CZ295896A3 - Cleansing agent containing bleaching agent - Google Patents

Abstract

There is provided a Biological Bleach Index ("BBI") by which bleach containing detergent compositions are defined which contain lower levels of bleach and bleach activator along with particular levels of chelants and enzymes. The detergent compositions of the invention have a Biological Bleach Index of greater than 65 as defined by a particular formula. In another aspect of the present invention, bleach-containing detergent compositions are provided which contain lower levels of bleach and bleach activator and higher levels of chelant and preferably higher levels of enzymes. Particularly, the level of bleach/activator reduction is represented by the equation [X]f= a[X]o where "a" is less than 1, the amount of chelant increase is represented by the equation [Y]f > 2/a [Y]o, and the amount of enzyme increase is represented by the equation [Z]f > 1/a [Z]o.

Description

Technical field

The invention relates to a cleaning composition comprising a bleaching agent. In particular, the invention relates to a cleaning composition having an effective bleaching strength containing a low amount of bleaching agent and bleach activator.

BACKGROUND OF THE INVENTION

The addition of a bleaching agent to the cleaning composition is often desirable for the beneficial bleaching agent to be treated. For example, detergent compositions containing a bleaching agent better remove stains, prevent the appearance of a shabby appearance, and maintain the whiteness of fabrics.

However, it is a disadvantage that a high content of bleaching agents in laundry detergents can under certain circumstances cause fading of fabric colors. High levels of bleaching agent in dishwasher detergents can, in certain cases, increase staining problems on silver dishes. In addition, high levels of bleach and bleach activators increase the cost of the detergent to the consumer. On the other hand, a low content of bleaching agent can cause poor cleaning performance. Accordingly, there is a need for detergent compositions having improved bleaching action, but having a low content of bleaching agent.

The invention solves this problem.

SUMMARY OF THE INVENTION A bleaching agent-containing detergent composition according to the invention comprises from about 5% to about 95% by weight of a detergent-surfactant, up to about 80% of a detergency builder,

0.5 to 40% peroxygen compound, 0.01 to 10% bleach activator, 0.1 to 10% chelating agent, and 0.05 to 5% enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof, wherein the composition has a biological bleaching index or BBI of greater than 65 by relationship

BBI = 4 [C] + 26 ([E] - ΓΒΑ1) + fBAlί PB1 320 12 where [C] = [chelating agent concentration (weight percent) x (number of chelating groups in the chelating agent)] - molecular weight of the chelating agent) x 1000; [E] = weight percent of enzymes in the detergent, assuming standard activities

2000 Cévu; [BA] = [(weight percent bleach activator) x (coefficient 6 for BOBS, coefficient 6 for cationic activators, coefficient 550 for dinucleic complex manganese activators and coefficient 4 for all other bleach activators)] - (molecular weight bleach activator) x 1000 and [PB] = (weight percent peroxygen bleach) x (weight percent oxygen available from peroxygen bleach) - 100.

The invention therefore relates to a detergent composition for washing machines and automatic dishwashers having a lower content of bleaching agents and bleach activators than prior art compositions, but a higher content of chelating agents and preferably a higher content of enzymes. The reduction in the concentration of bleaching agents / bleach activators is given by the equation [X] f = a [X] ₀ where f is finite and the original and where a is less than 1, the increase in the amount of chelating agent is given by [Y] t 2 2 / a TY] oa. . ... - ----- - - The increase in the amount of enzymes is given by the equation [Ζ] Ύ 2 i / a [Z] by all these equations are described and explained in detail below.

The invention is based on the surprising finding that higher levels of chelating agent and enzymes can compensate for lower levels of bleaching and detergent agents in the detergent composition. Thus, the cleaning action by improved stain removal, maintaining a non-dull appearance and whiteness with a certain concentration of bleaching agent can be achieved at lower concentrations of bleaching agent, if higher concentrations of chelating agent and enzymes are used.

1. Biological bleaching index

The biological bleaching index (BBI) is defined by the formula which refers to lower concentrations of peroxyborate bleach and bleach activator with particular desirable chelating agent and enzyme concentrations. Accordingly, the bleaching agent-containing cleaning composition according to the invention comprises from 5% to 5% by weight

VS% of detergent surfactant, up to 80 X detergency builder, 0.5 to 40 X peroxygen compound, 0.01 to 10 X bleach activator, 0.1 to 10 X chelating agent, and 0.05 to 5 X enzymes selected from the group consisting of proteases, amylases, " V " lipases, cellulases and mixtures thereof, wherein the composition has a biological bleaching index or BBI greater than 65 according to

BBI = 4 [C] + 26 ([E] - ΓΒΑ1) + ΓΒΑΤΓΡΒ1 320 12 where [C] = [chelating agent concentration (weight percent) x (number of chelating groups in the chelating agent)] + molecular weight of the chelating agent x 1000 [e] = weight percentage content of enzymes in the detergent composition assuming standard _{T e} and _Z y | 3 KNPU, amylase 300 KNU, lipase (165 KLU, and cellulase 2000 Cevu, [BA] = [(weight percent of bleach activator) x (Factor 6 for BOBS, Factor 6 for cationic activators, Factor 550 for dinucleic complex manganese activators, and Factor 4 for all other bleach activators)] + (molecular weight bleach activator) x 1000 and [PB] = (Percentage Peroxygen Bleach Mass%) x (weight percent oxygen available from peroxygen bleach) + 100.

The biological bleaching index defines a certain relationship between the chelating agent content, the enzyme content, the peroxygen bleach content and the bleach activator content. Accordingly, a detergent composition containing a minor amount of peroxygen bleach and a bleach activator may be formulated, but having the benefits of a laundry bleach-containing detergent composition. The detergent composition of the present invention has a biological bleaching index greater than 65, preferably greater than 75, and more preferably greater than 80.

As can be seen from the formula, [C] means the relationship [chelating agent concentration (weight percent) x (number of chelating groups in the chelating agent)] + molecular weight of the chelating agent) x 1000. The number of chelating groups in the chelating agent is multiplied by the chelating efficiency of the chelating agent (that is, the chelating activity is probably influenced by the number of chelating groups). By chelating groups is meant functional groups having a chelating capacity such as phosphonate and carboxylate groups. It is recalled that such chelating groups often contain anionically charged oxygen in solution. For example, ethylenediaminetetraacetic acid has four chelating (carboxylate) groups.

[E] means the percentage by weight of total enzymes in the detergent composition, assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Vascular. If the actual activities of these enzymes in the detergent are different from their standard activities, the factor [E] is adjusted accordingly. For example, if a protease with 26 KNPU activity is used instead of a standard 13 KNPU activity, the factor [E] is multiplied by two to compensate for the extra activity of ienzyme. The same applies to amylases, lipases and cellulases. The abbreviation KNPU means a kilo of Novo protease units; KNU means a kilo of Novo units used to measure amylase activity. The abbreviation KLU stands for standard pounds of units defined by Novo to measure lipase activity. The abbreviation Vascular means standard units for measuring cellulase activity. These units of standard enzyme activity are well known to those skilled in the art. The detergent compositions of the present invention may contain other types of enzymes (e.g., peroxidases or lignases).

* The coefficient [BA] in the formula defines the bleach activator content as determined by the coefficient indicating its peroxyactivity. Coefficient 6 is for BOBS and cationic activators, coefficient 550 for dinucleic complex manganese activators and coefficient 4 for all other bleach activators.

Again, in the formula, [PB] is set as the percentage by weight of the peroxygen bleaching agent by the percentage by weight of available oxygen from the peroxygen bleaching agent. Expression of mass percentage of available oxygen or active oxygen p. a peroxygen bleaching agent is known to those skilled in the art. _T »example percarbonates have a weight content of available oxygen

13.5 X, peroxyborate monohydrates 5.5 X and peroxyborate tetrahydrates

10.5 X.

. [C] thus means millimole of chelating agent / 100 g of detergent>. ·.

, ρ, whose composition is adjusted according to the number of chelating groups, [E]. total enzyme activity-corrected enzyme content, [BA] millimol bleach activator / 100 g activity-corrected detergent, and [PB] weight percent available oxygen from peroxygen bleach.

2. A reduced bleaching detergent and an increased chelating agent / enzyme system. A detergent composition comprising a bleaching agent according to the invention comprises a reduced amount of a bleaching agent and an increased amount of a chelating agent and / or enzymes. Accordingly, the cleaning composition comprises from about 5% to about 95% detergent surfactant, up to about 80% detergency builder, and a bleaching agent, a chelating agent, and / or enzymes in an amount as defined below.

It has been found that successful purification is achieved at a given amount [X] _{of the} bleaching agent used in a reduced amount [X] f when the amount of the chelating agent [Y] and / or the amount of enzymes [Z] increases according to the following formulas:

[X] f = a [X] ₀ [y] t 2 2 / a [y] oa [z] f 2 l / a [z] ₀

Increased amounts of both the chelating agent and the enzymes result in improved stain removal similar to high bleaching compositions.

In the above relationships, f is the final, i.e. the amount in the final cleaning composition of the invention, and the original, i.e. the amount prior to the reduction or increase according to the invention.

Individual symbols in equations have the following meaning:

[X] total weight percent bleaching agents in the composition, calculated at 100% bleaching activity. The bleaching agent is either a peroxygen bleaching agent and a bleach activator, an organic peroxyacid, or mixtures thereof. For example, a reduced bleaching effect may be due to a decrease in the peroxygen bleaching agent and / or bleach activator in the detergent composition. [Y] the total weight percent of chelating agents in the composition. An increase in the chelating agent content is possible as an increase in the type of chelating agent contained in the composition with optional high bleaching action and / or by adding at least one other type of chelating agent to the product. If the product with a high content of Dividing agent, i.e. [X] 0, contains no chelating agent, then preferably:

[Y] t 2 ([Χίο - [X] t) / 3 [Z] total_wt% enzyme content in the formulation assuming enzyme activity:

for proteases 13_KNRU, ...

for amylases 300 KNU, for lipases 165 KLU and for cellulases 2000 Blood.

The percentage of enzyme can be corrected for other enzyme activities such as:% protease (13KNPU) = X protease (P KNPU) X (P / 13); % amylase (300 KNU) - X amylase (A KNU) x A / 300;

similarly for lipolase and cellulose. If other types of enzymes (eg peroxidases or lignases) are present, they are used in standard activities. Percentages are by weight.

Enhancement of the enzyme content can be achieved by increasing the content of all or some of the enzymes in the high bleaching compositions by treating and / or adding different enzymes.

In the above equations, and is less than 1, [X] is about 3-80 X »[Y] o is 0 to 10% and [Z] is _about 0.01 to 10 preferably 0.2 X i <1, more preferably 0.5%. and <1, and in particular [Y] o is 0 to 3% and [Z] o is 0.05 to 5%.

Examples of formulas:

Components a = 1 a = 0.75 a = 0.50 a = 0.50 high-white low-white low-white low-white PB1 + 4.00 3.00 2.00 2.00 NOBS 3.20 2.40 1.60 1.60 [x]. “5 ' 7.20 5.40 3.60 3.60 [Y] Z DTPA- 0.40 1.20 1.60 1.60 Savinaset 0.18 0.24 0.36 0.18 BAN + 0.23 0.31 0.46 0.23 Lipolase 0.07 0.09 0.14 0.07 Cellulase * - - - - - - - - ’ [OF] 0.48 0.65 0.96 0.48

In the case of low-white [X] f products with an increased cellulose enzyme content, the cleaning agent should preferably have a powerful anti-redeposition system.

3. Bleaching agent

An essential feature of the invention is an oxygen bleaching system. According to one preferred embodiment, the bleach system comprises a peroxygen compound and an organic compound which is a bleach activator. The preparation of the organic peroxyacids is carried out in situ by means of a hydrogen peroxide activator cassette to obtain an oxygenated compound. Preferred peroxygen compounds are, for example, inorganic perhydrate bleaching agents. Compositions comprising mixtures of a peroxygen compound and a bleach activator with a treated organic peroxyacid are also contemplated.

Peroxygen compounds

Inorganic perhydrate salts are preferred peroxygen bleach compounds. These salts are generally incorporated in the form of an alkali metal salt, preferably sodium, in an amount of from 0.5 to 40%, in particular from 1 to 30%, in particular from 1 to 7%, based on the weight of the composition.

Examples of inorganic perhydrate salts are the perborate, especially peroxyborate monohydrate and peroxyborate tetrahydrate, percarbonate, peroxyphosphate, persulfate and persulfate salts. Inorganic perhydrate salts are generally alkali metal salts. The anoraganic perhydrate salts may be incorporated as crystalline solids without additional protection. For certain perhydrate salts, however, it is preferable to exclude such a granular form and are used in a coated form that imparts better storage stability to the perhydrate salts.

Sodium peroxyborate may be in the form of a monohydrate of the formula NaBO2H2O2 or a tetrahydrate of the formula NaBO2H2O2.3H2O.

Alkali metal peroxycarbonates, especially sodium percarbonate, are preferred perhydrates for incorporation into the compositions of the invention. Peroxycarbonate-containing compositions have a reduced tendency to form. undesirable gels in the presence of both surfactants and water as similar peroxyborate containing compositions. This is probably because the peroxycarbonate generally has a lower surface area and a lower porosity than peroxyborate monohydrate. This low surface and low porosity acts to prevent coagulation with fine particles of surfactant agglomerates and therefore does not adversely affect dosing. ,

Sodium peroxycarbonate has the formula corresponding to 2 Na 2 CO 3 .3H 2 O 2 and is commercially available as a crystalline solid. Most preferably, the peroxycarbonate is incorporated into such compositions in a coated form to achieve product stability. A suitable coating material to impart product stability is a mixed salt of water-soluble alkali metal sulfate and carbonate. Such coatings and coating methods are known and described in British Patent Specification GB 1 466799 (issued to Interox on March 9, 1977). The weight ratio of the mixed salt coating material to the peroxycarbonate is 1: 200 to 1: 4, especially 1: 99 to 49 to 1: 19. Preferably, the mixed salt is of the formula Na 2 SO 4. 0.3 to 1.0 and in particular 0.2 to 0.5.

Other coatings containing a silicate (alone or with a borate salt or boric acid or other inorganic substances), waxes, oils and fatty soaps may also advantageously be used according to the invention.

Potassium peroxymonoperoxysulfate is another perhydrate salt that can be used in the detergent compositions of the invention.

1: 9 and especially 1 sodium sulfate and sodium carbonate

Bleach activator

Bleach activators are compounds that react with hydrogen peroxide in a perhydrolysis reaction to form a peroxyacid. 0becně bleach activators may illustrate the formula ^{0 5}

X - C - L e where L is a liberated group and X is essentially any functional group, so that perhydrolysis creates a peroxyacid structure, for example by

- _.....- ..... ...... .....

X - C - COOH

The bleach activators are preferably incorporated in an amount of 0.01 to 10% by weight, more preferably 0.2 to 7% and especially 0.5 to 4%, based on the weight of the detergent composition.

Suitable bleach activators generally contain at least one N- or O-acyl group and are therefore compounds of various classes of compounds. Suitable classes of compounds include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of such compounds are disclosed in GB-A-1 586789. Suitable esters are described in GB-A-836988, 864798, U.S. Pat.

147871, 2 143231 and in European Patent Application Ser

EP-A-0170386.

Preferably, the bleach activator is selected from the group consisting of tetraacetylethylenediamine (TAED), natriumnonanoyloxybenzenesulfonate (NOBS), natriumbenzoyloxybenzenesulfonate (BOBS), benzoylcaprolactam, (6-nonanamidocaproyl) oxybenzene sulfonates, NACA-OBS, and NACA-OBS manganese or manganese. complexes and mixtures thereof. Most preferred is tetraacetylethylenediamine.

Relaxed group

The liberated moiety, referred to herein as L, must be sufficiently reactive for the perhydrolysis reaction to take place at the optimum time (e.g., during a wash cycle). However, if it is released. While the group is still reactive, the activator is difficult to stabilize for use in a bleaching agent. According to the invention, the preferred released group is an L group wherein the acid conjugate of the formed anion on L has a pK a of 4 to 13.

Preferred release groups are selected from the group consisting of

R ³

AND

-O-C 1 = C-CH = CH 2

Y

AND

-o — CH = C-CH = CK 2 o

H., -O-C-R ¹

CH2-C

H

II o

R ³ OY

I _ Β I _ <-O — C = CHR <and —N — S — CH — R ⁴

I, II R ³ O, and mixtures thereof, wherein

R ( ¹⁾ is alkyl, aryl or alkaryl having up to 14 carbon atoms,

R ³ is alkyl having 1 to 8 carbon atoms,

R ⁴ is hydrogen or R ³ a

Y is a hydrogen atom or a solubilizing group.

Each of R ¹ , R ³ , and R ⁴ may be substituted with essentially any functional group selected from alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl, amide, ammonium or alkyammonium groups.

Preferred solibulizing groups are -SO 3 M ⁺ , -CO 2 * M ⁺ , -SO 3 - M *, -N * (R ³ ) ⁴ X - and O 2 - N (R ³ ) 3, and most preferred are

-SOa ^- M ⁺ , -N ⁺ (R ³ ) aX "and O <- N (R ³ ) 3, and most preferred are -SO 3" M ⁺ , -CO 2 -M ⁺ , where R ^{3 is} an alkyl group of 1 to 3 4 carbon atoms, the M cation which imparts the solubility of the bleach activator and the X anion which imparts the solubility of the bleach activator. Preferably M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyl sulfate or acetate anion.

Peroxybenzoic Acid Activator The peroxybenzoic acid compound activator provides peroxybenzoic acid by perhydrolysis.

Suitable activator compounds O-acylated perbenzoic acid include substituted and unsubstituted benzoyloxybenzenové sulfonates, including for example benzoyloxy formula: _Λ

> _SO3- Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

OAc

AcO 1 \ VOAc

OAč

OBz wherein Ac is COCH 3 and Bz is benzoyl.

Peroxybenzoic acid activator compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted urea. Suitable imidazole-based peroxybenzoic acid activators include Nbenzoylimidazole and N-benzoylbenzimidazole and other useful N-acyl groups containing peroxybenzoic acid activators including N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Other peroxybenzoic acid activators include benzoyldiacyl peroxides, benzoyltetraacyl peroxides and compounds of the formula

COOH

Another suitable peroxybenzoic acid activator compound is a phthalic anhydride of formula

Suitable N-acylated peroxybenzoic acid lactam activators have the general formula

O

O C - CH2 - 9¾ _e II «I

Where ^R is n 0 to 8, preferably 0 to 2 and R ^{6 is} benzoyl.

Activators based on peroxybenzoic acid derivative

Peroxybenzoic acid derivative activators provide substituted peroxybenzoic acids by perhydrolysis.

Suitable substituted peroxy-14-benzoic acid derivative activators useful herein include any peroxybenzoic acid activator in which the benzoyl group is substituted by virtually any non-positively charged (i.e., non-ionic) functional group selected from, for example, alkyl, hydroxy, alkoxy, halogen, amino, nitrosyl and amide.

A preferred class of substituted peroxybenzoic acid activator compounds are amide substituted compounds of formula

R - C - N - ^R2 - C - L or R - N - C - ^R2 - C - L | |

RS 0 RS 0 0 where means

R1 is aryl or alkaryl having up to 14 carbon atoms,

R ² group, arylene or alkarylene having up to 14 carbon atoms, ^R is hydrogen, alkyl, aryl or alkaryl having up to 10 carbon atoms,

L is essentially any released group.

R1 is preferably 6 to 12 carbon atoms.

R @ ² is preferably 4 to 8 carbon atoms. R1 may be an aryl group, a substituted aryl group or an alkaryl group branched and / or substituted of synthetic or natural origin; for example, tallow may be the source. For radicals R ² are permissible analogous variations. Suitable substituents are alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents of organic compounds. R @ ⁵ is preferably hydrogen or methyl. Total have groups Rl and ^R contain more than 18 carbon atoms. Amide substituted bleach activators of this type are described in EP-A-0170386.

Cationic bleach activators

Cationic bleach activators produce cationic peroxyacids by perhydrolysis.

Generally, cationic bleach activators are prepared by substituting the peroxyacid moiety of a suitable activator compound with a positive charged functional group such as an ammonium or alkylammonium group, preferably a methylammonium or ethylammonium group. Cationic bleach activators are generally included in solid detergent compositions as salts with a suitable anion, for example a halide ion.

The bleach activator thus cationically substituted may be peroxybenzoic acid or a substituted derivative thereof, for example the activator compound described above. Alternatively, the bleach activator may be an alkylperoxycarboxylic acid or an amide-substituted compound described below.

Cationic bleach activators are described in U.S. Pat. 4,904,406; 4,751,015; 4,988,451; 4 397757; 5,299,662; 5,127852; 5 093022; and 5,106528; U.K. 1 382594; EP 475512; 458396; and 284292; and JP 87-318332.

Examples of preferred bleach activators are described in U.K. 9407944.9, U.S. Pat. 08/298903, 08/298650, 08/298904 and 08/298906.

Preferred cationic bleach activators include all ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyltetracetylglucosobenzoyl peroxides.

A preferred cationically substituted benzoyloxybenzenesulfonate is a 4- (trimethylammonium) methyl benzoyloxybenzenesulfonate derivative of the formula

A preferred cationically substituted alkyloxybenzenesulfonate has

Preferred cationic bleach activators of the class of N-acylated caprolatams include trialkylammoniummethylenebenzoylcaprolactams, in particular trimethylammoniummethylenebenzoylcaprolactam

Other preferred cationic bleach activators of the class of N-acylated caprolatams include trialkylammoniummethylenealkylcaprolactams of formula

where a is 0 to 12.

Another preferred cationic bleach activator is 2- (Ν, Ν, im trimethylammonium) ethylnatrim-4-sulfophenyl carbonate chloride.

Alkyl peroxycarboxylic acid bleach activators

Alkyl peroxycarboxylic acid bleach activators produce peroxycarboxylic acids by perhydrolysis. Preferred activators of this type provide peroxyacetic acid by perhydrolysis.

Preferred imide-type peroxycarboxylic activator compounds include Ν, Ν, Ν1, N1-tetraacetylated alkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially the compound having an alkylene moiety having 1, 2 and 6 carbon atoms. Tetraacetyl ethylenediamine (TAED) is particularly preferred.

Other preferred alkyl peroxycarboxylic acid activators include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), natriumnonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide substituted alkyl peroxyacid bleach activators

Amide substituted alkyl peroxyacid bleach activators are also suitable, including compounds of formula

R - C - N - R2-C - L or R - N - C - ^R2 - C - L

II

R ^s 0 R 5 o 0 where is

R 1 is C 1 -C 14 alkyl,

R 2 is C 1 -C 14 alkylene,

R ( ⁵⁾ is hydrogen or (C1-C10) -alkyl,

L is essentially any released group.

R1 is preferably 6 to 12 carbon atoms. R @ ² is preferably 4 to 8 carbon atoms. The group R1 may be straight or branched and / or substituted of synthetic or natural origin; the source may be, for example, tallow. For radicals R ² are permissible analogous variations. Suitable substituents are alkyl, halogen, nitrogen, sulfur and other typical substituents of organic compounds. R @ ⁵ is preferably hydrogen or methyl. In total, R ¹ and R ^{5 should not} contain more than 18 carbon atoms. Amide substituted bleach activators of this type are described in EP-A0170386.

Benzoxazine Organic Peroxy Acid Activators

Also suitable are the benzoxazine-type activator compounds described, for example, in EP-A-332294 and EP-A-482807, in particular compounds of the general formula:

where it means

Ri a hydrogen atom, an alkyl group, tr 1 Λ tr * v * rt 1% st Λ tr tr 1 η 1 Ix tr 1 λ cu uuu aijxaiájiu * uu |

R @ 2, R @ 3, R @ 6 and R @ 8 independently of one another are hydrogen, alkyl, alkenyl, alkaryl and halogen, aryl, hydroxyl, alkoxy, amino, alkylano, COOR5 (where R @ 5 is hydrogen or alkyl) and carbonyl group.

A particularly preferred bleach activator of the benzoxxazine type is the compound of formula

Dinuclear manganese complex activators

Another preferred class of bleach activators are dinucleic manganite or manganese complexes, as described, for example, in U.S. Patent Nos. 5,246,621 and 5,245,494.

Preferred activators of this class are compounds of formula

1) [Mn ^1v 2 (m-O) 3 (Me-TACN) 2] (PF 6) 2

2) ^[Μη ιυ 2 (m-0) 3 (Me / Me-TACN) 2] (PFO) 2

3) [Mn ¹¹¹ 2 (m-O) (m-OAc) 2 (Me-TACN) 2] (PFe) 2

4) [Mn ¹¹¹ 2 (m-O) (m-OAc) 2 (Me / Me-TACN) 2] (PF 6) 2 where Me-TACN is 1,4,7-trimethyl-1,4,7-triazacyclononate and a Me / Me-TACN 1,2,4,7-tetramethyl-1,4,7-triazacyclononane group.

Organic peroxyacid precursor

The bleaching system may contain an organic peroxyacid precursor, generally in an amount of 0.1 to 20% by weight, preferably 0.2 to 10%, and in particular 0.3 to 5%.

A preferred class of organic peroxyacid compounds are amide substituted compounds of formula

^R1 - C - N - R2-C - 00H or R ¹ - N - C - ^R2 - C - j 00H ¹¹ _ _ _ _ | ^{11 11}

R ⁵ 0 RS o 0 where means

R1 is an alkyl, aryl or alkaryl group having up to 14 carbon atoms,

R ² is an alkylene, arylene, alkarylene having 14 carbon atoms,

R @ ⁵ is hydrogen, alkyl, aryl or alkaryl having up to 10 carbon atoms. -.- ··

The symbol R ^L is preferably a group having 6 to 12 carbon atoms. R @ ² is preferably 4 to 8 carbon atoms. R @ ¹ may be a straight or branched chain alkyl group, a substituted aryl group, or a branched and / or substituted alkylaryl group of synthetic or natural origin; the source may be, for example, tallow. For radicals R ² are permissible analogous variations. Suitable substituents are alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents of organic compounds. The radical R is preferably ^a hydrogen atom or a methyl group. In total, R ¹ and R ^{5 should not} contain more than 18 carbon atoms. Amide substituted organic peroxyacid compounds of this type are disclosed in EPA-O17O386.

Other peroxyacids include diacyl peroxides and tetraacyl peroxides, especially diperoxy dodecanedioic acid, diperoxytetradecanedioic acid and diperoxy hexadecanedioic acid. Also suitable for the purposes of the invention are monoperoxyazelaic and diperoxyazelaic acid, monoperoxybrassylic and diperoxybrassylic acid, and N-phthaloylaminoperoxycaproic acid.

4. Chelating agent

Suitable chelating agents have sequestering capability with respect to heavy metal ions (e.g., manganese, ferrous and copper ions) in solution. Such chelating agents include amine carboxylates, aminophosphonates and polyfunctionally substituted aromatic chelating agents.

Aminocarboxylates useful as chelating agents in the compositions of the invention have at least one, preferably at least two, units of the formula

CH2

Ν - (CH 2) χ - COOM wherein M represents a hydrogen, alkali metal, ammonium or substituted ammonium group (for example, an ethanolamine group) and χ 1 to 3, preferably 1. Preferably, these aminocarboxylates contain no alkyl or alkenyl groups with more than 6 carbon atoms. Suitable aminocarboxylates include ethylenediamine tetraacetates, Nhydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine disuccinates, ethlendiamine-N, N'-diglutamates, 2-hydroxypropylenediamine-Ν, Ν'-di-succinates, ethylenediamine tetra-triethates, alkylammonium salts.

Amino phosphonates are also suitable as chelating agents in the detergent compositions of the present invention, wherein at least a small amount of total phosphorus is allowed in the detergent composition. Compounds containing at least one, preferably at least two groups of the general formula are useful

CH2

In which case M represents a hydrogen atom, an alkali metal atom, an ammonium or substituted ammonium group and a χ 1 to 3, preferably 1. Exemplary examples are ethylenediaminetetramethylene phosphonates, hexamethylenediaminetetramethylene phosphonates, aminotetramethylenephosphonates, nitrile dimethylenephosphonates and nitriaminimethylenephosphonates. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms. Alkylene groups can be a fraction of substructures.

Polyfunctionally substituted chelating agents may also be used in the detergent compositions of the present invention. Such agents include compounds of formula

wherein at least one R group comprises a -SO 3 H or COOH chelating-group, or a soluble salt thereof, and mixtures thereof; U.S. Pat. No. 3,820,444, issued May 21, 1974,

Connor et al.) Discloses such polyfunctionally substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, for example 1,2-dihydroxy-3,5-disulfobenzene. Alkaline cleaning agents may contain these agents in the form of an alkali metal salt, ammonium or substituted ammonium (e.g., monoethanolamine or triethanolamine) salts.

Other suitable chelating agents include hydroxy-1,1-ethylidene diphosphonic acid and derivatives thereof; ethylenediamine disuccinate; trisodium salt of S, S-ethylenediamine disuccinate; iminodiacetic acid-N-2-hydroxypropylsulfonic acid; and aspartic acid-N-carboxyaethyl-N-2-hydroxypropyl-3-sulfonic acid (EP 516102, Dow Chemicals); O-alanine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, aspartic acid-N-monoacetic acid, and iminodisuccinic acid (EP 509382, Grace Co.); alkylimonodioacetic acid (EP 5269597 ~ Graè Co.); isochloro-diacetic acid (BASF); 2-phosphonobutane-1,2,4-tricarboxylic acid (Bayer); dipicolinic acid; collagen, keratin or casein-derived protein (EP 510331, Huls); amoacid-based chelating agents (EP 476257,

Huls); and 4024552, chelating agents Henkel) (German patent Are you sleeping DE number ho ₂ c HIM COOH ho ₂ cz nh ^z ^ COOH Preferred chelating reagents according to the invention are elected from

interactions including diethylenetriaminepentamethylene phosphonates, ethylenediaminetetramethylenephosphonates, diethylenetriaminepentaacetates, ethylenediamine disuccinates, ethylenediaminetetraacetates, and mixtures thereof.

Generally, the detergent composition of the invention comprises 0.1 to 10% by weight, preferably 0.2 to 7%, more preferably 0.4 to 3%, and most preferably 1 to 1.8% of the chelating agent.

5. Enzymes

Suitable enzymes for the detergent compositions of the invention include proteases, amylases, lipases, cellulases and mixtures thereof, and optionally other types of enzymes. Proteases and amylases are preferred.

Examples of suitable proteases include subtilisins obtained from strains of B. subtilis, B. lentus and B. licheniformis. Another suitable protease is a modified bacterial serine protease enzyme derived from Bacillus subtilis or Bacillus licheniformis having a maximum activity at pH 8-12 and developed and marketed by Novo Industries A / S (Denmark) under the trade name ESPERASE * Preparation of this enzyme and similar enzymes are disclosed in British Patent Specification No. 1 243784 (Novo). Proteolytic enzymes suitable for removing protein-based stains are commercially available under the names ALCALASE and SAVINASE (Novo Industries A / S) and MAXATASE (International Bio-Synthetics Inc.) (Netherlands). Other proteases are Protease A ( European Patent Publication No. 130756, published January 9, 1985) and Protease B (European Patent Application No. 87303761.8, filed April 28, 1987, and European Patent Application No. 130756, Bott et al., Published January 9, 1985). is termed Protease C herein, which is a variant of the alkaline serine protease Bacillus, especially Bacillus lentus, wherein arginine is replaced by lysine at position 27, tyrosine is replaced by valine at position 104, serine is replaced by asparagine at position 123 and alanine is replaced by threonine at position 274.

C is described in European Patent Specification No. 90915958: 4, in US Patent Nos. 5,185,250 and 5,204,015. Genetically modified variants in particular protease C also encompass the invention.

Amylases include, for example, α-amylases described in British Patent Specification No. 1,298,639 (Novo); RAPIDASE (International Bio-Synthetics, Inc .; and TERMAMYL and BAN (bacterial α-amylase) (Novo Industires).

Cellulases useful in the present invention include both bacterial and fungal cellulases. They preferably have an optimum action at a pH of 5 to 9.5. Suitable cellulases are described in U.S. Patent 4,435,307 (Barbesgoard et al., Issued Mar. 6, 1984) which are fungal cellulases produced by Humicola insolens and Humicola strain DSM 1800 or cellulases 212 produced by a fungus 212 belonging to the genus Aeromonas and cellulases extracted. from hepatopancreas seafish (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2 075028, GB-A-2 095275 and DE-OS-2 247832.

Suitable lipase enzymes for use in detergent compositions include lipases produced by Pseudomonas family microorganisms, such as Pseudomonas stutzeri ATCC 19.154, which are described in British Patent Specification GB 1 372034. Also disclosed are the lipases disclosed in Japanese Patent Application No. 53-20487, published February 28, 1978. These lipases are a commercial product of Amano Pharmaceutical Co. Ltd., Nagoya, Japan with the trade name Lipase P Amano and referred to herein as Amano-P for simplicity. Other commercial lipases include Amano-CES lipases from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673, a commercial product of Toyo Jozo Co., Tagata, Japan; and Chromobacter viscosum lipase from U.S. Pat. Biochemical Corp. U.S.A. and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. The LIPOLASE enzyme, derived from the fungus Humicola lanuginosa and expressed in Aspergillus oryzae as a guest commercial product of Novo (also European Patent Specification No. 341947), is a preferred lipase '4. 1 for the purposes of the invention.

Other enzymes such as peroxidases and / or lignases can also be used in the detergent compositions of the invention. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, published October 19, 1989 (Kirk, Novo Industries A / S).

The cleaning compositions according to the invention preferably contain from 0.05 to 5 Z, more preferably from 0.1 to 3 Z, more preferably from 0.2 to 2 Z, and in particular from 0.5 to 1.5 Z, of enzymes.

6. Detergent surfactant

Detergent surfactants useful herein are disclosed in U.S. Patent Nos. 3,666,661 (Norris, issued May 23, 1972) and 3,919,668 (Laughlin et al., Issued December 30, 1975). Representative examples of detergent surfactants useful herein are provided below.

Water-soluble salts of higher fatty acids, i.e. k

soaps are useful anionic surfactants for the detergent compositions of the invention. This group includes alkali metal soaps such as sodium and potassium and ammonium and alkylammonium salts of higher fatty acids containing 8 to 24 and preferably 12 to 18 carbon atoms. Soaps can be prepared by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.

Anionic surfactants also include water-soluble salts, preferably alkali metal salts, ammonium and alkylammonium salts of organic sulfur reaction products having in their molecular structure an alkyl group containing 10 to 20 carbon atoms and an ester group of a sulfonic or sulfuric acid (wherein the term alkyl includes alkyl portion of acyl groups). Examples of this class of synthetic surfactants are sodium and potassium alkyl sulfates, especially obtained by sulfating higher alcohols (C8-C18), for example prepared by reducing tallow or coconut oil glycerides; and sodium and potassium alkylbenzene sulfonates in which the alkyl moiety contains 9 to 15 straight or branched chain carbon atoms, as described, for example, in U.S. Pat. Nos. 2,20099 and 2,477383. Particularly preferred are linear straight chain alkylbenzene sulfonates with medium number of atoms. carbon in the alkyl moieties of 11 to 13, primary and secanary alkyl sulfates of 12 to 18 carbon atoms, and methyl ester sulfonates.

Other suitable anionic surfactants include sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil monoglyceride sulfonates and sulfates; sodium and potassium salts of alkylphenol ethylene oxide sulfates having 1 to 10 ethylene oxide units per molecule, the alkyl moiety having 8 to 12 carbon atoms; and sodium and potassium salts of alkyl27 ethylene oxide ether sulfates having 1 to 10 ethylene oxide units per molecule, the alkyl moiety having from 10 to 20 carbon atoms.

Other suitable anionic surfactants include water-soluble salts of esters of α-sulfonated fatty acids containing 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester moiety; water-soluble salts of 2-acyloxyalkane-1-sulfonic acid containing 2 to 9 carbon atoms in the acyl moiety and 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefinic and paraffinic sulfonates containing 12 to 20 carbon atoms; and β-alkyloxyalkane sulfonates having 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful for the detergent compositions of the present invention. Such nonionic materials include compounds prepared by the condensation of alkylene oxide groups (hydrophilic in nature)) with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the polyoxyalkylene group that is condensed with any particular hydrophobic group can be readily adjusted to provide a water-soluble compound with the desired degree of balance of hydrophilic and hydrophobic elements.

A particular class of nonionic surfactants particularly useful for the purposes of the invention includes polyhydroxy fatty acid amides of the formula

Rl

AND

R2 - C - N - Z where is

R1 is a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms,

A 2-hydroxyethyl group, a 2-hydroxypropyl group or mixtures thereof, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and most preferably an alkyl group having 1 carbon atom, i.e. a methyl group.

R ^{2 is a} C 5 -C 32 hydrocarbon group, preferably a C 7 -C 19 straight chain alkyl or alkenyl group, more preferably a C 9 -C 17 straight chain alkyl or alkenyl group, and most preferably a straight chain alkyl or alkenyl group having from 11 to 19 carbon atoms, or mixtures thereof; and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least two (in the case of glyceraldehyde) or at least three hydroxyl groups (in the case of other reducing sugars) directly linked to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof.

The group Z is preferably derived from reducing sugars by a reductive amination reaction; in particular Z represents a glycityl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose, as well as glyceraldehyde. Raw materials for obtaining said sugars are high dextrose corn syrup, high fructose corn syrup, and high malose corn syrup. These corn syrups may provide a mixture of sugar components for the Z component. However, the foregoing is not meant to limit the use of other suitable raw materials. Z is selected from the group consisting of -CH 2 - (CHOH) - CH 2 OH, -CH (CH 2 OH) - (CHOH) η-1-CH 2 OH

-CH 2 - (CHOH) 2 (CHOR 1) (CHOH) -CH 2 OH -...

wherein n is an integer from 1 to 5 and R 'is a hydrogen atom or a cyclic monosaccharide or polysaccharide group, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, especially groups of the formula -CH 2 - (CHOH) 4 -CH 2 OH. In formula (I), R1 may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-229 hydroxyethyl or N-2-hydroxypropyl. If desired, the highest sudsing, R ¹ is preferably methyl or hydr.oxyalkylovou group. If lower foaming is desired, R ¹ preferably represents a C 2 -C 8 alkyl group especially a propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethylhexyl group. The group R ² -CO-N může may be, for example, the cocamidic, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide and tallow acid amide groups.

Other nonionic surfactants include polyethylene oxide condensates of alkylphenols, for example, the condensation products of C 6 -C 15 alkylphenols in a straight or branched chain alkyl moiety with 3 to 12 moles of ethylene oxide per mole of alkylphenols.

Preferred nonionic surfactants are the water-soluble and water-dispersible condensation products of straight or branched chain aliphatic alcohols having from 8 to 22 carbon atoms with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of C 9 -C 15 alcohols with 4 to 8 moles of ethylene oxide per mole of alcohol.

Semi-polar nonionic surfactants include water-soluble amine oxides containing an alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl of 1 to 3 carbon atoms; water-soluble phosphine oxides containing an alkyl moiety of from 10 to 18 carbon atoms and having two moieties selected from the group consisting of alkyl and hydroxyalkyl of 1 to 3 carbon atoms; and water-soluble sulfoxides containing an alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl of 1 to 3 carbon atoms.

Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines whose alkyl moiety has a straight or branched chain, one of the aliphatic substituents having 8 to 18 carbon atoms and at least one aliphatic substituent having an anionic group water. '

Both ionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains 8 to 18 carbon atoms.

The detergent compositions of the invention comprise from about 5% to about 95%, preferably from about 5% to about 50%, and most preferably from about 10% to about 30%, of the detergent surfactant.

The detergent surfactants used in the cleaning compositions of the invention are preferably mixtures of anionic and nonionic surfactants.

7. Possible detergency builders

Optional detergent builders used in the detergent compositions herein are inorganic and / or organic detergency builders. Inorganic detergent builders include, but are not limited to, alkali metal salts, ammonium and alkylammonium salts such as polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid salts, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in some cases, non-phosphate builders are required.

Examples of silicate builders include alkali metal silicates especially with a SiO 2: Na 2 O ratio of 1.6: 1 to 3.2: 1 and layered silicates, such as layered silicates, as described in U.S. Patent 4,648,439 (Rieck HP, issued May 12). 1987). which are a product of Hoechst's trade name SKS; a particularly preferred layered silicate builder is SKS-6.

As a preferred carbonate builder, finely ground ground calcium carbonate having a surface area greater than 10 m ² / g can be used in granular compositions. The density of such an alkali metal carbonate detergent composition may be 450 to 850 g / l with a moisture content preferably below 4%. Examples of carbonate builders include the alkaline earth and alkali metal carbonates described in German Patent Application No. 2 321001, published November 15, 1973.

Aluminosilicate builders are particularly useful according to the invention. Preferred aluminosilicates are zeolite builders of the general formula

Naz [(A102) z (SiO 2) y] -xH 2 O where y is an integer of at least 6, the molar ratio of z to y is 1.0 to 0.5 and x is an integer of 15 to 264. Useful aluminosic ion exchange materials are commercially available available. These aluminosilicates may be crystalline or amorphous and may be natural or synthetic aluminosilicates. Methods for producing aluminosilicate ion exchange materials are described in U.S. Patent Nos. 3,985,669 (Krummel et al., Issued October 12, 1976) and 4,605,509 (Corkill et al., Issued August 12, 1986). Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the detergent compositions of the present invention are available as commercial products of Zeolite A, Zeolite ® (B) (including the products of European Patent Specification No. 384070) and Zeolite X. Preferably aluminosilicates having a particle diameter of 0 are used. 1 to 10 microns.

Organic detergent builders suitable for the detergent compositions of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds, for example, ether polycarboxylates including oxydi succinate, described in U.S. Pat. No. 3,128,287 (Berg, issued Apr. 7, 1964) and 3,635,830 ( Lamberti et al., Issued January 18, 1972). Also mentioned are the TMS / TDS builders described in U.S. Patent 4,666,3071 (Bush et al., Issued May 5, 1987). Other suitable polycarboxylates include cyclic compounds, in particular α32 bicyclic compounds, as described, for example, in U.S. Patent Nos. 3,936,779, 3,835,163, 4,186,835, 4,120,874, and 4,110,903. ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethoxyoxysuccinic acid, various alkali metal salts, ammonium and substituted ammonium salts of polyacetic acids, for example ethylenediaminetetraacetic and nitrilotriacetic acids, and polycarboxylates such as mellicarboxylates , succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, for example citric acid and soluble salts thereof (for example sodium salt) are preferred polycarboxylate builders, which can also be used in the granular detergent compositions of the invention, especially in admixture with zeolite or layered silicate builders.

Also suitable for the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and derivatives thereof, described in U.S. Patent 4,566,984 (Bush, issued Jan. 28, 1986).

In cases where builders based on phosphorus can be used, and especially in the form of bars used in handwashing, various alkali metal phosphates such as the well known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (for example, described in U.S. Pat. Nos. 3,159,581, 3,230,303, 3,422,221, 3,400,148, and 3,421,237) can also be used.

If builders are used in the cleaning compositions according to the invention, they are used in an amount of from 1 to 80% by weight, preferably from 5 to 60% and in particular from 10 to 50%.

8. Detergent adjuvants, if any

The cleaning compositions of the invention may optionally contain at least one optional detergent adjuvant or other agents to assist or promote the cleaning action, treatment of the cleaned substrate, or to modify the aesthetic appearance of the cleaning composition. Possible detergent adjuvants for the detergent compositions of the present invention include those disclosed in U.S. Pat. No. 3,936,537 to Baskterville et al. Such optional detergent adjuvants which may be incorporated into the detergent compositions of the present invention in conventional amounts (generally up to 30%, preferably 0.5 to 20%, based on the detergent component) include, for example, stain removers, suds suppressors, anti-foaming agents lathering, anti-shine and / or anti-corrosion agents, soil suspending agents, soil release agents, dyes, fillers, optically brightening agents, germicides, alkalinity sources, hydrotropes, antioxidants, perfumes, solvents, solubilizers, redeposition agents for clay dirt and soil release agents, polymeric dispersants, processing aids, fabric softeners, and antistatic agents.

The detergent compositions of the invention may be in various physical forms as known to those skilled in the art, for example in the form of granules or powder, liquids, sticks, gels or pastes. Such cleaning agents may be laundry detergents, including those suitable for washing machines and / or hand washing, dishwashing detergents in automatic dishwashing machines, means for removing large amounts of dirt from hands, or other means. Preferably, however, they are laundry detergents.

The invention is illustrated, but not limited, by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1 '

In the following example, Comparative Example A and Comparative Example do not fall within the scope of the invention, and Example 1 illustrates the cleaning composition of the invention. The whiteness characteristics for Comparative Example A (referred to in the table as A) and Comparative Example B (referred to in the table as B) are poor compared to Example 1 (referred to in the table as 1). Example 1 also exhibits a milder color fading than Comparative Example A because less TAED is used. Values are given for machine washing.

C 1-6 -alkylsulfate AND 9.00 (B) 9.00 1 9.00 C12 -15AE3S 2.00 2.00 2.00 Cl 2-14E5 4.00 4.00 4.00 N-methylglucamide C12-1-fatty 2.00 2.00 2.00 acid sodium aluminosilicate 14.00 14.00 14.00 layered silicate (SKS-6) 12.00 12.00 12.00 citric acid 4.00 4.00 4.00 carbonate 8.00 8.00 8.00 acrylic acid copolymer and meleinové 5.00 5.00 5.00 soil release polymer 0.50 0.50 0.50 carboxymethylcellulose -. . .. - 0,50 ..... . 0, 50 0,50- zinc phthalocyanisulphate 0.03 0.03 0.03 magnesium sulfate 0.80 About _T 8o 0.80 a brightening agent 0.30 0.30 0.30 polydimethylsiloxane 0.40 0.40 0.40 perfume 0.50 0.50 0.50 sodium percarbonate (13.5%) 22.50 22.50 22.50

TAED (100X) 6.30 5.00 5.00 Savinase (14KNPU) 0.55 0.55 0.81 lipase (165 KLU) 0.15 0.15 0.15 Carezyme (2000 Blood) 0.09 0.09 0.17 diethylenetriaminpentamethylene- phosphonate (100X) 0.51 0.51 0.80 BBI 57 53 72

Description of the whiteness test

The characteristics of the three compositions (according to Comparative Example A and B and according to Example 1 of the invention) are compared for six wash cycles in a Miele 701. Each wash cycle comprises only a main wash cycle. It is washed in a 40 ° C bath in water with a hardness of 25 * German hardness scale (calcium: magnesium = 3: 1). Four 15 cm x 30 cm pieces of white friction towel, knitted cotton and cotton cloth are placed in the washing machine. Before starting the first wash cycle, soiled fabrics, which are a commercial product of EMPA Institute, Switzerland under the name of the combined EMPA washing test number 103 ', containing strips of 8 cotton test samples of 12 cm x 12 cm in bleached cotton without optical brightener, cotton EMPA standard soiling, blood stained cotton, cocoa stained cotton, blood stained milk, soot cotton stained, sulfur black dyed cotton, raw cotton and red wine stained with a 75 g detergent granulet dispenser. For each of the following five wash cycles, the same amount of detergent and soiled fabric strips are used. At the end of the sixth full wash cycle, the contents are removed from the washing machine drum, air dried, and the whiteness / dirtiness of the three types of fabric is assessed.

Whiteness

The whiteness / scuffiness of each piece of fabric is judged on a scale. The mean values are compared with respect to Comparative Example A.

Comparative example A Comparative example B Example 1 reference 37:63 73: 27 * ♦ = statistically significant at 95% confidence level

Description of the color fading test

The color fading caused by the three test means (Comparative Example A, Comparative Example B and Example 1) in the Miele 698 washing test is compared. German hardness (calcium: magnesium = 3: 1).

For each type of product, the washing machine is filled with a 43 cm x 43 cm, whitish-violet woolen fabric (sensitive to bleaching) and two white sheets as ballast. Before starting the first full wash cycle, a granulete dispenser containing 75 g of detergent is placed in the drum of the machine. Samples of red-violet woolen fabric are placed adjacent to the granule dispensing orifice.

The stopwatch starts when the short wash cycle is first turned. The cycle is interrupted 10 minutes from now and the contents are removed from the drum. The red-violet wool samples are then dried and the fading of the wool samples is evaluated.

The process is repeated four times for each type of product using a fresh red-violet woolen sample.

Assess the color fading

The color fading of each of the four samples of red-violet wool obtained after the above tests is assessed by a panel of experts using an un washed-out red-violet woolen sample for comparison. The following table compares the mean values of the test results.

Comparative Example A Comparative Example B Example 1 Color Fading (X Damage) 30 X 30 X 50 X

Example 2

Component X Linear alkylbenzene sulfonate 21.00 Sodium tripolyphosphate 31.50 Acrylic acid / Maaleinic acid copolymer 1.00 Sodium carbonate 18.00 Sodium silicate 8.60 Sodium peroxyborate monohydrate 2.00 Monanoyloxybenzenesulfonate 1.60 Diethylenetriaminepentaacetic acid 1.60

Savinase / Ban 6.0 / 170T 0.80 carboxymethylcellulose 0.40

Lipolase 100T 0,12 various up to 100,00

The percentages are by weight and refer to the cleaning agent as a whole.

Example 3

Component X surfactant

C 1-4 4-alkylsulfate 9.00

C12-15AE3S 2,00

C12-14E5 4,00

C12-fatty acid N-methylglucamide 2.00 acids

Sodium Aluminosilicate Builder 14.00 Layered Silicate (SKS-6) 12.00 Citric Acid 4.00

Buffer carbonate 8,00

Polymer copolymer — acrylic acid ameleic 5.00 soil release polymer 0.50 carboxymethylcellulose 0.50

Enzyme

Savinase (13KNPU) 1.00 Lipolase (165 KLU) 0.30 Clululase (1000 Vessel) 0.30 Endogluconase A (5000 SCevu) 0.10 Termamyl (120T) 0.50

Bleaching additives

TAED 5.00 sodium percarbonate 22.00 zinc phthalocyanine sulfonate 0.03

Chelating agent - - _ - ·. . - diethylenetriamine pentamethyleneTosTonate 0.80

Other magnesium sulfate ingredients

0.80

Brightening agent 0.30 polydimethylsiloxane 0.40 perfume 0.50

Γ; t

Industrial applicability

Washing and dishwashing detergent compositions with improved bleaching action having a low content of bleaching agent, however, with an increased content of chelating agents and / or enzymes according to a certain mathematical relationship.

Claims (13)

PATENT CLAIMS A detergent composition comprising a bleaching agent comprising from 5 to 95% by weight detergent surfactant, up to 80% detergent builder, 0.5 to 40% peroxygen compound, 0.01 to 10% bleach activator, 0.1 to 10% X of a chelating agent and 0.05 to 5 X of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof, wherein the composition has a biological bleaching index or BBI of greater than 65 according to BBI = 4 [C] + 26 ([E] - f BA1) + ÍΑ1IPB] 320 12 where [C] = [chelating agent concentration (weight percent) x (number of chelating groups in the chelating agent)] + molecular weight of the chelating agent) x 1000, [E] = weight percent enzyme content of the detergent assuming standard protease 13 KNPU, amylases 300 KNU, lipases (165 KLU and cellulase 2000 Vascular, [BA] = [(weight percent bleach activator) x (factor 6 for BOBS, factor 6 for cationic activators, factor 550 for dinucleic complex manganese activators and factor 4 for all other bleach activators)] + (molecular weight bleach activator) x 1000 and [PB] = (weight percent peroxygen bleach) x (weight percent oxygen available from peroxygen bleach) + 100. 2. A cleaning composition comprising a bleaching agent according to claim 1 · v 'and y Zn C ~ ^_ u c j i Í - i n -that biological bleach-index is greater than the 75th A bleaching agent-containing cleaning composition according to claim 1, wherein the peroxygen bleaching agent comprises an alkali metal percarbonate. 4. A bleaching composition according to claim 1 wherein the bleach activator is selected from the group consisting of tetraacetylethylenediamine, benzoyl caprolactam, (6-nonanamidocaproyl) oxybenzenesulfonate, natriumnonanoyloxybenzenesulfonate, sodium benzoyloxybenzenesulfonate, and phosphonoylbenzenesulfonate activators. , cationic nitriles, dinuclear manganese or manganese complexes, and mixtures thereof. A bleaching agent-containing composition according to claim 4, wherein the bleach activator is tetraacetylethylenediamine. 6. A bleaching agent-containing composition according to claim 1 wherein the bleach activator has the general formula: 0 I I R - C - L wherein L is a liberated group, wherein the acid conjugate of the anion formed on L has a pK a of 4 to 13. 7. A bleaching composition according to claim 1 wherein the chelating agent is selected from the group consisting of diethylenetriamine pentamethylene phosphonates, ethylenediaminetetramethylene phosphonates, diethylenetriaminepentaacetates, ethylenediamine disuccinates, ethylenediaminetetraacetates, and mixtures thereof. and 8. A bleaching detergent composition according to claim 1 wherein the enzymes are selected from the group consisting of proteases, amylases, and mixtures thereof. A cleaning composition comprising a bleaching agent as claimed in claim 1, characterized in that it contains from 1 to 30% by weight of a peroxygen bleaching agent. 10. A bleaching agent-containing composition according to claim 1 comprising from about 0.2% to about 7% of a bleach activator. A cleaning composition comprising a bleaching agent as claimed in claim 1, comprising from 0.2 to 7% by weight of the chelating agent. 12. A bleaching agent-containing composition according to claim 1 comprising 0.1 to 3% by weight of enzymes. A detergent composition comprising a bleaching agent comprising from about 5% to about 95% detergent surfactant, up to about 80% detergent builder, a bleaching agent, a chelating agent, and / or enzymes and having the formulas [X] f = a [X] o [Y] ] t 2 2 / a [Y] o and [Z] f> l / a [Z] o where means 'finite a' original and where means rvi L Λ J Calculated on 100X activity, wherein the bleaching agents are selected from the group consisting of (i) peroxygen bleaching agents; and bleach activator, (ii) organic peroxyacids, and (iii) mixtures thereof, [Y] the total weight percent of chelating agents in the composition and [Z] the total weight percent of enzymes in the composition calculated for standard enzyme activities for proteases 13 of KNPU, for amylases 300 KNU, for lipases 165 KLU.a for cellulases 2000 Vascular and standard activities for other types of enzymes, where a is less than 1, [X] 0 is 3 to 80 X, [Y] 0 is 0 to 10 X, and [Z] 10% is 0.01 to 10%. 14. 13, v y Cleaning brand composition comprising bleaching m that an agent according to claim 0.5 a a ¹ 1 1 1. u is three 15 Dec Cleaning means containing bleaching the agent of claim 13, v y brand u is three m that [Y] o is up to 3 X. 16. Cleaning means containing bleaching the agent of claim 13, v y brand u is three m that [Z] o is 0.05 to 5%. 17. Cleaning means containing bleaching the agent of claim 13, v y brand u is three m that [Y] o is 0a [Y] t> (CX) □ - [X] f) 3. 18. Cleaning means containing bleaching the agent of claim 13, v y brand u is three m that contains by weight 1 to 30 of a peroxygen bleaching agent. A cleaning composition comprising a bleaching agent according to claim 1 wherein the bleaching agent is a bleaching agent 19 Dec 13, characterized in that the peroxygen bleaching agent and the activator composition comprise 1 to 7% by weight of the agent and 0.2 to 7% of the bleach activator. whitening, while cleaning peroxygen bleach A cleaning composition comprising a bleaching agent according to claim 13, comprising from 0.2 to 7% by weight of a chelating agent. 21. A bleaching detergent composition as claimed in claim 13 comprising 0.05 to 5% by weight of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof. 22. A bleaching composition according to claim 13, wherein the peroxygen bleach is selected from the group consisting of alkali metal peroxycarbonates, alkali metal perborate monohydrates, alkali metal perborate tetrahydrates, and mixtures thereof. A cleaning composition comprising a bleaching agent according to claim 13, wherein the chelating agent is selected from the group consisting of amine phosphonate chelating agents, aminocarboxylate chelating agents, and mixtures thereof.