CZ101999A3 - Detergent preparations - Google Patents

Abstract

The present invention relates to granular detergent compositions or components thereof, which comprise an oxygen-releasing bleaching system, containing a peroxygen source and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes.

Description

The present invention relates to granular detergent preparations or their components, which contain cationic compounds removing particulate impurities with anti-redeposition properties, and an oxygen-releasing bleach. The products can be used for laundry and dishwashing.

Current state of the art

A very important feature of a detergent product is its ability to remove particulate type pollution from various fabrics during washing. The most significant pollution of the particulate type is clay impurities. Clay particles typically contain negatively charged layers of aluminosilicates and positively charged cations (eg calcium) located between and holding these layers tightly together.

A number of model compounds can be proposed that can remove particulate type pollution. A model of such a compound must meet two basic characteristics. The first property is the compound's ability to adsorb onto negatively charged layers of clay particles. The second property is the ability of the adsorbed compound to separate (swell) the negatively charged layers, thereby reducing the cohesiveness of the clay particle and enabling its removal by washing with water.

In addition to the removal of dirt, another requirement of the washing (washing) v

cycle, the necessity to keep the loosened dirt in suspension. Spina released from the fabrics and suspended in the washing solution can be redeposited on the surface of the fabrics. This redeposited dirt causes graying of fabrics, which is particularly visible on white fabrics. This deficiency can be reduced by using anti-redeposition agents in the detergent preparation.

- 2 ř-ι • · · · · · · ·« · · • · · ··« ··· · • ··· · · · · · · · · · • ······· ·· · · · · · ··· • · · ···· · · • · · ·· · · · · · ·

For example, EP-B-111 965 describes cationic compounds, as components of detergents, removing particulate pollution with anti-redeposition properties.

U.S. 4,659,802 and U.S. Pat. 4,664,848 discloses quaternized particulate fouling amines with anti-redeposition properties that can be used in combination with anionic surfactants.

A model of a positively charged compound with anti-redeposition properties was created. Adsorption of a positively charged compound on the surface of clay particles in the washing solution gives these particles the dispersion properties of their own molecules. The more molecules are adsorbed on the clay particles, the better these particles are coated with a hydrophilic layer of ethoxyl units. The clay particle coated in this way is no longer deposited back on the fabric (especially hydrophobic polyesters) during the washing (washing) cycle.

Another ingredient traditionally used in detergents is bleach, which removes bleachable stains and dirt from fabrics, such as oxygen-releasing bleach.

The disadvantage of most bleaches is that many other components of the detergent are sensitive to bleach, are oxidized by it and lose their original properties. That is, not all detergent components are compatible with bleach.

In the present invention, it was found that cationic (partially) quaternized ethoxylated (poly)amines removing particulate pollution with anti-redeposition properties are fully compatible with oxygen-releasing bleaches. The overall cleaning and/or bleaching effect of the detergent preparation or its components, which contains both cationic quaternized ethoxylated (poly)amines and bleach, is improved, because there is a more effective removal of bleachable stains from fabrics.

Furthermore, it has also been found that the use of oxygen-releasing bleach in detergent preparations in combination with fully quaternized ethoxylated (poly)amines increases the cleaning or bleaching effects, compared to the use of (oxygen-releasing) bleach in combination with partially quaternized ethoxylated (poly)amines. However, even these partially

quaternized ethoxylated (poly)amines provide improved cleaning and bleaching effects in combination with bleach.

Regardless of theory, the following explanation can be given for the compatibility of cationic, quaternized ethoxylated (poly)amines with bleach. The quaternization of the nitrogen groups in these molecules serves a dual purpose. It provides the molecule with a cationic charge that increases the adsorption capacity for clay particles present on the fabric and in the washing solution and removes the oxidizable free electron pair from the nitrogen. This protects the compound from the effects of bleaches and is therefore a stable component of laundry detergents containing bleaches.

All cited documents of the present description are referenced in the relevant section.

The essence of the invention

The present invention relates to granular detergent compositions or components thereof that contain an oxygen-releasing bleach and a source of hydrogen peroxide and one or more cationic compounds. Cationic compounds are cationic, (partially) quaternized ethoxylated (poly)amines removing particulate pollution, with anti-redeposition properties.

Specifically, the present invention relates to granular detergent preparations and their components containing:

(a) an oxygen-releasing bleach with a source of hydrogen peroxide (b) a water-soluble cationic particulate fouling compound with anti-redeposition properties selected from the group consisting of:

1) ethoxylated cationic monoamines of the general formula:

9 • · · · · 9 9 9

9 9 9 9 9 9 ···· · ·« · »

- 4 R ²

I r2_N+_L_X

R ²

2) ethoxylated cationic diamines of the general formula:

(R3) _d R3

X -L— M ¹ - R ¹ — N ⁺ —L -X or i

(R3) _d R3

R?_ M ¹ _R ¹ _N ⁺ _R or even II

L L L

I I I

XXX (R ³ ) R ³

II (X—L— )2- M ² -Rl _M ² _ R ²

R ² where M1 is an N ⁺ or N- group; each is an N ⁺ or N- group and at least one is an N ⁺ containing group;

3) ethoxylated cationic polyamines of the general formula:

(R ³ )d

AND

R ⁴ - [(A>)q - (R ^S )r M ² - LX]p R ²

4) their mixtures; where

A* is -N(R)C(O)-, -N(R)C(O)O-, -N(R)C(O)N(R)-, -C(O)N(R) -, -OC(O)N(R)-, -C(O)O-, -OC(O)O-, -OC(O)-, -C(O)NC(O), or -O- ,

R is H or C 1-6 alkyl or hydroxyalkyl, R 1 is C 2-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C 2-3 oxyalkylene containing 2 to 20 oxyalkylene units provided that ON bonds are not formed; each R ² _is C 1_4 alkyl or hydroxyalkyl, the group -LX or two R ² together form the group (CH 2 )rA ² -(CH 2 )s ₅ where A ² is -O- or -CH 2 -, r is 1 or 2, s is 1 or 2 and r+s is 3 or 4; each R 1 is C 1-8 alkyl, hydroxyalkyl, benzyl, -LX, or two R 1 or one

R ² and one R 2 together form the group -(CH 2 ) r A ² -(CH 2 ) s S R 2 is a substituted C 342 alkyl, hydroxyalkyl, alkenyl, aryl or aralkyl containing p substituents; R 1 is C 1-1 2 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C 2-3 oxyalkylene containing 2 to 20 oxyalkylene units, provided no 0-0 or ON bonds are formed; X is a nonionic group selected from the group consisting of H, C1-4 alkyl or hydroxyalkyl ester or ether and mixtures thereof; L is a hydrophobic chain containing a polyoxyalkylene group -[(R 6 O) _m (CH 2 CH 2 O) _n ]-; where R^ C3.4 alkylene or hydroxyalkylene aman are the numbers of these groups satisfying the requirement that 50 wt.% from this group formed polyoxyalkylene units; d is 1 when M ² is N ⁺ d is 0 when M ² is N; n is at least 16 for cationic monoamines, at least 6 for cationic diamines and at least 3 for cationic polyamines; p is 3 to 8; q is 1 or 1; t is 1 or 0 provided that t is 1 if q is 1.

and wherein the ratio of compound (a) to (b) is in the range of 80:1 to 1:5.

Detailed description of the invention

The basic feature of the present invention is a water-soluble cationic compound removing particulate pollution with anti-redeposition properties, selected from the group including cationic mono-, di- and polyamines.

The ratio of oxygen releasing bleach to water-soluble cationic compound is in the range of 80:1 to 1:5, more preferably in the range of 40:1 to 1:2, and most preferably in the range of 20:1 to 1:1.

The water-soluble cationic compound is preferably present in an amount of 0.01 to 30% by weight, more preferably 0.1 to 15% by weight, most preferably 0.2 to 3.0% by weight. due to the weight of the detergent product.

Cationic amines

A water-soluble cationic compound of the present invention useful in granular detergent compositions or components thereof in accordance with the present invention includes ethoxylated cationic monoamines, ethoxylated cationic diamines, and ethoxylated cationic polyamines as defined above.

In the listed general formulas of cationic amines, R1 can be branched (e.g.

_ CH ₂ —CH c ₃ cyclic (e.g.

CH ₃ i

CH _ CH phenyl ), or most preferably linear (eg -CH2CH2-, -CH2CH2CH2-), alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. For ethoxylated cationic diamines, R 1 is preferably C 2-6 alkylene. Each is preferably methyl or -L-X; each R 1 is preferably C 1-4 alkyl or hydroxylalkyl and most preferably methyl.

The positive charge of the N ⁺ group is balanced by the appropriate number of counterions. Suitable counterions are Cl, Br ^- , SO 3 2 -, POz 2 -, MeSO 3 , etc. Particularly preferred counterions are Cl and Br.

X is a nonionic group selected from the group consisting of H, C 1-4 alkyl or hydroxyalkyl ester or ether, or mixtures thereof. Preferred esters or ethers are acetate ester and methyl ether. Particularly preferred nonionic groups are H and methyl ether.

In the above-mentioned general formulas, the hydrophilic chain L usually contains exclusively polyoxyalkylene groups -[(R6O) _/w (CH2CH2O) _w ]-. The groups -(R6O) _m - and -(CH2CH2O) _n - polyoxyalkylene can be mixed, or preferably form blocks of groups -(R6()) _m - and

-(CH2CH2O) _n -. R 6 is preferably C 3 II 5 (propylene); m is 0 to 5, most preferably 0, i.e. polyoxyalkylenes are formed only by ·· · ·9 99 99 99 groups

9 9 9 99 9 9 9 9

999 9 9999 9 99 9

9999999 99 99 999 999 •99 9999 9 9

-(CH2CH2O)- _n . The group -(CH2CH2O) _n - preferably makes up at least 85% by weight. polyoxyalkylene and most preferably 100 wt.% polyoxyalkylene (m is O).

In the above general formulas for cationic diamines and polyamines, and is each preferably an N ⁺ group.

Preferred ethoxylated cationic monoamines and diamines are compounds of the general formula:

CH ₃ ch ₃

I I

X-(-OCH ₂ CH ₂ ) _n -[N ⁺ -CH2-CH2-(CH2)a-]bN ⁺ -CH2CH ₂ O-)- _n X (CH ₂ CH ₂ O-)- _n X (CH ₂ CH ₂ O-)- _n X where X and have the meaning defined above, and is 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene, ) b is 1 or 0. For preferred cationic monoamines (bO), n is preferably at least 16, typically 20 to 35. For preferred cationic diamines (b=1), n is at least 12, typically 12 to 42.

In the above general formulas for ethoxylated cationic polyamines, R ⁴ (linear, branched or cyclic) is preferably substituted C 3-g alkyl, hydroxyalkyl or aryl; is preferably -C(O)NII-; n is preferably at least 12, typically 12 to 42; p is preferably 3 to

6. If R 4 is substituted aryl or aralkyl, q is preferably 1 and R 4 is preferably C 2-3 alkylene. If R 1 is substituted alkyl, hydroxyalkyl or alkenyl and q is 0, R 1 is preferably C 2-3 oxyalkylene; when q is 1 it is preferably C2-3 alkylene.

• that · that · ♦* ·♦ ·· this • · · · ·· · • · · · ♦ · ·· * • · · that ♦ and · «

These ethoxylated cationic polyamines can be derived from polyaminoamides such as:

r— C(O)NH-(-C ₃ H ₆ -)-NH ₂

HIM

C(O)NH-(-C ₃ H ₆ -)-NH 2 or

C(O)NH-(-C3H^“)NH ₂ ]3

C(O)NH-(-C3H ₆ -)-NII ₂

These ethoxylated cationic polyamines can also be derived from polyaminopropylene oxide derivatives such as:

C(OC ₃ H ₆ -) _c -NH ₂ ch ₃

C(OC ₃ H ₆ -) _c -NH ₂

LC(OC ₃ H ₆ -) _c -NH ₂ where each c is 2 to 20.

Oxygen releasing bleach

The second basic feature of the detergent preparation or its components according to the present invention is an oxygen-releasing bleach and a source of hydrogen peroxide. This bleaching system preferably constitutes 1 to 40% by weight of the preparation. It includes, for example, inorganic perhydrate bleaches and organic peroxy acids.

• 4

- 10 ·· Μ 4 9 9 • · 4 · 4 4

4« « 4 44 4

4 4 4 4 • 44 44

44 * 4 4 4

444 444

4

44

The weight ratio of the oxygen-releasing bleach to the water-soluble cationic compound is in the range of 80:1 to 1:5, more preferably 40:1 to 1:2, most preferably 20:1 to 1:1.

According to a preferred embodiment of the invention, the bleaching system contains a source of hydrogen peroxide and a peroxyacid bleach precursor. Peroxyacid is produced in situ by the reaction of a precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide are inorganic perhydrate bleaches.

Silicates are used as stabilizers of the granular detergent preparations of the present invention (containing oxygen-releasing bleaches). Alkali metal silicates with a ratio of SiO ₂ :Na ₂ O ("R") in the range of 1.6:1 to 3.2:1 are particularly suitable. Silicates that do not meet this definition can also be used, but are less advantageous. Sodium silicates are typically used, however the inclusion of magnesium further increases the stability of the overall formulation, as explained in more detail below. It is also possible to prepare the magnesium form in situ by adding magnesium salt and sodium silicate to the detergent particles (e.g. during the operation of drying the particles by spraying a thick suspension). A suitable magnesium salt is, for example, magnesium sulfate or magnesium chloride. Suitable silicates for the present formulations are 1.6 R sodium silicate solution, 2.0 R solid sodium silicate, or 3.2 R solid sodium silicate available from Hoechst or Akzo. The ratio of silicate to stabilized oxygen sensitive detergent component is preferably 1:1.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are usually alkali metal salts, preferably sodium, and constitute 1 to 40% by weight, more preferably 2 to 30% by weight, most preferably 5 to 20% by weight. preparation.

• 4

- 11 • 4 4 « 4 · • 4 · 4

4 44» • · 4 • 4 · ·· ·« ø · 4 » 4 4 4 4

I 4 4 fl ··

Examples of inorganic perhydrate salts are peroxyborate, percarbonate, peroxyphosphate, peroxysulfate and peroxysilicate. Inorganic perhydrate salts are usually alkali metal salts. They are added to the preparation in crystalline form without additional protection. However, for some perhydrate salts, it is more suitable if they are contained in a coated form in the granulated detergent preparation, which improves the storage stability of the granulated product.

Sodium peroxyborate can be used in the form of monohydrate with the general formula NaBO2H2O2 or tetrahydrate NaBO2H2O2-3H2O.

A preferred perhydrate of the present invention is sodium percarbonate, a compound of general formula 2Na2CC> _3.3H2O2 commercially available in crystalline form. Percarbonate is preferably used in a coated form in the detergent preparation, which increases the stability of the product.

A suitable coating material that increases product stability is a mixed salt of water-soluble sulfate and alkali metal carbonate. These coatings and coating methods are listed in GB-1 466 799. The mass ratio of the mixed salt to the inorganic perhydrate ranges from 1:200 to 1:4, more preferably from 1:99 to 1:9 and most preferably from 1:49 to 1:19 . Preferred mixed salts are substances of the general formula Na ₂ SO ₄ .«.Na ₂ CO ₃ , where n is 0.1 to 3, preferably 0.3 to 1.0 and most preferably 0.2 to 0.5.

In the presented preparations, other coating materials can also advantageously be used, e.g. containing silicates (alone or in a mixture with borates, boric acid and other inorganic materials), waxes, oils and fatty soaps.

Another perhydrate salt useful in the present preparations is potassium peroxyhydrogen sulfate.

- 12 • ♦ · • 0 0

0

0 0·0

0 0

0

0 0 · 000

0 ··

0 0 0 ' 0 0 0

0 0 0

00

Peroxyacid bleach precursor

The peroxyacid bleach precursor comprises 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, most preferably 1.5 to 10% by weight. preparation.

A suitable peroxyacid bleach precursor typically contains one or more N- or O-acyl groups and may be selected from a variety of compound types. Suitable types of compounds are anhydrides, esters, imides and acyl derivatives of imidazoles and oximes. Suitable materials of this type can be found in GB-A-1 586 789. Suitable esters are described in GB-A-836 988, 864 798, 1 147 871, 2 143 231 and EP-A-0 170 386.

N-acylated lactam precursors

N-acylated lactam precursors are generally disclosed in GB-A-955 735. Preferred materials of this type include caprolactam. In the broader concept of the present invention, any lactam can be used as a bleach precursor, but caprolactams and valerolactams are more preferable.

Suitable N-acylated carpolactam precursors are compounds of the general formula:

R ⁶ — C(O)

CH ₂ [CH ₂ ]n where n is 0 to 8, preferably 0 to 2 and R ⁶ is C 1-12 alkyl, aryl, alkoxyaryl or alkaryl or substituted phenyl.

Preferred carpolactam precursors are substances of the general formula:

- 13 C(O)

CH ₂

CHR ¹ — C(O)

CH, ² \

CHj /

CHj where R ¹ is H, Cm ₂ alkyl, aryl, alkoxyaryl or alkaryl, preferably C ₆ "i ₂ . R1 is most preferably phenyl.

Preferred valerolactam precursors are substances of the general formula:

C(O) —CH ₂ —CH ₂

R ¹ — C(O)-N

CH ₂ where R ¹ is H, Cm ₂ alkyl, aryl, alkoxyaryl or alkaryl, preferably C ₆ - ₁₂ . R1 is most preferably selected from the group of phenyl, heptyl, octyl, nonyl, 2,4,4trimethylphenyl, decenyl and mixtures thereof.

The most advantageous are materials in the solid state at temperatures up to 30°C, especially phenyl derivatives, e.g. benzoyl valerolactam, benzoyl caprolactam and relevant analogs substituted on benzoyl such as chlorine, aminoalkyl, alkyl, aryl and alkoxy derivatives.

Precursors of caprolactam and valerolactam, where R ¹ contains 6, preferably 6 to 12 carbon atoms, provide hydrophobic peroxyacids with good cleaning properties by perhydrolysis. Precursor compounds where R ¹ contains 6 to 12 carbon atoms show hydrophilic • · • ·

bleaches are particularly effective in cleaning beverage stains. Mixtures of hydrophobic and hydrophilic caprolactams and valerolactams suitable for the present preparations are typically in weight ratios of 1:5 to 5:1, preferably 1:1.

Highly preferred precursors of caprolactams and valerolactams are benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecanoyl caprolactam, undecanoyl valerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6decanamidocaproyl)oxybenzenesulfonate and mixtures thereof. Examples of highly preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, t-butylbenzoyl caprolactam, t-butylbenzoyl valerolactam, pentyl benzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl valerolactam, ethoxybenzoyl valerolactam, ethoxybenzoyl valerolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl valerolactam, isopropoxybenzoyl valerolactam, butoxybenzoyl valerolactam, t-butoxybenzoyl caprolactam, t-butoxybenzoyl valerolactam there, pentoxybenzoyl caprolactam, pentoxybenzoyl valerolactam, hexoxybenzoyl caprolactam, hexoxybenzoyl valerolactam, 2,4,6-trichlorobenzoyl caprolactam, 2,4,6-trichlorobenzoyl valerolactam, valerolactam, caprolactam, pentafluorobenzoyl dichlorobenzoyl

4-Chlorobenzoyl Caprolactam, Caprolactam, Caprolactam, Pentafluorobenzoyl Dimethoxybenzoyl

2,4-dichlorobenzoyl caprolactam, terephthaloyl dicaprolactam, pentafluorobenzoyl caprolactam, pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam, dimethoxybenzoyl valerolactam, 4-chlorobenzoyl valerolactam, 2,4dichlorobenzoyl valerolactam, terephthaloyl divalerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam and mixtures thereof.

Precursor of perbenzoic acid

For the purposes presented, any perbenzoic acid precursors are suitable, including and preferably the class of N-acyl lactams.

Suitable O-acyl precursors of perbenzoic acid include substituted and unsubstituted benzoyl oxybenzene sulfonates, including, for example, benzoyl oxybenzene sulfonate:

Also suitable are benzoylation products of sorbitol, glucose and other carbohydrates, including e.g.:

Ac = COCH ₃ ; Bz = Benzoyl

Preferred imide-type perbenzoic acid precursors are N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole precursor derivatives of perbenzoic acid are perbenzoic acid derivatives containing N-benzoyl imidazole and N-benzoylbenzimidiol as well as other suitable N-acyl groups such as N-benzoyl pyrrolidone, dibenzoyl taurion and benzoyl pyroglutamic acid.

·« ·

- 16 Preferred precursors of perbenzoic acid are benzoyl diacyl peroxides, benzoyl tetraacyl peroxides and compounds of the general formula:

O

COOH

Another preferred perbenzoic acid precursor is phthalic anhydride:

Precursors of perbenzoic acid derivatives

Suitable precursors of perbenzoic acid derivatives include the aforementioned perbenzoic acid precursors in which the perbenzoic group is substituted with essentially any functional group, including alkyl groups.

Precursors of cationic peroxyacids

Cationic peroxyacid precursors are also suitable for the present invention. A cationic peroxyacid precursor is typically formed by introducing a positively charged functional group into a suitable peroxyacid precursor molecule, e.g. ammonium or alkylammonium, preferably ethyl or methylammonium

Cationic peroxyacid precursors are described in U.S. Pat.

904,406, 4,751,015, 4,988,451, 4,397,757, 5,269,962, 5,127,852,

093 022, 5 106 528, U.K. 1,382,594, EP 475,512, 458,396 and 284,292, and JP 87-318,332.

·* ·» ·« ·· • · · · · · • · · · · · · 9 ·· · • ·

- 17 Examples of preferred cationic peroxyacid precursors are described in U.K. 9,407,944.9 and U.S. 08/298 903, 08/298 650, 08/298 904 and 08/298 906.

Suitable cationic peroxyacid precursors include various ammonium or alkylammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylcaprolactams, and monobenzoyltetraacetyl glucosebenzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzenesulfonate is the 4(trimethylammonium)methyl derivative of benzoyl oxybenzenesulfonate:

A preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,2,3-trimethyl hexanoyloxybenzene sulfonate.

Preferred cationic precursors of peroxyacids of the N-acyl caprolactam class include trialkyl ammonium methylene benzoyl caprolactams, especially trimethyl ammonium methylene benzoyl caprolactam:

Another preferred cationic peroxyacid precursor is sodium 2Ν,Ν,Ν-trimethylammonium) ethyl 4-sulfophenyl carbonate chloride Alkylperoxycarboxylic fatty acid bleach precursors «· » • · 4 • ·

- 18 Fatty peroxycarboxylic acids are formed from alkylperoxycarboxylic fatty acid precursors by perhydrolysis. Advantageous precursors of this type provide peroxyacetic acid.

Preferred precursors of alkylperoxycarboxylic acids are imide-type compounds such as Ν,Ν,Ν^Ν^-tetraaeethylated Cj_6 alkylene diamines, especially Cj, C2 and C5 alkylenes. Tetraacetylethylenediamine (TAED) is particularly preferred.

4 4 » 4 4 1

- 19 Organic peroxyacids

The presented detergent preparations contain as an additional component an oxygen-releasing bleach based on an organic peroxyacid, typically in an amount of 1 to 15% by weight, more preferably 1 to 10% by weight. due to the weight of the product.

Cationic polymers

Detergent preparations and their components optionally further contain other polymer cationic ethoxylated amino compounds removing particulate pollution with anti-redeposition properties, selected from the group including water-soluble cationic polymers. These polymers have a polymer backbone, at least 2M groups and at least one L-X group, where M is an attached cationic group or an integral part of the backbone; X is a nonionic group selected from the group consisting of H, C1-4 alkyl or hydroxyalkyl ester or ether and mixtures thereof; and L is a hydrophilic chain connecting the groups M and X, or connecting X to the polymer backbone.

Polymeric cationic ethoxylated amino compounds are present in the preparations in an amount of 0.01 to 30% by weight, more preferably 0.1 to 15% by weight, most preferably 0.2 to 3% by weight. due to the weight of the detergent product.

The term polymer backbone as used refers to the polymer group to which the groups M and L-X are attached or are an integral part thereof. Polymer backbone includes oligomeric backbone (2 to 4 units) and polymeric backbone (5 or more units).

The term attached to means that the group is attached to a polymer backbone, e.g. caused by the following structural formulas A and B:

·« ·· ·· ·· • · » · · · • · · · · · · · ·* · • · • · · · · ·· ·· 0 · 0 0

- 20 M ML ί Á i

(A) (B)

The term integral component used means that the group is part of the polymer backbone as in the following structural formulas C and D:

(C) (D)

Essentially any polymer backbone can be used as long as the cationic polymer in question is water soluble, removes particulate impurities and has anti-redeposition properties. Suitable polymer frameworks can be derived from polymers such as polyurethanes, polyesters, polyethers, polyamides, polyimides, etc.; polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes and similar polyalkylenes, polystyrenes and similar polyalkylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines, polyaminotriazoles, polyvinyl alcohol, aminopolyureylenes and their mixtures.

M is any compatible cationic group containing an N ⁺ (quaternium) positively charged center. A quaternium, a positively charged center is represented, for example, by the structural formulas E and F:

·· ·· ·· 9 9

9 9 9 9 9 9

9 9 99 9 9 9 9

- 21 — +N —

·· «

9 9 9 9 9

9 99 9 9 9 9 (E) (F)

Preferred groups M contain a quaternium center represented by structure E. The cationic group is preferably an integral part of the polymer backbone, or at least located near it.

The positive charge of the N ⁺ group is balanced by the appropriate number of counterions. Suitable counterions are Cl, Br, δΟβ^-, POz^-, ΜβΟδΟβ, etc. Particularly preferred counterions are Cl and Br.

X is a nonionic group selected from the group consisting of H, C1-4 alkyl or hydroxyalkyl ester or ether, or mixtures thereof. Preferred esters or ethers are acetate ester and methyl ether. Particularly preferred nonionic groups are H and methyl ether.

In the cationic polymers suitable for the detergent preparations of the present invention, the ratio of cationic groups M to nonionic groups X is usually in the range of 1:1 to 1:2. by appropriate copolymerization of cationic, nonionic (i.e. containing the L-X group) and mixed cationic/nonionic monomers, the M:X ratio can be varied. The M:X ratio usually ranges from 2:1 to 1:10. Preferred cationic polymers have an M:X ratio in the range of 1:1 to 1:5. Polymers formed by such copolymerization are typically random, i.e., cationic, nonionic, and mixed cationic/nonionic monomers copolymerize in non-repeating sequences.

Units containing groups M and L-X contain 100% wt. cationic polymers of the present invention. However, it is permissible to

44

4 4 4

4 4 4 • 9 ·4

- 22 if these polymers also include other units (preferably non-ionic). Examples of other units are acrylamides, vinyl ethers and non-quaternized tertiary amino group (MÚ) units containing a nitrogen center. These other units make up 0 to 90% by weight. of the polymer (10 to 100% by weight of the polymer is made up of M and L-X groups, including M^-L-X groups). Usually these other units make up 0 to 50% by weight. of the polymer (50 to 100% by weight of the polymer formed by M and L-X groups).

Groups M and L-X are each present typically in numbers of 2 to 200. Typically in numbers of 3 to 100. Preferably in numbers of 3 to 40.

In addition to the groups connecting the M and X groups and connecting them to the polymer backbone, the hydrophilic chain L contains exclusively polyoxyalkylene units -[(ROj^CL^Ci^O)^]-. The groups -(R'O) _W - and -(CI-^CH^O)^- can be mixed or preferably form the blocks -(R'O) _WZ - and -(CH2CH2O) _w -. R' is preferably ΟβΙΙβ (propylene); m is preferably up to 5, most preferably 0 (i.e. polyoxyalkylene is made up exclusively of units -(Cl^CIIýO)//-· Units -(CH2CH2O) _W - preferably make up 85% by weight

polyoxyalkylene, most preferably 100 wt.% (zw=0). The number of -(CH2CH2O)//-« units is usually 3 to 100, preferably « is 12 to 42.

Several (2 or more) -L-X groups may also be joined together and attached to the M group, or directly to the polymer backbone, as for example shown by structural formulas G and H:

·

9«

99 • · · 9 • 9 9 *

9 9 * 9999999 9 9 9 9 999 999 • 99 9999 9 9

9 9 99 »9 99 99

M 1 L L L

k Jí i (G) (H)

Structures G and H are created, for example, by the reaction of the glycidol group with the M group or by the backbone polymer and ethoxylation of the subsequently formed hydroxyl groups.

Representative classes of cationic polymers are:

A. Polyurethanes, Polyesters, Polyethers, Polyamides or similar polymers.

The class of cationic polymers of the present invention derived from polyurethanes, polyesters, polyethers, polyamides, etc. These polymers are formed by units selected from units of general formulas I, II and III:

9 «9 99 99 99

9 9 9 9 9 9 99 9

999 9 9999 9 99 9

9999999 99 9* 999 999

9 9999 9 9

9 99 9« 99 99

R ⁴

-[-(A1-R1-a1) _x -r2-N+-r3-] _x - (i)

L (R^-KCsHeOW^^OJnJ-X (R ⁶ 2)k

AND

-[-(Al-Rl-Al) _x -R2-N+-R3-] _y - (Π)

R7

-(A1-R1-A^) _x -R2-C-R3-]- (in)

I (R5) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ]-X where A* is

-N(R)C(O)-, -C(O)N(R)-, -C(O)O-, -OC(O)- or -C(O)-;

X is 0 or 1; R is H or C 1-4 alkyl or hydroxyalkyl; R 1 is C 212 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or C 2-3 oxyalkylene containing 2 to 20 oxyalkylene units, provided that Al does not contain 0-0 or ON bonds; if X is 1, then R ² is -R ⁵ - except when A ^J is -C(O)-, or -(OR ⁸ )y- or • A AA

A A A A

A A A A

AA · • · « • A A

A· AA A A A

A A A A A

A* A

A A A A AA A·

And A

AA AA

- 25 -0R\ provided that it does not contain 0-0 or O-N bonds and R3 is -R5, except when A i is -C(O)-, or -(OR^jy or -R^O-, provided that A* does not contain 0-0 or O-N bonds; if x is O, then R^ is -(ORSy, -OR5-, -C(O)OR5-, -C(O)R5- \ -N(R)C(O)R5-, -N(R)C(0)0R5-, -C(0)N(R)R5- or -OC(O)N(R)R5, and R³ is -R5-; r 4 is C 1-4 alkyl or hydroxyalkyl or -(R 4 ) k [(C3H6O)m(CH2CH2O)n]-X; R³ is 0Η2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R 6 is C 1-4 alkyl or hydroxyalkyl or -(CH₂)_year-A2-(CH₂)_with-, where A 2 is -O- or -CH₂-; R? is H or R 1 ; r8 j_E C₂_3 alkylene or hydroxyalkylene; X is H, -C(O)R 9 , r 9 or a mixture thereof, where R 1 is C 1-4 alkyl or hydroxyalkyl; k is 0 or 1; m and n satisfy the requirement that the group -[(C3H6O)_m(CH₂CH₂O)_nj- made up about 85% by weight; m is 0 to 5; n is at least 3; r is 1 or 2, and r + s are 3 or 4; y is 2 to 20; u, v and w satisfy the requirement that the molecule contains at least 2 N+ centers and at least 2 X groups.

·· 99 • · · 9

9 9 4 ··

9

99

- 26 In the above formulas, preferably -C(O)N(R)-;

-N(R)C(O)- or is preferably -O-; x is preferably 1 and R is preferably H. R^ is linear (e.g. -CH 2 -CH 2 -CH 2 -, -CH ₂ -CH(phenyl)-) or branched (e.g. (-CH ₂ -CH(CH ₃ )- , -CH(CH ₃ )-CH(phenyl)-), alkylene, hydroxyalkylene, cycloalkylene or oxyalkylene; where R 1 is C 2-3 oxyalkylene, the number of oxyalkylene units is preferably 2 to 12; R 1 is preferably C 2-6 alkylene or phenylene, most preferably C2-6 alkylene (e.g. ethylene, propylene, hexamethylene). and R 6 are preferably methyl, like R 1 is linear or branched, preferably R _{1 is H or C 1 - 3 alkyl} ;

R 9 is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0 and r and s are both preferably 2; y is preferably 2 to 12.

In the above formulas, n is preferably at least 6 if the number of N+ centers and X groups is 2 or 3; n is most preferably at least 12, typically in the range of 12 to 42 for all ranges of u+v+w. For homopolymers (v and w are 0), u is preferably 3 to 20. For random copolymers (u is at least 1, preferably 0), v and w are each preferably 3 to 40.

·« · ·· ·» ·· ·· • · · Β · · 9 9 9 9

999 9 9999 9 99 9

9 9999 99 99 99 999 999

9 9 9 9 9 9 9 9

9 ΒΒ ·· ΒΒ ΒΒ

- 27 B. Polyacrylates, Polyacrylamides, Polyvinylether or similar polymers.

The class of cationic polymers of the present invention derived from polyacrylates, polyacrylamides, polyvinyl ethers, etc. These polymers are formed by units selected from units of general formulas IV, V and VI.

— [R^u

(R ³ ), — N' — (R ² X — KCjH^WCHjCítOM — X

-ť R'l·I (A ¹ )]

I (R ² ) _k — [(CsHeOWCHaCHzOjJ-— X (V)

-4 R'4.

i (A ¹ )] (VI) (X (R ⁴ ) ₃ where A ¹ is -O-, -N(R)C(O)-, -N(R)C(O)O-, -C( O)N(R)C(O)-, -C(O)N(R)-, -OC(O)N(R)-, -OC(O)-, -OC(O)O-, - C(O)O- or -N(R)C(O)N(R)-;

·« «4 44 44 • 4 4 4 4 4 4

4 444 4 4 4 4

4 4 4 4 4

44 44 44

- 28 R is H or C1-4 alkyl or hydroxyalkyl; is substituted C2-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C2-3 oxyalkylene; each R 1 is C 1-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R^ is C]-4 alkyl or hydroxyalkyl, the group -(R^)] _f -[(C3H6O) _m (CH2CH2O) _n ]-X, or together form the group -(CH2) _r -A^-(CH2) _s -, where is -O- or -CH2-; each R 4 is C 1-4 alkyl or hydroxyalkyl, or two R 4 together form the group -(CH 2 ) _r -A 2 -(CH 2 ) _s -; X is H, -C(O)R 5 , r 5 or a mixture thereof, wherein R 1 is C 1-4 alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; man are chosen so that the group -(CH2CH2O) _n - constitutes at least 85% by weight. from the group -[(C3H6O) _m (CH2CH2O) _n ]-; m is 0 to 5, n is at least 3; r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; the number of u, vaw meets the requirement that the molecule contains 2 N+ centers and 2 X groups.

In the above formulas, A 2 is preferably -C(O)N(R)-, C(O)O or -O-; A^ is preferably -O-; R is preferably H. Rl is linear ·· ·

- 29 (e.g. -CH2-CH2-CH2-, -CH2-CH(phenyl)-) or branched (e.g. (-CH2-C(CH3)-, -CH2-CH(CH3>,

-CH2-C(CH3)(phenyl)-, -CH2-C(phenyl)(CH2-)-), substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; RJ is preferably substituted C2-6 alkylene or substituted C2-3 oxyalkylene; most preferably -CH2CH- or -CH2C(CH3)-.

Each is preferably C 2-3 alkylene, each R 1 and R 2 are preferably methyl; R 1 is preferably methyl; X is preferably H or methyl; j is preferably 1, k is preferably 0; m is preferably 0; r and s are both preferably 2.

In the above formulas, the values of n, u, v, and w vary similarly to polyurethanes and similar polymers.

C. Polyalkyleneamines, Polyalkyleneimines or similar polymers

The class of cationic polymers of the present invention derived from polyalkyleneamines, polyalkylenimines, etc. These polymers are formed by units selected from units of general formulas VII and VIII and IX.

·· ·· » · · « ·· · • « ·· ·· ► · · » » · · · ·· ··

- 30 (R ² )d (R ¹

M' ) (R ² )d (R ¹

M')

-Jy (R ³ )k [(CsHeOWC^^Ojnl·- X (R ² )di

(R ¹ - M' )-_J z (R\__ [(C ₃ H<mCH ₂ CH ₂ O) _n ]_ X where R 1 is C 2-12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or C 2 ^-3 oxyalkylene containing 2 _to 20 units ^, _provided that no ON bonds are ^formed ; is C1-12 alkylene, hydroxyalkylene, arylene or alkarylene; M' is N+ or n center; X is H, -C(O)R4,

99

9 9 9

9 9 9

999,999

9 · 9 4

9 • 4 9

4 4 4 • 4 4 9 9 4 ·

9 · ♦ 4 44 «4 • 4 9 4 4 • 9 9 9

4 4 9

4·

- 31 -R 4 or a mixture thereof, where R 4 is C 1-4 alkyl or hydroxyalkyl; d is 1 if M' is N+ and d is 0 if M' is N; e is 2 if M' is N+ and e is 1 if M' is N; k is 1 or 0; man are chosen so that the group -(CH2CH2O) _n - constitutes at least 85% by weight. from the group -[(C3H6O) _m (CH2CH2O) _n ]~; m is 0 to 5; n is at least 3; the number of x, yz meets the requirement that the molecule contains at least 2 M' groups, 2 N+ centers and 2 X groups.

In the formulas above, Rl varies similarly to RJ for polyurethanes and similar polymers; each R 1 is preferably methyl or the group -(R ³ ) k -[(C 3 H ₆ O) _m (CH 2 CH 2 O) _n ]-X; R ³ is preferably C 2-3 alkylene; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.

In the above formulas, N is preferably at least 6 if the number of groups M' and X is 2 or 3; no is most preferably at least 2, typically in the range of 12 to 42 for all x+y+z ranges. Typically x+y+z is in the range of 2 to 40 and preferably 2 to 20. For short chain polymers x+y+z is in the range of 2 to 9 with 2 to 9 N+ centers and 2 to 11 X groups. For long chain polymers chain is x+y+z at least 10, preferably 10 to 42. For polymers with both short and long chains, M' groups are typically a mixture of 50 to 100 wt.%. N+ centers and 0 to 50% wt. N centers.

Preferred cationic polymers within this class are derived from C2-3 polyalkyleneamines (x+y+z is 2 to 9) and polyalkylenimines (x+y+z is at least 10, preferably 10 to 42). Particularly preferred cationic polyalkylene amines and polyalkylene imines are polyethylene amines (PEA) and polyethylene imines (PEI). These advantageous cationic polymers are formed by units of the general formula:

this this this · · • this this this • · ···» * • this ·· · this· ·· • this • · • ··· ·· this ·· · this • this ·· • ·· · • · « · ··· ··· • · • c· »·

- 32 (R ² )d (R ² )d

II [M]a- — [CHr- CH ₂ M'] _x — [(CH ₂ CH ₂ O)n_ X] ₂ (R ² )a — [CH ₂ CH ₂ M'] _y — (CH ₂ CH ₂ O)„_ X (R ² )d — [CH ₂ CH ₂ M'] _z — [(CH ₂ CH ₂ O)„—_ X] ₂ where (preferably methyl), Μ', X, d, x, y, zan have the meaning defined above; and is 1 or 0.

Before ethoxylation, the PEA used to prepare the present cationic polymers has the general formula:

[H ₂ Nla- _ [CH ₂ CH ₂ N] _x „ _ [CTÍ ₂ CH ₂ NH] _y _ _ [CH ₂ CH ₂ NH ₂ ] _Z where x+y+z is 2 to 9, and is 0 or 1 (molecular weight 100 to 400). Each hydrogen atom attached to the nitrogen is an active site for subsequent ethoxylation. For preferred PEAs, x+y+zv ranges from 3 to 7 (molecular weight 140 to 310). These PEAs can be obtained by reacting ammonia with dichloroethane and subsequent fracking by distillation. Commonly prepared PEAs are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Higher derivatives •· 44 44

4 4 ·

4 · 4 · 4 • 4

4

- 33 than pentamines, i.e. hexamines, heptamines, octamines and possibly nonamines, as related mixtures can no longer be separated by distillation and possibly contain other materials such as cyclic amines and partly piperazines. Cyclic amines with side chains containing nitrogen atoms may also be present. See U.S. 2,792,372, Dickson, issued May 14, 1957, dealing with the preparation of PEA.

The minimum degree of ethoxylation required for the beneficial properties of the polymer (ie, removing particulate pollution with anti-redeposition properties) varies with the number of PEA forming units. Where y+z is 2 or 3, n is preferably at least 6. Where y+z is 4 to 9, suitable properties are achieved when n is at least 3. For preferred cationic PEAs, n is at least 12, typically 12 to 42.

The PEIs used to prepare the present polymers have a molecular weight before ethoxylation of at least 440, which is at least 10 units. Preferred PEIs used for the preparation of these polymers have a molecular weight of 600 to 1800. The polymer backbone of these PEIs is represented by the general formula:

[H ₂ N]-ECH ₂ CH ₂ N-fe -[ CH ₂ CH ₂ NHHy—[CH ₂ CH ₂ NH ₂ ] _z where the sum of x+y+z must meet the intended molecular weight of the prepared polymer. Both straight and branched polymer skeletons are suitable. The relative proportion of primary, secondary and tertiary amino groups in the polymer varies according to the method of preparation. Typically, the representation of individual types of amino groups is as follows:

-CH 2 CH 2 -NH 2 30% -CH2CH2-NH- 40% -CH ₂ CH ₂ -N- 30%

• 0 • · · · · • ·

- 34 Each hydrogen atom bonded to a PEI nitrogen represents an active center for subsequent ethoxylation. These PEIs can be prepared, for example, by polymerization of ethyleneimine in the presence of a catalyst such as CO2, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods of preparation are given in U.S. Pat. 2,182,306, Ulrich et al, issued December 5, 1939; U.S. 3,033,746, Mayle et al, issued May 8, 1962; U.S. 2,208,095, Esselmann et al, issued July 16, 1940; U.S. 2,806,839, Crowther, issued 9/17/1957; and the U.S. 2,533,696, Wilson, published May 21, 1951 (all documents incorporated by reference).

As defined for the formulas above, n is at least 3 for cationic PEI. However, it should be noted that the minimum degree of ethoxylation required for the beneficial properties of the polymer (i.e. removing particulate pollution with anti-redeposition properties) can increase the molecular weight of PEI well above 1800. The same degree of ethoxylation increases with increasing molecular weight of PEI. For PEI with a molecular weight of at least 600, n is preferably at least 12, typically 12 to 42. For PEI with a molecular weight of at least 1800, n is preferably at least 24, typically 24 to 42.

D. Diallylamine polymers

A class of cationic polymers of the present invention derived from diallylamine polymers. These polymers are made up of units chosen from units of the general formulas X and XI:

·

4 (CH ₂ ) _y (CH ₂ ) (X) (CH ₂ ) _x

N>

/ \

R ¹ (R ² )k— [(C ₃ H 6 O), _and (CH ₂ CH ₂ O)»4_ X (CH ₂ ) _y (CH ₂ ) (Xi) (CH ₂ )x-

hydroxyalkyl, or R ² is C 1-12 where R 1 is C 1-4 alkyl or -(R 2 ) _k -[(C ₃ H ₆ O) _m (CH 2 CH ₂ O) _n ]-X; hydroxyalkylene, alkenylene, arylene or alkarylene; each R 1 is C 1-4 alkyl or hydroxyalkyl or together form the group -(CH 2 ) _r -A 2 -(CH 2 ) _s -; where A is -O- or -CH2-; X is H, -C(O)R 4 , r 4 or a mixture thereof, where R 4 is C 1-4 alkyl or hydroxyalkyl; k is 1 or 0; man are chosen so that the group -(CH2CH2O) _n - constitutes at least 85% by weight. from the group -[(C3H6O) _m (CH2CH2O) _n ]”; m is 0 to 5; n is at least 3; r is 1 or 2, s is or 2, and r+s is 3 or 4; x is 1 or 0; y is 1 if x is 0 and if x is 1; the number of uav meets the requirement that the molecule contains at least 2 N+ centers and 2 X groups.

alkylene group,

9 • 9 ««

9 9 9

9 9 9 9 9

- 36 In the above formulas, A is preferably -O-; R 1 is preferably methyl; each R 1 is preferably C 2-3 alkylene; each R 1 is preferably methyl;

r 4 _is preferably methyl; X is preferably H, k is preferably 0; n is preferably 0; m is preferably 0; aras are both advantageously 2.

In the above formulas, n is preferably at least 6, if the number of N+ centers and X groups is 2 or 3, n is preferably at least 12, typically 12 to 42 for all u+v ranges. Typically v is 0 and u is 2 to 40, preferably 2 to

20.

Other components of the detergent product

The detergent preparation or its components according to the present invention optionally contain other detergent components. The exact nature of these other components and their amount used is determined by the physical form of the product or component and the intended type of laundry operation for which the product is to be used.

The preparations or components of the present invention preferably contain as additional detergent components one or more substances selected from the group including other surface-active substances, other bleaches, bleach catalysts, systems of substances affecting alkalinity, building components, bleach, bleach precursors, bleach catalysts, organic polymer compounds, other enzymes, defoamers, calcium soap dispersants, other particle impurity suspending agents and anti-redeposition agents, perfumes and corrosion inhibitors.

Other surfactants

The detergent composition of the present invention or its components preferably contain other surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and their mixtures.

A typical set of such anionic, nonionic, ampholytic, and zwitterionic surfactant classes and species is disclosed in U.S. Pat. 3,929,678, Laughlin, Heuring, 12/30/1975. More examples

0 · · • · · • « • « • ·

- 37 are listed in Surface Active Agents and Detergents (parts I and II, Schwarz, Pěny, Berch). A set of suitable cationic surfactants is disclosed in U.S. Pat. 4,259,217, Murphy, 3/31/1981.

Ampholytic, amphothemic and zwitterionic surfactants are usually accompanied by one or more anionic and/or nonionic surfactants in the formulations.

Anionic surfactants

The detergent preparation of the present invention or its components preferably contain additional anionic surfactants. The present detergent composition may contain essentially any anionic surfactant usable for cleaning purposes. E.g. salts (sodium, potassium, ammonium and substituted ammonium such as mono-, di- and triethanolamine) of sulfate, sulfonate, carboxylate and sarcosinate surface-active substances are suitable. Anionic sulfate surfactants are preferred.

Other anionic surfactants are isethionates such as acyl isethionates, N-acyl taurates, methyl tauride and fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C42-18 monoesters), sulfosuccinate diesters (especially saturated and unsaturated 05.44 diesters), N-acyl sarcosinates.

Acid resins and hydrogenated acid resins such as rosin, hydrogenated rosin and acid resins and hydrogenated acid resins derived from tallow oil or its derivatives are suitable.

Anionic sulfate surfactants

Anionic sulfate surfactants suitable for the present purposes include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C5.47 acyl-N-(Ci_4 alkyl) and -N-(Cj_2 hydroxyalkyl) glucamine sulfates and sulfates of alkylpolysaccharides such as sulfates of alkylpolyglucosides (the nonionic nonsulfonylated compounds mentioned).

• 4 • 4 • 4 4 4 « 4 4 4 4 4

444 4 4444 4 *4 4 • ······<* 44 »· 444 444 • 44 4444 4 4 ·· 4 44 4 » 44 44

- 38 Alkyl sulfate surfactants are preferably selected from linear and branched primary C1 943 alkyl sulfates, more preferably from branched C1]45 alkyl sulfates and linear C12-14 alkyl sulfates.

Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C 10-18 alkyl sulfates which have been ethoxylated from 0.5 to 0.5 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is C _n _i ₈ , most preferably C _n . ₁₅ alkyl ethoxy sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred embodiment of the present invention uses a mixture of preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. These compositions were described in PCT patent application WO 93/18124.

Anionic sulfonate surfactants

Anionic sulfonate surfactants suitable for the present invention include salts of linear C5..20 alkyl benzene sulfonates, alkyl ester sulfonates, C8-22 primary or secondary alkanesulfonates, C0-24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, (fatty acyl)-glycerol sulfonates, and any mixture of these substances.

Anionic carboxylate surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyls'), especially certain secondary soaps as noted herein.

Suitable alkyl ethoxy carboxylates include those of the general formula RO(CH 2 CH 2 O) _x CH 2 COO'M ⁺ where R is C 1-6 alkyl, x is 0 to 10; in the case where x is 0, the amount of ethoxylate groups does not exceed 20%. ···· 99 · · 999 9 9 9

9 9 9 9 9 9 · · • · * · * * » ·· »♦

- 39 wt., M is the cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the general formula RO-(CHRi-CHR2-O)-R3 where R is alkyl, x is 1 to 25, Rj and R2 are selected from the group H, methyl acid radical, succinic acid radical , a hydroxysuccinic acid radical and mixtures thereof, R 3 is selected from the group consisting of H, a substituted or unsubstituted C 1-8 hydrocarbon and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants containing a carboxyl moiety attached to a secondary carbon. Preferred soap surface-active substances for the purposes of the present invention are water-soluble substances selected from the group comprising water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-undecanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid acid and 2-pentyl-1-heptanoic acid. Certain soaps can act as suds suppressors.

Surfactant salt of sarcosinate and alkali metal

Other suitable anionic surfactants are salts of sarcosinates with alkali metals of the general formula R-CON(Rl)CH2COOM where R is C5..

alkyl or alkenyl, straight or branched, R 1 is C 1-4 alkyl and M is an alkali metal ion. Preferred examples are sodium myristyl and oleoyl methyl sacrosinates.

Alkoxylated nonionic surfactants

For the purposes presented, essentially any alkylated nonionic surfactants are suitable. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated nonionic surfactants are selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated condensates with propylene glycol, and nonionic ethoxylated condensation products with propylene oxide/ethylenediamine adducts.

• · ·» »· ·· ♦ · · · · ♦ ···· • 9 · · · » · · · 9 9 9 9 .

99999999 99 99 999 9 99

9 9 9 9 9 9 9 ·

9» · 9 9 9 9 9 9 9 9

- 40 Nonionic surface-active alkylated alcohol

Condensation products of aliphatic alcohols with 1 to 25 mol of alkylene oxide, especially ethylene oxide and/or propylene oxide, are suitable for the purposes presented. The alkyl chain of an aliphatic alcohol can be straight or branched, primary or secondary, and usually contains 6 to 22 carbon atoms. Condensation products of Cg_2() alcohols with 2 to 10 mol of ethylene oxide per 1 mol of alcohol are particularly preferred.

Nonionic surfactant amide of polyhydroxy fatty acid

Amides of polyhydroxy fatty acids suitable for the purposes presented are substances of the structural formula R^CONRJZ where R1 is H, Cj_4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or their mixtures, preferably C1_4 alkyl, more preferably Cj_2 alkyl, most preferably methyl; and R 1 is a C 5-31 hydrocarbon, preferably a straight C 5-19 alkyl or alkenyl, more preferably a straight C 947 alkyl or alkenyl, most preferably a straight C 1-17 alkyl or alkenyl or mixtures thereof; and Z is a polyhydroxy hydrocarbon containing a linear hydrocarbon chain with at least 3 hydroxyls attached directly to the chain, or an alkoxy derivative thereof (preferably ethoxy or propoxy). Z is preferably derived from a reducing sugar by a reductive amination reaction; more preferably Z is glycityl.

Nonionic surfactant fatty acid amide

Suitable surface-active fatty acid amides are substances of the general formula R6cON(R7)2 where R^ is C7-2i alkyl, preferably C9-47 alkyl, each R^ is selected from the group consisting of H, C1-4 alkyl, C1-4 hydroxyalkyl and (C2fl4O) _x H, where x is 1 to 3.

Nonionic surface-active alkyl polysaccharide

Alkylpolysaccharides suitable for the present invention are disclosed in U.S. Pat. 4,565,647, Llenado, issued 1/21/1986. These substances have hydrophobic «

- 41 group consisting of 6 to 30 carbon atoms and a polysaccharide, e.g. polyglycoside, hydrophilic part consisting of 1.3 to 10 sugar units.

Preferred alkyl polysaccharides are substances of the general formula

R ² O(C _n H 2 _n O)t(glycosyl) _x where R ² is selected from the group consisting of C 10-18 alkyl, (C 10-18 alkyl)phenyl, hydroxy(C 10-18 alkyl), hydroxy(C 10-18 alkyl )phenyl and their mixtures; n is 2 or 3; t is 0 to 10, and x is 1.3 to 8. A preferred glycosyl is derived from glucose.

Amphoteric surfactants

Amphoteric surfactants suitable for the present purposes include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxide surfactants are substances of the general formula r3(OR4) _x nO(R5)2 where R^ is selected from the group C8-26 alkyl, hydroxy(C8-26 alkyl), C8-26 acylamidopropoyl and (C8-26 alkyl)phenyl or their mixtures; R 4 is C 2-3 alkylene or hydroxy(C 2-3 alkylene) or mixtures thereof; x is 0 to 5, preferably 0 to 3; each R 1 is C 1-3 alkyl or hydroxyalkyl or a polyethylene oxide group consisting of 1 to 3 ethylene oxide units. Preferred is C1-C18 alkyl dimethylamine oxide and C10-18 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl-amphodicarboxylic acid is Miranol (TM) C2M conc. made by Miranol, lne., Dayton, NJ.

Zwitterionic surfactants

The presented detergent preparations or their components possibly also contain zwitterionic surfactants. These superficially • · 9 99 ·· 99 99 • 9 9 9 9 9 9 φ 9 9 • *99 9 9999 9 t 9 9 • 99*9999 99 ·· ·99 » · ·

999 9999 9 9 ·· 9 99 99 99 99

- 42 active substances can generally be described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of suitable zwitterionic surfactants are betaine and sultaine surfactants.

Suitable betaines are compounds of the general formula R(R') 2 N ⁺ R 2 cOO", where R is a C 1-1 hydrocarbon group, each Id is typically a C 1-3 alkyl and R 2 is a C 1-5 hydrocarbon group. Preferred betaines are Oj2-18 dimethylammonio hexanoate and Cj()_]g acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for the present invention.

Cationic surfactants

Cationic surfactants suitable for the present detergent compositions or components thereof include quaternary ammonium surfactants selected from the group comprising preferably

C0-io N-alkyl or alkenyl ammonium surfactants where the free valence nitrogen is substituted with methyl, hydroxyethyl or hydroxypropyl.

Another suitable group of cationic surfactants usable for the present detergent preparations or their components are cationic ester surfactants.

Cationic ester surfactants are preferably compounds dispersible in water, have surface-active properties, contain at least one ester (i.e. -COO-) bond and at least one positively charged cationic group.

Suitable cationic ester surfactants including cholinester surfactants are listed in, e.g., U.S. Pat. 4,228,042, 4,239,660 and 4,260,529.

According to a preferred embodiment, the ester bond and the cationic group in the surfactant molecule are separated from each other by a spacer formed by a chain containing at least 3 atoms (with a length of 3 atoms),

- 43 preferably 3 to 8 atoms, more preferably 3 to 5 atoms, most preferably 3 atoms. The atoms forming the spacer chain are selected from the group consisting of C, N and O and combinations thereof, provided that the O and N atoms are always bonded only to carbon. Thus, the spacer must not contain -O-O- (i.e. peroxide), -N-N- and -N-O- bonds; -CH2-O-CH2- and -CH2-NH-CH2- bonds are allowed. It is advantageous if the spacer contains only carbon atoms, the most advantageous chain being a hydrocarbon.

Water-soluble building components

The present detergent preparations or their components preferably contain water-soluble building components, typically in an amount of 1 to 80% by weight, preferably 10 to 70% by weight, most preferably 20 to 60% by weight.

Suitable water-soluble building components include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymer polycarboxylic acids or their salts containing at least two carboxyl groups separated from each other by no more than two carbon atoms, borates, phosphates and mixtures of the mentioned components.

Carboxylate or polycarboxylate building components are of the monomeric or oligomeric type, monomeric polycarboxylates are usually more advantageous in terms of use and price.

Suitable carboxylates containing one carboxyl group are water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxyl groups are water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid. maleic, diglycol, tartaric, tartroic and fumaric, as well as ether carboxylates and sulfmyl carboxylates. Polycarboxylates containing three carboxyl groups include specifically water-soluble citrates, aconitrates and citraconates, succinic acid derivatives such as carboxymethyloxysuccinates described in British Patent 1,389,732 and aminosuccinates described in Dutch Patent Application 7,205,873 and oxypolycarboxylates such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent 1,387,447.

4 4 4 4 4

4 4 4 4 4

4444 4 44 »•44 4

44 ·*

- 44 Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent 1261 869, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinic acid derivatives described in British Patents 1,398,421 and 1,398,422 and in U.S. Pat. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups in the molecule, especially citrates.

Appropriate acids of monomeric or oligomeric chelating agents or mixtures thereof with salts, e.g. citric acid or a citrate/citric acid mixture are also suitable building components.

Both borate building blocks and borate precursors from which borates are formed during detergent storage or wash cycle conditions are also useful water-soluble building blocks of the present invention.

Suitable examples of water-soluble phosphate building components are alkali metal tripolyphosphates such as sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium poly/metaphosphate with a degree of polymerization in the range of 6 to 21 and salts of phytic acid.

Partially soluble or insoluble building components

The presented detergent preparations or their components optionally contain partially soluble or insoluble building components, typically in an amount of 1 to 80% by weight, preferably 10 to 70% by weight, most preferably 20 to 60% by weight. due to the weight of the product.

• ·

0 0 · 0 0 0« · 0 00 «0

- 45 An example of building components mainly insoluble in water are sodium aluminosilicates.

Suitable aluminosilicate zeolites are substances with the general formula Na _z [(AlO2)z(SiO2)y].xH2O where z and z are at least 6; the molar ratio z:y is in the range of 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. Aluminosilicates are in hydrated form, are preferably crystalline, contain bound water in an amount of 10 to 28 wt.%, more preferably 18 to 22 wt.%

Aluminosilicate zeolites are naturally occurring substances, preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchangers are available as Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and their mixtures. Zeolite A is a substance of general formula

Nai2[(AlO2)l2(SiO2)l2]xH ₂ O where x is 20 to 30, especially 27. Zeolite X is a substance of general formula

Na ₈₆ [(AlO 2 ) 86 (SiO 2 ) 10 6 ]-276 H ₂ O .

Another preferred aluminosilicate zeolite is the zeolite building component MAP. MAP is contained in an amount of 1 to 80% by weight, more preferably 15 to 40% by weight. due to the weight of the product.

Zeolite MAP is described in EP-384 070 A (Unilever). It is an alkali metal aluminosilicate of the zeolite P type, the ratio of silicon to aluminum is not higher than 1.33, preferably in the range of 0.9 to 1.33, more preferably in the range of 0.9 to 1.2.

Particularly interesting is the zeolite MAP with a ratio of silicon to aluminum not higher than 1.15, preferably not higher than 1.07.

·· 99

9 9 9

9 9 9

999,999

9

9· ·♦ » * · · • · · * • 9♦ ··· • 99

99 • 9 9 • 9 9 99

9 9 9 * • 9 9 9

9 9 9

- 46 According to a preferred embodiment, the zeolite building component MAP has particles with a size of 1.0 to 10.0 µm (expressed as a d50 value), more preferably 2.7 to 7.0 µm/m, most preferably 2.5 to 5.0 µm.

The d5o value means that 50 wt.% particles have a diameter smaller than the specified range. Particle size can be determined by conventional analytical procedures such as microscopic determination using a scanning electron microscope or a laser granulometer. Other methods of determining d5Q values are described in EP-384 070 A.

Heavy metal ion chelators

The present detergent preparations or their components preferably contain heavy metal ion chelators as an optional component. A chelator is a compound capable of chelating heavy metal ions. These substances can also chelate calcium and magnesium ions, but preferably selectively chelate heavy metal ions such as iron, manganese and copper ions.

Heavy metal ion chelators are usually contained in an amount of 0.005 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to

7.5 wt% and most preferably 0.5 to 5 wt.% due to the weight of the product.

Suitable heavy metal ion chelators for the present invention are organic phosphonates such as amino alkylene poly(alkylene phosphonates), ethane 1-hydroxy alkali metal diphosphonates and nitrile trimethylene phosphonates.

Of the above substances, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1-diphosphonate are preferred.

• 9 • 9 ·· 9 • · 9

9 9 9

9 9 9 9 9 9

9 9 99 99 99

- 47 Other suitable heavy metal ion chelators for the present invention are nitrilotriacetic acids and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediamineglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or their salts. Particularly preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or its salt with an alkali metal, an alkaline earth metal, an ammonium or substituted ammonium salt, or mixtures thereof.

Other suitable heavy metal ion chelators for the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid described in EP-A-317 542 and EP-A-399 133. The chelators iminodiacetic-N-2-hydroxypropyl sulfonic acid and aspartic- The N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516 102 are also suitable for the present purposes. The chelators β-alanine-N,N'-diacetic acid, aspartic-N,N'-diacetic acid, aspartic-N-monoacetic acid, and iminodisuccinic acid described in EP-A-509 382 are also suitable.

EP-A-476 257 describes suitable amine-based chelators. EP-A510 331 describes a suitable chelator derived from collagen, keratin or casein. EP-A-528 859 describes a suitable chelator alkyl iminodiacetic acid. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Also suitable are glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N,N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS).

Bleach catalysts

The oxygen-evolving bleaching system may include a transition metal-containing bleach catalyst.

A suitable type of bleach catalyst is a catalytic system containing transition metal cations with a defined catalytic efficiency, e.g. copper, iron or manganese cations; additional cations with low or no catalytic activity such as zinc or aluminum cations, and a chelator with a defined stability constant for both catalyst cations and additional cations, especially ethylenediaminetetraacetic acid, acid • · 44

9 4 4

4 4 4 ·· 9 • *

9·4

9 9 4 4 9 9

4 44 94

- 48 ethylenediaminetetra(methylenephosphonic) and their water-soluble salts. These catalysts are described in U.S. Pat. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in US 5,246,621 and US 5,244,594. Preferred substances of this type are MnIV2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2- (PF6)2, MnIR2( ^u O) 1 (uO Ac)2( 1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)2, MnRlMn^4(uO) ] (u- OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(0104)3, and their mixtures. Others are described in EP 549 272. Other ligands suitable for the present invention include 1,5,9-trimethyl-1,5,9triazacyclododecane, 2-methyl-1,4,7-trazacyclononane, 2-methyl-1,4,7trazacyclononane , 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and their mixtures.

Other suitable examples of bleach catalysts useful in the present invention can be found in U.S. Pat. 4,246,612 and U.S. Pat. heel 5,227,084. See also U.S. Pat. 5,194,416 citing mononuclear manganese complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PFg).

Still another type of bleach catalyst, as disclosed in US Pat. 5,114,606, is a water-soluble complex of Mn^ ³ and/or Mn^ with a ligand based on a non-carboxylic polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands are sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof.

U.S. 5 114611 discloses a bleach catalyst comprising a complex of transition metals including Mn, Co, Fe or Cu with a non-(macro)-cyclic ligand. It is a ligand of the general formula

4 44 4« 44 44 • 4 4 444 4 4 4 · • 444 4 4444 4 44 4

4 44 · · · · · · · ··· ··· • 4 4 4444 4 4

4 4444 44 44

- 49 f ² i ^{R 3} r 1 -N=OBC=N-R 4 where R 1 , R 3 , R ³ and r 4 are selected from H, substituted alkyl and aryl such that each group R 1 -N=C-R 2 and R - -C ^;;: N-R4 forms a five- or six-membered ring. This ring is optionally further substituted B is a bridge selected from O, S, CR5r6? NR? and C=O, where R^ _? R6 _and R? are selected from H, substituted alkyl and aryl, including substituted and unsubstituted groups. Preferred ligands are pyridine, pyridazine, pyridine, pyrazine, imidazole, pyrazole and triazole. These rings may be substituted with groups such as alkyl, aryl, alkoxy, halide and nitro. A particularly preferred ligand is 2,2'bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Very preferred catalysts include Co(2,2'-bispyridylamine)Cl2, di(isothiocyanato)bispyridylamine-cobalt(II), trisdipyridylaminecobalt(II) perchlorate, Co(2,2'-bispyridylamine)2O2ClO4, bis-(2,2' -bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate and their mixtures.

Other examples include binuclear manganese complexes with tetra-Ndentate and bi-N-dentate ligands, including N4Mn^(uO)2Mn^N4) ⁺ and [Bipy2Mn^i(uO)2Mn^bipy2]-(ClO4)3.

Other bleach catalysts are described, for example, in European Patent Application 408,131 (cobalt complex catalysts), European Patent Applications 384,503 and 306,089 (metal porphyrin catalysts), U.S. Pat. 4,728,455 (manganese/multidentate ligand catalysts), U.S. Pat. 4,711,748 and European Patent Application 224,952 (manganese catalyst absorbed on aluminosilicate), U.S. Pat. 4,601,845 (aluminosilicate support with manganese, zinc or magnesium salts), U.S. Pat. 4,626,373 (manganese/ligand catalyst), U.S. Pat. pat 4,119,557 (iron complex catalyst), German Patent Specification 2,054,019 (cobalt/chelate group catalyst), Canadian Patent 866,191 (transition metal salts), U.S. Pat. 4,430,243 (chelating groups with manganese cations and non-catalytic metal cations) and U.S. Pat. 4,728,455 (manganese gluconate catalysts).

·· 4 • 4

- 50 The bleach catalyst is typically included in the preparation in a catalytically effective amount for the ongoing processes. A catalytically effective amount is a dose sufficient under any test conditions to activate the bleach and remove stains from the target substrate. Test conditions vary according to the type of laundry operation and the user's habits. Some users prefer very hot water; some in lukewarm or even cold water when washing. The effectiveness of the bleach catalyst is of course affected by this, and the choice of the amount of catalyst in the finished detergent preparation is governed by such considerations. The recommended, non-limiting dosage is such that the present preparations provide at least 1 ppm of effective bleach catalyst in the washing solution, preferably 1 to 200 ppm. A more concrete illustration is, for example, on the order of 3 wmol.l! manganese catalyst concentration at 40°C, pH 10 in European conditions using peroxyborate and bleach precursor. In the U.S. conditions, the required concentration may be 3 to 5 times higher to achieve the same result.

Enzymes

Another advantageous component of the presented detergent preparations or their components is one or several additional enzymes.

Preferred additional enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, pectinases, lactases and peroxidases, commonly used as ingredients in detergent formulations. Suitable enzymes are discussed in U.S. Pat. 3,519,570 and 3,533,139.

Preferred commercially available proteases are sold under the trade names Alcaiase, Savinase, Primase, Durazym and Esperase (Novo Industries A/S, Denmark), Maxatase, Maxacal and Maxapem (GistBrocades), enzymes sold by Genencor International and enzymes sold under the trade names Opticlean and Optimase (Solvay Enzymes). Proteases are usually contained in the presented preparation in an amount of 0.0001 to 4% by weight. active enzyme.

4

4 44

4 4 4

4 4 4

444 444

4

44

4 4« 4

Preferred amylases are, for example, oc-amylases obtained from the strain B licheniformis, described in more detail in GB-1 269 839 (Novo). Preferred commercially available amylases are, for example, amylases sold under the trade name Rapidase (Gist-Brocades) and Termamyl and BAN (Novo Industries A/S). Amylases are usually contained in the presented preparation in an amount of 0.0001 to 2% by weight. active enzyme.

Lipolytic enzymes are usually contained in the presented preparation in an amount of 0.0001 to 2% by weight, preferably 0.001 to 1% by weight, more preferably 0.001 to 0.5% by weight. active enzyme.

Lipases are of fungal or bacterial origin, e.g. lipase obtained from Humicola sp., Thermomyces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipase originating from chemically or genetically modified mutants of these strains is also suitable. A preferred lipase is derived from a strain of Pseudomonas pseudoalcaligenes, which is described in granted European patent EP-B-0 218 272.

Other preferred lipases for the present preparations are obtained by cloning the gene from Humicola lanuginosa and expressing it in Aspergillus oryza as a host, as described in European patent application EP-A-0 258 068. This enzyme is commercially available from Novo Industri A/S, Bagsvaerd , Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. 4,810,414, Huge-Jensen et al., Pub.

7/3/1989.

Organic polymer compounds

Organic polymer compounds are preferred additional components of the present detergent preparations or their components, they are preferably present as all components having the ability to bind particulate

44

4 4 4

4 4 4

444 444

4

44

44 ♦ · * • · 4 · · φ 4 4

4 4

4 44

- 52 folders. By the term organic polymer compound is meant essentially any organic polymer compound commonly used in detergent preparations as dispersants, anti-redeposition agents and dirt suspending agents. They include high molecular weight organic polymer compounds described as substances that precipitate clay particles into flakes, while this is not the case with the previously mentioned quartemized ethoxylated (poly)amines, which have the ability to remove clay particle impurities and act as anti-redeposition agents.

Organic polymer compounds are usually contained in the present detergent preparation in an amount of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, most preferably 1 to 10% by weight.

Suitable organic polymer compounds are, for example, water-soluble organic homo- or copolymer polycarboxylic acids or their salts containing at least two carboxyl groups separated from each other by no more than two carbon atoms. Polymers of the second type are described in GB-A-1 596 756. Examples of such salts are polyacrylates with a molecular weight of 1000 to 5000 molecular weight. and their copolymers with maleic anhydride with a molecular weight of 2000 to 100,000 molecular weight, preferably 40,000 to 80,000.

Polyamino compounds suitable for the present invention are compounds derived from aspartic acid, such as those described in EP-A-305 282, EP-A-305 283 and EP-A-351 629.

Terpolymers containing monomer units selected from the group consisting of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially with a molecular weight of 5,000 to 10,000 molecular weight, are also suitable for the present invention.

Other organic polymer compounds suitable for the present invention are cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

9

9·

• 9 9

99 99 • · · 99 9 • · · 9

- 53 Other suitable organic polymer compounds are polyethylene glycols, especially with a molecular weight of 1,000 to 10,000, preferably 2,000 to 8,000 and most preferably 4,000.

Antifoaming agents

The presented detergent preparations intended for washing machines preferably further contain suds-reducing substances in an amount of 0.01 to 15% by weight, preferably 0.05 to 10% by weight, most preferably 0.1 to 5% by weight.

Antifoam systems suitable for the present invention may contain essentially any antifoam compound, including, for example, a siliceous antifoam compound and a 2-alkyl alkanol antifoam compound.

The term antifoam compound means a compound or a mixture of compounds that reduce the formation of foam or suds formed in the detergent solution, especially during mixing.

Preferred antifoam compounds are siliceous antifoam compounds defined herein as any antifoam compound including siliceous. Siliceous antifoam compounds typically contain a siliceous component. The term siliceous, as in industry, includes relatively high molecular weight polymers containing siloxane units and hydrocarbon groups of various types. Preferred siliceous antifoam compounds contain trimethylsilyl end groups.

Other suitable antifoam compounds are monocarboxylic fatty acids and their soluble salts. These substances are described in U.S. Pat. 2,954,347, issued 9/27/1960, Wayne St. John. Monocarboxylic fatty acids and their salts used as antifoam additives typically contain a C12-24 hydrocarbon chain, preferably a C12-18 chain. Suitable salts are alkali metal salts such as sodium, potassium and lithium, ammonium and alkanolammonium salts.

• 9 9 9

9 9 9

- 54 99 9 * 9 9

9 9 9

9 99

9 9

9,999

9 9 · • * 99

99

Other suitable antifoam compounds are, for example, high molecular weight fatty esters (e.g. triglycerides of fatty acids), esters of fatty acids and monohydric alcohols, aliphatic C] g_24 ketones (e.g. stearone),

N-alkylaminotriazines such as tri- to hexaalkylmelamines or di- to tetraalkyldiamine chlorotriazines formed by the reaction of cyanuric chloride with two or three moles of a primary or secondary C]_24 amine, propylene oxide, bis(stearyl)amide and monostearyl phosphate (e.g. sodium, potassium, lithium) and phosphate esters.

Preferred antifoam systems contain (a) an antifoam compound, preferably siliceous, most preferably a combination of siliceous compounds containing (i) 50 to 99% by weight, preferably 75 to 95% by weight.

polydimethylsiloxane (due to the weight of siliceous antifoam components); and (ii) 1 to 50% by weight, preferably 5 to 25% by weight. silicon (due to the weight of siliceous antifoam components);

whereby siliceous antifoam components make up 5 to 50% by weight, preferably 10 to 40% by weight. preparation;

(b) a dispersion compound, most preferably containing a silicone glycol rake copolymer containing 72 to 78% by weight. polyoxyalkylene and with a ratio of ethylene oxide to propylene oxide in the range of 1:0.9 to 1:1.1 in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight; a very preferred silicone glycol rake copolymer of this type is commercially available DCO544 (DOW Corning);

- 55 ·· · • · · • · · · • ····· • · · ·· · ·· ·Β • · · • · ··· • · · · 9 9 • * · · ·· ·· ·· • · • 9

999 •

Β· ·· • · • ·

999 (c) an inert liquid carrier, most preferably comprising

Ci 6-18 ethoxylated alcohol with a degree of ethoxylation of 5 to 50, preferably 8 to 15 in an amount of 5 to 80% by weight, preferably 10 to 70% by weight.

Highly preferred antifoam particulate systems are described in EP-A-0 210 731 and comprise a siliceous antifoam compound and an organic carrier having a melting point in the range of 50 to 85°C, this organic carrier comprising a monoester of glycerol and a fatty acid containing C12-20 carbon string. EP-A-0 210 721 describes other advantageous particulate antifoam systems where the organic component is a C]2-20 fatty acid or alcohol or a mixture thereof with a melting point in the range of 45 to 80°C.

9

9 9 9

9999 · 9

- 56 Polymer color transfer inhibitors

The present detergent preparations or their components preferably contain 0.01 to 10% by weight, preferably 0.5 to 0.5% by weight, of polymeric color transfer inhibitors.

Polymeric color transfer inhibitors are preferably selected from the group including N-oxides of polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or their combinations, the polymers can also be cross-linked.

a) Polyamine N-oxides of polymers

Polyamine N-oxide polymers suitable for the present use contain units of the structural formula I;

Ax (I) where P is a polymerizable unit and A is -NC(O)-, -C(O)O-, -C(O)- -O-, -S-, -N-; x is 0 or 1; R are aliphatic, ethoxylated aliphatic, aromatic or heterocyclic alicyclic groups or combinations thereof to which the NO group is attached or is part thereof.

The N-0 group is represented by the following general structures:

- 57 O (R 1 ) x -^-(R 2 ) y or

About t

-N-(Ri)x (R3)z where Rj, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z are 0 or 1 and where nitrogen is attached as an N-O group , or the N-O group is part of the defined groups. The N-O group can be part of the polymerizable unit (P), or attached to the polymer backbone, or present in both ways.

Suitable polyamine N-oxides, where N-O is part of the polymerizable unit, are N-oxides whose R is selected from the group of aliphatic, aromatic, alicyclic or heterocyclic groups. One class of these substances are polyamine N-oxides where the N-O group is part of the R group. The R group of preferred polyamine N-oxides is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and their derivatives.

Other suitable polyamine N-oxides are those in which the N-O group is attached to a polymerizable unit. A preferred class of such substances is the polyamine N-oxides of general formula I, where R is an aromatic, heterocyclic or alicyclic group, and the N-O group is part of the R group. Examples are polyamine N-oxides whose R is pyridine, pyrrole imidazole and their derivatives.

Polyamine N-oxides can be prepared with essentially any degree of polymerization. The degree of polymerization is not important if the substance has the required solubility in water and the ability to suspend dyes. The typical average molecular weight of these substances is in the range of 500 to 1,000,000.

• 4

- 58 b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Copolymers suitable for the present invention are copolymers of N-vinylpyrrolidone and N-vinylimidazole with an average molecular weight in the range of 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2.

c) Polyvinylpyrrolidone

The present detergent compositions also utilize polyvinylpyrrolidone (PVP) having an average molecular weight in the range of 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trade names PVP K-15 (viscosity molecular weight 10 000), PVP K-30 (viscosity molecular weight 40,000), PVP K-60 (viscosity molecular weight 160,000), and PVP K-90 (viscosity molecular weight 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones are available from BASF Cooperation as Sokalan HP 165 and Sokalan HP 12.

d) Poles of fault loxazolidone

The presented detergent preparations also use polyvinyloxazolidones as polymeric color transfer inhibitors. These polyvinyl oxazolidones have an average molecular weight in the range of 2,500 to 400,000.

e) Polyvinylimidazole

The presented detergent preparations also use polyvinylimidazole as a polymeric color transfer inhibitor. These polyvinylimidazoles have an average molecular weight in the range of 2,500 to 400,000.

• · · · • · · · • · · · · ·

- 59 Optically brightening substances

The presented detergent preparations or their components as optional components further contain 0.005 to 5% by weight. certain type of hydrophilic optical brighteners.

Hydrophilic optical brighteners suitable for the present invention are substances with the structural formula:

wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl and N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation, eg sodium or potassium.

Where, in the above formula, R 1 is anilino, R 2 is N-2-bishydroxyethyl and M is a sodium cation, the optical brightener is the disodium salt of 4,4'-bis[(4-anilino-6-(N-2-bis -hydroxyethyl)-s-triazin-2-yl)amino]-2,2'stilbenesulfonic acid. This brightener is commercially available under the trade name Tinopal-UNPA-GX (Ciba-Geigy Corporation). Tinopal-UNPA-GX is a preferred hydrophilic optical brightener for the present invention.

Where, in the above formula, R 1 is anilino, R 2 is N-2hydroxyethyl-N-methylamino and M is a sodium cation, the optical brightener is the disodium salt of 4,4'-bis[(4-anilino-6-(N-2 -hydroxyethyl-Nmethylamino)-s-triazin-2-yl)amino]-2,2'-stilbendi-sulfonic acid. This brightener is commercially available under the trade name 5BM-GX (Ciba-Geigy Corporation).

·« 00 » · 0

I 0 0 0 0

I · 0

0 0·

- 60 Where, in the above formula, Rf is anilino, R2 is morpholino and M is a sodium cation, the optical brightener is 4,4'-bis[(4-anilino-6morpholino-s-triazin-2-yl) sodium salt amino]-2,2'-stilbenesulfonic acids. This brightener is commercially available under the trade name TinopalAMS-GX (Ciba-Geigy Corporation).

- 61 Polymeric agent releasing particulate impurities

In the presented preparations or their components, known polymers of agents releasing particulate impurities (hereafter SRA) can be used. If the preparation contains SRAs, they are usually present in an amount of 0.01 to 10.0% by weight, typically 0.1 to 5% by weight, preferably 0.2 to 3.0% by weight, relative to the weight of the preparation.

Preferred SRAs typically contain hydrophilic segments that hydrophilize the surface of hydrophobic fibers such as polyesters and nylon, and hydrophobic segments that deposit on the hydrophobic fibers and remain on them during the wash and rinse cycle. The fibers act as an anchor for these segments and facilitate the subsequent cleaning of stains with SRA.

Preferred SRAs are oligomeric terephthalate esters, typically prepared by transesterification/oligomerization, often using a metal catalyst such as titanium alkoxide. Terephthalate esters can contain additional monomers incorporated into their structure in one, two, three, four or more positions, but a densely cross-linked structure must not be formed.

Suitable SRAs include sulfonylated products of substantially linear ester oligomers, consisting of an oligomeric ester backbone of repeating terephthalate and oxyalkylenoxy units and sulfonylated allyl end groups covalently attached to the backbone. An example of such an oligomer is provided, for example, in U.S. Pat. 4,968,451, 6/11/1990, ·· ·

4 4 * 4 4 4 ·

4 4

- 62 Scheibel JJ, Gosselink EP. The preparation of these ester oligomers involves (a) ethoxylation of allyl alcohol; (b) reacting product (a) with dimethyl terephthalate (DMT) and 1,2-propylene glycol (PG) in a two-step transesterification/oligomerization reaction; and (c) reacting product (b) with sodium pyrosulfite in water. Other SRAs include 1,2 propylene/polyoxyethylene terephthalate polyesters with non-ionically capped ends, described in U.S. Pat. 4,711,730, Dec. 8, 1987, Gosselink et al. E.g. these are substances prepared by transesterification/oligomerization reactions involving poly(ethylene glycol) methyl ether, DMT, PG and poly(ethylene glycol) (PEG). Other examples of SRAs: partially- and fully-anion-capped oligomeric esters listed in U.S. Pat. 4,721,580, 1/26/1988, Gosselink. These are, for example, oligomers from ethylene glycol (EG), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; non-ionic droplet block polyester oligomeric compounds listed in U.S. Pat. 4,702,857, 10/27/1987, Gosselink, eg oligomers of DMT, methyl (Me)-capped PEG and EG and/or PG, or combinations of DMT, EG and/or PG, (Me)-capped PEG and N-dimethyl5 -sulfoisophthalate; and anionic, especially sulfoaryl end-capped terephthalate esters from the U.S. 4,877,896, 10/31/1989, Malonado, Gosselink et al. These last oligomers are very suitable as components of conditioners for clothes and fabrics, an example is an ester preparation made from the sodium salt of sulfobenzoic acid, PG and DMT, possibly (but preferably) also containing PEG, e.g. PEG 3400.

SRAs also include; single block copolymers of ethyl terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230, Hays, 5/25/1976 and U.S. Pat. 3,893,929, Basadur 7/8/1975; cellulose derivatives such as hydroxyether cellulose polymers available as METHOCEL, Dow, C1-4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, Nicol, et al.,

28/12/1976; and methyl cellulose ethers with an average degree of methylation per unit of anhydroglucose in the range of 1.6 to 2.3 and a solution viscosity in the range of 0.80 to 1.20 g cmúsec-1 at 20°C in 2 wt.%. aqueous solution. These materials are available under the names METOLOSE SMI00 and METOLOSE SM200, which are methyl cellulose ethers manufactured by Shinetsu Kagaku Kogyo KK.

• · ·

- 63 Other classes of SRAs include: (1) nonionic terephthalates using diisocyanate polymer ester structures as linking agents, viz. U.S. 4,201,824, Villand et al., and U.S. Pat. 4,240,918, Lagasse et al:, and (2) SRA containing carboxylate end groups prepared by reaction with trimellitic anhydride, converting the terminal hydroxyl groups to trimellite esters. The formation of ester bonds between the free carboxyl group of trimellitic acid anhydride and terminal hydroxyls can be favored by a suitable choice of catalyst, against the reaction involving the opening of the anhydride. Both nonionic and anionic SRAs can be chosen as starting substances, provided they have esterifiable terminal hydroxyl groups. See U.S. 4,525,524, Tung et al.. Other classes of SRAs include (3) Urethane-type anionic terephthalate SRAs, see U.S. Pat. 4,201,824, Violland et al.

Other optional folders

Other optional ingredients suitable for the presented preparations are perfumes, dyes and fillers, the preferred filler being sodium sulfate.

Laundry detergent product with an almost neutral pH

The presented detergent preparations are effective in a wide range of pH values (e.g. 5 to 12), however, they are particularly advantageous if their composition ensures effectiveness in a washing environment with an almost neutral pH, i.e. at an initial pH of 7 to 10.5, at a concentration of 0, 1 to 2 wt.% at 20 °C. Preparations with a pH close to 7 are more favorable for enzyme stability and prevent staining. The pH of the washing solutions of these preparations is preferably in the range of 7.0 to 10.5, more preferably 8.0 to 10.5, most preferably 8.0 to 9.0.

Preferred near-neutral pH detergents are described in European Patent Application 83.200688.6, published 5/16/1983, Wertz, J.H.M and Goffinet P.C.E.

· · ♦ • » ··* «4 · · * « · · 4 «4 44

- 64 Very advantageous preparations of the mentioned type also advantageously contain 2 to 10 wt.%. citric acid and small amounts (e.g. less than 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotopes, enzymes, enzyme stabilizers, polyacids, foam regulators, opalescent agents, anti-oxidants, bactericidal agents, dyes, perfumes and brighteners , similar to that shown in U.S. Pat. 4,285,841, Barrat et al., issued 8/25/1981 (incorporated by reference).

Form of preparations

The components of the present detergents can be prepared by various methods, including dry mixing and agglomeration of the various compounds contained in the detergent component.

The detergent component is preferably part of the detergent preparation. The compositions of the present invention may take various forms, including granules, tablets, flakes, lozenges and sticks. The preparations are mainly in concentrated granular form, suitable for adding to washing machines using a device for dispersing the preparation in the washing drum with soiled textiles.

The presented preparations can also be used together with additional bleaching preparations, e.g. containing chlorine bleach.

The present granular detergent compositions can be prepared by various processes, including dry mixing, spray drying, agglomeration and granulation. The present quartemized particulate clay remover, with anti-redeposition properties, can also be added to other detergent ingredients by dry mixing, agglomeration (preferably in combination with a carrier) or as an ingredient delivered by a spray drying process.

• *

44 • · 4 • 4 · • 4 4 4 • · · · 4 • 4 4 • « ·

4 4 • · 4 4 · • · 4 ♦ • 4 « · « 4 4 4

- 65 The recommended mean particle size of the components of the granular preparation of the present invention, containing water-soluble cationic compounds for removing particulate clay impurities, with anti-redeposition properties, is such that no more than 15% by wt. of particles did not exceed a diameter of 1.8 mm and no more than 15 wt.% particles had a diameter smaller than 0.25 mm. The preferred average particle size is such that 10 to 50 wt.% of particles had a diameter in the range of 0.2 to 0.7 mm.

The average particle size is determined by sieving a sample of the preparation into several fractions (typically 5) using a series of sieves, preferably of the Tyler type. The weight of the obtained fractions is plotted on a curve against the mesh size of individual sieves. The average particle size is equal to the mesh size of the sieve through which 50% by weight passed. sample.

The total density of the granular detergent preparation of the present invention is typically at least 600 g/1, more preferably 650 to 1200 g/1. The total density is determined using a simple device consisting of a funnel and a weighing container. The funnel is firmly placed on the base and has a flap at the lower narrow end. This allows the contents of the funnel to be emptied into an axially connected measuring container below the funnel. The funnel is 130 mm high, has an internal diameter of 130 mm or 40 mm at the top and bottom. The funnel is fixed so that its lower edge is at a height of 140 mm above the base. The measuring cup has a height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

When determining the total density, the funnel is filled with the ganulate sample, the valve is opened and the measuring container is allowed to overflow. The filled container is removed and the excess loose material is removed straight along the edges, e.g. with a knife. The filled measuring container is further weighed and the obtained weight of the sample is multiplied by two. The result is the total density of the sample in g/1. Depending on the requirements, the determination can be carried out repeatedly.

0*0

- 66 Preparations in a compact solid form can be produced using suitable procedures such as tableting, briquetting or extrusion, preferably tableting. The tablet form of the preparation, suitable especially for dishwashers, is prepared on a standard rotary tablet press at a compression force of 5 to 13 kN.cm"2, more preferably 5 to 11 kN.cm2, so that the compact solid form has a minimum hardness of 176 to 275 N, preferably 195 to 245 N, measured using a Cl00 hardness test supplied by I. Holland Instruments. The procedure can be used for the preparation of homogeneous and layered tablets of any shape and size. Preferably, the tablets are symmetrical, enabling uniform dissolution in the washing solution.

Method of washing clothes

When washing clothes in washing machines according to the presented method, soiled clothes come into contact with the washing solution in the washing machine, in which an effective amount of the presented washing agent has been dissolved or dispersed

detergent intended for washing machines. An effective amount of detergent is 10 to 300 g of product dissolved or dispersed in 5 to 65 L of washing solution, as is common for washing in washing machines.

In an advantageous embodiment, a device for dispersing the preparation is used in the washing machine. This device is filled with detergent and inserted directly into the washing drum before starting the washing cycle. The device must have an adequate volume to hold a sufficient amount of detergent, usually used in the washing process.

The device for dispersing the detergent preparation is inserted into the washing drum before starting washing, before or at the same time as the laundry. When washing is started, the drum rotates periodically. The shape of the device for dispersing the preparation must be such that the preparation is kept in a dry state and released during mixing and rotation of the drum and subsequently dissolved or dispersed in the washing solution.

00

• 0 4 • 4 4 4 • 4 4 4 4

4 4 » 4 ·

♦

4 0 0 0 0 ·

0 0

- 67 In order to release the preparation, the device must have a series of holes. Alternatively, it may be made of a material permeable to liquids and impermeable to solids, then permeable to a solution of the dissolved preparation. It is advantageous if the preparation is released quickly right at the start of the wash and at this stage creates transitional zones of higher concentration in the drum.

The device for dispersing the preparation is advantageously used repeatedly and its shape does not change in dry or wet environments during washing. Apparatus for dispersing the formulation particularly advantageous for the present invention are described in the following patents: GB-B-2 157 717, GB-B-2 157 718, EPA-0 201 376, EP-A-0 288 345 and EP-A-0 288 346. An article by Bland, J„ Manufacturing Chemist, 41-46, (November 1989) also describes particularly advantageous formulation dispersing devices for granular detergent laundry preparations, commonly referred to as granulettes. Another preferred device for dispersing the formulation for the present use is described in PCT Patent Application WO94/11562.

Particularly advantageous devices for dispersing the preparation are described in EP-A-0 343 069 and 0 343 070. The second of the mentioned applications describes a device comprising a flexible sheath in the form of a bag with a defined circular mouth and of a suitable size to contain a sufficient amount of product for one washing cycle. Part of the washing solution flows through the mouth into the bag, dissolves the product and the solution leaves again through the mouth into the washing medium. The circular opening is equipped with a masking arrangement that prevents the escape of moistened, undissolved product. The masking arrangement typically includes walls arranged radially from the central ring or a similar structure of helically arranged walls.

» * · ♦ Β 9 9

9,999 · 9

9 ·

9 9 9

9 9

9 9 99

9 9 9 • 9 · ♦ · 9 9

Β Β

99

- 68 An alternative device for dispersing the preparation is a flexible container, e.g. a bag or bag. The pouch has a fibrous construction coated with an impermeable protective material to retain the contents as disclosed in EP-A-0 018 678. Alternatively, it may be formed of a water-insoluble synthetic polymeric material that includes sharp embossing or water-rupturing closures as disclosed in EP-A -0 011 500, 0 011 501, 0 011 502 and 0 011 968. A convenient form of such a closure that opens under the influence of an aqueous environment is, for example, a bag made of a water-insoluble polymer film such as polyethylene or polypropylene, the mouth of which is sealed with a water-soluble adhesive.

Method of washing dishes in a dishwasher

Any method of washing dishes in a dishwasher is suitable for the present invention, especially silver dishes.

A preferred method of washing dishes in a dishwasher includes washing dirty dishes such as porcelain, glass, hollow containers, silverware and cutlery and their mixture, with an aqueous solution or dispersion containing an effective amount of the dishwasher preparation according to the present invention. An effective amount of the dishwashing composition is 8 to 60 g of the composition dissolved or dispersed in 3 to 10 l washing solution as commonly recommended for dishwashing procedures in a dishwasher.

Adjustment of products into packaging

Commercial bleaching products are sold in a variety of suitable packaging, made from papim, cardboard, plastics and suitable laminates. A preferred packaging is described in EP-A-94 921 505.7.

Examples of embodiments of the invention

Abbreviations used in the examples:

- 69 The abbreviations of the names of the ingredients of detergent preparations have the following meaning:

LAS: Linear C12 sodium alkylbenzene sulfonate

TAS : Sodium tallow alkyl sulfate

CxyAS : Clx“ly sodium alkyl sulfate

C46SAS : C14-16 secondary (2,3) alkyl sodium sulfate

CxyEzS : Ci _x ~iy sodium alkyl sulfate condensed from a mole of ethylene oxide

CxyEz : predominantly linear primary C} _x -] y alcohol condensed with an average of z moles of ethylene oxide

QAS : R ₂ -N + (CH ₃ )2(C ₂ H4OH), where R ₂ is C ₁₂ -14

Soap : Linear alkyl carboxylate derived from an 80/20 blend of tallow and coconut oil

CFAA: C12-14 (coco) alkyl N-methyl glucamide

TFAA: C16-18 alkyl N-methyl glucamide

TPKFA: modified C12-14 fatty acids

STPP : Sodium tripolyphosphate anhydrous

TSPP : Tetrasodium pyrophosphate

Zeolite A: Hydrated sodium aluminosilicate of general formula Nai2(AlO2SiO2)12-27H2O, with primary particle size in the range of 0.1 to 10 µm

Zeolite MAP: Hydrated sodium aluminosilicate MAP with a silicon to aluminum ratio of 1.07

NaSKS-6 : Crystalline layered silicate of general formula δNa2SÍ2O5

Citric acid: Anhydrous citric acid

Borate : Sodium borate

Carbonate : Anhydrous sodium carbonate with a particle size in the range of 200 to 900 wm

Bicarbonate: Anhydrous sodium bicarbonate with a particle size in the range of 400 to 1200 µm

- 70 Silicate : Amorphous sodium silicate (SÍ2O:Na2O 2,():l)

Sodium sulfate : Sodium sulfate anhydrous

Citrate: Trisodium citrate dihydrate with an activity of 86.4%, with a particle size in the range of 425 to 850 µm

MA/AA : A copolymer of maleic and acrylic acid (1:4) with an average molecular weight of 70,000

AA : Average molecular weight sodium polyacrylate polymer

4500

CMC : Sodium Carboxymethyl Cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650, available from Shin Etsu Chemicals

Protease: Proteolytic enzyme with an activity of 4 KNPU/g, available from NOVO Industries A/S under the trade name Savináza

Alkalase : A proteolytic enzyme with an activity of 3 AU/g, available from NOVO Industries A/S

Cellulase: A cellulolytic enzyme with an activity of lOOOCEVU/g, available from NOVO Industries A/S under the trade name Carezyme

Amylase: Amylolytic enzyme with an activity of 120 KNPU/g, available from NOVO Industries A/S under the trade name Termamyl 120 T

Lipase: A lipolytic enzyme with an activity of 100 KLU/g, available from NOVO

Industries A/S under the trade name Lipolaza

Endolase: Endoglucanase enzyme with an activity of 3000 CEVU/g, available from NOVO Industries A/S

PB4 : Sodium peroxyborate tetrahydrate of general formula

_{NaBO2.3H2O.2H2O2}

PB1 : Anhydrous sodium peroxyborate with bleaching effects of the general formula NaBO2.2H2O2

Percarbonate: Sodium percarbonate of general formula 2Na ₂ CO3.3H2O2 • 9 · • '9 9

9 9 9 • 9 9 9 9 9 · • 99 ·

9 • 9 9 • 9 9 9 9 • 9 · 9

9 9 9 ·9

9 9 9 « · 9 ·

999 99 9 • 9

9 9 9

- 71 NOBS : Nonanoyloxybenzene sulfonate sodium

TAED : Tetraacetylethylenediamine

Mn catalyst: Mn 2 ( ^m O ) 3 (N 4,7-trimethyl-1,4,7-triaza-cyclononane) 2 (PF 2 ) 2 , ^as described in US 5,246,621 and 5,244,594.

DTPA : Diethylene triamine pentaacetic acid

DTPMP : Diethylene triamine penta(methylenephosphonate), available from

Monstanto under the trade name Dequest 2060

Photoactivated bleach: Sulfonylated zinc phthalocyanide encapsulated in a soluble dextrin polymer with whitening effects

Brightener 1 : 4,4'-bis(2-sulfostyryl)biphenyl disodium

Brightener 2 : 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazinyl)amino)stilbene 2,2'-disulfonate

HEDP : 1,1-hydroxyethane diphosphonic acid

EDDS : Ethylenediamine-N,N'-disuccinic acid

QEA 1: bis((C2H ₅ O)(C ₂ H4O) _n XCH3)-N ⁺ -C6Hi2-N ⁺ (CH3)bis((C ₂ H5O)(C2H4O) _n ) where n is 20 to 30

QEA2 : bis(( _C2H5O )( _C2H4O ) _nXCH3 )-N+-Ri where R1 is _{C4_12} alkyl and n is ₂₀ to 30

QEA3: tri{bis((C ₂ H5OXC ₂ H ₄ O) _n XCH3XCONC3H6)}·

C3H6O, n is 20 to 26

PEGX : Polyethylene glycol of molecular weight X

PEO : Polyethylene oxide with a molecular weight of 50,000

TEPAE : Tetraethylenepentamine ethoxylate

PVP : Polyvinylpyrrolidone polymer

PVNO : Polyvinylpyridine N-oxide

PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole

SRP 1 : Sulfobenzoyl and capped esters with oxyethyleneoxy and teraphthaloyl backbone ·· ·· to ·· to • · · · ··· ··« • · • · «·

- 72 · t ·· • · · · • ···· • · · «· · ·· ·· • this « · ·· · • · ·· · this this· · ·« this*

SRP 2: Diethoxylated poly(1,2-propylene teraphialate) short block polymer

Silicic antifoam agent: a mixture of polydimethylsiloxane foaming agent and siloxane-oxyalkylene copolymer as a dispersing agent in a ratio of 10:1 to 100:1

Wax: Paraffin wax

In the following examples, the weight data are given in % by weight. relative to the total weight of the product.

Example 1

The composition of highly concentrated granular laundry detergent preparations A to F, suitable for use in European washing conditions in a washing machine, according to the present invention:

AND B C D E F FOREST 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C46AS 1.0 2.0 2.5 - 3.0 4.0 C68AS 3.0 2.0 5.0 7.0 1.0 0.5 QAS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP - 4.0 3.5 - - - Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1

AA·Α

A A A A

A A A A

And AAAAAA

And A

AA AA

- 73 • A A

A A A ·

A A AAAA

AAA

AA · ·· AA

A A A

And AAAA

A A · A

A A A A » A A A

MA/AA 0.3 CMC 0.2 PB4 9.0 TAED 1.5 Mn catalyst DTPMP 0.25 HEDP 0.3 EDDS - QEA1 1.0 QEA2 - Protease 0.26 Amylase 0.1 Photoactive. bleach (ppm) 15 Brightener 1 0.09 Perfume 0.3 Silicic antifoam sl. 0.5 Various minors. (up to 100%) Density (g/l) 850

0.3 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.2 9.0 9.0 9.0 9.0 9.0 1.5 1.0 1.5 - 1.5 0.03 0.07 - - - 0.25 0.25 0.25 0.25 0.25 0.3 0.2 0.2 0.3 0.3 - 0.4 0.2 - - 0.8 0.7 1.2 - 0.5 - - - 1.0 0.5 0.26 0.26 0.26 0.26 0.26 0.1 0.4 0.3 0.1 0.1 15 15 15 15 15 0.09 0.09 0.09 0.09 0.09 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 850 850 850 850 850

4 4 4

4 4 4

444 444

4

Example 2 • 444 4 • 4 4 4 4

4 4 4

4 4 4

44

- 74 Composition of granulated laundry detergent preparations G to I, suitable for use in European washing conditions in a washing machine, according to the present invention:

FOREST G 5.25 H 5.61 AND 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25E3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 2.0 STPP 19.7 - - Zeolite A - 19.5 19.5 Zeolite MAP 2.0 - - NaSKS-6/citrate (79:21) - 10.6 10.6 Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 - - Sodium sulfate 39.8 - 14.3 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4

··· 999 • ··· * · · · * • 9 9 9 9 • · · 9 ·· 9· • · • 4 44

PB4 Peroxycarbonate 5.0 5.0 12.7 12.7 TAED 0.5 3.1 - Mn catalyst 0.04 - - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 QEA1 0.9 1.2 - QEA 2 - - 1.0 Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.4 0.1 0.1 PVP 0.9 1.3 0.8 Photoactive. bleach (ppm) 15 27 27 Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 Perfume 0.3 0.3 0.3 Silicon antifoam. sl. 0.5 2.4 2.4

Various minors. (up to 100%) • · ·

• 4

44 44

4 4 4

4 4444 4

4» 4 4 44 44 444 ···

4 4 4 4 · ·

44 44 ·· ··

- 76 Example 3

The composition of laundry detergent preparations suitable for use in European washing conditions in a washing machine, according to the present invention:

J TO L M Spray: FOREST 6.0 5.0 11.0 6.0 TAS 2.0 - - 2.0 Zeolite A - 27.0 - 20.0 STPP 24.0 - 24.0 - Sulfate 9.0 6.0 13.0 - MA/AA 2.0 4.0 6.0 4.0 Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 QEA1 0.8 1.0 1.4 0.5 QEA2 - - - 0.5 Brightener 0.2 0.2 0.2 0.2 Silicon antifoam. sl. 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Splash: C45E7 5.0 C45E2 2.5 2.5 2.0 - C45E3 2.6 2.5 2.0 - Perfume 0.3 0.3 0.3 0.2 Silicon antifoam. sl. 0.3 0.3 0.3 - Dry ingredients Sulfate 3.0 3.0 5.0 10.0 Carbonate 6.0 13.0 15.0 14.0 PB 1 - - - 1.5 PB4 18.0 18.0 10.0 18.5 TAED 3.0 2.0 - 2.0 EDDS - 2.0 2.4 - Protease 1.0 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 0.2

99 99 99

9 9 9 9 9 9

9 99 9 9 9 9 9

99 99 999 999

9 9 9 9 9

9 9 9 9 99 ·· · • · « • · 4 · • 9 9999

9 9 ·

Amylase 0.2 0.2 0.2 0.4 Photoactive. bleach - - - 0.15 In total 100 100 100 100

Example 4 • 9 9

4 9

9 9 9

9 9999 9

9 9

9

9« • 9 9

4 4*9

9 9 9

9 9 «

4 *

94

9 4 4

9 4 4 «»9,494

9 »9 99

- 78 Composition of laundry detergent preparations according to the present invention.

Preparation N is suitable for use in Japanese washing conditions in the washing machine, products O to S are machine washable. appropriate for use in the U.S. conditions ________!. _________ r. ..t-llJ·........ N 0 P Q R WITH Spray: FOREST 22.0 5.0 4.0 9.0 8.0 7.0 C45AS 7.0 7.0 6.0 - - - C46AS - 4.0 3.0 - - - C45E35 - 3.0 2.0 8.0 5.0 4.0 Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0 MA/AA 6.0 3.0 3.0 - - - AA - 3.0 3.0 2.0 3.0 3.0 Sodium sulfate 7.0 18.3 11.3 24.0 19.3 19.3 Silicate 5.0 1.0 1.0 2.0 1.0 1.0 Carbonate 28.3 9.0 7.0 25.7 8.0 6.0 QEA1 0.9 0.9 - - 0.5 1.1 QEA2 - - 0.8 1.0 - - QEA3 - - 0.4 - - - PEG 4000 0.5 1.5 1.5 1.0 1.5 1.0 Sodium oleate 2.0 - - - - - DTPA 0.4 - 0.5 - - 0.5 Brightener 0.2 0.3 0.3 0.3 0.3 0.3 Splash: C25E9 1.0 - - - - - C45E7 - 2.0 2.0 0.5 2.0 2.0 Perfume 1.0 0.3 0.3 1.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 - 5.0 5.0 FOREST - 2.0 2.0 - 2.0 2.0 Zeolite A - 7.5 7.5 - 7.5 7.5 HEDP - 1.0 - - 2.0 - Carbonate - 4.0 4.0 - 4.0 4.0

• 9 ·« ·

• · · • »··· • 9 ·· ·*» • · · • « ··· • · · · • · · · «9 ·« ·· ·· • · · · • · · · • fc· ··· 9 ·

99 ··

PEG4000 - 0.5 0.5 - 0.5 0.5 Miscellaneous (water, etc.) Dry ingredients 2.0 2.0 - 2.0 2.0 TAED 1.0 2.0 3.0 1.0 3.0 2.0 PB4 - 1.0 4.0 - 5.0 0.5 PB 1 6.0 - - - - - Peroxycarbonate - 5.0 12.5 - - - Carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.5 - 6.0 - - 0.6 Cumeme sulfonic acid. - 2.0 2.0 - 2.0 2.0 Lipase 0.4 0.4 0.4 - 0.4 0.4 Cellulase 0.1 0.2 0.2 - 0.2 0.2 Amylase 0.1 0.3 0.3 - - - Protease 1.0 0.5 0.5 0.5 0.5 0.5 PVPVI - 0.5 0.5 - - - PVP 0.5 0.5 0.5 - - - PVNO - 0.5 0.5 - - - SRP1 - 0.5 0.5 - - - Silicon antifoam. sl. - 0.2 0.2 - 0.2 0.2 In total 100 100 100 100 100 100

Example 5

- 80 Composition of laundry detergent preparations according to the present invention. Formulations W and X are suitable for use in the U.S. washing conditions in the washing machine. Product Y is very suitable for use in Japanese machine wash conditions.

T at IN Spray: Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 FOREST 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 QEA1 0.6 2.0 1.0 Carbonate 8.0 16.0 20.0 DTMP - 0.4 0.4 Splash C45E7 1.0 1.0 1.0 Dry ingredients HEDP 1.0 - - PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.4 0.1 TAED - 6.1 4.5 PB 1 11.0 5.0 6.0 Sodium sulfate - 6.0 - Rest (moisture and miscellaneous)

- 81 Example 6

Composition of granulated detergent preparations according to the present invention suitable for use in European washing conditions in a washing machine.

W X Spray: Zeolite A 20.0 - STPP - 20.0 FOREST 6.0 6.0 C68AS 2.0 2.0 Silicate 3.0 8.0 MA/AA 4.0 2.0 CMC 0.6 0.6 QEA 1 0.9 0.6 QEA 3 0.1 - Brightener 0.2 0.2 DTPMP 0.4 0.4 Splash C45E7 5.0 5.0 Silicon antifoam. sl. 0.3 0.3 Perfume 0.2 0.2 Dry ingredients Carbonate 14.0 9.0 PB 1 L5 2.0 PB4 18.5 13.0 TAED 2.0 2.0 Photoactive. bleach (ppm) 15 15 Protease L0 1.0 Lipase 0.2 0.2 Amylase 0.4 0.4 Cellulase 0.1 0.1 Sulfate 10.0 20.0 Rest (moisture and miscellaneous) Density (g/1) 700 700

• ·

- 82 Example 7

The composition of laundry detergent preparations as presented

of the invention. "of......... ah~ Spray: Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 FOREST 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates FOREST 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 QEA1 1.0 2.5 0.6 Mn catalyst 0.03 - - Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Splash Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - - Dry ingredients Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 15.0 10.0 Peroxycarbon Read - 7.0 10.0 TAED 6.0 2.0 5.0 PB 1 14.0 7.0 10.0 EDDS - 2.0 - Polyethylene oxide m.h. - - 0.2 5,000,000 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicon antifoam. sl. 5.0 5.0 5.0 Dry ingredients Sodium sulfate 0.0 3.0 0.0 Rest (moisture and miscellaneous) 100 100 100 Density (g/l) 850 850 850

Example 8 ·· · • ·

- 84 Composition of detergent preparations according to the present invention:

FOREST BB 20.0 CC 14.0 DD 24.0 EE 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - - C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 - - STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 - - Peroxycarbonate - 5.0 9.0 15.0 DTPMP 0.7 1.0 - - QEA1 0.4 1.2 0.5 2.0 QEA2 0.4 - - - SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 - - Photoactive. bleach (ppm) 70 45 - 10 Brightener 1 0.2 0.2 0.08 0.2 PB 1 6.0 2.0 - - I-IEDP - - 2.3 - TAED 2.0 1.0 - - Rest (water and miscellaneous)

- 85 Example 9

Composition of highly concentrated (0.96 kg) detergent preparations for washing dishes FF to KK according to the present invention. Meaning of used abbreviations:

Metasilicate: Sodium metasilicate (with a ratio of SiO ₂ :Na ₂ O = 1.0)

Non-ionic component: C ₁₃ . ₁₅ mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac FF404, BASF GmbH (low-level)

PAAC: Cobalt(III) Pentaamine Acetate

PzB: Benzoyl peroxide

Paraffin: Paraffin oil sold under the trade name Winog 70,

Wintershall

BTA: Benzotriazole

Bismuth Nitrate: Bismuth Nitrate

Terpolymer: Terpolymer with an average molecular weight of 7000 containing acrylic/maleic//methacrylic acid units in a weight ratio of 60:20:20

480N: A random copolymer of acrylic/methacrylic acids with an average molecular weight of 3500

FF GG HH II JJ KK STPP 24.80 24.80 25.00 28,39 28.50 20.00 Citrate - - - - 10.00 10.00 Carbonate - - 17.50 17.50 - - QEA1 0.5 1.5 2.0 1.0 0.3 0.8 Silicate 20.36 20.36 14.81 14.81 14.81 - Metasilicate 2.50 2.50 2.50 - - - PB 1 7.79 7.79 9.74 14.28 9.74 - PB4 - - - - - 10.4 Peroxycarbonate - - - - - 6.70 Non-ionic component 1.50 1.50 2.00 1.50 2.00 2.60 TAED 2.39 2.00 2.70 2.00 3.60 4.00 HEDP 0.46 0.46 1.00 - 0.83 - DETPMP - - 0.65 - - - PAAC - - - 0.20 - - BzP - - - 4.44 - - Paraffin 0.50 0.50 0.50 0.50 - 0.20 Protease 2.20 2.20 2.20 2.20 2.00 0.50 Amylase 1.50 1.50 1.20 1.50 1.00 1.10 BTA 0.30 0.30 0.30 0.30 - - Bismuth nitrate - - 0.30 - - - Terpolymer - - - 4.00 - - 480N 2.77 2.77 6.00 - 6.67 - Sulfate 8.44 8.44 20.77 - 23,24 1.00 Miscellaneous, incl. humidity to 100% pH (1% solution) 10.90 10.90 11.00 10.80 10.90 9.60

Industrial applicability

The invention brings an industrially usable granulated detergent preparation for washing clothes in a washing machine, containing cationic compounds for removing particle impurities with anti-redeposition properties and a cellulolytic enzyme. Cellulases catalyze the removal of cellulosic materials and soften or smooth fabrics.

• · · · · · · · · 4 · ··· 4 · · 4 4 4 4

40/9-99

Claims (4)

PATENT CLAIMS A granular detergent composition or component thereof, comprising: (a) an oxygen-releasing bleach and a peroxide source; and (b) a water-soluble cationic clay soil removal composition having anti-redeposition properties selected from the group consisting of: (1) ethoxylated cationic monoamines of the general formula: R ² _r 2 _ _N + _ _L _ _X Ir ² (2) ethoxylated cationic diamines of the general formula: (R ³⁾ d R ³ L-X or (R ³ ) d R ³ II r 3 - _M 1 - R 1 - N ⁺ - R or AND L L L • 4 • 4 - 88 (R ³ ) d R ³ (XL -) ₂ "Μ ² -R ¹ - M ² " R ² R ² wherein M 1 is N ⁺ or N-group; each is an N ⁺ or N-group and at least one is an N ⁺ group; (3) ethoxylated cationic polyamines of the general formula: (R ³⁾ di R ⁴ - [(A ¹ ), - (R ⁵ ) t -M ² - I - X 1 R ² 4) mixtures thereof; wherein Al is -N (R) C (O) -, -N (R) C (O) O-, -N (R) C (O) N (R) -, -C (O) N (R) -, -OC (O) N (R) -, -C (O) O-, -OC (O) O-, -OC (O) -, -C (O) N (R) C (O) - or -O-, R is H or C 1-4 alkyl or hydroxyalkyl, R 1 is C 2-12 alkylene, hydroxvalkylene, alkenylene, arylene or alkarylene, or C 2-3 oxyalkylene containing from 2 to 20 oxyalkylene units, provided that no ON bonds are formed; each R 6 is C 1-4 alkyl or hydroxyalkyl, -LX or two R 6 together form a - (CH 2) _r -A 2 - (CH 2) _s - group, wherein A 1 is -O- or -C kQ-, r is 1 or 2 5 is 1 or 2 and r + s is 3 or 4; each R 6 is C 1-8 alkyl, hydroxyalkyl, benzyl, -LX, or two R 6 or one R 2 and one R 6 together form a - (CH 2) _r -A 2 - (CH 2) _s group R 6 is substituted C 3-42 alkyl, hydroxyalkyl, alkenyl, aryl or aralkyl containing p substituent sites; R 6 is C 1. 12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C 2-3 oxyalkylene containing from 2 to 20 44 44 44 94 · 9 · 9 4 4 449 9 44 4 . 9 4 9 4 9 4 93 44 44 44 The granular detergent composition or component thereof of claim 6, wherein the cationic compound is an ethoxylated cationic diamine, wherein R 1 is hexamethylene. A granular detergent composition or component thereof according to any one of claims 6 or 7, wherein in the cationic compound each is methyl or -LX, each R ³ is methyl and each is N ⁺ . A granular detergent composition or component thereof according to any one of claims 6 to 8, wherein zw is 0 and n is at least 12. The detergent composition or component thereof according to any one of claims 1 to 4, wherein the cationic compound is an ethoxylated cationic polyamine, wherein R 6 is substituted C 1-6 alkyl, hydroxyalkyl or aryl; is -C (O) NH-? is 3 to 6. 11. A granular detergent composition or component thereof according to claim 6 to 8, wherein m is 0 and n is at least 20. A granular detergent composition or component thereof according to any one of claims 1 to 11, characterized in that the present cationic clay soil removal particulate polymer having antiredeposition properties has a backbone, at least 2 M groups and at least one -LX group, wherein M is a cationic group attached to or integral with the backbone and contains a positively charged N ⁺ center; and L connects the groups M and X or attaches the group X to the polymer backbone; X is a nonionic group selected from the group consisting of H, C 1-4 alkyl or hydroxyalkyl ester or ether and mixtures thereof; L is a hydrophilic chain containing polyoxyalkylene groups - [(R 6 O) _m (CH 2 CH 2 O) _n ] -. The granular detergent composition or component thereof of claim 12, wherein the cationic polymer present is an ethoxylated polymer with a backbone selected from the group consisting of polyurethanes, polyesters, polyethers, polyimides, polyalkylenimines, and mixtures thereof. · Toto toto toto toto • • • • toto to to to to to to to to to to to to to to to to to · · ·· ···· · to this · ········· A granular detergent composition or component thereof according to any one of claims 1 to 13, wherein the oxygen-releasing bleach containing the hydrogen peroxide source is present in an amount of 1 to 40% by weight. relative to the weight of the preparation. A granular detergent composition or component thereof according to any one of claims 1 to 14, wherein the source of hydrogen peroxide is an inorganic perhydrate salt and is present in an amount of 2 to 30% by weight. relative to the weight of the preparation. The granular detergent composition or component thereof of claim 15, wherein the inorganic perhydrate salt is sodium percarbonate or sodium perborate. The granular detergent composition or component thereof of any one of claims 1 to 14, wherein the oxygen-relieving bleach system comprises a source of hydrogen peroxide and a peroxyacid bleach precursor. The granular detergent composition or component thereof of claim 17, wherein the peroxyacid bleach precursor is present in an amount of 1.0 to 15% by weight. relative to the weight of the preparation. A granular detergent composition or component thereof according to any one of claims 1 to 18, wherein the bleach catalyst present is selected from the group consisting of Mn ^IV 2 (µO) ₃ (1,4,7-trimethyl-1), 4,7-triazacyclononane) 2- (PF ₆ ) ₂ ; Mii ⁱⁱⁱ 2 (µO) i (µ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (ClO 4) 2; Mn ^IV 4 (µO) ₆ (1,4,7-trimethyl, 4,7-triazacyclononane) _4- (ClO ₄ ) ₂ ; Mn ⁱⁿ Mn ^IV 4 (µO) ₁ (µ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₃ ; Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ - (PF ₆ ); Co (2,2'-bispyridylamine) Cl ₂ ', di- (isothiocyanato) bispyridylamine-cobalt (II); trisdipyridylamine cobalt (II) perchlorate; Co (2,2'-bispyridylamine) 2-O ₂ ClO ₄ ; bis- (2,2'-bispyridylamine) copper (II) perchlorate; tris (di-2-pyridylamine) iron (II) perchlorate; Mn gluconate; Mn (CF ₃ SO ₃ ) ₂ ; Co (NH ₃ ) ₅ Cl; binuclear Mn complexes with tetra-Ndentátovými and bi-Ndentátovými ligands, including N ₄ Mn ^m (UO) 2mn ^IV N4 ⁺ and [Bipy2Mn ^In (UO) 2mn ^Iv bipy2] - (ClO4) 3, and mixtures thereof. - 92 • 9 9 4 4 4 0 4 4 0 4 0 · 4 4 · 4 4 · 4 4 9 99 9 9 A granular detergent composition according to any one of claims 1 to 19, wherein its composition provides a wash solution having a pH in the range of 8.0 to 10.5. 21. A granular detergent composition according to any one of claims 1 to 20 comprising a heavy ion chelator in an amount of 0.1 to 10% by weight. relative to the weight of the preparation. A granular detergent composition according to any one of claims 1 to 21 comprising a surfactant selected from the group of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. A method of washing laundry in a household, comprising adding an effective amount of a granular detergent composition according to any one of claims 1 to 22 to the drum of the washing machine, preferably before commencing the washing, and using a dispersing device that allows for progressive release of the composition into the wash solution. during washing. Use of a granular detergent composition or component thereof according to any one of claims 1 to 22 for dishwashing.