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 compositions or components thereof which contain cationic particulate soil removing compounds with anti-redeposition properties and an oxygen-releasing bleach. The compositions are useful in laundry and dishwashing.

State of the art

A very important property of a detergent composition is its ability to remove particulate type of soil from various fabrics during washing. The most important particulate type of soil is clay soil. Clay particles usually contain negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) located between and holding these layers firmly together.

A number of model compounds can be proposed that can remove particulate type of pollution. A model of such a compound must meet two basic characteristics. The first property is the ability of the compound to adsorb onto the 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 allowing its removal by washing with water.

In addition to removing dirt, another requirement of a washing machine is

cycle the need to keep loosened soil in suspension. Soil loosened from fabrics and suspended in the wash solution can redeposit on the surface of fabrics. This redeposited soil causes graying of fabrics, which is particularly visible on white fabrics. This deficiency can be reduced by the use of anti-redeposition agents in the detergent composition.

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

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

U.S. 4,659,802 and U.S. 4,664,848 describe quaternized amines for removing particulate soil with anti-redeposition properties that can be used in combination with anionic surfactants.

A model of a positively charged compound with anti-redeposition properties has been created. Adsorption of a positively charged compound onto the surface of clay particles in a washing solution gives these particles the dispersion properties of their own molecule. The more molecules adsorbed onto the clay particles, the better these particles are coated with a hydrophilic layer of ethoxyl units. The hydrophilically coated clay particle thus no longer deposits back onto the fabric (especially hydrophobic polyesters) during the washing cycle.

Another ingredient traditionally used in detergent preparations is bleach, which removes bleachable stains and dirt from fabrics, for example, 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. In other words, not all detergent components are compatible with bleach.

In the present invention, it has been found that cationic (partially) quaternized ethoxylated (poly)amines with anti-redeposition properties are fully compatible with oxygen-releasing bleaches. The overall cleaning and/or bleaching performance of a detergent composition or its components containing cationic quaternized ethoxylated (poly)amines and bleach is improved because bleachable stains are more effectively removed from fabrics.

Furthermore, it has also been found that the use of oxygen-releasing bleach in detergent compositions 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 whitening effects in combination with bleach.

Without wishing to be bound by theory, the following explanation can be given for the bleach compatibility of cationic, quaternized ethoxylated (poly)amines. The quaternization of the nitrogen groups in these molecules serves a dual purpose. It provides the molecule with a cationic charge that increases its adsorption capacity to clay particles present on the fabric and in the wash solution, and it removes an oxidizable lone 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 disclosure are incorporated by reference in their relevant parts.

The essence of the invention

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

Specifically, the present invention relates to granular detergent compositions and their components comprising:

(a) an oxygen-releasing bleach with a hydrogen peroxide source (b) a water-soluble cationic particulate soil removal 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 M 1 is an N ⁺ or N-group; each is an N ⁺ or N-group and at least one is a group containing N ⁺ ;

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) mixtures thereof; 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 C1-12 alkyl or hydroxyalkyl, R1 is C2-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 oxyalkylene units provided that ON bonds are not formed; each ^R2 is C1-4 alkyl or hydroxyalkyl, a group -LX or two ^R2 together form a group (CH2) ^rA2- (CH2) _s5 where ^A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r+s is 3 or 4; each R^ is C1-8 alkyl, hydroxyalkyl, benzyl, a group -LX, or two R^ or one

R ² and one R^ together form the group -(CH2)rA ² -(CH2)sS R^ is a substituted C3-42 alkyl, hydroxyalkyl, alkenyl, aryl or aralkyl containing p substitution sites; R^ is C}-j2 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 oxyalkylene units provided that no 0-0 or ON bonds are formed; X is a nonionic group selected from the group consisting of H, C{-4 alkyl or hydroxyalkyl ester or ether and mixtures thereof; L is a hydrophobic chain containing a polyoxyalkylene group -[(R6O) _m (CH2CH2O) _n ]-; where R^ is C3-4 alkylene or hydroxyalkylene and aman are the numbers of these groups satisfying the requirement that 50 wt. % of this group consists of polyoxyalkylene units; d is 1 when M ² is N ⁺ and 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 with the proviso that t is 1 when 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 essential feature of the present invention is a water-soluble cationic particulate soil removal compound with anti-redeposition properties, selected from the group consisting of 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, based on the weight of the detergent composition.

Cationic amines

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

In the general formulas of cationic amines given above, R1 may be branched (e.g.

_ CH ₂ —CH c ₃ cyclic (e.g.

CH ₃ i

CH_CH phenyl), or most preferably linear (e.g. -CH2CH2-, -CH2CH2CH2-), alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. For ethoxylated cationic diamines, R1 is preferably C2-6 alkylene. Each is preferably methyl or a group -L-X; each R1 is preferably C1-4 alkyl or hydroxylalkyl and most preferably methyl.

The positive charge of the N ⁺ group is balanced by an appropriate number of counterions. Suitable counterions are Cl, Br ^- , SO 3 2 - , PO 2 2 - , Me0 SO 3 , 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 above general formulas, the hydrophilic chain L usually contains exclusively polyoxyalkylene groups -[(R6O) _/w (CH2CH2O) _w ]-. The -(R6O) _m - and -(CH2CH2O) _n - groups of the polyoxyalkylene may be mixed, or preferably form blocks of -(R6()) _m - and -(CH2CH2O) n - groups.

-(CH2CH2O) _n -. R6 is preferably C3II5 (propylene); m is 0 to 5, most preferably 0, i.e. the polyoxyalkylenes are formed only by groups ·· · ·9 99 99 99

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 constitutes at least 85% by weight of the polyoxyalkylene and most preferably 100% by weight of the polyoxyalkylene (m is O).

In the above general formulas for cationic diamines and polyamines, a 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 n are as defined above, a is 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene, ) b is 1 or 0. In preferred cationic monoamines (bO), n is preferably at least 16, typically 20 to 35. In 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 3-8 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. When R4 is substituted aryl or aralkyl, q is preferably 1 and R4 is preferably C2-3 alkylene. When R4 is substituted alkyl, hydroxyalkyl or alkenyl and q is 0, R4 is preferably C2-3 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 -)-NH2 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 essential feature of the detergent composition 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 composition. It includes, for example, inorganic perhydrate bleaches as well as 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 oxygen-releasing bleach to 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 comprises a source of hydrogen peroxide and a peroxyacid bleach precursor. The peroxyacid is formed in situ by reaction of the precursor with the source of hydrogen peroxide. Preferred sources of hydrogen peroxide are inorganic perhydrate bleaches.

Silicates are used as stabilizers for the granular detergent compositions of the present invention (containing oxygen-releasing bleaches). Alkali metal silicates with a _SiO2 : _Na2O ("R") ratio of 1.6:1 to 3.2:1 are particularly suitable. Silicates not meeting this definition may also be used but are less preferred. Sodium silicates are typically used, but the inclusion of magnesium further enhances the stability of the overall composition, as explained in more detail below. It is also possible to prepare the magnesium form in situ by adding a magnesium salt and sodium silicate to the detergent particles (e.g., during a spray drying operation of the particles). A suitable magnesium salt is, for example, magnesium sulfate or magnesium chloride. Suitable silicates for the present compositions are sodium silicate solution 1.6 R, solid sodium silicate 2.0 R or solid sodium silicate 3.2 R, 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 salts, and constitute 1 to 40% by weight, more preferably 2 to 30% by weight, most preferably 5 to 20% by weight of the composition.

• 4

- 11 • 4 4 « 4 · • 4 · 4

4 44» • · 4 • 4 · ·· ·« ř · 4 » 4 4 4 4

I 4 4 fl ··

Examples of inorganic perhydrate salts are perborate, percarbonate, perphosphate, persulfate and persilicate. Inorganic perhydrate salts are usually alkali metal salts. They are added to the composition in crystalline form without further protection. However, for some perhydrate salts it is more convenient to include them in a coated form in a granular detergent composition, which improves the storage stability of the granular product.

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

The preferred perhydrate of the present invention is sodium percarbonate, a compound of the general formula 2Na2CO3.3H2O2 ₅ commercially available in crystalline form. The percarbonate is preferably used in a coated form in the detergent composition, which increases the stability of the product.

A suitable coating material which increases the stability of the product is a mixed salt of a water-soluble sulphate and an alkali metal carbonate. These coatings and methods of coating are disclosed in GB-1 466 799. The weight ratio of the mixed salt to the inorganic perhydrate is in the range of 1:200 to 1:4, more preferably 1:99 to 1:9 and most preferably 1:49 to 1:19. Preferred mixed salts are those 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.

Other coating materials, e.g., those containing silicates (alone or in admixture with borates, boric acid, and other inorganic materials), waxes, oils, and fatty soaps, may be advantageously used in the present compositions.

Another perhydrate salt useful in the present compositions 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 constitutes 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, most preferably 1.5 to 10% by weight of the composition.

A suitable peroxyacid bleach precursor typically contains one or more N- or O-acyl groups and can be selected from a variety of compound types. Suitable compound types include 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 context of the present invention, any lactam may be used as a bleach precursor, but caprolactams and valerolactams are more preferred.

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 6-12 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 /

CH 2 where R ¹ is H, C _1-2 alkyl, aryl, alkoxyaryl or alkaryl, preferably _{C 6-12} . R 1 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, C _1-2 alkyl, aryl, alkoxyaryl or alkaryl, preferably _{C 6-12 .} R 1 is most preferably selected from the group consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylphenyl, decenyl and mixtures thereof.

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

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

bleaches particularly effective in cleaning beverage stains. Mixtures of hydrophobic and hydrophilic caprolactams and valerolactams suitable for the present compositions 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, 3,5,5-trimethylhexanoyl 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 caprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, t-butylbenzoyl caprolactam, t-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, ethoxybenzoyl valerolactam, propoxybenzoyl caprolactam, propoxybenzoyl valerolactam, isopropoxybenzoyl caprolactam, isopropoxybenzoyl valerolactam, butoxybenzoyl caprolactam, butoxybenzoyl valerolactam, t-butoxybenzoyl caprolactam, t-Butoxybenzoyl valerolactam, 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 their mixtures.

Precursor of perbenzoic acid

Any perbenzoic acid precursors are suitable for the present purposes, 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 products of benzoylation of sorbitol, glucose and other carbohydrates, including e.g.:

Ac = COCH ₃ ; Bz = Benzoyl

Preferred precursors of perbenzoic acid of the imide type 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-benzoylbenzimidayol 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 precursor of perbenzoic acid 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 molecule of a suitable peroxyacid precursor, e.g., ammonium or alkyl ammonium, preferably ethyl or methyl ammonium.

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 precursors of cationic peroxyacids include various ammonium or alkylammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acyl caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

A preferred cationic substituted benzoyl oxybenzene sulfonate is the 4(trimethyl ammonium)methyl derivative of benzoyl oxybenzene sulfonate:

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

Preferred cationic peroxyacid precursors 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 salt of (2Ν,Ν,Ν-trimethylammonium) ethyl 4-sulfophenyl carbonate chloride. Precursors of bleaching alkylperoxycarboxylic fatty acids «· » • · 4 • ·

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

Preferred precursors of alkyl peroxycarboxylic acids are imide-type compounds such as N,N,N^N^-tetraacetylated C1-6 alkylene diamines, especially C1, C2 and C5 alkylenes. Tetraacetylethylenediamine (TAED) is particularly preferred.

4 4 » 4 4 1

- 19 Organic peroxyacids

The present detergent compositions contain as a further component an organic peroxyacid-based oxygen-releasing bleach, typically in an amount of 1 to 15% by weight, more preferably 1 to 10% by weight, based on the weight of the composition.

Cationic polymers

The detergent compositions and their components optionally further comprise additional polymeric cationic ethoxylated amino compounds with particulate soil removal and anti-redeposition properties selected from the group consisting of water-soluble cationic polymers. These polymers have a polymer backbone, at least 2M groups and at least one L-X group, where M is a cationic group attached 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.

The polymeric cationic ethoxylated amino compounds are present in the compositions 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, based on the weight of the detergent composition.

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

The term "linked to" used means that the group is attached to the polymer backbone, e.g., due to, which are represented by the following structural formulas A and B:

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

- 20 M ML ί Á i

(A) (B)

The term integral part is used to mean 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 is water soluble, removes particulate contaminants, and has anti-redeposition properties. Suitable polymer backbones can be derived from polymers such as polyurethanes, polyesters, polyethers, polyamides, polyimides, and the like; polyacrylates, polyacrylamides, polyvinyl ethers, polyethylenes, polypropylenes, and similar polyalkylenes, polystyrenes, and similar polyalkarylenes, polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridines, polyaminotriazoles, polyvinyl alcohol, aminopolyurethanes, and mixtures thereof.

M is any compatible cationic group containing an N ⁺ (quaternary) positively charged center. Quaternary, positively charged centers are 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 M groups contain a quaternary center represented by structure E. The cationic group is preferably an integral part of the polymer backbone, or at least located in close proximity thereto.

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

The units containing the groups M and L-X comprise 100% by weight of the cationic polymers of the present invention. However, it is permissible that

44

4 4 4

4 4 4 • 9 ·4

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

The groups M and L-X are each usually present in an amount of 2 to 200. Typically in an amount of 3 to 100. Preferably in an amount of 3 to 40.

In addition to the groups connecting the groups M and X and linking them to the polymer backbone, the hydrophilic chain L contains exclusively polyoxyalkylene units -[(ROj^CL^Cí^O)^]-. The groups -(R'O) _W - and -(CI-^CH^O)^- may be mixed or preferably form blocks -(R'O) _WZ - and -(CH2CH2O) _w -. R' is preferably ΟβΙΙβ (propylene); m is preferably up to 5, most preferably 0 (i.e. the polyoxyalkylene is formed exclusively by units -(CI^CIIýO)//-. The units -(CH2CH2O) _W - preferably constitute 85 wt.

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

Several (2 or more) -L-X groups can also be linked together and attached to the M group, or directly to the polymer backbone, as shown for example 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

to Her (G) (H)

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

Representative classes of cationic polymers are:

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

A 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 C1-4 alkyl or hydroxyalkyl; R1 is C2-12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 oxyalkylene units provided that A1 does not contain 0-0 or ON bonds; if X is 1, then ^R2 is ^-R5 - except when ^AJ is -C(O)-, or -( ^OR8 )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 A A A A A A

A A

AA AA

- 25 -OR\ provided that it does not contain 0-0 or O-N bonds and R3 is -R5except 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-, -C(O)R\ -N(R)C(O)R5-, -N(R)C(0)OR5-, -C(0)N(R)R5- or -OC(O)N(R)R5, and R³is -R5-; r4 is C1-4 alkyl or hydroxyalkyl or the group -(R4)k [(C3H6O)m(CH2CH2O)n]-X; R³is 0Η2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R6 is C1-4 alkyl or hydroxyalkyl or a group -(CH₂)_r-A2-(CH₂)_with-, where A^ is -O- or -CH₂-; R? is H or R^; r8 j_EC₂_3 alkylene or hydroxyalkylene; X is H, -C(O)R9, r9 or a mixture thereof, where R^ is C1_4 alkyl or hydroxyalkyl; k is O or 1; m and n satisfy the requirement that the group -[(C3H6O)_m(CH₂CH₂O)_nj- constituted 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 contain at least 2 N+ centers and at least 2 X groups.

·· 99 • · · 9

9 9 4 ··

9

99

- 26 In the above formulas, it is 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. -CH2-CH2-CH2-, _-CH2- CH(phenyl)-) or branched (e.g. ( _-CH2 -CH( _CH3 )-, -CH( _CH3 )-CH(phenyl)-), alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; where Rl is C2-3 oxyalkylene the number of oxyalkylene units is preferably 2 to 12; Rl is preferably C2-6 alkylene or phenylene, most preferably C2-6 alkylene (e.g. ethylene, propylene, hexamethylene). R^ is preferably OR^ or -(OR^)y; R^ is preferably -R^O- or -(OR^jy; R^ and R6 are preferably methyl. Similarly to Rl, R^ is linear or branched, preferably _C2-3 alkylene; R^ is preferably H or Cj- ₃ alkyl; R& is preferably ethylene;

R9 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 when 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 BB ·· BB BB

- 27 B. Polyacrylates, Polyacrylamides, Polyvinyl ether or similar polymers.

A 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)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 C]_4 alkyl or hydroxyalkyl; is substituted C2-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C2-3 oxyalkylene; each R^ is Cj_i2 alkylene, hydroxyalkylene, alkenyl ene, 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 -O- or -CH2-; each R4 is Cj_4 alkyl or hydroxyalkyl, or two R^ together form the group -(CH2) _r -A2-(CH2) _s -; X is H, -C(O)R5, r5 or a mixture thereof, where R^ is Cj_4 alkyl or hydroxyalkyl; j is 1 or 0; k is 1 or 0; m and a are chosen such that the group -(CH2CH2O) _n - constitutes at least 85 wt. % of 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 are 3 or 4; the number of u, v and w satisfies the requirement that the molecule contains 2 N+ centers and 2 X groups.

In the above formulas, A^ 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 C2-3 alkylene, each R^ and R^ are preferably methyl; R^ 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 those for polyurethanes and similar polymers.

C. Polyalkyleneamines, Polyalkyleneimines or similar polymers

A class of cationic polymers of the present invention derived from polyalkyleneamines, polyalkyleneimines, and the like. 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 Rl is C2-12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 units provided that ON bonds are not formed; each R2 is C]_4 alkyl or hydroxyalkyl or the group -(R ³ )k-[( ^c 3H5O) _m (CH2CH2O) _n ]-X; R ³ is C1_i2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an 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^ is C}_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 ae is 1 if M' is N; k is 1 or 0; m and a are chosen such that the group -(CH2CH2O) _n - constitutes at least 85 wt. % of the group -[(C3H6O) _m (CH2CH2O) _n ]~; m is 0 to 5; n is at least 3; the number of x, z and a satisfies the requirement that the molecule contains at least 2 M' groups, 2 N+ centers and 2 X groups.

In the above formulas, R1 varies similarly to RJ for polyurethanes and similar polymers; each R1 is preferably methyl or the group -( ^R3 )k-[( _C3H6O ) _m (CH2CH2O) _n ]-X; ^R3 is preferably C2-3 alkylene; R4 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 when the number of M' and X groups is 2 or 3; most preferably at least 2, typically in the range of 12 to 42 for all ranges of x+y+z. 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, x+y+z is at least 10, preferably 10 to 42. For both short and long chain polymers, the 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 polyalkyleneimines (x+y+z is at least 10, preferably 10 to 42). Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are polyethyleneamines (PEA) and polyethyleneimines (PEI). These preferred cationic polymers are formed from 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), M', X, d, x, y, and z are as defined above; a is 1 or 0.

Before ethoxylation, the PEA used for the preparation of 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 center for subsequent ethoxylation. For preferred PEAs, x+y+z is in the range of 3 to 7 (molecular weight 140 to 310). These PEAs can be obtained by reacting ammonia with dichloroethane and subsequent fractional 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, can no longer be separated by distillation as related derived mixtures and possibly also 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, published May 14, 1957, dealing with the preparation of PEA.

The minimum degree of ethoxylation required for the advantageous properties of the polymer (i.e., particulate fouling removal with anti-redeposition properties) varies with the number of units forming the PEA. Where y+z is 2 or 3, n is preferably at least 6. Where y+z is 4 to 9, advantageous properties are obtained 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 represents at least 10 units. Preferred PEIs used to prepare 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 correspond to the intended molecular weight of the prepared polymer. Both straight and branched polymer backbones 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:

-CH2CH2-NH2 30% -CH2CH2-NH- 40% -CH ₂ CH ₂ -N- 30%

• 0 • · · · · • ·

- 34 Each hydrogen atom bonded to the nitrogen of PEI 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 preparation procedures are given in U.S. 2,182,306, Ulrich et al, published December 5, 1939; U.S. 3,033,746, Mayle et al, published May 8, 1962; U.S. 2,208,095, Esselmann et al, published July 16, 1940; U.S. 2,806,839, Crowther, published September 17, 1957; and U.S. 2,533,696, Wilson, published May 21, 1951 (all documents cited in references).

As defined for the above formulas, n is at least 3 for cationic PEIs. It should be noted, however, that the minimum degree of ethoxylation required for the advantageous properties of the polymer (i.e., particulate fouling removal with anti-redeposition properties) can increase the molecular weight of the PEI well above 1800. The degree of ethoxylation also increases with increasing molecular weight of the PEI. For PEIs of molecular weight at least 600, n is preferably at least 12, typically 12 to 42. For PEIs of molecular weight 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 formed by units selected from units of general formulae X and XI:

·

4 (CH ₂ ) _y (CH ₂ ) (X) (CH ₂ ) _x

N>

/ \

R ¹ (R ² )k— [(C ₃ H6O), _and (CH ₂ CH ₂ O)»4_ X (CH ₂ ) _y (CH ₂ ) (Xi) (CH ₂ )x-

hydroxyalkyl, or R ² is Cj_i2 where Rl is Cj_4 alkyl or -(R2) _k -[(C ₃ H ₆ O) _m (CH2CH ₂ O) _n ]-X; hydroxyalkylene, alkenylene, arylene or alkarylene; each R^ is C]_4 alkyl or hydroxyalkyl or together form the group -(CH2) _r -A2-(CH2) _s -; where A is -O- or -CH2-; X is H, -C(O)R4, r4 or a mixture thereof, where R4 is Cj_4 alkyl or hydroxyalkyl; k is 1 or 0; and m are selected such 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 a if x is 1; the number u and v satisfies 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-; R1 is preferably methyl; each R2 is preferably C2-3 alkylene; each R3 is preferably methyl;

r4 _is preferably methyl; X is preferably H, k is preferably 0; n is preferably 0; m is preferably 0; a and r are both preferably 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 ranges of u+v. Typically v is 0 and u is 2 to 40, preferably 2 to

20.

Other ingredients of the detergent product

The detergent composition or components thereof according to the present invention optionally contain other detergent components. The precise nature of these other components and their amounts used will be determined by the physical form of the composition or component and the intended type of washing operation for which the composition is to be used.

The compositions or components of the present invention preferably contain as additional detergent components one or more substances selected from the group consisting of additional surfactants, additional bleaches, bleach catalysts, alkalinity control systems, builders, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds reducers, calcium soap dispersants, additional particulate soil suspending agents and anti-redeposition agents, perfumes and corrosion inhibitors.

Other surfactants

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

A typical collection of such anionic, nonionic, ampholytic, and zwitterionic classes and types of surfactants is disclosed in U.S. 3,929,678, Lauglin, Heuring, December 30, 1975. Other examples

0 · · • · · • « • « • ·

- 37 are listed in Surface Active Agents and Detergents (Vols. I and II, Schwarz, Pěny, Berch). A collection of suitable cationic surfactants is listed in U.S. 4,259,217, Murphy, March 31, 1981.

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

Anionic surfactants

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

Other anionic surfactants are isethionates such as acyl isethionates, N-acyl taurates, methyl tauride 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.

Suitable are acid resins and hydrogenated acid resins such as rosin, hydrogenated rosin, and acid resins and hydrogenated acid resins derived from tallow oil or derivatives thereof.

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-(C1-4 alkyl) and -N-(C1-2 hydroxyalkyl) glucamine sulfates, and alkyl polysaccharide sulfates such as alkyl polyglucoside sulfates (the aforementioned nonionic non-sulfonylated compounds).

• 4 • 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 C 1-9-43 alkyl sulfates, more preferably from branched C 1-45 alkyl sulfates and linear C 12-14 alkyl sulfates.

Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C10-18 alkyl sulfates which have been ethoxylated with 0.5 to ₁₀ moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a _C10-18 , most preferably a _{C15 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 utilizes a mixture of preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. These mixtures have been 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 alkylbenzene sulfonates, alkyl ester sulfonates, C8-22 primary or secondary alkane sulfonates, C6-24 olefin sulfonates, sulfonylated polycarboxylic acids, alkylglycerol sulfonates, (fatty acyl)glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactants

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

Suitable alkyl ethoxy carboxylates include those of the general formula RO(CH2CH2O) _x CH2COO'M ⁺ where R is C^.g alkyl, x is 0 to 10; in the case where x is 0 the amount of ethoxylate groups does not exceed 20% • · · · · · · · · · · · · · · · · · · · · · · * · · · · · · · · · » ·· 9 • ········ 99 · · 999 9 9 9

9 9 9 9 9 9 · · • · * · * * » ·· »♦

- 39 wt., M is a 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 consisting of H, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, R3 is selected from the group consisting of H, substituted or unsubstituted Cj.g hydrocarbon and mixtures thereof.

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

Sarcosinate alkali metal surfactant salt

Other suitable anionic surfactants are alkali metal salts of sarcosinates of the general formula R-CON(R1)CH2COOM where R is C5.

alkyl or alkenyl, straight or branched, R1 is C1-4 alkyl and M is an alkali metal ion. Preferred examples are sodium myristyl and oleoyl methyl sacrosinates.

Alkoxylated nonionic surfactants

Essentially any alkoxylated nonionic surfactant is suitable for the present purposes. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated nonionic surfactants are selected from the classes of nonionic alkylphenol condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated propylene glycol condensates, 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 9

- 40 Nonionic surfactant alkoxylated alcohol

Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, especially ethylene oxide and/or propylene oxide, are suitable for the present purposes. The alkyl chain of the aliphatic alcohol may 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 moles of ethylene oxide per mole of alcohol are particularly preferred.

Nonionic surfactant polyhydroxy fatty acid amide

Polyhydroxy fatty acid amides suitable for the present purposes are compounds of the structural formula R^CONRJZ where Rl is H, Cj_4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably Cj_4 alkyl, more preferably Cj_2 alkyl, most preferably methyl; and R^ is C5..31 hydrocarbon, preferably straight C5_19 alkyl or alkenyl, more preferably straight C9_47 alkyl or alkenyl, most preferably straight C1_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 those of the general formula R6cON(R7)2 where R^ is C7-21 alkyl, preferably C9-47 alkyl, each R^ is selected from the group consisting of H, C1-4 alkyl, C1-4 hydroxyalkyl and (C2fl4O) _xH , where x is 1 to 3.

Nonionic surfactant alkyl polysaccharide

Alkyl polysaccharides suitable for the present invention are disclosed in U.S. 4,565,647, Llenado, issued January 21, 1986. These materials have hydrophobic "

- a 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 mixtures thereof; 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 those of the general formula r3(OR4) _xnO (R5)2 where R^ is selected from the group of Cg_26 alkyl, hydroxy(Cg_26 alkyl), Cg_26 acylamidopropoyl and (Cg_26 alkyl)phenyl or mixtures thereof; R4 is C2-3 alkylene or hydroxy(C2-3 alkylene) or mixtures thereof; x is 0 to 5, preferably 0 to 3; each R^ is Cj_3 alkyl or hydroxyalkyl or a polyethylene oxide group formed from 1 to 3 ethylene oxide units. Preferred are Cj_18 alkyl dimethylamine oxide and Cj_0-18 acylamido alkyl dimethylamine oxide.

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

Zwitterionic surfactants

The present detergent compositions or their components optionally also contain zwitterionic surfactants. These surfactants • · 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 be generally 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')2N ⁺ R2cOO", where R is a Cg_ig hydrocarbon group, each Id is typically C1_3 alkyl and R^ is a Cj_5 hydrocarbon group. Preferred betaines are Oj2-18 dimethyl-ammonio hexanoate and Cj()_18 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 consisting preferably of

C 6-10 N-alkyl or alkenyl ammonium surfactants, where the free nitrogen valence is substituted with methyl, hydroxyethyl or hydroxypropyl.

Another suitable group of cationic surfactants useful in the present detergent compositions or components thereof are cationic ester surfactants.

Cationic ester surfactants are preferably water-dispersible compounds having surface-active properties, containing at least one ester (i.e., -COO-) linkage and at least one positively charged cationic group.

Suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in U.S. 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 (of length 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. The spacer must therefore not contain -O-O- (i.e. peroxide), -N-N- and -N-0- bonds; the bonds -CH2-O-CH2- and -CH2-NH-CH2- are permitted. It is preferred that the spacer contains only carbon atoms, the most preferred chain is hydrocarbon.

Water-soluble building components

The present detergent compositions or components thereof preferably contain water-soluble builders, 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 blocks include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts containing at least two carboxyl groups separated by no more than two carbon atoms, borates, phosphates, and mixtures thereof.

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

Suitable carboxylates containing one carboxyl group are the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxyl groups are the water-soluble salts of succinic, malonic, (ethylenedioxy)diacetic, maleic, diglycolic, tartaric, tartronic and fumaric acids, as well as ether carboxylates and sulphamyl carboxylates. Polycarboxylates containing three carboxyl groups include in particular the 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 1261869, 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 1398421 and 1398422 and in U.S. 1439000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups per molecule, especially citrates.

The corresponding 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 blocks.

Borate builders, as well as borate precursors, which form borates during detergent storage or under wash cycle conditions, are also useful water-soluble builders of the present invention.

Suitable examples of water-soluble phosphate builders 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 phytic acid salts.

Partially soluble or insoluble building components

The present detergent compositions or components thereof optionally contain partially soluble or insoluble builders, typically in an amount of 1 to 80% by weight, preferably 10 to 70% by weight, most preferably 20 to 60% by weight, based on the weight of the composition.

• ·

0 0 · 0 0 0« · 0 00 «0

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

Suitable aluminosilicate zeolites are substances of the general formula Na _z [(AlO2)z(SiO2)y].xH2O where z and 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. The 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 derived synthetically. Synthetic crystalline aluminosilicate ion exchangers are available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A is a substance with the general formula

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

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

Another preferred aluminosilicate zeolite is the zeolite building block MAP. MAP is present in an amount of 1 to 80 wt. %, more preferably 15 to 40 wt. %, based on the weight of the formulation.

Zeolite MAP is described in EP-384 070 A (Unilever). It is an alkali metal aluminosilicate of the zeolite P type, the silicon to aluminium ratio being 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.

Of particular interest is a MAP zeolite with a silicon to aluminum ratio of no higher than 1.15, preferably no 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 block MAP has particles with a size of 1.0 to 10.0 µm (expressed as d50 value), more preferably 2.7 to 7.0 µm, most preferably 2.5 to 5.0 µm.

The d50 value means that 50% by weight of the particles have a diameter smaller than the specified range. The particle size can be determined by conventional analytical methods such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods for determining d50 values are described in EP-384 070 A.

Heavy metal ion chelators

The present detergent compositions or components thereof preferably contain, as an optional component, heavy metal ion chelators. By chelator is meant 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.

Chelators of heavy metal ions are usually present in an amount of 0.005 to 20 wt. %, preferably 0.1 to 10 wt. %, more preferably 0.25 to

7.5% by weight and most preferably 0.5 to 5% by weight based on the weight of the preparation.

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

Of the above, 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, ethylenediamineglutaric acid, 2-hydroxypropylenediaminedisuccinic acid or salts thereof. Ethylenediamine-N,N'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salt, or mixtures thereof, is particularly preferred.

Other suitable heavy metal ion chelators for the present invention are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid described in EP-A-317 542 and EP-A-399 133. The chelators iminodiacetic-N-2-hydroxypropyl sulfonic acid and aspartic-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516 102 are also suitable for the present purposes. The chelators p-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-A-510 331 describes a suitable chelator derived from collagen, keratin or casein. EP-A-528 859 describes a suitable alkyl iminodiacetic acid chelator. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. 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-releasing 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 defined catalytic activity, e.g. copper, iron or manganese cations; additional cations with low or no catalytic activity such as zinc or aluminium cations, and a chelator with a defined stability constant for both the catalyst cations and the additional cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetraacetic 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. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in U.S. Patent Nos. 5,246,621 and 5,244,594. Preferred materials of this type are MnIV2(uO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIR2( ^uO )1(uOAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)2, MnR1Mn^4(uO)](u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(O104)3, and mixtures thereof. Others are described in EP 549 272. Other ligands suitable for the present invention include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-trazacyclononane, 2-methyl-1,4,7-trazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

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

Yet another type of bleach catalyst, as disclosed in U.S. Pat. No. 5,114,606, is a water-soluble complex of ^MnO3 and/or MnO4 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. 5,114,611 discloses a bleach catalyst comprising a complex of a transition metal including Mn, Co, Fe or Cu with a non-(macro)cyclic ligand. The ligand is 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 ^R3 r1-N=OBC=N-R4 where R1, R^, R ³ and r4 are selected from H, substituted alkyl and aryl such that each of the groups R1-N=C-R2 and R-^-C ^;;: N-R4 forms a five or six membered ring. This ring is optionally further substituted by 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. Highly 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 mixtures thereof.

Other examples include binuclear manganese complexes with tetra-N-dentate and bi-N-dentate ligands, including N4Mn^(uO)2Mn^N4) ⁺ and [Bipy2Mn^í(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 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalysts), U.S. 4,711,748 and European Patent Application 224,952 (manganese catalyst absorbed on aluminosilicate), U.S. 4,601,845 (aluminosilicate support with manganese, zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 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. 4,430,243 (chelate groups with manganese cations and non-catalytic metal cations) and U.S. 4,728,455 (manganese gluconate catalysts).

·· 4 • 4

- 50 The bleach catalyst is typically included in the composition in a catalytically effective amount for the processes taking place. A catalytically effective amount is a dose sufficient under any test conditions to activate the bleach and remove stains from the target substrate. The test conditions vary with the type of washing operation and the habits of the user. Some users prefer very hot water; some prefer lukewarm or even cold water for 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 composition is guided by such considerations. The recommended dose, not limiting, is such that the present compositions provide on the order of at least 1 ppm of effective bleach catalyst in the wash solution, preferably 1 to 200 ppm. A more specific illustration is, for example, on the order of 3 wmol.l! concentration of manganese catalyst at 40°C, pH 10 under European conditions using perborate and bleach precursor. In U.S. conditions, the required concentration may be 3 to 5 times higher to achieve the same result.

Enzymes

Another preferred component of the present detergent compositions or components thereof is one or more additional enzymes.

Preferred additional enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, pectinases, lactases and peroxidases, commonly used as components of detergent compositions. Suitable enzymes are discussed in U.S. 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). The proteases are typically present in the present formulation in an amount of 0.0001 to 4% by weight of active enzyme.

4

4 44

4 4 4

4 4 4

444 444

4

44

4 4« 4

Preferred amylases are, for example, α-amylases obtained from 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 names Rapidase (Gist-Brocades) and Termamyl and BAN (Novo Industries A/S). The amylases are usually present in the present preparation in an amount of 0.0001 to 2% by weight of active enzyme.

Lipolytic enzymes are usually contained in the present 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 of active enzyme.

Lipases are of fungal or bacterial origin, e.g. lipase obtained from a strain of Humicola sp., Thermomyces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipase derived 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 compositions are obtained by cloning a 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. 4,810,414, Huge-Jensen et al., ed.

7.3.1989.

Organic polymer compounds

Organic polymeric compounds are preferred additional components of the present detergent compositions or their components, being preferably present as all components having the ability to bind particulate matter.

44

4 4 4

4 4 4

444 444

4

44

44 ♦ · * • · 4 · · φ 4 4

4 4

4 44

- 52 components. The term organic polymeric compounds refers to essentially any organic polymeric compounds commonly used in detergent compositions as dispersants, anti-redeposition agents and soil suspending agents. They include high molecular weight organic polymeric compounds described as clay particle flocculants, not including the previously mentioned quaternized ethoxylated (poly)amines which have the ability to remove clay particle dirt and act as anti-redeposition agents.

Organic polymeric compounds are usually contained in the present detergent composition in an amount of 0.1 to 30 wt. %, preferably 0.5 to 15 wt. %, most preferably 1 to 10 wt. %.

Suitable organic polymeric compounds are, for example, water-soluble organic homo- or copolymeric polycarboxylic acids or salts thereof containing at least two carboxyl groups separated by not 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 and their copolymers with maleic anhydride with a molecular weight of 2000 to 100,000, 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 of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially with a molecular weight of 5000 to 10,000 d.u., are also suitable for the present invention.

Other organic polymeric 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 polymeric compounds are polyethylene glycols, especially with a molecular weight of 1000 to 10,000, preferably 2000 to 8000 and most preferably 4000.

Foam reducing agents

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

Foam suppressant systems suitable for the present invention may contain essentially any antifoam compound, including, for example, silicon antifoam compounds and 2-alkyl alkanol antifoam compounds.

The term antifoam compound refers to a compound or mixture of compounds that reduce the formation of foam or suds in a detergent composition solution, particularly during agitation.

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

Other suitable antifoaming compounds are monocarboxylic fatty acids and their soluble salts. These substances are described in U.S. 2,954,347, issued September 27, 1960, to Wayne St. John. Monocarboxylic fatty acids and their salts used as antifoaming agents 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. fatty acid triglycerides), esters of fatty acids and monohydric alcohols, aliphatic C1 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 C1-24 amine, propylene oxide, bis(stearyl)amide and monostearyl phosphate (e.g. sodium, potassium, lithium) and phosphate esters.

Preferred suds reducing agent systems comprise (a) an antifoam compound, preferably a silicon compound, most preferably a combination of silicon compounds comprising (i) 50 to 99% by weight, preferably 75 to 95% by weight.

polydimethylsiloxane (based on the weight of the silicon antifoaming components); and (ii) 1 to 50 wt.%, preferably 5 to 25 wt.% silicon (based on the weight of the silicon antifoaming components);

wherein the siliceous antifoam components constitute 5 to 50% by weight, preferably 10 to 40% by weight of the preparation;

(b) a dispersion compound, most preferably comprising a silicone glycol rake copolymer containing 72 to 78% by weight of polyoxyalkylene and having an ethylene oxide to propylene oxide ratio 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 •

B· ·· • · • ·

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 particulate foam reducing agent 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, the organic carrier comprising a monoester of glycerol and a fatty acid containing a C12-20 carbon chain. EP-A-0 210 721 describes other preferred particulate antifoam systems, wherein the organic component is a C12-20 fatty acid or alcohol or a mixture thereof having a melting point in the range of 45 to 80°C.

9

9 9 9

9999 9

- 56 Polymeric dye transfer inhibitors

The present detergent compositions or components thereof preferably contain 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight, of polymeric dye transfer inhibitors.

Polymeric dye transfer inhibitors are preferably selected from the group comprising N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, the polymers may also be crosslinked.

a) Polyamine N-oxides of polymers

Polyamine N-oxide polymers suitable for the present use contain units of 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 of.

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

- 57 O (R1)x-^-(R2)y or

About

-N-(Ri)x (R3)z where Rj, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and/or y and/or z are 0 or 1 and where the nitrogen is attached as an N-O group, or the N-O group is part of the defined groups. The N-O group may 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, where R is selected from the group of aliphatic, aromatic, alicyclic or heterocyclic groups. One class of such materials are polyamine N-oxides, where the N-O group is part of the group R. The group R of preferred polyamine N-oxides is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

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

Polyamine N-oxides can be prepared with essentially any degree of polymerization. The degree of polymerization is not important as long as the substance has the desired water solubility and dye-suspending ability. Typical average molecular weights of these substances are 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 having 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 guilt loxazolidone

The present detergent compositions also utilize polyvinyloxazolidones as polymeric dye transfer inhibitors. These polyvinyloxazolidones have an average molecular weight in the range of 2,500 to 400,000.

e) Polyvinylimidazole

The present detergent compositions also utilize polyvinylimidazole as a polymeric dye transfer inhibitor. These polyvinylimidazoles have an average molecular weight in the range of 2,500 to 400,000.

• · · · • · · · • · · · ·

- 59 Optical brighteners

The present detergent compositions or their components further contain, as optional components, 0.005 to 5% by weight of a certain type of hydrophilic optical brighteners.

Hydrophilic optical brighteners suitable for the present invention are those having the structural formula:

where R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl and N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation, e.g. sodium or potassium.

Where, in the above formula, Rj is anilino, R2 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'stilbenedisulfonic 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, R1 is anilino, R2 is N-2-hydroxyethyl-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-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic 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-6-morpholino-s-triazin-2-yl)amino]-2,2'-stilbenedisulfonic acid sodium salt. This brightener is commercially available under the trade name TinopalAMS-GX (Ciba-Geigy Corporation).

- 61 Polymeric Particulate Release Agent

Known polymeric particulate soil release agents (hereinafter referred to as SRAs) may be used in the present compositions or their components. When SRAs are present in the composition, 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, based on the weight of the composition.

Preferred SRAs typically contain hydrophilic segments that hydrophilize the surface of hydrophobic fibers such as polyesters and nylons, and hydrophobic segments that deposit on the hydrophobic fibers and remain there during the wash and rinse cycle. The fibers serve as an anchor for these segments, facilitating subsequent stain removal by the SRA.

Preferred SRAs are oligomeric terephthalate esters, typically prepared by transesterification/oligomerization, often using a metal catalyst such as titanium alkoxide. The terephthalate esters may contain additional monomers incorporated into their structure at one, two, three, four or more positions, but a densely crosslinked 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 oxyalkyleneoxy units and sulfonylated allyl end groups covalently attached to the backbone. An example of such an oligomer is disclosed, e.g., in U.S. 4,968,451, November 6, 1990, ·· ·

4 4 * 4 4 4 ·

4 4

- 62 Scheibel J.J., Gosselink E.P. The preparation of these ester oligomers involves (a) ethoxylation of allyl alcohol; (b) reaction of product (a) with dimethyl terephthalate (DMT) and 1,2-propylene glycol (PG) in a two-step transesterification/oligomerization reaction; and (c) reaction of product (b) with sodium pyrosulfite in water. Other SRAs include non-ionically end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters, described in U.S. 4,711,730, December 8, 1987, Gosselink et al. For example, these are compounds prepared by a transesterification/oligomerization reaction involving poly(ethylene glycol) methyl ether, DMT, PG, and poly(ethylene glycol) (PEG). Other examples of SRAs: oligomeric esters partially and fully anionically end-capped as disclosed in U.S. 4,721,580, Jan. 26, 1988, Gosselink. These include, for example, oligomers of ethylene glycol (EG), PG, DMT and Na-3,6-dioxa-8-hydroxyoctane sulfonate; non-ionically capped block polyester oligomeric compounds disclosed in U.S. 4,702,857, Oct. 27, 1987, Gosselink, e.g., 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-dimethyl-5-sulfoisophthalate; and anionic, especially sulfoaryl end-capped terephthalate esters disclosed in U.S. 4,702,857, Oct. 27, 1987, Gosselink. 4,877,896, October 31, 1989, Malonado, Gosselink et al. These latter oligomers are very suitable as components of fabric and laundry conditioners, an example being an ester preparation made from sodium sulfobenzoic acid, PG and DMT, optionally (but preferably) also containing PEG, e.g. PEG 3400.

SRA also include; simple copolymer blocks of ethyl terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230, Hays, May 25, 1976 and U.S. 3,893,929, Basadur, July 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 having an average degree of methylation per anhydroglucose unit in the range of 1.6 to 2.3 and a solution viscosity in the range of 0.80 to 1.20 g cm3-1 at 20°C in a 2% w/w aqueous solution. These materials are available under the designations METOLOSE SMI00 and METOLOSE SM200, which are methyl cellulose ethers manufactured by Shinetsu Kagaku Kogyo KK.

• · ·

- 63 Other classes of SRA include: (1) nonionic terephthalates utilizing diisocyanate polymer ester crosslinking agents, see U.S. 4,201,824, Villand et al., and U.S. 4,240,918, Lagasse et al., and (2) SRAs containing carboxylate end groups prepared by reaction with trimellitic anhydride to convert the terminal hydroxyl groups to trimellitic esters. By appropriate choice of catalyst, the formation of ester bonds between the free carboxyl group of trimellitic anhydride and the terminal hydroxyls can be favored over a reaction involving anhydride opening. Both nonionic and anionic SRAs can be selected as starting materials, provided that they have esterifiable terminal hydroxyl groups. See U.S. 4,525,524, Tung et al.. Other classes of SRA include (3) SRA based on anionic urethane-type terephthalates, see U.S. 4,201,824, Violland et al..

Other optional components

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

Laundry detergent with a near-neutral pH

The present detergent compositions are effective over a wide range of pH values (e.g. 5 to 12), but are particularly advantageous if their formulation provides effectiveness in a washing environment of near neutral pH, i.e. at an initial pH of 7 to 10.5, at a concentration of 0.1 to 2% by weight at 20°C. Compositions with a pH approaching 7 are more advantageous for enzyme stability and stain prevention. The pH of the washing solutions of these compositions 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 laundry detergents with a near neutral pH are described in European Patent Application 83.200688.6, published May 16, 1983, Wertz, J.H.M and Goffinet P.C.E.

· · ♦ • » ··* «4 · · * « · · 4 «4 44

- 64 Very preferred preparations of the type mentioned also preferably contain 2 to 10% by weight 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, bactericides, dyes, perfumes and brighteners, similar to those disclosed in U.S. 4,285,841, Barrat et al., issued August 25, 1981 (incorporated by reference).

Form of preparations

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

The detergent component is preferably part of a detergent composition. The compositions of the present invention may take various forms, including granules, tablets, flakes, lozenges and sticks. The compositions are particularly in concentrated granular form, suitable for addition to washing machines by means of a device for dispersing the composition in the washing drum with soiled fabrics.

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

The present granular detergent compositions can be prepared by a variety of processes, including dry blending, spray drying, agglomeration and granulation. The present quaternized particulate clay soil removal agent with anti-redeposition properties can also be added to other detergent ingredients by dry blending, 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 composition of the present invention, containing water-soluble cationic compounds for removing particulate clay contaminants, with anti-redeposition properties, is such that not more than 15% by weight of the particles do not exceed a diameter of 1.8 mm and not more than 15% by weight of the particles do not have a diameter of less than 0.25 mm. The preferred mean particle size is such that 10 to 50% by weight of the particles have a diameter in the range of 0.2 to 0.7 mm.

The mean 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 fractions obtained is plotted against the mesh size of the individual sieves. The mean particle size is equal to the mesh size of the sieve through which 50% by weight of the sample passes.

The bulk density of the granular detergent composition of the present invention is typically at least 600 g/l, more preferably 650 to 1200 g/l. The bulk density is determined using a simple device consisting of a funnel and a measuring vessel. The funnel is fixedly mounted on a base and is provided with a valve at the lower narrow end. This allows the contents of the funnel to be emptied into an axially connected measuring vessel below the funnel. The funnel is 130 mm high, has internal diameters of 130 mm and 40 mm at the top and bottom, respectively. The funnel is mounted so that its lower edge is at a height of 140 mm above the base. The measuring vessel 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 a granulate sample, the valve is opened and the measuring container is allowed to overflow. The filled container is removed and the excess bulk material is removed straight along the edges, e.g. with a knife. The filled measuring container is then weighed and the obtained sample weight is multiplied by two. The result is the total density of the sample in g/1. The determination can be performed repeatedly, as required.

0*0

- 66 Preparations in compact solid form can be produced by suitable processes such as tableting, briquetting or extrusion, preferably tableting. The tablet form of the preparation, particularly suitable 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 the Cl00 hardness test supplied by I. Holland Instruments. The process can be used to prepare homogeneous and layered tablets of any shape and size. The tablets are preferably symmetrical, allowing uniform dissolution in the washing solution.

Laundry method

When washing laundry in washing machines according to the present method, the soiled laundry is brought into contact with a washing solution in the washing machine in which an effective amount of the present washing agent has been dissolved or dispersed.

of a 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 customary for washing in washing machines.

In a preferred embodiment, a detergent dispenser is used in the washing machine. This dispenser is filled with detergent and placed directly into the washing drum before the wash cycle begins. The dispenser must be of sufficient volume to accommodate the amount of detergent typically used in the washing process.

The detergent dispersion device is placed in the washing drum before the start of the wash cycle, before or at the same time as the laundry. The drum rotates periodically during the wash cycle. The design of the detergent dispersion device must be such that the detergent is kept dry and released by the agitation 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 The device must have a series of holes for the release of the product. Alternatively, it can be made of a material permeable to liquids and impermeable to solids, then permeable to the solution of the dissolved product. It is advantageous if the product is released quickly at the beginning of the wash, creating transitional zones of higher concentration in the drum at this stage.

The composition dispersing device is preferably reusable and its shape does not change during washing in both dry and wet environments. Composition dispersing devices 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. Bland, J. Manufacturing Chemist, 41-46, (November 1989) also describes particularly advantageous composition dispersing devices for granular detergent laundry compositions, commonly referred to as granulettes. Another advantageous composition dispersing device 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 latter of the said 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 quantity of product for one wash cycle. Part of the washing solution flows through the mouth into the bag, dissolves the product and the solution exits through the mouth into the wash medium. The circular opening is provided with a masking arrangement which prevents the escape of the moistened, undissolved product. The masking arrangement typically comprises walls arranged radially from a central ring or a similar structure of helically arranged walls.

» * · ♦ B 9 9

9,999 · 9

9 ·

9 9 9

9 9

9 9 99

9 9 9 • 9 · ♦ · 9 9

B B

99

- 68 An alternative device for dispensing the preparation is a flexible container, e.g. a sachet or bag. The sachet has a fibrous structure covered 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 which contains sharp embossed points or water-bursting 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 which is opened by the influence of an aqueous environment is, for example, a sachet made of a water-insoluble polymeric film such as polyethylene or polypropylene, the mouth of which is sealed with a water-soluble adhesive.

How to wash dishes in a dishwasher

Any dishwasher cleaning process, especially silverware, is suitable for the present invention.

A preferred dishwashing process involves washing soiled dishes such as china, glass, hollowware, silverware and cutlery, and mixtures thereof, with an aqueous solution or dispersion containing an effective amount of a dishwashing composition of the present invention. An effective amount of dishwashing composition is 8 to 60 g of the composition dissolved or dispersed in 3 to 101 of washing solution, as is commonly recommended for dishwashing processes.

Adjusting products into packaging

Commercial bleaching preparations are sold in a variety of suitable packagings made from paper, 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 Abbreviations of the names of detergent ingredients have the following meanings:

LAS: Sodium linear Cj2 alkylbenzene sulfonate

TAS : Sodium tallow alkyl sulfate

CxyAS : Clx“ly sodium alkyl sulfate

C46SAS: Sodium C14-16 secondary (2,3) alkyl 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 H 4 OH), where R ₂ is C ₁₂ -14

Soap: Linear alkyl carboxylate derived from an 80/20 mixture 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 with the general formula Nai2(AlO2SiO2)l2-27H2O, with a 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 with the formula δNa2SÍ2O5

Citric acid: Anhydrous citric acid

Borate: Sodium borate

Carbonate: Anhydrous sodium carbonate with particle sizes ranging from 200 to 900 μm

Bicarbonate: Anhydrous sodium bicarbonate with particle sizes ranging from 400 to 1200 µm

- 70 Silicate: Amorphous sodium silicate (SiO:NaO 2.0:1)

Sodium sulfate : Sodium sulfate anhydrous

Citrate: Trisodium citrate dihydrate with an activity of 86.4%, with a particle size ranging from 425 to 850 µm

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

AA: Sodium polyacrylate polymer with an average molecular weight

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 Savinase

Alcalase: Proteolytic enzyme with activity of 3 AU/g, available from NOVO Industries A/S

Cellulase: Cellulolytic enzyme with activity of 1000 CFU/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: Lipolytic enzyme with an activity of 100 KLU/g, available from NOVO

Industries A/S under the trade name Lipolase

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

PB4 : Sodium peroxyborate tetrahydrate of general formula

NaBO2.3H2O.2H ₂ O2

PB1: Sodium peroxyborate anhydrous with bleaching effects, 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( ^mO )3(N4,7-trimethyl-1,4,7-triaza-cyclononane)2(PF6)2» ^As described in US 5,246,621 and 5,244,594.

DTPA : Diethylene triamine pentaacetic acid

DTPMP: Diethylene triamine penta(methylenephosphonate), available from

Monsanto under the trade name Dequest 2060

Photoactivated bleach: Sulfonated zinc phthalocyanide encapsulated in a soluble dextrin polymer with bleaching 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 terephthaloyl skeleton ·· ·· to ·· to • · · · ··· ··« • · • · «·

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

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

Silicon antifoam agent: a mixture of polydimethylsiloxane as a 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 preparation.

Example 1

Composition of highly concentrated granular laundry detergent compositions A to F, suitable for use in European machine washing conditions, according to the present invention:

A B C D E F LAS 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

A AAA AAA

A A

AA AA

- 73 • A A

A A A ·

A A AAAA

AAA

AA · ·· AA

A A A

A 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 Silicone antifoaming agent 0.5 Various minor. (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 granular laundry detergent preparations G to I, suitable for use in European machine washing conditions, according to the present invention:

LAS G 5.25 H 5.61 I 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 Percarbonate 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 Silicone antifoam. 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

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

J To L M Spray: LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2.0 Zeolite A - 27.0 - 20.0 STPP 24.0 - 24.0 - Sulphate 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 Silicone antifoam. 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray: 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 Silicone antifoam. 0.3 0.3 0.3 - Dry ingredients Sulphate 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 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 compositions according to the present invention.

Preparation N is suitable for use in Japanese washing conditions in the washing machine, preparations O to S are machine washable. suitable for use in the U.S. conditions ________!. _________ r. ..t-llJ·........ N 0 P Q R With Spray: LAS 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 Spray: 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 LAS - 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 - - - SEP1 - 0.5 0.5 - - - Silicone antifoam. - 0.2 0.2 - 0.2 0.2 Total 100 100 100 100 100 100

Example 5

- 80 Composition of laundry detergent compositions according to the present invention. Compositions W and X are suitable for use in U.S. machine washing conditions. Composition Y is very suitable for use in Japanese machine washing 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 LAS 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 Spray 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 - Residual (moisture and miscellaneous)

- 81 Example 6

Composition of granular detergent compositions according to the present invention suitable for use in European machine washing conditions.

W X Spray: Zeolite A 20.0 - STPP - 20.0 LAS 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 Spray C45E7 5.0 5.0 Silicone antifoam. 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 Sulphate 10.0 20.0 Residual (moisture and miscellaneous) Density (g/1) 700 700

• ·

- 82 Example 7

Composition of laundry detergent preparations according to the present invention

invention. "from......... a~ Spray: Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 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 LAS 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 Spray 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 Carbon Peroxide - 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 Silicone antifoam. 5.0 5.0 5.0 Dry ingredients Sodium sulfate 0.0 3.0 0.0 Residual (moisture and miscellaneous) 100 100 100 Density (g/l) 850 850 850

Example 8 ·· · • ·

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

LAS 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 - - Percarbonate - 5.0 9.0 15.0 DTPMP 0.7 1.0 - - QEA1 0.4 1.2 0.5 2.0 QEA2 0.4 - - - SEP 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 - - Í-IEDP - - 2.3 - TAED 2.0 1.0 - - The rest (water and miscellaneous)

- 85 Example 9

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

Metasilicate: Sodium metasilicate (with a ratio of _SiO2 : _Na2O = 1.0)

Nonionic 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 foaming)

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: 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 Percarbonate - - - - - 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 - Sulphate 8.44 8.44 20.77 - 23.24 1.00 Various, incl. humidity to 100% pH (1% solution) 10.90 10.90 11.00 10.80 10.90 9.60

Industrial applicability

The invention provides an industrially usable granular detergent composition for washing laundry in a washing machine, comprising cationic compounds for removing particulate soil 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 1. A granular detergent composition or component thereof, characterized in that it contains: (a) an oxygen-releasing bleach and peroxide source; and (b) a water-soluble cationic clay particulate soil removal compound with anti-redeposition properties, selected from the group consisting of: 1) ethoxylated cationic monoamines of the general formula: R ² _r 2 _ _N +_ _L _ _X Irish ² 2) ethoxylated cationic diamines of the general formula: (R ³ )d R ³ L~X or (R ³ )d R ³ II r3 - _M 1 - Rl - 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 where M 1 is an N ⁺ or N-group; each is an N ⁺ or N-group and at least one is a group containing N ⁺ ; 3) ethoxylated cationic polyamines of the general formula: (R ³ )di R ⁴ — [(A ¹ ),- (R ⁵ )t -M ² _ I - Xlp R ² 4) mixtures thereof; where A1 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 C1-4 alkyl or hydroxyalkyl, R1 is C2-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 oxyalkylene units provided that ON bonds are not formed; each R^ is C1_4 alkyl or hydroxyalkyl, a group -LX or two R^ together form a group -(CH2) _r -A2-(CH2) _s -, where A^ is -O- or -CkQ-, r is 1 or 2, 5 is 1 or 2 and r+s is 3 or 4; each R^ is C1.8 alkyl, hydroxyalkyl, benzyl, a group -LX, or two R^ or one R2 and one R^ together form a group -(CH2) _r -A2-(CH2)sS R^ is a substituted C3-42 alkyl, hydroxyalkyl, alkenyl, aryl or aralkyl containing p substitution sites; R^ is C1.12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-3 oxyalkylene containing 2 to 20 44 44 44 94 ·9· 9 4 4 9 4 4 449 9 44 4 9 4 9 4 9 4 94 44 44 44 - 90 7. A granular detergent composition or component thereof according to claim 6, characterized in that the cationic compound is an ethoxylated cationic diamine, wherein R1 is hexamethylene. 8. 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 a group -LX, each R ³ is methyl and each is a group N ⁺ . 9. A granular detergent composition or component thereof according to any one of claims 6 to 8, wherein zw is 0 and « is at least 12. 10. A 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^ is substituted C^-β alkyl, hydroxyalkyl or aryl; is -C(O)NH- and p is 3 to 6. 11. A granular detergent composition or component thereof according to claims 6 to 8, characterized in that m is 0 and n is at least 20. 12. A granular detergent composition or component thereof according to any one of claims 1 to 11, wherein the cationic clay soil removal polymer with anti-redeposition properties has a backbone, at least 2 M groups and at least one -LX group, where M is a cationic group attached to or integral to the backbone and contains a positively charged N ⁺ center; and L connects the M and X groups or attaches the X group 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 10 O) _m (CH 2 CH 2 O) _n ]-. 13. A granular detergent composition or component thereof according to claim 12, characterized in that the cationic polymer present is an ethoxylated polymer with a backbone selected from the group consisting of polyurethanes, polyesters, polyethers, polyimides, polyalkyleneimines and mixtures thereof. ·· this this ·· ·· this • this · · · · this this this • « · · · · · · · · · · · • « ···· ·· ·· ·· ··* ··· ··· ···· · this this - 91 14. A granular detergent composition or component thereof according to any one of claims 1 to 13, characterized in that the oxygen-releasing bleach comprising a source of hydrogen peroxide is present in an amount of 1 to 40% by weight based on the weight of the composition. 15. A granular detergent composition or component thereof according to any one of claims 1 to 14, characterized in that 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 composition. 16. A granular detergent composition or component thereof according to claim 15, characterized in that the inorganic perhydrate salt is sodium percarbonate or sodium perborate. 17. A granular detergent composition or component thereof according to any one of claims 1 to 14, characterized in that the oxygen-releasing bleaching system comprises a source of hydrogen peroxide and a bleaching peroxyacid precursor. 18. A granular detergent composition or component thereof according to claim 17, characterized in that the bleaching peroxyacid precursor is present in an amount of 1.0 to 15% by weight based on the weight of the composition. 19. 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(uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF ₆ ) ₂ ; Mn ^{IV iii} 2(uO)i(u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO 4 ) 2 ; Mn ^IV 4(uO) ₆ (1,4,7-trimethyl1,4,7-triazacyclononane) ₄ -(ClO ₄ ) ₂ ; Mn ⁱⁿ Mn ^IV 4(uO) ₁ (u-OAc) ₂ (l,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 C1; binuclear Mn complex with tetra-Ndentate and bi-N-dentate ligands, including N ₄ Mn ^m (uO)2Mn ^IV N4 ⁺ and [Bipy2Mn ^In (uO)2Mn ^Iv bipy2]-(ClO4)3 and mixtures thereof. - 92 • · 9 • · · • · · · • 4 4 4 0 4 4 0 4 0 ·· 4 • · · · • · 4 4 ·« 4 · ·· 4 9 99 9 9 20. A granular detergent composition according to any one of claims 1 to 19, characterized in that its composition provides a washing solution with 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, characterized in that it contains a heavy ion chelator in an amount of 0.1 to 10% by weight relative to the weight of the composition. 22. A granular detergent composition according to any one of claims 1 to 21, characterized in that it contains a surfactant selected from the group of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. 23. A method of washing laundry in a household, characterized in that an effective amount of a granular detergent composition according to any one of claims 1 to 22 is added to the drum of a washing machine, preferably before the start of the wash and using a device for dispersing the composition which allows the progressive release of the composition into the wash solution during the wash. 24. Use of a granular detergent composition or component thereof according to any one of claims 1 to 22 for dishwashing.