SK174597A3 - Peroxygen bleaching compositions comprising a fabric protection agent - Google Patents

Abstract

The present invention relates to aqueous, acidic compositions comprising a peroxygen bleach and a specific fabric protection agent. 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

An aqueous bleaching composition composed of an effective amount of a peroxygen bleaching component and a textile-protecting agent, the preservative having a mobility factor greater than 0,7, a stability constant of at least log K = 3 for Cu ²⁺ and a C concentration measured as a percentage by mass of a liquid bleach, calculated according to the formula: {[C] x [stability constant for Cu ²⁺ ]}> 2.5.

Peroxide bleaching agents containing an agent protect the textile material which

Technical field

The invention relates to aqueous compositions comprising a bleaching composition suitable for use as a prewash and for the prewash process itself in which the safe preservation and / or dyeing of the textile is improved. Preferred bleaching compositions are acidic in nature and comprise a peroxygen bleaching composition, preferably hydrogen peroxide or a source thereof, and a fabric protecting agent.

as laundry or prewash was already

BACKGROUND OF THE INVENTION

The use of bleaching detergents, laundry additives described in detail.

It is well known to use such bleaching compositions for prewashing laundry to accelerate removal of spots and dirt, and problem stains from fats, coffee, tea, grass and clay, which are otherwise particularly difficult to remove in typical machine washing. However, a disadvantage of these bleaching agents is that they can damage the textile products such that the coloring and / or the loss of tensile strength of the textile fiber is damaged, especially if the prewash occurs under stressful conditions, i.e., wear. if such means are used e.g. directly to the textile for a long time before washing, especially if the washed material is contaminated. metal ions such as copper, iron, manganese, or chromium. Without being limited by theory, it is believed that it is a peroxygen bleaching agent that causes dye and textile material damage. Furthermore, we believe that metal ions on the surface of textile products, especially cellulosic products, catalyze the decomposition of such peroxide bleaching agents such as hydrogen peroxide.

The composition may therefore be contaminated with the material and / or its compositions

Accelerated peroxide decomposition cause damage to textile coloring.

When these compositions are applied directly to the textile, the various components of the composition diffuse or migrate through the fibers of the article (probably at different rates).

The solution to this deterioration of textile products that are prewashed with peroxide bleaching agents is to add certain fabric-protecting agents that reduce fabric and / or dye damage. It has been found that these preservatives greatly reduce the damage to textiles by these peroxide bleaching agents, especially for textiles by metal ions. Suitable preservatives are characterized by a sufficiently high stability to metal ions such as copper and iron, so that the decomposition catalysis of the peroxide bleach produced by the metal ions is prevented, slowed and / or minimized. In addition, the fabric protecting agent must have a sufficiently high mobility to migrate with the peroxygen bleach at the same time as the agent disperses or migrates across the fibers of the fabric immediately after the composition has been applied to the textile product.

The invention thus addresses a long felt need for an effective and color-safe bleaching composition suitable for use on a prewash that does not damage textile products. In addition, the compositions of the invention also have excellent performance in other applications, such as prewash, e.g. as a laundry detergent or laundry additive, for cleaning applications of heavily soiled surfaces, or for cleaning carpets.

Citations and previous sources

Peroxygen bleaching agents described in the prior art. So they were already in detail eg. RP-629.691A discloses emulsions of nonionic surfactants (surfactants) containing a silicone compound, and optionally hydrogen peroxide or a water-soluble source thereof. EP-629.690A discloses nonionic surfactant emulsions comprising a terephthalate-based polymer and, as an optional component, hydrogen peroxide or a water-soluble source thereof. EP-209.228B discloses compositions comprising hydrogen peroxide as a peroxide source. 209-209.228Β also states that compositions containing hydrogen peroxide can also be used in a prewash. See also U.S. Pat. No. 4,891,147, issued Jan. 2, 1990, and U.S. Pat. No. 5,019,289, issued May 28, 1991.

SUMMARY OF THE INVENTION

The present invention includes an aqueous composition comprising a peroxygen bleach component, such as hydrogen peroxide or a source thereof, and a textile protecting agent; wherein the preservative has a mobility factor greater than 0.7, which will be defined later, and a stability constant of at least log K = 3 for Cu ² *. Furthermore, the minimum C concentration of the textile material protecting agent, measured as a percentage by weight of the liquid bleach, is calculated according to the following formula: / (C) x (stability constant for Cu ² ) / s 2.5. It is preferred that the fabric protecting agent have a ratio of a Cu ² * stability constant to a Ca ² * stability constant of at least 2: 1.

The present invention further includes a process wherein a liquid aqueous composition consisting of a peroxygen bleach component and a fabric protecting agent having a mobility factor of greater than 0.7, as measured according to the definition below, penetrates dirty textiles, the process comprising the individual steps of application. a composition (preferably in its pure form) for the textile, and leaving the composition in contact with the textile, preferably so that the textile composition does not dry before being washed.

In another process, the aqueous composition is applied to the soiled fabric prior to washing, wherein the loss in tensile strength of the textile product is less than that of products treated with the same peroxygen bleach, but without the fabric protection agent of the present invention.

In yet another process, the aqueous composition is applied to colored / dyed textile articles prior to washing, wherein the dyeing damage of the article is limited and the tensile strength loss of the article is less compared to articles treated with the same peroxygen bleach, but without the agent of the invention textile product.

By the pre-wash of the soiled textile, it is understood that the aqueous composition is applied in its pure form to the soiled textile and allowed to act for a while as it is washed. Alternatively, the aqueous composition is applied to the fabric along with sufficient water to wet the fabric.

In preferred embodiments, the aqueous composition has a pH greater than zero and up to 6 and a viscosity of 50 cps or greater, preferably 50 to 2000 cps, at 20 ° C as measured by a Brookfield viscometer at 50 rpm. Špindlou číslo. Third

All percentages, ratios and (parts) by weight are by weight unless otherwise stated. All documents cited are hereby incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an aqueous composition comprising a peroxygen bleach component, such as hydrogen peroxide or a source thereof, and a textile protecting agent. This protective agent has been found to significantly reduce damage to textile material under the action of a peroxygen bleach, particularly textile products contaminated with metal ions such as copper, iron, chromium and manganese. A suitable preservative is characterized by a sufficiently large stability constant for metal ions such as copper and iron to prevent catalysis of the peroxide bleach by metal ions. In addition, the textile protecting agent has sufficient mobility to ensure that the agent disperses upon application of the bleaching agent. and migrates along the fibers of the textile product together with the bleaching agent.

The textile protecting agent of the present invention is characterized by having a mobility factor (defined below) of greater than 0.7, more preferably greater than 0.8, and most preferably greater than 0.9. In addition, the preservative has a copper (2+) stability constant of at least log K = 3, more preferably at least log.K = 6, and most preferably at least log K = 9, at 25 ° C and an ionic strength of 0.1. Further, the textile protecting agent has an iron (Fe 3+) stability constant of at least log K = 6, more preferably at least log K = 9, and most preferably at least log K = 12, at 25 ° C and an ionic strength of 0.1. In preferred embodiments, the fabric protection agent has a ratio of stability constant for Cu2 ⁺ the stability constant of Ca ² * at least 3: 1, more preferably at least 4: 1st Stability constants are defined and their experimental assay procedures described in Martell AE, Smith RM: Critical Stability Constants, Plenum Press: New York 1974, Vol. 1, and references cited therein. The stability constant of the invention is referred to as the log K value, also referred to as the log K * value as defined by Martell, cited above.

The textile-protecting agents of the invention preferably consist of at least two (semi) metal ion chelating or binding groups, such as e.g. carboxyl, amino (primary, secondary or tertiary), amido, hydroxy, and mixtures thereof. One skilled in the art will appreciate that carboxylic acid or carboxylic (carbonic) acid or non-protonated carboxylate. A highly preferred textile protecting agent of the present invention is selected from the group consisting of glycine, salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, aspartic acid, glutamic acid, malonic acid, the corresponding conjugated basic salts (ie _; and mixtures thereof. The structures of these compounds are as follows:

5-Sulfosalicylic acid 5-Bromosalicylic acid 5-Chlorosalicylic acid

Hin-. "COOH

L 'COOH

BOOC-xCOOH glutamic acid malonic acid

In a preferred embodiment of the present invention as a fabric protection agent having a ratio of stability constant for copper ^and * to the constant ^Ca2 * of at least 4: 1, is selected from the following: glycine, kyseliha salicylic acid,

5-sulfosalicylic acid, 5-bromosalicylic acid, glutamic acid, aspartic acid, the corresponding conjugated basic salts (i.e., monosodium glutamate), and mixtures thereof.

In a most preferred embodiment of the invention, the textile protecting agent is selected from salicylic acid and derivatives thereof, including 5-sulfosalicylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, the corresponding conjugated (pooled basic salts), and mixtures thereof.

The minimum textile preservative concentration in the bleaching composition is calculated according to formula (C) (stability constant for Cu ² *) and 2.5, more preferably with 5, where C is the weight percent preservative in the bleaching composition. In any case, the concentration of the textile protective agent must be less than 50% of the total bleaching composition. Example: if there is 3 stability constant for Cu ² for a certain preservative, then the concentration is calculated as (C) (3) & 2.5, or if C is 0.83% of the total weight of the bleaching composition.

In any case, the preferred range of preservative content is 0.3 to 3%, more preferably 1% to 1.5% of the total weight of the bleaching composition.

The compositions of the present invention are liquid cleaning compositions containing water. These aqueous compositions are formulated to an acidic pH, preferably a pH of greater than zero to a pH of 6, more preferably a pH of from 3 to 6. Formulation of a composition of the invention to an acidic pH contributes to the stability of the compositions. The pH of the compositions of the invention is adjusted with an organic or inorganic acid or base.

Damage to a textile material refers to the degree of loss of tensile strength of the material. The tensile strength loss is measured by the Tensile Loss Test described below in Example II.

Mobility factor. The mobility factor is a measure of the ability of the preservative to migrate on a cellulosic substrate and is determined experimentally by thin-layer chromatographic test. This test is performed as follows: A sample of the measured preservative is dropped onto a Baker cellulose F, a thin-layer chromatography plate, using a capillary applicator, which is then developed in a sealed chamber with 0.00IN-aqueous acetic acid: ethanol (50:50 mixture). as eluent. After drying, the plates are visualized under UV / custom. light or iodine vapor. Thus, the mobility factor used in the invention is defined as the retention factor (R *), commonly known to those skilled in the art, as the distance achieved by the sample process divided by the distance that the solvent in the thin layer of the chromatographic plate has reached.

Thus, the mobility factor, equal to the retention factor, reaches values from 0 to 1, with 1 being the greatest mobility. The textile protecting agents of the invention have excellent cellulose mobility as measured by this mobility test. In fact, the most preferred preservatives have a mobility factor of 0.9 or higher.

Said thin layer chromatography methods are well known to those skilled in the art and are described e.g. in J.C. Touchstone: Practice of Thin Layer Chromatography, 3rd

ed., John Wiley & Sons, New York, 1992.

Peroxide bleaching. The composition according to the invention is based on peroxide bleaching. A preferred peroxygen bleach of the invention is hydrogen peroxide or a water-soluble source thereof, or mixtures thereof. Hydrogen peroxide is most preferred. Indeed, the presence of a peroxygen bleach, preferably hydrogen peroxide, imparts strong whitening effects, which are particularly appreciated when washing laundry. As used herein, a hydrogen peroxide source refers to any compound that releases hydrogen peroxide in contact with water.

According to the invention, preferred water-soluble sources of hydrogen peroxide are sodium carbonate peroxohydrate or the corresponding percarbonate salts, persilicate, perborates, such as e.g. sodium perborate (any hydrate, but preferably mono or tetrahydrate), sodium pyrophosphate peroxohydrate, urea peroxohydrate, sodium peroxide, and mixtures thereof. Alternative sources of peroxide are persulfates such as monopersulfate, peroxyacids such as diperoxydodecanedioic acid (DPDA), magnesium perfthalate, perbenzoic and alkyl perbenzoic acid, and mixtures thereof.

An effective amount of a peroxygen bleaching composition is that which measurably removes dirt and stains from the textile substrate as compared to the non-peroxygen bleaching composition when the soiled substrate is washed in the presence of alkali. Typical compositions of the present invention comprise 0.5% to 20% of a peroxygen bleach, more preferably 2% to 15%, and most preferably 1% to 6% of the total weight of the composition.

Optional bleach activators. The peroxide-containing compositions of the invention may optionally but preferably further comprise a bleach activator. As a bleach activator, a compound reacting with hydrogen peroxide to form a peracid is referred to herein. The peracid thus formed is the essence of the activated bleaching composition. Acetyl triethyl citrate is particularly preferred. These bleach activators (if used) comprise 0.5% to 20%, more preferably 2% to 10%, and most preferably 3% to 7% of the total weight of the composition.

Bleach activators suitable according to the invention are known activators referred to as NOBS (nonanoyl oxybenzenesulfonate), TAED (tetraacetyl ethylenediamine), or ATC (acetyl triethyl citrate). Many other bleach activators are known. See e.g. activators disclosed in USP 4,915,854, Ed. On Mar. 10, 1990, Mao et al., And USP 4,412,934. For other bleaching see also USP 4, amide derivatives of the formula typical conventional activators 634.551. Also known are R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ^X C (O) N (R ⁵ ) R ² C (O) L, wherein R ¹ is an alkyl group containing 6 to 6 carbon atoms. 12 carbon atoms, R ² is alkylene of 1 to 6 carbon atoms, ^R is H or alkyl, aryl or alkaryl having 1 to 10 carbon atoms, and L is any suitable leaving groups. Other examples of bleach activators of the above formulas are (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidoproproyl) oxybenzenesulfonate, (6-decanamidolaproyl) oxybenzenesulfonate, and mixtures thereof, as described in USP 4,634,551. Another class of bleach activators are the benzoxazine-type activators disclosed by Hodg et al. in USP 4,966,723, eds. October 30, 1990. Yet another class of bleach activators are acyl lactam activators such as substituted or unsubstituted benzoyl caprolactam, tert-butyl benzoyl caprolactam, n-octanoyl caprolactam,

3.5.5-trimethylhexanoylcaprolactam, nonanoyl-caprolactam, decanoyl-caprolactam, undecanoyl-caprolactam, octanoyl-valerolactam, decanoyl-valerolactam, undecanoyl-valerolactam, nonanoyl-valerolactam, 3,5,5-trimethylbutyl-tert-butyl ester mixture.

Preferred for use herein are bleach activators selected from the group of: acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, n-octanoylvalerolactam, 3,5,5-trimethylhexanoyl caprolactam valerolactam, nonanoylvalerolactam, decanoyl-valerolactam, nitrobenzoyl-caprolactam, nitrobenzoyl-valerolactam, and mixtures thereof. Particularly preferred are bleach activators which are liquid or oily at room temperature. Examples of liquid bleach activators are acetyltriethyl citrate, n-octanoyl caprolactam,

3.5.5-trimethylhexanoyl * caprolactam, nonanoyl caprolactam, decanoyl caprolactam, and mixtures thereof. The compositions of the invention may also contain aryl benzoates, such as phenyl benzoate.

Preliminary Process The preferred use of the compositions described herein is based on a laundry prewash, but these compositions can also be used as laundry detergents or auxiliary laundry detergents, as household or bathroom cleaners, dishwashing or cleaning agents. carpets.

Said compositions must remain in contact with the textile material for 1 minute to 24 hours, more preferably 1 minute to 1 hour, and even more preferably 5 to 30 minutes or the like, so that the composition does not dry on the textile material. In the case of textiles with a stain or dirt which would otherwise be difficult to remove, it is also possible to wipe and / or brush the composition according to the invention e.g. sponge or brush, or simply rub two pieces of fabric against each other.

Washing herein refers to a simple rinsing of the fabric with water, or the fabric is washed with conventional laundry detergents containing at least one surfactant, either in a washing machine or simply by hand.

The term in its pure form indicates that the compositions described in the invention are applied to the prewash without any dilution, ie. they are used in the form described in the invention.

Other common ingredients for cleaning products.

The aqueous bleaching compositions according to the invention may also contain other optional conventional ingredients (s) to improve or modify the efficacy. Typical but non-limiting examples of such ingredients are set forth below for the purpose of formulators.

Organic Stabilizers The compositions described herein may also optionally contain organic stabilizers to improve the chemical stability of the composition, provided that these materials are compatible or suitably formulated. Organic stabilizers are selected from the following compounds: monophenols such as 2,6-di-tert-butylphenol or 2,6-di-tert-butyl-4-methylphenol;

diphenols such as 2,2-methylene-bis (4-methyl-6-tert-butylphenol) or 4-4methylene-bis (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-butyl hydroquinone; aromatic amines such as is N-phenyl-N- (1,3-dimethylbutyl) -p-phenylenediamine or

N-phenyl-naphthylamine; dihydroquinolines such as 2,2,4-trimethyl-1,2-dihydroquinoline; ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, e.g., USP 3,159,581; 3,213.030; 3,422.021; 3,400.148 and 3,442,137), and mixtures thereof.

The organic stabilizers are used in the compositions of the invention in an amount of 0.01% to 5.0%, more preferably 0.1% to 0.5%.

The peroxygen bleach-containing compositions may further comprise 0.5% to 5%, more preferably 2% to 4% by weight of the alcohol of the formula HO-CR'R-OH, wherein R and R are independently H or a C _2-10 hydrocarbon chain or cycle ( circle). A preferred alcohol of the formula is propanediol.

Inorganic Stabilizers. Examples of inorganic stabilizers are sodium stannate and various alkali metal phosphates such as the known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophosphates.

Surfactants Surfactants are used according to the invention for their cleaning performance, and in preferred embodiments of the instant compositions are used in an amount customary for detergents. Usually, the surfactants are used in an amount of 0.1% to 50%, more preferably 1% to 30%, and most preferably 5% to 25% by weight of the liquid bleaching composition of the invention.

Non-limiting examples of surfactants that are useful in the invention include the conventional C _xe -alkylbenzénsulfonáty (LAS) and primary branched and straight C _2o alkyl sulfates _also _ (AS); secondary

_Xe C -alkylsulfonyl sulfates of the formula _{CH3 (CH2) 3 C} ^(_ _CHOSO3 M +) CH ₃ and CH _{and (CH2)} ^ _(CHOSO3 "M +) _{CH2 CH3} where x and (y + 1) are integers, at least 7, more preferably at least 9, and M is a solubilizing cation, especially sodium; unsaturated sulfates such as oleyl sulfate; alkyl alkoxysulfates (AEES), especially those wherein A is 1 to 7; C _1-6 -alkyl-alkoxycarboxylates (especially EO 1-5 ethoxycarboxylates) C 1 -glycerin ethers C 1 -alkyl polyglycosides and their corresponding sulfated polyglycosides; and esters of alpha-sulfonated C 2 _{x 6-} fatty acids. To improve performance, detergent surfactants can be mixed in varying proportions, as is well known to those skilled in the art. Optionally, the compositions can use conventional nonionic and amphoteric surfactants such as the _{C-X 2} alkyl ethoxylates (AE) including the so-called. narrowband alkyl ethoxylates and -alkylfenol alkoxylates (especially ethoxylates and ethoxylate the mixture / propoxylates), C ^ _x2 θ-betaines and sulfobetaines (sultaines), C _{s well as} amine oxide and the like, which may be. added to detergents. It is also possible to use _C1-10 -N-alkyl polyhydroxy fatty acids (their amides). Typical examples are C11 _and N-methylglucamides.

WO 9,206.154. Other sugar-derived surfactants are N-alkoxy-polyhydroxy fatty acid amides, such as C _{10 -ox} N- (3-methoxypropyl) glucamide. For small soap bubbles formation, N-propyl to N-hexyl C-glucamides can be used. It can also be used, conventional _{2 °} C _io _ -mydlá. If high saponification is required, branched chain _{C10, L6} soaps can be used. Mixtures of anionic and nonionic surfactants are particularly preferred.

Strengthening components. Detergent enhancers may also be added to the compositions of the invention to help control mineral hardness. Both inorganic and organic components are used. These auxiliary components are used in detergent compositions to help remove particularly coarse dirt.

The content of the auxiliary components may vary depending on the end use of the composition and the desired physical form. In use, these compositions comprise at least 1% of a booster component. Highly effective compositions comprise 10% to 80%, more preferably 15% to 50% by weight of the detergent component. However, neither higher nor lower content is excluded.

¹ 1

The oranganic detergent components suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. According to the present invention, polycarboxylates refer to compounds having several carboxylate groups, i.e. at least 3 carboxylates. The polycarboxylate components may generally be added to the composition in acid form, but may be added in the form of a neutral salt or a cross-linked. When used in the form of salts, alkali metal salts such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Among the carboxylate components there are several categories of useful materials. One important category is the polycarboxylate ethers, including oxydisuccinate (oxydisuccinate) disclosed by Berg in USP 3,128,287, eds. April 7, 1964, and Lambert et al. in USP 3,635,830, eds.

January 18, 1972. See also TMS / TDS components in USP 4,663,071, Bush et al., Eds. Suitable ethers of polycarboxylates also include the cyclic compounds, especially the alicyclic compounds described in US Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful detergent components are hydroxypolycarboxylate ethers, copolymers of maleic anhydride with ethylene or vinylmethyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, various alkali metal salts, ammonium and substituted polyoctonic ammonium salts acids such as nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-1-carboxylic acid, carboxymethoxy iodine, and soluble salts thereof.

Citrate auxiliary components, e.g. citric acid and its soluble salts (especially the sodium salt) are polycarboxylate components of particular importance because they are available from renewable sources and because of their biodegradability. Oxydisuccinates are also very useful in these compositions and combinations.

Also suitable detergent components of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and their derivative compounds disclosed by Bush in USP 4,566,984, eds. 28.1.1986. Useful succinic acid component is _a C _{2 O} _ alkyl- and alkenyl-succinic acids and salts thereof. Specific examples of succinate components are: lauryl succinate, myristyl succinate, palmityl succinate,

2-dodecenylsuccinate (particularly preferred),

2-pentadecenylsuccinate, etc. Most preferred in this family of components are the lauryl succinates described in European Patent Application 86200690.5 / 0.200.263, published November 5, 1986.

Other suitable polycarboxylates are disclosed by Crutchfield et al. in USP 4,144,226, issued March 13, 1979, and Diehl in USP 3,308,067, issued March 7, 1967. See also USP 3,723,322.

Fatty acids, e.g. C _{i2 x s} -monocarboxylic acids can also be used in these compositions, alone or in combination with the aforesaid builders, especially citrate and / or the succinate builders, in order to increase activity. The use of fatty acids usually results in a reduction of soap suds in the wash, which must be taken into account by the formulator.

Where phosphorus-based booster components can be used, alkali metal phosphates such as the known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophosphates are used. Phosphonate components such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, e.g., USP 3,159,581; 3,213,030; 3,422.021; 3,400.148;

No. 3,422,137), although these materials are more commonly used in smaller amounts than chelating agents or stabilizers.

Inorganic and β-containing detergent components include, but are not limited to, alkali metal salts, ammonium and alkanolammonium, and polyphosphates (e.g., pyrophosphates and phosphonates, acid carbonates (including bicarbonates, sulfates, and aluminosilicates).

Chelating Agents The compositions comprise selective sequestering glassy polymeric phytic, silicates, and sesquicarbonates), according to the present invention (masking agents, tripolyphosphates, metaphosphates), with transition metals i.e. chelating agents, e.g.

chelating agents for iron and / or copper and / or manganese, provided that these materials are compatible and suitably formulated. Chelating agents suitable for use in the invention are selected from the group of: aminocarboxylates, phosphonates (especially aminophosphonates), polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Without wishing to be bound by theory, we assume that the convenience of these materials is due in part to their unusual ability to extract iron, copper and manganese ions from washing solutions by forming soluble chelates; another advantage is to prevent the formation of an inorganic film or boiler scale. Commercial chelating agents for use in the present invention are products of the DEQUEST ^R series, and chelants of Monsanto, DuPont and Nalco Inc.

Aminocarboxylates useful as optional chelating agents further include ethylenediamine tetraacetates, N-hydroxyethyl ethylenediamine triacetates; nitrilotriacetates, ethylenediamine tetrapropionates, triethylene tetraamine hexacetates, diethylenetriamine pentaacetates and ethanediglycines as their alkali metal, ammonium and substituted ammonium salts. Generally speaking, chelator mixtures are used to combine functions such as the regulation of transition metals, the long-term stabilization of the product, and / or the regulation of oxides and / or hydroxides of precipitated transition metals.

Polyfunctionally-substituted aromatic chelating agents may also be used in the compositions of the invention, see Connor et al., USP 3,812.044, eds; May 21, 1974. Preferred compounds of this type in acid form are dihydroxy disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. Another preferred chelator has the formula:

where R _x ,

R is independently selected from the group of substances

- 17 are in detergent levels of total composed of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO 4, -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 _s , R _g , R _{? 2} and R _e are independently selected from the group consisting of -H and alkyl.

Aminophosphonates are also suitable as chelators in the compositions of the invention if the compositions permit at least low phosphorus. These are ethylenediamine-tetrakis (methylene phosphonates) and diethylenetriamine-pentakis (methylene phosphonates). Preferably, the aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

When using chelating agents or selective transition metal sequestrants, it is preferred that their content is 0.001% to 10%, more preferably 0.05% to 1% by weight of the composition of the invention.

Enzymes. - Enzymes are supplied in instant formulations for a variety of washing or other cleaning purposes, including stain removal containing proteins, carbohydrates or triglycerides, and to prevent paint leakage or to freshen textiles. The enzymes to be supplied may be proteases, amylases, lipases, cellulases and peroxidases, but also mixtures thereof. It is also possible to add other types of enzymes. They must be of suitable origin, eg. plant, animal, bacterial, fungal and yeast. However, the choice is governed by several factors such as pH-activity and / or optimal stability, thermostability, stability to active detergents, enhancing components, etc. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred. The enzymes used according to the invention may also be protected by a coating for protection in an aqueous environment.

The enzymes are normally supplied in an amount containing up to 5 mg, more preferably 0.01 to 3 mg, of active enzyme per gram of composition. In other words, the compositions of the invention will contain 0.001% to 5%, more preferably 0.01% to 1% by weight, of a commercial enzyme preparation. Proteases in such a commercial composition are typically present in an amount sufficient to deliver 0.005 to 0.1 Anson Units (AU) of activity per gram of composition.

A suitable example of proteases is subtilisins obtained from particular strains of B. subtilis and B. licheniformis. Another suitable protease is obtained from a Bacillus strain with a maximum activity in the pH range of 8-12, developed and marketed by Novo Industries A / S as ESPERASE ^R. The preparation of this and analogous enzymes is described in British Patent Application 1,243,784 (Novo). Commercially available proteolytic enzymes suitable for protein-based stain removal are sold under the trade names ALCALASE ^R and SAVINASE ^r by Novo Industries A / S (Denmark) of International Bio-Synthethics, Ind. Other proteases are Protease A (see European Patent Application 130.756, published Jan. 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed March 28, 1987, and European Patent Application 130.756, Bott et al., Issued Jan. 9, 1985).

A particularly preferred protease referred to as Protease D is a carbonyl hydrolase variant with amino acid content not found in nature. This protease is derived from a carbonyl hydrolase precursor by replacing various amino acids with several amino acid residues at position +76 in combination with one or more amino acid residues at positions +99, +101, +103, +107 and +123 in the subtilisant of amyloliquefaciens, such as this has been described in MAXATASE ^R (Netherlands)

Bacillus patent application A. Baeck, C.K. Ghoshe, P.P. Greycara, R.R. Botta and L.J. Wilson with Compositions and US named Protease-Containing Cleaning Serial No. 08 / 136,797 (PaG Time

5040), and Bleaching Compositions Comprising Protease

Enzymes (bleaching compositions containing protease enzymes) with U.S. Serial No. 08 / 136,626.

Amylases include e.g. alpha-amylases described in British Pat. application no. 1,296,839 (Novo), RAPIDASE ^R , International Bio-Synthetics, Inc. | and TERMÄNYL ^R , Novo Industries.

The cellulases according to the invention can be used both bacterially and fungally. A preferred pH is 5-9,5. Suitable cellulases are described in USP 4,435,307, Barbesgoard et al., Eds. On March 6, 1984, which discloses fungal cellulase produced by the fungus Humicola strain DSM1800, or a fungus producing cellulase 212 belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of the marine gastropod (Dolabella Auricula Solander). Suitable cellulases are also described in GB-A-2,075.P28, GB-A-2,095.275, and DE-OS-2,247.832 CAREZYME ^R (Novo) is very suitable.

Lipase enzymes suitable for use with detergents produce microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, described in British Patent 1,372,034. See also lipase in Japanese Patent Application 53,20487, published Feb. 24, 1978. This lipase is supplied by Amano Pharmaceutical Co. Ltd. Ltd, Nagoya, Japan, under the name Lipase P Amano, hereinafter referred to as Amano-P. Other commercial lipases are Amano-CES from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; and other lipases from Chromobacter viscosum from US Biochemical Corp. USA and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. A preferred lipase for use in the present invention is LIPOLASE ^K , derived from

I

Humicola lanuginosa and supplied by Novo (see also EPO 341.947).

Peroxidase enzymes are useful in combination with oxygen sources, e.g. with percarbonates, perborates, persulfates, hydrogen peroxide, etc. They are used for bleaching in solution, ie. to prevent the transfer of dyes or pigments from the substrate during the wash to other substrates in the wash solution. Peroxidase enzymes are already well known and include e.g. horseradish peroxidase, ligninase, and haloperoxidases such as e.g. chloro and bromo-peroxidase. Peroxidase-containing detergent compositions are described e.g. in (PCT) International Application WO 89/099813, published October 19, 1989 by O. Kirk to Novo Industries A / S.

A wide selection of enzyme materials and compositions for their addition to synthetic detergent compositions is also disclosed in USP 3,553,139, eds. January 5, 1971, McCarty et al. Enzymes are further disclosed in USP 4.101.457, Plac et al., Eds. On July 18, 1978, USP 4,507,219, Hughes, eds. March 26th

Enzyme materials for liquid detergent formulations, and their addition to these formulations, are described in USP 4,261,868, Mountain et al., Eds. 14 April 1981. The enzymes used in detergents can be stabilized by various methods. Methods of enzyme stabilization are also exemplified in USP 3,600,319, Gedge et al., Eds. August 17, 1971, and in the European Pat. applications no. 0 199 405, application no. No. 86200586.5, published by Venegas on October 29

Enzyme stabilization systems are also described in USP 3,519,570.

Polymeric soil release agents. Optionally, some of the commonly known soil release polymeric agents can be used in the compositions and processes of the invention. Polymeric soil release agents are characterized by having not only a hydrophilic component to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, but also a hydrophobic component that settles on the hydrophobic fibers and remains adhered until the wash and rinse cycle is completed anchor function for the hydrophilic component. This allows stains formed after the action of the soil release agent to be easier to clean in a further washing process.

The polymeric soil release agents useful in the invention have (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 2 to 10; wherein the hydrophilic segment does not encircle any oxypropylene unit because it is bound to the adjacent groups at each end by an ether bond, or (iii) a mixture of oxyalkylene units composed of oxyethylene and 1 to 30 oxypropylene units, said mixture containing a sufficient number of oxyethylene units such that the hydrophilic component has a hydrophilicity sufficient to increase the hydrophilicity of the surfaces of the conventional polyester synthetic fiber after the soil release agent has deposited thereon, said hydrophilic segments preferably containing at least 25% oxyethyl new units, and more preferably (in particular for the components 20 to 30 oxypropylene units), at least 50% oxyethylene units; (b) one or more hydrophobic components

C ₃ -oxyalkylén terephthalate and hydrophobic components, a ratio of oxyethylene terephthalate composed of: (i) segments, these comprise oxyethylene terephthalate, the C--oxyalkylén terephthalate units is 2: 1 or lower, (ii) oxy-C ^ _g - alkylene segments, or poly (vinyl ester) segments of -ových C ₄ -alkylene, or mixtures thereof, (iii) (a preferred, or mixtures thereof, a polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C _x _ ₄ ~ alkyl ether

C ₄ -hydroxyalkylether substituents, or wherein the substituents are represented in the C ₄ -hydroxyalkyl ether substituents

I

_X _ C ₄ or C ₄ -alkyléterových -hydroxyalkyléterových cellulose derivatives, or mixtures thereof, and such cellulose derivatives are amphiphilic, as they have sufficient C _x _ ₄ -alkyléterových or C ₄ -hydroxyalkyléterových units of adhesion to the surface of conventional polyester fibers and the maintenance of a sufficient the number of hydroxyls adhered to the surface of these conventional fibers so that the hydrophilicity of the surface of the fibers is increased; or combinations (a) and (b).

Typically, the polyoxyethylene segments of type (a) (i) must have a degree of polymerization of 1 to 200, although it can also be used above the level of, preferably from 3 to 150, and more preferably from 6 to 100. Suitable oxy C ₄ _ _E alkylene hydrophobe segments include (but not limited to) end groups of polymeric soil release agents such as MO S (CH) OCH CH O-, wherein M is sodium and n is an integer from 4 to 6 as disclosed in USP 4,721.580, Gosselink, eds. . January 26, 1988.

The soil release polymeric compositions of the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. These agents are commercially available and contain cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents useful in the invention also comprise selected groups comprising a C _i4-alkyl-C ^ hydroxyalkyl celluloses, see U.S. 4,000.093, Nicol et al., Eds. 28 December 1976.

Soil release agents characterized by poly (vinyl ester) hydrophobic segments include grafted poly (vinyl ester) copolymers, e.g.

_{X 6} -vinylesterov, preferably poly (vinyl acetate) grafted onto polyalkylene oxide main chain locus, such as polyethylene oxide backbones. See European Patent Application 0 219 048, Kud et al., Eds. On March 22, 1987. Commercially available soil release agents of this type include SOKALAN type material, e.g. SOKALAN HP-22, which is available from BASF (Germany).

One type of preferred soil release agent is a copolymer with non-oriented blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of the soil release polymer is between 25,000 and 50,000. See USP 3,959,230, Hays, eds. May 25, 1976, and USP 3,893,929, Basadur, eds. 8 July 1975.

Another preferred soil release polymer is a polyester comprising ethylene terephthalate repeat units, 10-15% by weight of ethylene terephthalate together with 90 to 80% by weight polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 300 to 5000. material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also USP 4,702,857, Gosselink, eds. October 27, 1987.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer composed of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and with terminal groups attached to the backbone. These release agents are described in detail in USP 4,968,451, J. J. Scheibel and E.P. Gosselink, ed. November 6, 1990. Another suitable polymeric agent is terephthalate polyesters of USP 4,711,730, Gosselink et al., Eds. On Dec. 8, 1987, the anionic end-capped anionic oligomer esters of USP 4,721.580, Gosselink, eds. January 26, 1988, and block polyester oligomeric compounds of USP 4,702,857, Gosselink, eds. October 27, 1987.

Preferred soil release polymeric agents are also those of USP 4,877,896, Maldonado et al., Eds. On Oct. 31, 1989, which describes anionic, especially sulfoaroyl terephthalate, end-capped esters.

Another preferred soil release agent is an oligomer with repeated terephthaloyl, sulfoisoterephthaloyl, oxyethyleneoxy and oxy-1,2-propylene units. repeated

The I units form the backbone of the oligomer and are preferably terminated with modified isethionate end groups. A particularly preferred release agent of this type consists of one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two 2- (terminal) unit 2- ( Sodium 2-hydroxyethoxy) ethanesulfonate. The agent also contains from 0.5% to 20% (by weight of oligomer) of a crystallinity reducing stabilizer, which is preferably selected from the group of xylene sulfonate, cumene sulfonate, toluenesulfonate, and mixtures thereof. See USP 5,415,807, Gosselink et al., Eds. 16 May 1995.

When used, the soil release agent will be present in the detergent composition of the present invention in an amount of 0.01% to 10.0% by weight, more preferably 0.1% to 5%, and even more preferably 0.2% to 3.0%.

Other Ingredients - The optional detergent ingredient or addition to the instant composition may be one or more materials to assist or enhance the cleaning process, the treatment of the cleaned substrate, or the aesthetic appearance of the composition. Such materials are described in more detail in USP 3,936.537, Baskerville et al. Other active ingredients, such as dispersant polymers from BASF corp., Are also added to the compositions of the present invention in an amount commonly used (0-20% detergent ingredient, more preferably 0.5% to 10%). or Rohm and Haas, furthermore anti-shine or anti-corrosive agents, dyes, fillers, optical brighteners, germicides, hydrotropes, enzyme stabilizers, fragrances, solubilizing agents, carriers, processing aids, pigments, solvents, fabric softeners, antistatic agents, etc. .

Color transfer inhibitors. The compositions of the invention may also contain one or more materials preventing the transfer of dye (dye) during the cleaning process from one color surface to another. Such dye transfer inhibitors are polyvinyl-1-pyrrolidone, polyamine-N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents are present in an amount of 0.01% to 10%, more preferably 0.01% to 5%, and most preferably 0.05% to 2% by weight of the composition.

More specifically, the polyamine-N-oxide polymers used according to the invention comprise units having the following structural formula: R - Α _χ - P, where P is a polymerizable unit »to which N -> O can be attached or N -> 0 forms part of the polymerizable unit »or the group N -> O can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S- »-Ο-, -N =; x is 0 or 1;

and R is an aliphatic »ethoxylated aliphatic» aromatic, heterocyclic or alicyclic group or any combination thereof »to which nitrogen of the group N -> O can be attached, or the group N -> O is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrolidinazole, pyrrolidine, piperidine and derivatives thereof.

The group N -> 0 is represented by the following structural formula:

° θ (Rik - N - <R ₂ ) y; —N— (RiK (Rj> z

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 of the N -> O group may be attached or form part of any of the aforementioned groups. The amine-oxide unit of the polyamine-N-oxides has a pka <10, more preferably pK a <7, and most preferably pK a <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and does not transfer dye (dye). Examples of suitable polymer backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include unoriented or block copolymers in which one monotonic type is an amine N-oxide and the other monomeric type is an N-oxide. The amine-N-oxide polymers have a usual amine to amine-N-oxide ratio of from 10: 1 to: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide copolymerization The polyamine oxide is polymerization.

variance

The chemical polymers can be altered by a suitable or appropriate degree of N-oxidation. can be obtained in almost every stage. The average molecular weight is in the range of 500 to 1,000,000, more preferably 1000 to 500,000, and most preferably 5,000 to 100,000. This preferred class of materials can be referred to as PVNO. The most preferred polyamine N-oxide used in the detergent compositions of the present invention is a poly (4-vinylpyridine N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of 1: 4.

Equally preferred for this use are copolymers of N-vinyl-pyrrolidone and N-vinyl-imidazole polymers (referred to as PVPVI class). Preferred PVPVIs have an average molecular weight of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000. (The average molecular weight is determined by light as described by Barth et al. In Analysis vol. 113 in Modern Methods of

The polymerization polymer, the conclusions of which are incorporated herein by reference.) PVPVI copolymers have a molar ratio

N-vinylimidazole to N-vinylpyrrolidone in the range of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1 and most preferably 0.6:

These copolymers may be either linear or branched.

The compositions of the invention may also contain polyvinylpyrrolidone with an average molecular weight of 5,000 to 400,000, more preferably 5,000 to 200,000, and most preferably 5,000 to 50,000.

detergents are PVP known, see and EP-A-256,696, which is incorporated herein by reference. Formulations containing PVP may also contain polyethylene glycol (PEG) with an average molecular weight of 500 to 100,000,

Those skilled in the art e.g. EP-A-262 897

More preferably from 1,000 to 10,000. The preferred ratio of PEG to PVP based on ppm (millionths) in wash solutions is 2: 1 to 50: 1, more preferably 3: 1 to 10: 1.

Soap enhancers. - If more soapiness (soapiness) is required, soap-enhancing additives such as

_Xoie -alkanolamidy C, in an amount of 1 to 10% by wt .. A typical class of such additions are _also C _i4 _ -monoetanola diethanolamides. It is also preferred to use these additives together with soap surfactants such as the amine oxides, betaines and sultaines mentioned above. Soluble magnesium salts such as MgCl ₂ , MgSO ₄ and the like are added, if desired, to promote soap and fat removal, e.g. 0.1 to 2%.

Brighteners. Brighteners and bleaching agents known to those skilled in the art are added to the instant fabric conditioning or laundry compositions in an amount of 0.05% to 1.2% by weight of the detergent composition of the invention. Commercial optical brighteners useful in the present invention can be subdivided into sub-groups including, but not limited to, stilbene derivatives, pyrazoline, coumarin, carbonic acids, dibenzothiophene-5,5-dioxide methanesanines, azoles, 5-and 6-membered heterocyclic brightener rings, this appointment is merely exemplary and non-limiting. Examples of such brighteners are given in The Production and Application of Fluorescent Brightening Agents, M. Zahradnik, ed. John Wiley, New York (1982).

Specific examples of optical brighteners useful in the compositions of this invention are disclosed in USP 4,790,856, Wixon, Ed. December 13, 1988. Among them is PHORWHITE - a series of brighteners from Verona. Others in this reference are: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, which are available from Ciba-Geigy; Artic White CC and CWD from Hilton-Davis in Italy 2- (styryl-phenyl) -2H-naphthol [1,2-d] triazole; 4,4 ' -bis (1,2,3-triazol-2-yl) -stil- benes; 4,4'-bis (styryl) bis; and aminocoumarins. Specific examples of these brighteners are 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 USP 3,646,015, Hamilton, Ed. February 29, 1972. Anionic brighteners are preferred according to the present invention.

Coating The various detergent ingredients used in the compositions of the invention can further be stabilized by absorbing it into a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. It is preferred that the detergent ingredients be mixed with the surfactant before being absorbed into the porous substrate. During use, the detergent ingredient is released from the substrate into the wash water where it exerts its intended detergent effect.

For a more detailed depiction of the method of mixing a porous hydrophobic silica (SiO ₂₎ (a trade name SIPERNAT ^R D10, Degussa) with a proteolytic enzyme solution containing 3% -5% _{X 3} C _ _{x with} -etoxylovaného alcohol (E07) as a nonionic surfactant. The enzyme and surfactant solution is typically 2.5 times the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (different silicone oil viscosities in the range of 500 - 12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. In this way, ingredients such as the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescent additives, textile conditioners and hydrolyzable surfactants can be protected for use in detergents, including liquid laundry detergent compositions.

The compositions of the invention may also contain liquids other than carriers; low molecular weight primary or secondary alcohols such as e.g. methanol, ethanol, propanol and isopropanol. Monohydroxyalcohols are preferred for solubilizing surfactants, but polyols having 2 to 6 carbon atoms and 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol) may also be used. The compositions of the invention may contain from 5% to 90%, more usually from 10% to 50%, of such carriers.

Bleach Catalysts If desired, the compositions of the invention further comprise a catalyst or accelerator to further improve bleaching or soil removal. Any suitable bleach catalyst may be used. In the case of detergent compositions used in a total concentration of 1,000 to 5,000 ppm (million parts) in water, a catalyst concentration of 0.1 to 700 ppm, more preferably 1 ppm to 50 ppm, is added to the wash water.

Typical bleach catalysts comprise a transition metal complex in which ligands coordinated to the metal are sufficiently resistant to labilization (release) so that they do not visibly deposit (do not) metal oxides or hydroxides under typical alkaline washing conditions. Such catalysts include the manganese-based catalysts disclosed in USP 5,246,621, USP 5,244,594, USP 5,194,416, USP 5,114.606; and EP Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; Preferred examples of these catalysts are Mn ₂ ^IV (μ-Ο) ₃ (TACN) ₂ - (PF _g ) ₂ , Mn ¹¹¹ (μ-O), (μ-OAc), (TACN), (CIO) ,;

Mn ^ιν (μ-0) (TACN) (CIO)

4 * 6 44

^{4η ΙΙΧ} Μη4 ^ιν (μ-0) χ (μ-OAc) ₂ - (TACN) ₂ - (C10 ₄ ) ₃ ,

Mn ^IV - (TACN) - (OCH) (PF), and mixtures thereof, wherein the TACN is trimethyl-1,4,7-triazacyclononane or another equivalent macrocycle; however, ligands coordinating to another metal, as well as mononuclear complexes and monometallic, di- and poly-metallic complexes, and complexes with other metals such as iron and ruthenium are possible. Other bleach catalysts are described in USP 4,430,243 and USP 5,114,611. The use of manganese with various complex ligands to improve bleaching is also described in the following US 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.

the metals may be complexed in advance or in donor ligands, which are selected according to the oxidation state, and according to the dentition, the complexes useful herein are disclosed in U.S. Pat. No. 08 / 210,186, filed March 17

Transient situation with suitable metal and its ligands. Other application with 1994.

Formulation of prewash reagents. Preferred compositions of the present invention have a viscosity of 50 cps or greater (at 20 ° C), as measured by a Brookfield viscometer at 50 rpm and with a pin number. 3, more preferably 50 to 2000 cps, and most preferably 200 to 1500 cps. Any surfactant or polymer thickener system used by those skilled in the art to increase the viscosity of the composition can be used to achieve a preferred viscosity. Therefore, surfactants suitable for use in the present invention are thickened surfactants, i.e., non-ionic, anionic, cationic, zwitterionic and / or amphoteric surfactants.

The bleaching composition according to the invention contains water in any amount up to 95% of the total weight of the composition. A water content of 5% to 95%, more preferably 10% to 90% by weight of the bleaching composition is preferred.

If the peroxygen bleach-containing compositions of the present invention still contain an optional bleach activator, then it is desirable to formulate these compositions as a microemulsion or as a stable emulsion.

When formulated as a microemulsion, the composition comprises a bleach activator, a peroxygen bleach, and hydrophilic anionic and nonionic surfactants in the mother water. Suitable anionic surfactants are alkylbenzene sulfonates, alkyl sulfates, alkoxylated alkyl sulfates, and mixtures thereof. Suitable nonionic surfactants for use in microemulsions are the hydrophilic nonionic surfactants as defined below.

When formulated as an emulsion, the composition comprises at least one hydrophilic surfactant having an HLB (hydrophilic lipophilic balance) above 10, and at least one hydrophobic surfactant with an HLB of up to 9, wherein said bleach activator is emulsified by these surfactants.

In order to form a stable emulsion, the two different surfactants must have different HLB values, and it is preferred that the difference in the HLB values of the two surfactants is at least 1, and more preferably at least 3. In other words forms a stable emulsion, i. emulsion which does not separate into two different layers if it is standing for at least two weeks at 50 ° C. The emulsion comprises said hydrophilic and hydrophobic surfactants in an amount of 2% to 50% by weight of the total composition, more preferably 5% to 40%, and most preferably 8% to 30%. The emulsion comprises one or more hydrophobic surfactants in an amount of at least 0.1%, preferably at least 3%, and most preferably at least 5% of the total weight of the emulsion, and one or more hydrophilic surfactants in an amount of at least 0.1%, more preferably at least 3%, and at least 5% of the total weight of the emulsion. Hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are preferred for use in the present invention. The hydrophobic nonionic surfactants must have an HLB of up to 9, more preferably below 9, and most preferably below 8, and the hydrophilic surfactants must have an HLB of above 10, more preferably above 11, and most preferably above 12. The nonionic surfactants suitable for use herein are alkoxylated fatty alcohols, preferably ethoxylates and / or propoxylates of fatty alcohols. Many alkoxylated fatty alcohols with different HLB values are commercially available. For further details on HLB theory and its application in emulsion formation, see Becher P .: Encyclopedia of Emulsion Technology, ed. Marcel Dekker, Inc., New York 1985, Vol. 1 and 2, and the references therein.

For a particularly preferred embodiment of an emulsion containing acetyltriethyl citrate as a bleach activator, a nonionic system comprising a hydrophobic nonionic surfactant with HLB 6 such as Dobanol ^R 23-2 and a hydrophilic nonionic surfactant with HLB 15 such as Dobanol ^R 91-10 is appropriate. . Other suitable nonionic surfactant systems include e.g. Dobanol ^R 23-6.5 (HLB 12) and Dobanol ^R 23 (HLB below 6) or Dobanol ^R 45-7 (HLB = 11.6), and LutensolT * T03 (HLB = 8). Commercially available nonionic Dobanol ¹ * surfactants are supplied by Shell Corp. and Lutensol ¹ * supplied by BASF Corp.

The peroxygen bleach compositions of the present invention further comprise an amine oxide surfactant of the formula R ¹ R ² R ³ NO, wherein C

R ^{@ 1} , R ^{@ 2} and R ^{@ 3} are preferably independent hydrocarbon chains

10-30 'observed to further improve the ability of greasy stains. It is considered the ability is independent of achieving this advantage

6-30 was, and most preferably, the C prewash presence of an amine oxide or a purifying agent and / or that this improvement in the purification mother liquor. The amine oxides must be present in an amount of 0.1% to 10%, more preferably 1.5% to 3% by weight of the total composition.

Products. Preferred products comprise compositions according to the invention suitable for use described in the invention and which are in a package which permits direct application of the compositions to the soiled laundry. A preferred package is a collapsible package with an application closure. Packaging which allows direct application to the dirty laundry by squeezing or pouring the composition through the application closure is suitable. Such containers include those described in USP 4,107,067. Suitable caps and caps are (dispensing) nozzles, brush caps, ball applicators and caps (without being limited by this calculation). The containers for the process herein have a content of 4 to 32 ounces (124 to 1,052 flip-top described grams), more preferably 4 to 24 ounces (124 to 768 g) of the composition of the invention.

Examples

The following are non-limiting examples of compositions according to the invention. All materials in the Examples meet the functional limitations of the invention.

Example I

The following compositions were made by mixing the listed ingredients in the proportions indicated (in percent by weight unless otherwise stated).

means I II III IV IN Na-C-alkyl sulfate 2 2 2 2 2 Dobanol ^R 45-7 8.6 8.6 8.6 8.6 8.6 Dobanol ^R 23-3 6.4 6.4 6.4 6.4 6.4 ATC 3.5 3.5 3.5 3.5 3.5 H 0 2 2 6 6 6 6 6 BHT ² 0.05 0.05 0.05 0.05 0.05 Salicylic acid ¹ - 1.5 - - - Malonic acid ¹ - - 1.5 - - Glycine ¹ - - - 1 - Kys. glutamic ¹ - - - - 1.5 Water and some additives ³⁰ -doplniť to 100 % -----

With the help of H ₂ SO _{4 to} adjust pH 4 ¹ agents protecting the textile material ^x small, the additives are fragrances (fragrances), dyes, etc.

² butylated hydroxytoluene

Formulation I contains hydrogen peroxide and is free of fabric protecting agents. Compositions II-V comprise a textile material protecting agent which is representative of the present invention.

The compositions in Example I differ only in the fabric protecting agent. Therefore, to compare the tensile strength loss for a textile material washed with peroxide bleaching agents containing the respective textile protecting agent, this formulation was used as the basic peroxide bleaching agent to which the respective textile protecting agent was added.

tensile strength for Krefeld tape ² ) containing

Example II

Method for testing the tensile strength. - Loss of textile material is determined as follows: Cotton fabric (dimensions 12.5 x Cu ² * 30 ppm concentration per gram of cotton) is treated with 2 ml of the test composition of Example I. The test composition is left in contact with the tapes. The tapes are then rinsed with water and the tensile strength is lost on the INSTRON, Model No. 4411. Damage to the cotton tapes is evaluated by pulling them to tear, the tensile strength of the tapes, i.e. the tensile strength, is measured on damp tapes with the INSTRON Model 4411. The smaller the net required to rupture the cotton tapes, the more serious is the damage to the textile material.High probability (confidence level) results (standard deviation = 2 - 4 kg) are achieved if Five repetitions, the loss in strength of the composition, measured as a percentage above, and this will be used at each tensile to test The method is expressed in the tensile strength of the reference cotton tape (ie, not bleached) by dividing the strength of the tape to which the tensile strength of the test tape treated with the test composition is divided. '

The results are as follows:

means

Loss of tensile strength (%) (30 PPM Cu per gram of fabric,

I II 70 11

III IV V 19 40 45 interim treatment 24 hours)

The above results clearly indicate an unexpected improvement in the tensile strength loss (i.e., lower numerical values) when using the bleaching compositions of the present invention which contained not only a peroxide bleaching agent but also a textile protecting agent compared to using the same bleaching agent. without preservative (composition I). The tensile strength loss will be reduced if the fabric is soaked by the compositions of the present invention (see Formulas II-V), even after prolonged contact times, i.e.. after 24 hours, and in the presence of a high copper concentration on the textile surface, i. 30 ppm per gram of cotton fabric.

Example III

The following compositions were made by mixing the listed ingredients in the proportions indicated (in percent by weight unless otherwise stated).

Device 1

H O 2 2

ATC Na-C x o-xe

Dobanol 23-3

-alkylsulfonyl

A

3.5

B

3

C

3

D

3.5

Glycine ^x

Salicylic acid ¹ Malonic acid ¹ Glutamic acid ¹ Water and small ingredients ³¹ With H ₂ SO ₄ adjust to pH 4 ¹ Textile protecting agent ^x Small ingredients are fragrances and dyes

1.5

1.5

1.5

-fill up to 100

Means 2 A -B C D H 0 2 2 6 6 6 6 ATC 3.5 3.5 3.5 3.5 Na-C-alkyl sulfate 12 12 12 12 Dobanol 23-3 12 12 12 12 Glycine ¹ 1 - - - Salicylic acid ¹ - 1.5 - - Malonic acid ¹ - - 1.5 - Glutamic acid ¹ - - - 1.5 Water and small ingredients ² * complete to 100 0th about

With the aid of H ₂ SO ₄ to pH 4 ¹ fabric protection agent

* small ingredients are fragrances and dyes Means 3 A B C D H 0 7 7 7 7 2 2 Na-C-alkyl sulfate 2 2 2 2 Dobanol 23-3 3 3 3 3 Glycine ¹ 1 - - - Salicylic acid ¹ - 1.5 - - Malonic acid ¹ - - 1.5 - Glutamic acid ¹ - - - 1.5 Water and small ingredients ² * complete to 100 %

With the help of H ₌ SO ₄ adjust to pH 4 ¹ textile protection agent ^x small ingredients are fragrances and dyes

The Krefeld cotton tapes were soaked in compositions A to D in the same manner as in Example I.

The tensile strength loss is reduced if the fabric material is soaked with the compositions A to D of this example, even after prolonged contact time of the material, i.e., the material has a tensile strength. after 24 hours, and in the presence of a high copper concentration on the textile surface, i. 30 ppm per gram of cotton fabric.

Even when using compositions A to D on colored laundry in the same manner as above, no discoloration and / or discoloration is observed.

Γ? 74Γ37

Claims (10)

An aqueous bleaching composition comprising an effective amount of a peroxygen bleaching component and a textile protecting agent, said preservative having a mobility factor of greater than 0.7 and a stability constant of at least log K = 3 for Cu ² * , and a concentration C measured as a percentage by weight of the liquid bleach, calculated according to the following formula: {[C] x [stability constant for Cu ² ^]} with 2.5. Aqueous bleaching composition according to claim 1, characterized in that the textile protecting agent has a ratio of the copper (2+) stability constant to the calcium (2+) stability constant of at least 2: 1, more preferably 4: 1. Composition according to any one of the preceding claims, characterized in that the textile protecting agent has a stability constant for Fe ³ * of at least log K = 6, more preferably at least log K = 9. Composition according to any one of the preceding claims, characterized in that the textile protecting agent has a mobility factor greater than 0.8, preferably greater than 0.9, and a stability constant for Cu ² * of at least log K = 6. Composition according to any one of the preceding claims, characterized in that the textile protecting agent has a stability constant for Fe ³ * of at least log K = 12 and a stability constant for Fe ³ *. Cu ² * at least log = 9. Composition according to any one of the preceding claims, characterized in that the textile-protecting agent is selected from the group of substances: glycine, salicylic acid, acid 5-sulfosalicylic acid, 5-bromosalicylic acid, acid 5-chlorosalicylic acid, aspartic acid, glutamic acid, malonic acid, their conjugated basic salts, and mixtures thereof. Aqueous bleaching composition according to any one of the preceding claims, characterized in that its peroxygen bleaching component is hydrogen peroxide or a water-soluble source thereof in an amount of 0.5% to 20% by weight of the total composition. a total preferably selected acetyl triethyl citrate, Aqueous bleaching composition according to any one of the preceding claims, characterized in that it further comprises in an amount of 0.5% to 20% by weight of the composition a bleach activator selected from the group of substances: n oktanoy1 caprolactam, 3.5.5-trimethylhexanol-caprolactam, nonanoyl-caprolactam, decanoyl-caprolactam, n-octanoyl-vaerolactam, 3.5.5-trimethylhexanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, nitrobenzoyl caprolactam, nitrobenzoyl valerolactam, and mixtures thereof. The method of pretreatment with a composition according to the claims, comprising the steps of laundry, and with laundry into that dirty laundry with aqueous bleaching any of the foregoing, wherein the application of said composition to keep the composition in contact for a period of washing. A product suitable for individual use for cleaning dirty laundry (textile from an application closure in the form of (container) containing according to any of the distinguishing aqueous material), the lids and the bleaching composition of the preceding claims, being suitable for applying said composition directly clothes (textile material).