents or substances that selectively enhance the yield of transition metals, they will preferably comprise from about 0.001 to about 10%, more preferably from about 0.05 to about 1%, of the total weight of the compositions described herein.

 Polymer contaminant releasing agent. In the compositions and methods of this invention, any polymeric contaminant-releasing agent known to one skilled in the art may optionally be used. Polymeric contaminating release agents are characterized in that they contain both hydrophilic segments to impart hydrophilic properties to the surfaces of hydrophobic fibers, such as polyester or nylon, and hydrophobic segments in order to accumulate on hydrophobic fibers and remain attached to them until the end of the washing and rinsing cycles and thus serve as an anchor for hydrophilic segments. This will make it easier to clean stains after treatment with a contaminant releasing agent during further washing steps.

Polymeric contaminant releasing agents useful herein in particular include those contaminant releasing agents that contain: (a) one or more non-ionic hydrophilic components, mainly consisting of (1) polyoxyethylene segments with a degree of polymerization of at least 2 or (2 ) oxypropylene or polyoxypropylene segments with a degree of polymerization from 2 to 10, where the specified hydrophilic segment does not mean any oxypropylene unit until it is connected with neighboring radicals on each the end via ether bonds, or (3) a mixture of oxyalkylene units containing oxyethylene and from 1 to 30 oxypropylene units, where the mixture contains a sufficient amount of oxyethylene units so that the hydrophilic component has sufficiently hydrophilicity to increase the hydrophilicity of the surface of a typical polyester synthetic fiber upon accumulation of contaminating release agents on such a surface, said hydrophilic segments preferably containing at least about 25% of oxyethylene units and more preferably especially for such components containing from about 20 to 30 oxypropylene units, at least about 50% of oxyethylene units; or (b) one or more hydrophobic components containing (1) C ₃ oxyalkylene terephthalate segments, where if said hydrophobic components also contain oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is about 2: 1 or less, (2) C ₄ - C ₆ alkylene or hydroxy-C ₄ -C ₆ alkylene segments or mixtures thereof, (3) segments consisting of a vinyl ester polymer, preferably polyvinyl acetate having a degree of polymerization of at least 2, or (4) substituents consisting of C ₁ -C ₄ lkilovyh ether or C ₄ hydroxyalkyl esters or gidroksialkilnoefirnyh cellulose derivatives or mixtures thereof, and such cellulose derivatives are amphiphilic, whereby they comprise a sufficient amount of C ₁ -C ₄ alkilnoefirnyh and / or C ₄ gidroksialkilnoefirnyh units to accumulate on the surface of a typical polyester synthetic fiber and maintaining a sufficient amount of hydroxyls bound to the surface of such a typical synthetic fiber to increase the hydrophilicity of the surface of the fiber, or a combination of (a) and (b).

Typically, the polyoxyethylene segments from (a) (1) will have a degree of polymerization of from about 1 to about 200, although higher values can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable hydroxy-C ₄ -C ₆ alkylene hydrophobic segments include, but are not limited to, heads of polymeric contaminating release agents such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium and n is an integer 4 to 6, as described in US Pat. No. 4,721,580, you annom January 26, 1988 to Gosselink.

Polymeric contaminant releasing agents useful in the present invention include cellulose derivatives such as cellulose hydroxy ester polymers, block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate and the like. Such agents are commercially available and include cellulose hydroxyesters such as METHOCEL (Dow). The cellulosic contaminating release agents useful here also include those selected from the group consisting of C ₁ -C ₄ alkyl or C ₄ hydroxyalkyl cellulose; see U.S. Patent 40,00093, issued December 28, 1976 to Nicol et al.

Pollution-releasing agents characterized by the presence of hydrophobic segments composed of vinyl ester polymers include grafted vinyl ester copolymers, for example C ₁ -C ₆ vinyl esters, preferably polyvinyl acetate grafted onto polyalkylene oxide scaffolds such as polyethylene oxide scaffolds. See European Patent Application 0219048, published April 22, 1987 by Kud et al. Commercially available contaminating release agents of this type include preparations of the SOKALAN type, for example SOKALAN HP-22, which can be obtained from BASF (Germany).

 One type of preferred contaminant releasing agent is a copolymer containing random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric contaminant releasing agent is in the range of from about 25,000 to about 55,000. See US Patent 3,959,230, issued May 25, 1976 to Hays, and US Patent 3,894,929, issued to July 8, 1975 to Basadur.

 Another preferred contaminant releasing agent is an ethylene terephthalate repeating polyester containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 300-5000. Examples of this polymer include the commercially available preparation ZELCON 512.6 (from DuPont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

 Another preferred contaminant releasing agent is the sulfonated product of an essentially linear linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeating units and terminal radicals covalently attached to the backbone. These contaminating release agents are fully described in US Pat. No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E. P. Gosselink. Other suitable polymeric contaminant-releasing agents include terephthalate esters from US Pat. No. 4,711,730 issued December 8, 1987 to Gosselink et al., Oligomeric anionic esters from US Pat. No. 4,721,580, issued January 26, 1988 to Gosselink, and oligomeric block polyester compounds from the patent US 4702857, issued October 27, 1987 by Gosselink.

 Preferred pollution releasing agents include pollution releasing agents from US Pat. No. 4,877,896, issued October 31, 1989 to Maldonado et al., Which describes anionic, especially sulfoaroyl, esters with a terephthalate end group.

 Another preferred contaminant releasing agent is a repeating oligomer of terephthaloyl units, sulfoisoterephthaloyl units, oxyethylene and oxy-1,2-propylene units. The repeating units constitute the oligomer backbone and, preferably, modified isothionate end groups are attached to their end. A particularly preferred contaminating release agent of this type contains approximately one sulfoisophthaloyl unit, 5 terephthaloyl units, hydroxyethyleneoxy and hydroxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two units of end groups consisting of 2- ( 2-hydroxyethoxy) ethanesulfonate sodium. Said contaminating release agent also contains from about 0.5 to about 20% by weight of an anti-crystallization inhibitor oligomer of a stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluenesulfonate, and mixtures thereof. See U.S. Patent 5,415,807, issued May 16, 1995 to Gosselink et al.

 If present, contaminating release agents will typically comprise from about 0.01 to about 10.0% by weight of the aqueous formulations described herein, usually from about 0.1 to about 5%, preferably from about 0.2 to about 3, 0%.

 Other ingredients Detergent components and additives, optionally included in the present compositions, may include one or more substances to facilitate or improve the quality of cleaning, processing of the substrate to be cleaned, or are developed to improve the aesthetic qualities of the compositions. Such substances are further illustrated in US patent N 3936537, Baskervilie et al. Additives that can also be included in the compositions of the present invention in their usual contents for the given field (typically from 0 to about 20% of detergent ingredients, preferably from about 0.5 to about 10%), include other active ingredients, such as dispersing polymers from BASF Corp. or Rohm &Haas; anti-bleaching and / or anticorrosive agents, colorants, fillers, optical brighteners, antibacterial agents, hydrotropic compounds, enzyme stabilizing agents, flavoring agents, solubilizing agents, clay removal / redeposition agents, carrier agents for treating additives, pigments, solvents, softeners tissues, static-stress relieving agents, etc.

 Dye-suppressing agents. The compositions of the present invention may also include one or more substances effective to suppress the transition of dyes from one painted surface to another during the cleaning process. Typically, such dye-suppressing agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, N-vinyl pyrrolidone and N-vinylimidazole copolymers, manganese phthalocyanine, peroxidase, and mixtures thereof. If present, these agents typically contain from about 0.01 to about 10% by weight of the composition, preferably from about 0.01 to about 5%, and more preferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for the use described herein comprise units having the following structural formula: RA _x —P; where P is a polymerizable unit to which a NO group can be attached, or a NO group can form part of a polymerizable unit, or a NO group can be attached to both units; A represents one of the following structures: —NC (O) -, —C (O) O—, —S—, —O—, —N =; x is 0 or 1; a R represents aliphatic, ethoxylated alaphatic, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which a nitrogen atom of the NO group may be attached, or the NO group may form part of these groups. Preferred polyamine oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

где R₁, R₂, R₃ представляют собой алифатические, ароматические, гетероциклические или алициклические группы или их сочетания; x, y и z равны 0 или 1; а атом азота группы N-O может быть присоединен или может образовывать часть любой из вышеперечисленных групп. Аминоксидное звено полиамин-H-оксидов имеет pK_a<10, предпочтительно pK_a<7, более предпочтительно pK_a<6.The NO group can be represented by the following general structures:

where R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups, or combinations thereof; x, y and z are 0 or 1; and the nitrogen atom of the NO group may be attached or may form part of any of the above groups. The amine oxide unit of the polyamine H-oxides has pK _a <10, preferably pK _a <7, more preferably pK _a <6.

 Any polymer skeleton may be used provided that the resulting amine oxide polymer is water soluble and possesses dye transfer inhibiting properties. Examples of suitable polymer scaffolds are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include disordered or block copolymers, where one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. Amine-N-oxide polymers typically have an amine to amine-N-oxide ratio of from 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can vary by suitable copolymerization or by a suitable N-oxidation state. Polyamine oxides can be obtained with almost any degree of polymerization. Typically, the average molecular weight is in the range of 500 to 1,000,000; more preferably from 1000 to 500000; most preferably from 5000 to 100000. This preferred class of substances may be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions described herein is poly (4-vinylpyridine-N-oxide), which has an average molecular weight of about 50,000 and an amine to amine-N-oxide ratio of about 1: 4.

 Copolymers of N-vinylpyrrolidone and N-vinylimidazole (referred to as the "PVPVI" class) are also preferred for the use described herein. Preferably, the PVPVIs have an average molecular weight ranging from 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, Volume 113. " Modern Methods of Polymer Characterization ", the descriptions of which are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of 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 include polyvinylpyrrolidone (PVP) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVPs are known to those skilled in the art of detergents; see, for example, EP-A-262897 and EP-A-256696, incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol (PEG) having an average molecular weight of from about 500 to about 100,000, preferably from about 1000 to about 10,000. Preferably, the ratio of PEG to PVP in parts per million generated in washing solutions is from about 2 : 1 to about 50: 1, and more preferably from about 3: 1 to about 10: 1.

Foam enhancers. If high foaming is desired, foaming enhancers such as C ₁₀ -C ₁₆ alkanolamides, typically in a content of 1-10%, may be included in the compositions. C ₁₀ -C ₁₄ monoethanol and diethanolamides are an example of a typical class of such foaming enhancers. The use of such foaming enhancers with highly foaming additional surfactants, such as the amine oxides, betaines and sultaines mentioned above, is also advantageous. If desired, soluble magnesium salts, such as MgCl ₂ , MgSO ₄ and the like, can be added in amounts of, for example, 0.1-2%, to provide additional foaming and to improve the quality of the removal of oily stains.

 Clarifier Any optical brighteners, fluorescent brighteners, or other brightening or bleaching agents known in the art can be included in the present formulations if they are designed for treating fabrics or launders, typically in amounts from about 0.05 to about 1.2% by weight. weight of the detergent compositions described herein. Commercial optical brighteners that can be used according to the present invention can be divided into subgroups, which include, but are not limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acids, methincyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered heterocyclic brighteners, the list being illustrative and non-limiting. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982).

 Specific examples of optical brighteners that are used in the present compositions are those defined in US Pat. No. 4,790,856, issued to Wixon on December 13, 1988. These bleaches include the Verona PHORWHITE series of bleaches. Other bleaches described in this link include: Tinopal UNPA, Tinopal CBS, Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from HiltonDavis in Italy; 2- (4-styrylphenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis (1,2, 3-triazol-2-yl) stilbene; 4,4'-bis (styryl) bisphenyls; and aminocoumarins. Specific examples of these bleaches include 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styrylnaphtha [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Generally preferred are nonionic bleaches.

 Bleach catalysts. If desired, the compositions described herein may further include a catalyst or accelerator to further improve bleaching or contaminant removal. Any suitable bleach catalyst may be used. As for detergent compositions, where its total content is from about 1000 to about 5000 ppm. in water, the composition will typically provide a concentration of from about 0.1 to about 700 ppm, more preferably from 1 to about 50 ppm, or less of the catalyst in the washing solution.

Typical bleach catalysts contain a transition metal complex, for example, one where the ligands forming the coordination sphere of the metal atom are completely immune to labilization and the use of which does not lead to the accumulation of metal oxides or hydroxides to any noticeable degree under typical alkaline washing conditions. Such catalysts include manganese-based catalysts described in US Pat. No. 5,246,621, US Pat. No. 5,245,494, US Pat. No. 5,194,416, US Pat. No. 5,114,606; and in EP N 549271 A1, 549272 A1, 544440 A2 and 544490 A1; preferred examples of these catalysts include Mn ₂ ^IV (μ-O) ₃ (TACN) ₂ (PF) ₂ , Mn ₂ ^III (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ (ClO ₄ ) ₂ , Mn ₄ ^IV (μ-O) ₆ (TACN) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ₄ ^IV (μ-O) ₁ (μ-OAc) ₂ - (TACN) ₂ - (ClO ₄ ) ₃ , Mn ^IV - ( TACN) (OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof, where TACN is trimethyl-1,4,7-triazacyclononan or an equivalent macrocycle; although additional ligands are possible that form the coordination sphere of the metal, as well as mononuclear complexes and monometallic, as well as di-polymetallic complexes, and complexes of alternative metals, such as iron or ruthenium, are in the area under discussion. Other metal-based bleach catalysts include those described in US Pat. No. 4,430,243 and US Pat. No. 5,114,111. The use of manganese with various complex ligands to improve bleaching is also reported in the following United States patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5153161 and 5227084.

 Complexes with transition metals can be formed preliminarily or in situ with suitable donor ligands selected depending on the choice of metal, the degree of its oxidation, and the dentinality of the ligands. Other complexes that may be included in the described compositions are presented in US patent application Ser. N 08/210186, filed March 17, 1994.

Getting funds for pre-treatment. Preferred compositions of the present invention are liquid, they have a viscosity of 1 cP or more at 20 ^° C. as measured by a Brookfield viscometer at 50 vol. / min using a spindle N 3, more preferably from about 50 to about 2000 cP, even more preferably from about 200 to about 1500 cP. To achieve a preferred viscosity, any surfactant system or polymer thickener known in the art can be used to increase the viscosity of the composition. Thus, surfactants suitable for the described application can be thickening surfactants, such as nonionic, anionic, cationic, zwitterionic and / or amphoteric surfactants.

 The liquid whitening composition described herein contains water in any amount up to about 98% of the total weight of the composition. Preferably, the compositions described herein will contain from about 5 to about 98%, more preferably from about 10 to about 95%, by weight of the weight of the whitening composition.

 If the peroxide bleach-containing formulations of the present invention further comprise an optional bleach activator, it is highly desirable to prepare said formulations either as a microemulsion or as a stable emulsion.

 Obtained in the form of a microemulsion, the composition contains a water-based bleach activator, peroxide bleach and hydrophilic anionic and nonionic surfactants. Suitable anionic surfactants herein include alkyl benzenesulfonates, alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof. Suitable nonionic surfactants for use in microemulsions include hydrophilic nonionic surfactants as defined hereinafter for the emulsions of the present invention.

Being prepared in the form of an emulsion, the composition contains at least a hydrophilic surfactant having a HLB value (hydrophilic-lipophilic balance) of more than 10, and at least a hydrophobic surfactant having a HLB value of up to 9, where the specified bleach activator is emulsified in said surfactants. In order to form stable emulsions, two different surfactants must have different HLB values, and preferably the difference between the HLB values of the two surfactants is at least 1, preferably at least 3. In other words, by combining properly, at least two of these surface-active substances with different HLB values in water will form stable emulsions, i.e. emulsions that do not essentially separate into two separate layers when standing for at least two weeks at 40 ^° C, preferably at 50 ^° C. Emulsions contain from about 2 to about 50% by weight of the total composition of said hydrophilic and hydrophobic surface active substances, preferably from about 5 to about 40%, more preferably from about 8 to about 30%. Emulsions contain at least about 0.1, preferably at least 3%, more preferably at least 5% of one or more hydrophobic surfactants based on the total weight of the emulsion and at least about 0.1%, preferably at least 3%, more preferably at least 5% of one or more hydrophilic surfactants based on the total weight of the emulsion. Preferred for use herein are hydrophobic nonionic surfactants and hydrophilic nonionic surfactants. The hydrophobic non-ionic surfactants that are applicable here have an HLB value of up to 9, preferably less than 9, more preferably less than 8, and these hydrophilic surfactants have an HLB value of more than 10, preferably more than 11, more preferably more than 12. Suitable non-ionic ones applicable here surfactants include alkoxylated fatty alcohols, preferably ethoxylates and / or propoxylates of fatty alcohols. Many alkoxylated fatty alcohols that have extremely different HLB values are commercially available. For further discussion of the HLB theory and its application to the preparation of emulsions, see: Encyclopedia of Emulsion Technology; Becher, P., Ed .; Marcel Dekker, Inc .; New York, 1985; Volume 1 and 2, and with the links there.

In a particularly preferred embodiment, the emulsion, if present, wherein the emulsions comprise acetyl triethyl citrate as the bleach activator, an adequate nonionic system surfactant will comprise a hydrophobic nonionic surfactant, e.g., an HLB of 6, such as a Dobanol ^® 23-2 and a hydrophilic nonionic surfactant, for example, with an HLB value of 15, such as Dobanol ^® 91-10. Other suitable nonionic surfactant systems include, for example, Dobanol ^® 23-6.5 (HLB value of approximately 12 Dobanol ^® 23 (HLB value less than 6) or Dobanol ^® 45-7 (HLB value = 11.6) and Lutensol ^® TOZ (HLB value = 8). Dobanol ^® is a commercially available non-ionic surfactant that can be obtained from Shell Corp. Lutensol ^® is a commercially available non-ionic surfactant that can be obtained from BASF Corp.

The peroxide bleach compositions of the present invention may further comprise an amine oxide surfactant according to the formula R ¹ R ² R ³ NO, where each of R ¹ , R ² and R ^{3 is} independently C ₆ -C ₃₀ , preferably C ₁₀ - C ₃₀ , most preferably C ₁₂ -C ₁₆ hydrocarbon chain. Further, it was noted that during the pretreatment, the presence of said amine oxide further improves the cleaning quality of difficult to remove and / or grease stains. It is believed that this improvement in cleaning quality is independent of the basis. To achieve any of these advantages, amine oxides, if present, should be present in amounts ranging from 0.1 to 10% of the total weight of the composition, preferably from 1.5 to 3%.

 The following examples illustrate the compositions of this invention, but are not intended to limit them. All substances in the examples satisfy the functional requirements given here.

Composition 1
Alkyl sulfate Na - 2.0
Dobanol ^® 45-7 - 6.5
Dobanol ^® 23-3 - 8.5
ATC - 3.5
H ₂ O ₂ - 4.0
OSH - 0.05
ATMF - 0.15
H ₂ SO ₄ - Up to pH 4
Water - Up to 100%
Composition 2
Alkyl sulfate Na - 12.0
Dobanol ^® 45-7 - 6.0
Dobanol ^® 23-6.5 - 6.0
ATC - 3.5
H ₂ O ₂ - 6.0
OSH - 0.05
ATMF - 0.15
Propandiol - 3.0
H ₂ SO ₄ - Up to pH 4
Water - Up to 100%
Composition 3
Alkyl sulfate Na - 1,5
Dobanol ^® 45-7 - 1.5
Dobanol ^® 91-10 - 1.5
H ₂ O ₂ - 7.0
OSH - 0.02
ATMF - 0.02
Citric Acid - 0.02
H ₂ SO ₄ - Up to pH 4
Water - Up to 100%

Claims (10)

 1. A liquid whitening composition containing an effective amount of peroxide bleach and aminotrimethylene phosphonic acid and having a pH from above 0 to about 6.  2. The composition according to claim 1, which is an aqueous liquid.  3. The composition according to claim 2, which has a viscosity value of 1 cP or more, preferably from about 50 to about 2000 cP at 20 ° C. as measured by a Brookfield viscometer at 50 rpm using a spindle 3.  4. The composition according to any one of the preceding paragraphs, which contains from about 0.005 to about 5.0 wt.% Aminotrimethylene phosphonic acid of the total composition.  5. The composition according to any one of the preceding paragraphs, where the specified peroxide bleach is hydrogen peroxide or its water-soluble source and is present in an amount of from about 0.5 to about 20.0 wt.% The total composition.  6. The composition according to any one of the preceding paragraphs, which further comprises a bleach activator from about 0.5 to about 20.0 wt. % of the total composition.  7. The composition according to claim 6, wherein said bleach activator is selected from the group consisting of acetyl triethyl citrate, nonanoyloxybenzenesulfonate, n-octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, 3,5-octanolate, 3,5-octanolate nonanoyl valerolactam and mixtures thereof.  8. The composition according to claim 6 or 7, where the specified composition is obtained in the form of a microemulsion containing the specified bleach activator in a water-based matrix, the specified peroxide bleach and a hydrophilic surface-active system containing anionic and nonionic surfactants.  9. The aqueous whitening composition according to claim 6 or 7, which is obtained in the form of an aqueous emulsion containing at least a hydrophilic surfactant having an HLB value of more than 10, and at least a hydrophobic surfactant having an HLB value of up to 9 wherein said bleach activator is emulsified with said surfactants.  10. The method of pre-treatment of contaminated tissues with a composition according to any one of paragraphs. 2-9, comprising the steps of applying said composition to a fabric and contacting said composition with said fabric before washing said fabric.