KR960015159B1 - Bleaching composition for detergent formulations - Google Patents

Abstract

None.

Description

Detergent Bleach Composition

The present invention relates to a bleach composition for detergents.

Peroxide bleach used in laundry has been known for many years. Such bleaches are effective at removing contaminants such as tea, fruit and wine contamination from clothing at temperatures near or at the boiling point. The efficacy of the peroxide bleach drops rapidly at temperatures below 60 ° C.

It is known that many transition metal ions, H ₂ O ₂ and H ₂ O ₂ and catalytic decomposition of the emission with a compound such as sodium borate. It has also been proposed to use transition metal salts with chelating agents to activate peroxide compounds to achieve satisfactory bleaching at lower temperatures. However, not all transition metal and chelating agent combinations are suitable for improving the bleaching performance of peroxide bleaching agents. In fact, many formulations have no effect on bleaching performance at all, and may even adversely affect. There seems to be no suitable rule to anticipate the effects of transition metal ion / chelating agent combinations on the bleaching performance of peroxide bleach. All of these prior art proposals are based on systems which are freely active species of free metal ions, and consequently sometimes produce very inconsistent and unsatisfactory results, especially when used for laundry at low temperatures. .

In order for the transition metal to be useful as a bleaching catalyst in detergent bleaching compositions, the transition metal compound must not excessively promote peroxide decomposition by the unbleaching route and must be stable against hydrolysis and oxidation.

The most effective peroxide bleach catalysts to date are cobalt based catalysts as transition metals.

However, adding cobalt based catalysts to detergent compositions as transition metals is a less desirable method from an environmental point of view.

Many patent documents describe the use of manganese, an environmentally acceptable transition metal. However, all of these patent documents are based on the use of free manganese ions and thus do not meet a stable requirement for hydrolysis. U.S. Patent No. 4728455 describes the use of gluconic acid Mn (III) having high stability for hydrolysis and oxidation as a peroxide bleach catalyst, but the ratio of ligand (gluconate) to Mn must be relatively high to obtain the desired catalyst system. Moreover, the performance of these Mn based catalysts is inappropriate for use in bleaching at low temperatures of about 20-40 ° C. and is effective only for specific contamination.

The inventors have identified a class of transition metal complexes with a well defined definition that meets the requirements for stability (in the washing process and in the dispenser of the washing machine) and which are extremely active in catalyzing the bleaching of peroxy compounds against extensive contamination even at low temperatures. Found.

Recently, European Patent Specifications No. 458397 and 458398 have been described by coordination ligands, in particular 1, 4, 7-trimethyl-1, 4, 7-triazaclonan, in which binuclear manganese has a short bridge between metal centers. A series of enclosed manganese complexes is disclosed. These complexes are extremely active in catalyzing peroxy compounds even at low temperatures. These materials can eliminate a wide range of laundry contamination.

Binary manganese complex catalysts have made substantial advances in the art, but the cost of these materials is very expensive. It is also desirable to find a dexterity catalyst that is effective for low peroxy compounds (eg perborate) and that enhances the effect of removing hydrophobic contamination such as tomato sauce.

Accordingly, the present invention provides a transition metal catalyst that improves the bleaching activity of peroxy acid compounds, including peroxy acid precursors, as well as peroxy compounds, including oxidants, in particular hydrogen peroxide and hydrogen peroxide release or generating compounds, for various kinds of contamination at low temperatures. To provide.

The present invention provides an aqueous laundry cleaning medium containing an improved bleach containing detergent composition and an improved novel detergent bleaching composition effective for cleaning laundry at relatively low temperatures.

The present invention also provides peroxy compounds that are effectively used in the cleaning and bleaching of substrates including laundry, teeth and hard surfaces (e.g. dishwashers, general cleaners, etc.) and in the textile, paper and wood pulp industries and other related industries. Improved bleaching systems containing bleach and transition metal catalysts, and fabrics such as laundry, tableware and other hard surfaces, teeth, textiles, paper and pulp, and other substrates using novel transition metal catalysts and peroxy compound bleach To provide a way.

Accordingly, the present invention provides a catalyst having the following formula.

In this formula, Mn is manganese having an oxidation number of +4, R is a C ₁ to C ₂₀ radical selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, a benzyl group and a radical mixture thereof, and at least two R groups are Can be bonded to each other to form a bridging unit between two coordinating oxygen, L is a ligand selected from C ₃ ~ C ₆₀ radicals having at least 3 nitrogen atoms coordinating with manganese, Y is oxidatively stable It is a counter-ion.

According to another feature of the invention, there is provided a bleach composition comprising the following materials.

Manganese complex compounds having (i) about 1 to 60% by weight of peroxy compound, and (ii) an effective amount for catalyzing the bleaching activity of peroxy compound

Another feature of the present invention is to contaminate a contaminated substrate by contacting the contaminated substrate with an aqueous medium each containing an amount of a peroxy compound effective to provide a cleaning effect to the substrate and a manganese complex compound having the formula: It is to provide a way to bleach.

The mononuclear manganese (IV) complex of formula (A) is a very effective catalyst for bleaching substrates by activating peroxygen compounds. Unlike dinuclear manganese (IV) complexes, the complexes of the present invention may act at equivalent concentrations where the peroxygen compound is present in 30-50% or less. In addition, this novel complex is more effective in removing tomato contamination.

The counter ion Y is preferably ^{Cl -, Br -, I -} , No - 3, ClO 4 -, NCS -, PF 6 -, RSO 4 -, OAc -, BPh 4 -, CF 3 SO 3 -, RSO 3 ^- and RSO ₄ ^- is an anion selected from the group consisting of.

Ligands suitable for the present invention are described through the following cyclic and cyclic structural formulas for purposes of illustration only.

The most preferable of these is a ligand of (I)-(V).

Ligand (I) is designated as Me ₃ -TACN as 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, and ligand (II) is designated 1, 4, 7-triazacyclononane as TACN. Ligand (III) is designated as Me ₃ -TACD as 1, 5, 9-trimethyl-1, 5, 9-triazacyclododecane, ligand (IV) is 2-methyl-1, 4, 7 -Trimethyl-1, 4, 7-triazacyclononane is denoted Me / Me ₃ -TACN, and ligand (V) is denoted Me / TACN as 2-methyl-1, 4, 7-triazacyclononane. .

Any of these complexes are useful catalysts that activate the bleaching properties of peroxy compounds against a wide variety of contaminations at low temperatures in a much more effective way than Mn based catalysts of the art so far known. Moreover, these catalysts are highly stable to hydrolysis and corals, even in the presence of oxidants such as hyponitrate.

Another advantage is that these catalysts are in many respects superior to any other Mn complex proposed in the art. They are effective in enhancing the bleaching action of organic and inorganic peroxyacid compounds as well as hydrogen peroxide bleach.

A surprising feature of the bleach according to the invention is that it is effective against a wide range of contaminations, including both hydrophilic and hydrophobic contamination of both. This is in contrast to all conventionally proposed Mn based catalysts that are effective only for hydrophilic contamination.

Another surprising feature is that they are compatible with detergent enzymes such as proteases, cellulases, lipases, amylases, oxadases and the like.

Therefore, the present invention provides a method for bleaching or washing with a bleach selected from the group of peroxy compounds bleach, including hydrogen peroxide, hydrogen peroxide release or hydrogen peroxide generating compounds, peroxy acids and salts thereof, peroxy acid bleach precursors and mixtures thereof. In a provision, the process is characterized in that the bleach is activated by a catalytic amount of the Mn complex of formula (A) as defined above.

The catalyst component is a novel feature of the present invention. The effective amount of the Mn complex catalyst is expressed as the amount of manganese (1 million parts per million (ppm)) in an aqueous bleach solution, and generally ranges from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 20 ppm, more preferably from 0.1 ppm to 10 ppm. . Industrial bleaching processes such as textile and paper pulp-bleaching require high concentrations and can be used. Low concentrations of content are predominantly and preferably used for home washing and dish washing. The concentration of the peroxy compound in the aqueous solution is 0.01 to 250 ppm, preferably 0.5 to 100 ppm.

The improved bleaching compositions of the present invention are especially added to detergent compositions to contain peroxy compound bleaches, Mn complex catalysts defined above, surfactants, generally detergency and builders and other known ingredients added to such compositions. It forms new and improved detergent bleaching compositions that fall within the scope, and these bleaching compositions are also used in industrial bleaching of yarns, textiles, paper, wood and the like.

The Mn complex catalyst may be present in the detergent composition in an amount such that the concentration is desired in the wash liquor. When the amount of detergent bleaching composition used is relatively low, such as about 1 and 2 g / l, respectively in Japan and the United States, the Mn content in the composition is from 0.0025 to 0.5%, preferably from 0.005 to 0.25%. For example, when the amount of use is relatively high, such as for use by European consumers, the Mn content in the composition is from 0.0005 to 0.1%, preferably from 0.001 to 0.05%.

Compositions containing peroxy compound bleach and the aforementioned bleach catalysts are effective over a broad pH range of 7 to 13, with an optimal pH range of 8 to 11.

Peroxy compound bleaches that can be used in the present invention are hydrogen peroxide, hydrogen peroxide releasing compounds, hydrogen peroxide generators, peroxy acids and salts thereof, peroxy acid bleach precursor systems and mixtures thereof.

Hydrogen peroxide sources are well known in the art. These include alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide and inorganic perchlorate bleaching compounds such as alkali metal perborates, percarbonates, superphosphates and photosulphates. Mixtures of two or more of these compounds are also suitable. Particularly preferred materials are sodium percarbonate and sodium perborate, in particular sodium perborate monohydrate. Sodium perborate monohydrate is preferred over tetrahydrate because it has excellent storage stability and also dissolves very quickly in an aqueous bleach solution. Sodium percarbonate is preferred from the environmental point of view. These bleaching compounds may be used alone or in combination with peroxy acid bleach and precursors. The use of precursors not only improves the overall white appearance of the white fabric, but also has hygiene benefits.

Peroxy acid bleach precursors are known and are described in British Patents 836988, 864798, 907356, 1003310 and 1519351; German Patent No. 3333921; It is described in detail in European patents (EP-A) 0185522, 0174132, 0120591 and in US patents 1264139, 33332882, 4128494, 4412934 and 4675393.

Another useful class of peroxy acid bleach precursors is described in US Pat. Nos. 4771015 and 4397757, European Patents (EP-A) 284292, 331229, 03030520, 458396, and 464880. Quaternary ammonium substituted peroxy acid precursors as is. Examples of this class of peroxy acid bleach precursors are as follows.

2- (N, N, N-trimethylammonium) ethyl-4-sulfophenyl carbonate (CSPS), N-octyl-N, N-dimethyl-N ₁₀ -carbophenoxy decyl ammonium chloride (OCD), 3 -(N, N, N-trimethylammonium) propyl sodium-4-sulfophenyl carboxylate, N, N, N-trimethylammonium toluyloxy benzene sulfonate.

Preferred classes of this class of bleach precursors are esters, acyl-amides and quaternary ammonium substituted peroxy acid precursors, including acyl phenol sulfonates and acyl alkyl phenol sulfonates.

Particularly preferred active agents are sodium-4-benzoyloxybenzene sulfonate; N, N, N ', N'-tetraacetylethylenediamine, sodium-1-methyl-2-benzoyloxybenzene-4-sulfonneate; Sodium-4-methyl-3-benzoyloxybenzoate, trimethyl ammonium toluyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate; Sodium 3, 5, 5-trimethylhexanoyloxybenzene sulfonate, glucose phenthiacetate and tetraacetyl xylose.

Organic peroxy acids are also suitable as feoxy compounds. Such materials generally have the following general formula:

Wherein R is C ₁ -C ₂₂ alkylene or substituted alkylene or a phenylene or substituted phenylene group, Y is hydrogen, halogen, alkyl aryl or or to be.

Organic peroxy acids useful in the present invention may have one or two peroxy groups and are aliphatic or aromatic.

When the organic peroxy acid is aliphatic, the unsubstituted acid has the general formula:

In the formula, Y is, for example, are H, CH _3, CH ₂ Cl, COOH, COOOH, n is an integer from 1 to 20.

When the organic peroxy acid is aromatic, the unsubstituted acid has the general formula:

Wherein Y is hydrogen, alkyl, alkylhalogen, halogen or COOH or COOOH.

Typical monoperoxy acids useful in the present invention include the following alkyl peroxy acids and aryl peroxy acids.

i) peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxy-α-naphtho acid, ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxylauric acid, per Oxystearic acid and N, N-phthaloylaminoperoxycaproic acid (PAP).

Typical diperoxy acids useful in the present invention include the following alkyl diperoxy acids and aryldiperoxy acids.

iii) 1, 12-diperoxydodecanedioic acid, (iv) 1, 9-diperoxyazelaic acid, v) diperoxybrazilic acid, diperoxysebacic acid and diperoxyisophthalic acid, vi) 2-decyldiperoxybutane- 1,4-dioic acid, vii) 4,4'-sulfonylbioperoxybenzoic acid.

Inorganic peroxylates useful in the present invention are, for example, potassium monosulfate.

Detergent bleaching compositions of the present invention can be formulated by blending an effective amount of the component. As used herein, the term "effective amount" refers to an amount sufficient to serve the intended purpose when the resulting mixture is combined with water to form an aqueous medium that can be used to wash and clean clothes, fabrics and other objects. It means that each component is present.

In particular, the detergent bleaching composition may be formulated to contain, for example, about 2 to 30% by weight, preferably 5 to 20% by weight of peroxide compound.

Peroxy acids can be used in somewhat lower amounts, for example in amounts of 1 to about 15% by weight, preferably 2 to 10% by weight.

The peroxy acid precursor can be used with the peroxide compound in an amount substantially equal to peroxy acid, for example in an amount of 1 to 15% by weight, preferably 2 to 10% by weight.

The manganese complex catalyst is contained in the composition in an amount sufficient to provide the required amount of Mn in the wash liquor. Generally, the manganese complex catalyst is blended into the composition in an amount corresponding to an Mn content of 0.0005 to about 0.5% by weight, preferably 0.001 to 0.25% by weight.

The bleach catalyst of the present invention can be used with any conventional surfactant and detergent builder material known.

The surfactant may be a naturally derived material such as soap, or may be a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic active materials and mixtures thereof. Many suitable surfactant materials are commercially available and described in, for example, "Surface Active Agents and Detergents" [vol I and II, by schwartz, Perry and Berch]. The total content of surfactant is 50% by weight or less, preferably about 1-40% by weight, and most preferably 4-25% by weight of the composition.

Synthetic anionic surfactants are usually water soluble alkali metal salts of sulfonic acids and organic sulfur phases having alkyl groups of about C ₈ to C ₂₂ . The term alkyl is used herein to mean including the alkyl portion of the higher aryl group.

Examples of suitable synthetic anionic detergent compounds include those obtained by the sulfation of alkyl sodium sulfate and ammonium, in particular higher (C ₈ -C ₁₈ ) alcohols produced from tallow or coconut oil; Sodium alkyl (C ₉ -C ₂₀ ) benzenesulfonate and ammonium, in particular linear secondary alkyl (C ₁₀ -C ₁₅ ) benzene sodium sulfonate; Alkyl ethers of sodium glyceryl ethers, in particular the above ether materials of synthetic alcohols derived from higher alcohols and petroleum derived from tallow or coconut oil; Coconut oil fatty acid monoglyceride sulfuric acid and sodium sulfonate; Sodium and ammonium salts of sulfate esters of higher (C ₉ -C ₁₈ ) fatty alcohol alkylene oxides, in particular ethylene oxide; Reaction products esterified with isethionic acid and neutralized with sodium hydroxide, such as coconut fatty acids; Sodium and ammonium salts of fatty acid amides of methyl taurine; Alkane monosulfonates such as substances derived from reacting paraffins with SO ₂ and Cl ₂ and then hydrolyzing with bases to generate random sulfonates; C ₇ -C ₁₂ dialkyl sulfosuccinate and ammonium; Olefin sulfonates, which refer to substances obtained by reacting olefins (particularly C ₁₀ to C ₂₀ alpha-olefins) with SO ₃ and neutralizing and hydrolyzing the reaction product. Preferred anionic detergent compounds are sodium (C ₁₁ -C ₁₅ ) alkylbenzene sulfonates, sodium (C ₁₆ -C ₁₈ ) alkyne sulfates and sodium (C ₁₆ -C ₁₈ ) alkyl ether sulfates.

Suitable nonionic surfactants which can be used are, for example, in particular reaction products of alkylene oxide (usually ethylene oxide) with alkyl (C ₆ -C ₂₂ ) phenols (5-25 EO, ie generally per molecule 5-25 units of ethylene oxide): Condensation product of aliphatic (C ₈ -C ₁₈ ) primary or secondary straight or branched chain alcohol with atylene oxide () 3-30 EO as residue): Propylene oxide and ethylene diamine There is a condensation product of the reaction product with ethylene oxide. Other so-called nonionic surfactants include alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkylsulpooxides.

Amphoteric or zwitterionic surfactant compounds may also be used in the compositions of the present invention, but are generally not preferred because they are relatively expensive. Small amounts of amphoteric or zwitterionic detergent compounds are used in the compositions based on synthetic anionic and / or nonionic detergent compounds which are usually used in much higher amounts.

As mentioned above, soaps may also be incorporated into the compositions of the present invention in amounts up to 25% by weight. Soaps are also particularly useful in low amounts in tricomponent mixtures with bicomponent (soap / anionic compounds) mixtures or nonionic compounds or mixed synthetic anionic and nonionic compounds. The soaps used are preferably sodium salts of saturated or unsaturated C ₁₀ -C ₂₄ fatty acids or less preferably potassium salts and mixtures thereof. The amount of such soap may vary from about 0.5 to about 25% by weight, and generally at least about 0.5 to about 5% by weight is sufficient to control the foam. Soap is used in an amount of about 2 to about 20% by weight, preferably about 5 to about 10% by weight, to provide a beneficial effect on detergency. This is particularly important for compositions used in hard water when the soap acts as a supplementary builder.

Detergent compositions of the invention also generally contain a detergency builder. Builder material 1) calcium ion containment material, 2) precipitant material, 3) calcium ion exchange material and 4) mixtures thereof.

Calcium ion blockade builder materials include, for example, alkali metal salts of polyphosphoric acid such as sodium tripolyphosphate; Natrilotriacetic acid and its water-soluble salts; Alkali metal salts of ether polycarboxylic acids such as carboxymethyloxy succinic acid, oxydisuccinic acid and melic acid: ethylenediaminetetraacetic acid; Benzene polycarboxylic acid; Citric acid; And polyacetal carboxylates as described in US Pat. Nos. 4,144,226 and 4,146,495.

Examples of precipitant builder materials are sodium orthophosphate, sodium carbonate and sodium carbonate / calcite mixtures.

Examples of potassium ion exchange builder materials include various forms of water insoluble crystalline or amorphous aluminosilicates, of which zeolites are the most representative.

In particular, the compositions of the present invention may contain any organic or inorganic builder material, for example sodium tripolyphosphate or potassium, sodium pyrophosphate or potassium, sodium orthophosphate or potassium, sodium carbonate or sodium carbonate / calcite mixture, natrilotri Sodium salts of acetic acid, sodium citrate, carboxymethyl malonates, carboxymethyloxysuccinates, water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.

Such builder materials are present, for example, in amounts of 5 to 80% by weight, preferably 10 to 60% by weight of the composition.

In addition to the above-mentioned ingredients, the washing composition of the present invention may contain any conventional additives in the amounts conventionally used in the detergent composition for washing fabrics. Examples of such additives are alkanolamides, in particular foam accelerators such as monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, foam inhibitors such as alkylphosphates and silicates, ashes such as carboxymethyl cellulose sodium and alkyl or substituted alkyl cellulose ethers. Deposition inhibitors, ethylenediamine tetraacetic acid and phosphonic acid derivatives (ie dequest (Dequest Other stabilizers such as)), fabric softeners, inorganic salts such as sodium sulfate, molds, flavorings, enzymes (e.g., proteases, cellulase, lipases, amylases and oxidases) that are generally added in trace amounts, and fungicides and Coloring agents and the like.

Another optional but highly preferred multifunctional property contained in the detergent composition is a polymeric material having a molecular weight of 1,000 to 2,000,000, contained in an amount of 0.1 to about 3% by weight of the detergent composition, wherein the polymeric material is acrylic acid , Homopolymers or copolymers of maleic acid or their salts or anhydrides, vinyl pyrrolidone, methyl- or ethylbenyl ethers and other polymerizable vinyl monomers. Preferred examples of such polymeric materials include polyacrylic acid or polyacrylates; Polymaleic acid / acrylic acid copolymers; 70: 30 acrylic acid / hydroxyethyl maleic acid copolymer; 1: 1 styrene / maleic acid copolymer; Isobutylene / maleic acid and diisobutylene / maleic acid copolymers; Methyl- and ethylvinyl ether / maleic acid copolymers; Ethylene / maleic acid copolymers; Polyvinyl pyrrolidone; And vinyl pyrrolidone / maleic acid copolymers.

Detergent bleaching compositions of the present invention can be prepared by any conventional method used to prepare detergent compositions, when formulated as non-flowing particles, for example in powder or granule form. For example, a slurry can be formed and then spray dried to form a detergent based powder, which can then be added as a dry material and a heat sensitive component including a peroxy compound bleach and optionally other optional ingredients as desired.

However, the detergent based powder composition itself, to which the bleach catalyst is added, can be prepared by various other methods, such as so-called partial-part process, non-top process, dry mixing method, coagulation, granulation, injection method, concentration and densification process, etc. Can be prepared. Such methods are well known to those skilled in the art and do not constitute an integral part of the present invention.

The manganese complex is advantageously separated from the peroxygen compound and other components of the detergent base powder. This can be achieved by granulating or noodle (via injection machine) the manganese complex in a protective matrix shell. Sodium sulfate and other inorganic or organic materials with binders are useful for forming manganese complex protective particles.

Alternatively, the bleach catalyst may be added separately to the wash / bleach water containing the peroxycompound bleach.

In this case the bleach catalyst is present as a detergent additive. Such additive materials are intended to supplement or augment the performance of conventional detergent compositions and may contain any components of conventional detergent compositions but will not contain all of the components present in the finished detergent composition. Additives according to this feature of the invention are generally added to aqueous solutions containing a (alkaline) hydrogen peroxide source, but in some cases they can be used as separate treatments in pre-washing or rinsing.

The adduct according to this feature of the invention may contain only the compound or preferably together with a carrier such as a commercially available aqueous or non-aqueous liquid medium or particulate material or a flexible non-granular material.

In the following examples, embodiments of the present invention will be described in more detail. All parts, percentages, and ratios set forth herein and in the claims are by weight unless otherwise indicated.

EXAMPLE

Example 1

Preparation of Mn (IV) Me ₃ TACN (OMe) ₃ (PF ₆ )

Manganese (II) chloride was purchased from Strem Chemicals. Sodium hexafluorophosphate was purchased from Aldrich Chemical Company. Sodium methoxide was prepared from sodium hydride (Aldrich) and methanol. N, N ', N'-trimethyl-1, 4, 7-triazacyclonoronan (Me ₃ TACN) is described in "Organic Synthesis" [Atkins, et al., 58. 86, 1978]. It was prepared according to the method.

A solution of 2.5 g Me ₃ TACN degassed (middle manifold vacuum line method) in 40 mL methanol was cooled in an ice / salt bath. To this solution was added 1.84 g of manganese chloride dissolved in 10 ml of methanol. The solution turned light brown. Then, as soon as 20 ml of 1 M NaOME was added all at once, the solution turned dark brown. After stirring for about 10 minutes, 5.0 g of NaFP ₆ (in 20 mL of methanol) was added and the solution was exposed to air. After about 20-30 minutes, 5.0 g of NaPF ₆ (in 20 ml of methanol) was added and the solution was allowed to warm to room temperature. This solution was then filtered and cooled to 0 ° C. to promote crystallization. After 3 days dark brown crystals formed and were filtered. Yield was 0.5 g (16% -NaOMe basis). Longer crystallization results in higher amounts of crystallization, but often these crystals contain salts that crystallize together.

Elemental analysis: Calcd for C ₁₂ H ₃₀ F ₆ MN ₃ O ₃ P: C, 31.03: H, 6.47: Mn, 11.85: N, 9.05: P, 6.68.

Found: C, 29.28: H, 5.68: Mn, 10.60: N, 9.20: P, 6.86.

Mass spectral analysis: m / e 319

UN analysis (CH ₃ CN): maximum wavelength (nm) (E. L mol ⁻¹ cm ⁻¹ ) 326 (11.200), 287 (10.900), 228 (9800).

Melting point range: 160-165 degreeC.

Example 2

The bleaching activating ability of Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) was also contaminated with ragu (ie tomato products) at various active substance concentrations and at various active oxygen concentrations (BC-1). ) Is shown for cotton cloth.

Using a recommended amount of detergent powder (1.55 g / l zeolite-containing base powder) in deionized distilled water, wash two or four contaminated cloths per liter of pot at 40 ° C. for 15 minutes and use a cloth turk-o-tometer (Terg) -O-Tometer) experiment was performed. Bleach catalyst (manganese catalyst) was added as a 5% Na ₂ SO ₄ powder mixture. The performance of the monomer Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) is another manganese bleaching catalyst, dinuclear manganese complex, Mn (IV) ₂ (Me ₃ TACN) ₂ (μ-O) ₃ (PF ₆ ) compared with the performance of ₂ · H ₂ O. The results are shown in Table 1 below.

Bleach values are expressed as changes in reflectance [(R) or (B) units (LAB scale)] measured using a Colorgard / System / 05 Reflectometer. A control composition containing only peroxides was also performed for the same kind of contamination. Indeed, the bleach values are expressed as ΔΔB and ΔΔR, which are ΔΔR = ΔR (laundry) -ΔR (blinded), ΔΔB =-(ΔB (laid) -ΔB (blinded) Therefore, the higher the value, the better the bleaching performance.

Conditions: 4 ppm of Mn complex, 40 ° C., 15 minutes of washing, pH = 10, 1.55 g / L zeolite base, [0] = ignition oxygen added as sodium perborate

This result shows that the Mn monomer, Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ), removed the hydrophobic raguan contamination by activating hydrogen peroxide. It is shown that the same active substance concentration is much better than the corresponding dinuclear Mn catalyst for this oil pollution.

[Example 3]

This example shows the results of the bleaching capacity investigation of Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) on tea-contaminated cloth. The test values are shown in Table 2.

Conditions: 4 ppm Mn complex, 40 ° C., 15 minutes laundry, pH = 10, 1.55 g / L zeolite base powder, [0] = active oxygen added as sodium perborate

These results show that Mn monomer is a very effective bleaching material and somewhat better than the corresponding dinuclear Mn bleach catalyst in removing secondary contamination. As a result of comparing the bleaching performance at various active oxygen concentrations, it can be seen that the Mn monomers show comparable bleaching ability to the secondary pollution at 30 to 50% lower active oxygen concentration than the binuclear Mn bleaching catalyst.

Example 4

This example shows results similar to those of Example 3, but to evaluate the effect of the catalyst at extremely low concentrations. The test results are shown in Table 3.

Conditions: 40 ° C., 15 minutes washing, pH = 10, 48 ppm of active oxygen added as sodium perborate, 1.55 g / L zeolite base powder

This result shows that sufficient bleaching occurs at extremely low catalyst concentrations, which is about the same or somewhat better than the corresponding dinuclear manganese bleach catalyst.

Example 5

This example illustrates the effect of Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) on various conventional bleachable different contaminations. The test results are shown in Table 4.

Conditions: 4 ppm of Mn complex, 40 ° C., 15 minutes of washing, pH = 10, 1.55 g / L zeolite base powder, 48 ppm of active oxygen added as sodium perborate.

The results in Table 4 show that the Mn monomer, Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ), is effective against a variety of very different bleachable contaminations. This catalyst is effective against both hydrophobic and hydrophilic contamination and works even at very low concentrations to clean and bleach very different soils.

Example 6

This example shows the effect of Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) when working with different peracids.

The test results are shown in Table 5.

Conditions: 4 ppm Mn complex, 40 ° C., 15 minutes laundry, pH = 10, 1.55 g / l zeolite based powder, 8 × 10 ⁻³ M peracid, cloth contaminated with tea (BC-1)

This result shows that Mn (IV) (Me ₃ TACN) (OCH ₃ ) ₃ (PF ₆ ) effectively catalyzes the bleaching of peracid as well as hydrogen peroxide on the secondary named cloth at very low catalyst concentrations (4 ppm). Activated peracetic acid works about three times as effectively as peracid alone, and activated mono persulfate eliminates all tea contamination from the cloth by initially whitening the cloth, which is initially brown.

The foregoing description and examples illustrate selected embodiments of the invention. In view of this, those skilled in the art will be able to propose various modifications, all of which fall within the scope of the present invention.

Claims (9)

Bleach composition containing the following materials: (i) 1 to 60% by weight of the peroxy compound, (ii) the manganese complex of the following structural formula (A) present in an amount such that the manganese content is 0.0005% to 0.5% by weight Bleaching composition characterized by containing. Wherein Mn is manganese having an oxidation number of +4, R is a C ₁ to C ₂₀ radical selected from an alkyl group, a cycloalkyl group, an aryl group, a benzyl group and a radical mixture thereof, and is also a manganese and coordination of two or more R radicals May be bonded to each other to form a bridging unit between the two oxygens to be bonded, L is a ligand selected from radicals of C ₃ to C ₆₀ having at least 3 nitrogen atoms coordinated with manganese and Y is an oxidatively stable counter It is an ion. The composition according to claim 1, wherein the amount of peroxy compound is 2-30 wt% and the manganese content is 0.001-0.25 wt%. The composition of claim 1, wherein the peroxy compound is selected from the group consisting of hydrogen peroxide, hydrogen peroxide releasing compound, hydrogen peroxide generation system, peroxy acid and salts thereof, peroxy acid bleach precursor, and mixtures thereof. 1 to 60 wt% peroxy compound, manganese complex as described in claim 1 present in an amount such that the manganese content is 0.0005 to 0.5 wt%, and 0.5 to 50 wt% surfactant material Detergent composition. The detergent composition according to claim 4, further comprising 5 to 80% by weight of a detergent builder. 5. The detergent composition of claim 4, further comprising an enzyme selected from the group consisting of proteases, cellulases, lipases, amylases, oxidases, and mixtures thereof. A method of bleaching a contaminated substrate, characterized by contacting the contaminated substrate with the composition of claim 1 in an aqueous medium. 8. The method of claim 7, wherein the substrate is selected from fabrics, cutlery and teeth. 8. The method of claim 7, wherein the aqueous medium contains the manganese complex of claim 1 having a manganese content of 0.001 to 100 ppm and a peroxy compound releasing active oxygen at a concentration of 0.01 to 250 ppm.