WO1998035005A1 - A cleaning composition - Google Patents

A cleaning composition

Info

Publication number
WO1998035005A1
WO1998035005A1 PCT/US1998/002461 US9802461W WO9835005A1 WO 1998035005 A1 WO1998035005 A1 WO 1998035005A1 US 9802461 W US9802461 W US 9802461W WO 9835005 A1 WO9835005 A1 WO 9835005A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
preferably
group
composition
alkyl
acid
Prior art date
Application number
PCT/US1998/002461
Other languages
French (fr)
Inventor
Stephen Wayne Heinzman
Barry Thomas Ingram
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3907Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3915Sulfur-containing compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3917Nitrogen-containing compounds

Abstract

The present invention relates to a cleaning composition or component thereof, comprising a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group, and an oxygen releasing bleach system, in particular systems comprising a hydrophobic peroxyacid bleaching component. The compositions or components of the invention are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and bleachable stain removal.

Description

A Cleaning Composition

Technical Field

The present invention relates to a cleaning composition or component thereof, comprising a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group, and a oxygen releasing bleach system, in particular systems comprising a hydrophobic peroxyacid bleaching component. The compositions or components of the invention are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and bleachable stain removal.

Background to the Invention

Amongst consumers there is a need for detergents which provide improved cleaning and stain removal. Different stains can have different properties. Therefore, there is a need to provide detergent compositions which contain various components which together can ensure the removal of all the different stains. Thus, in the last few years detergents have been developed which contain various types of surfactants.

It is known to use cationic surfactants in detergent compositions. For example, GB 2040990A describes granular detergent compositions comprising cationic surfactants.

Furthermore, since certain stains are bleachable, detergent manufacturers have developed bleaches, which can act on the bleachable stains selectively, thus removing the bleachable stains whilst not damaging the fabrics. One type of bleach which is particularly useful therefor is a hydrophobic bleach.

However, many detergent ingredients are not compatible with bleach. Thus, when seeking improved cleaning of both bleachable and non-bleachable stains by combining bleaches and surfactants, it is important that the surfactants are bleach compatible to get the maximum cleaning benefits. The Applicants have now found that certain cationic surfactants, containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group are very good surfactants for use in cleaning or detergent compositions, which comprise bleach. These compounds are found to be very surface active, in particular under alkaline washing conditions, and they are found to give excellent cleaning performance benefits. This is believed to be due to the compounds containing both a positively charged group and a neutral, more hydrophobic group. Furthermore, several examples of these surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds. It has also been found that the stability of the cationic surfactants is not affected by changes of the pH. The Applicants have found that these surfactants are bleach compatible and they have found that an improved non- bleachable stain removal can be achieved, whilst also an excellent bleachable stain- removal is obtained. In particular, compositions or components, comprising the cationic surfactant and a hydrophobic bleach system, have been found to provide an excellent bleachable and non-bleachable stain removal

All documents cited in the present description are, in relevant part, incorporated herein by reference.

Summary of the invention

The present invention provides a detergent or cleaning composition or component thereof comprising:

(a) at least 0.01% by weight of the composition or component, one or more cationic surfactants, comprising a quaternized ammonium group and a primary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

(b) at least 0.05% by weight of the composition or component, an oxygen - releasing bleach system. Detailed description of the invention

Cationic surfactant

The compositions or components of the invention comprise at least 0.01%) by weight of the composition or the component thereof, a cationic surfactant, which contains at least a quaternized ammonium group and a primary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

Preferred cationic surfactant of the present invention are polyamine cationic surfactants of the general formula (I):

Figure imgf000005_0001

wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from

R2-

Figure imgf000005_0002

R, θ

B— = N- and

M"

R^ c— = -N- i

R

wherein Ri , R2, R3, R4, R5, Rό* R7 and Rg are independently selected from the group consisting of C1 -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of Ri , R2, R3, R4, R5, R , 7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, R1 and R2 and R3, R4 and R5 or R and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, Ri or R2 or R3 and R4 or R5 form together with the nitrogen atoms of A and D part of a ring structure; M" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of R\ , R2 or R3 is hydrogen, or at least one B is present in which neither R5 nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.

The units B-L and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units A- L and D.

Preferably, the value of x+y is from 1 to 4. Preferably, when x+y is greater than 1, at least one of present groups A, B, C or D is a secondary or primary ammonium group.

Highly preferred cationic surfactant of the present invention are cationic surfactants of the general formula (I)

Figure imgf000006_0001

wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B or D units; x is a number from 0 to 10; and wherein the unit A is

Figure imgf000007_0001

R,

R, θ

B N~

ΪVΓ

R~

and -D comprises a primary amine group and wherein Ri , R2, R3, R4 or R- are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of R\, R2, R3, R4 or R5 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, Rjand R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M" is one or more counterions.

Figure imgf000007_0002

wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B or D units; x is a number from 0 to 10; and wherein the unit A is

Figure imgf000008_0001

R, θ

B -N-

M"

R^

and -D comprises a primary and wherein R\, R2, R3, R4 or R- are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of Ri , R2, R3, R4 or R- can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or Rj and R2, Riand R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M" is one or more counterions.

Preferably, the value of x is from 1 to 4. More preferably, x is 0.

Preferably, R\ is a Cg-Ci 4 alkyl, (poly) hydroxyalkyl or alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group, R2 and R3 are each independently C\- Cg, more preferably C1-C3 alkyl or hydroxyalkyl groups and preferably R and R5 are each independently Cj-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups.

In a further preferred alternative, R4 is preferably a Cg-Ci4 alkyl, (poly) hydroxyalkyl, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group R- is preferably a Cj-Cg, more preferably a C1 -C3 alkyl, (poly) hydroxyalkyl group and Ri , R2 and R3 are each independently preferably C^-Cg, more preferably C1-C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or aralkyl groups. When R\ and R2, R\, 2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.

L groups are independently preferably a C2~C , more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x is 0, the L group is preferably a C2 alkyl group. If group L comprises more than 2 carbon atoms, the surfactant preferably comprises at least one primary or secondary A, B, C or D group.

Examples of preferred cationic surfactants of the present invention are:

Figure imgf000009_0001

R^ CH,

Figure imgf000009_0002

R-

Figure imgf000009_0003

wherein R and ^ are as described above; R2, R3 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups; Rjo is a methyl or hydroxyethyl group; L is as described above; R\ and/or R2 are most preferably a 2-ethylhexyl group. A highly preferred cationic polyamine surfactant is of formula IV, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and R ~ are methyl groups, L is C2-C3 alkyl group.

Highly preferred cationic surfactant are those of the formulas:

i

Figure imgf000010_0001
CHo CHo CH

\

R

Figure imgf000010_0002
11

or

Figure imgf000010_0003

wherein R\ is as described above, preferably a C2-C14, preferably Cg-Ci4 linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred R groups are hydroxyalkyl groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl R\ groups have up to 9 carbon atoms, most preferably R\ is a 2- ethylhexyl group; and R\ \ is a C2-C14 alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group or a A or D unit as described above .

The anion M" is a counterion for the cationically charged surfactant. Therefore, the number of M" anions present will depend on the cationic charge of the surfactant, which depends on the groups A, B, C and D. The number of M" anions will be at least 1. A preferred counterion is a halide anion, more preferably a sulphate anion.

The cationic surfactant is generally present in the composition or component thereof in an amount no greater than 60% by weight, preferably no greater than 10% by weight, most preferably in an amount no greater than 4.5%> or even 3% by weight. The benefits of the invention are found even with very small amounts of the cationic surfactant of the invention. Generally there will be preferably at least 0.05%) or at least 0.1% by weight of the cationic surfactant in the detergent compositions of the invention.

Oxygen releasing bleaching system

An essential feature of the composition or components thereof, of the invention is at least 0.05% by weight of the composition or component thereof, an oxygen- releasing bleaching system. The oxygen-releasing bleaching system preferably contains an oxygen bleaching species including for example, inorganic perhydrate bleaches or organic peroxyacids, whereby a hydrophobic peroxyacid bleaching component or system, as described below, can be highly preferred.

In a preferred execution the bleaching system contains a hydrogen peroxide source and a peroxyacid bleach precursor compound. The production of the peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the sodium salt at a level of from 1% to 95%) by weight, more preferably from 10% to 90%> by weight and most preferably from 20% to 80% by weight of the bleaching compositions. When incorporated in a bleaching composition which is comprised in a detergent composition in accordance with the present invention, the inorganic perhydrate salts are preferably present at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the detergent composition.

Examples of inorganic perhydrate salts include perphosphate, persulfate and persilicate salts. A preferred inorganic perhydrate salt is an alkali or alkaline earth metal, preferably sodium or potassium, perborate salt. Sodium perborate can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBO2H2θ2.3H2θ. Sodium or potassium percarbonate can be a highly preferred percarbonate salt for inclusion in the compositions or components thereof, in accordance with the invention. Sodium percarbonate has a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. The perhydrate salts and in particular percarbonate, is most preferably incorporated into such compositions or components thereof in a coated form which provides in product stability.

The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilise a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB- 1,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein. Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

O

X- C -L

where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is

O X-C -OOH

The group X can be any suitable substituent group. The highly preferred hydrophobic peroxyacid precursors will have a group X which contains at least 6 carbon atoms, preferably from 8 to 25, more preferably from 9 to 15 carbon atoms.

Peroxyacid bleach precursors are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and most preferably from 1.5% to 10% by weight of the composition or at a level of from 1% to 50% by weight, more preferably from 2% to 30%> by weight, most preferably from 5% to 20% by weight of the components of the compositions.

Suitable peroxyacid bleach precursors typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes, whereby it can be preferred that the precursor contains at least one N-acyl group. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

Figure imgf000014_0001

R I 3 Y I

-O-CH= =C-CH=CH2 -O-CH=C-CH=CH2

Figure imgf000014_0002

R3 O Y

11 ' -O-C=CHR4 , and — N— S-CH— R4

X II R3 O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from

1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups

The preferred solubilizing groups are, -SO. - M + , -N + (R 3 ) .X - and O<~N(R 3 )~ and

+ + + + most preferably -SOXM and -CO2 ~M > most preferably - SOXM , -COXM > 3 wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and

X is a halide, hydroxide, methylsulfate or acetate anion.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds are also suitable herein. Typically such cationic peroxyacid precursors are formed by substituting the peroxyacid part with an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

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

Figure imgf000015_0001

A preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3-tri-methyl hexanoyloxybenzene sulfonate. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

Figure imgf000016_0001

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl fatty peroxyacid bleach precursors

Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis. Preferred precursors of this type give rise to peracetic acid on perhydrolysis.

Preferred alkyl fatty peroxyacid precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Hydrophobic peroxyacid bleaching component

For the purpose of the invention it can be highly preferred that the oxygen-releasing bleach system comprises a hydrophobic peroxyacid bleaching component or system. Namely, it has been found that compositions or components thereof comprising the cationic surfactant of the invention and a hydrophobic bleaching system, preferably a hydrophobic peroxyacid bleaching system provide an excellent bleachable and non- bleachable stain removal.

Such a hydrophobic peroxyacid bleaching component or system is capable of providing a hydrophobic peroxyacid compound. By hydrophobic organic peroxyacid compound it is meant herein an organic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 20°-50°C. Preferably, the hydrophobic peroxyacid compound comprises at least one nitrogen atom.

Preferably the hydrophobic peroxyacid bleaching component or system comprises a hydrogen peroxide source and a hydrophobic peroxyacid bleach precursor compound. Preferably, the hydrophobic peroxyacid bleach precursor compound comprises at least one nitrogen atom. The production of the hydrophobic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches as described above. In an alternative preferred execution, the hydrophobic peroxyacid bleaching component comprises a preformed hydrophobic peroxyacid, comprising at least one nitrogen atom, which is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and hydrophobic peroxyacid precursor, in combination with a preformed hydrophobic peroxyacid are also envisaged.

Preferably, the hydrophobic peroxyacid contains at least 7 carbon atoms, more preferably at least 8 carbon atoms, or even more preferably at least 9 carbon atoms most preferably at least 11 carbon atoms. In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.

Amide substituted alkyl peroxyacid precursors

Preferred peroxyacid precursors are amide substituted alkyl peroxyacid precursor compounds, including those of the following general formulae:

R — c R , 11 N N — C — R R2^ i i - -N — R2 — C —

O R5 O or R >55 O O

wherein R^ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R- is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R\ preferably contains from about 6 to 12 carbon atoms. R- preferably contains from about 4 to 8 carbon atoms. Ri may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R-. R- can include alkyl, aryl, wherein said R- may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. Rl and R~ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that Rl and R^ forms together with the nitrogen and carbon atom a ring structure.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido- caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

Figure imgf000018_0001

wherein R, is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5 carbon atoms.

N-acylated lactam precursors

Still another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class disclosed generally in GB-A-955735. Preferred materials of this class comprise the caprolactams.

Suitable caprolactam bleach precursors are of the formula: C CH CH

CH.

CH - CH-

wherein Ri is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. Preferred hydrophobic N-acyl caprolactam bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam and mixtures thereof. A most preferred is nonanoyl caprolactam.

Suitable valero lactams have the formula:

o

I !

C H . C H .

R - N

C H . C H .

wherein Ri is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, Ri is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.

Mixtures of any of the peroxyacid bleach precursor, herein before described, may also be used.

Perbenzoic acid precursor

Essentially any perbenzoic acid precursors can be suitable herein, including those of the N-acylated lactam class, which are preferred.

Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

Figure imgf000020_0001

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

Figure imgf000020_0002

Ac = COCH3; Bz = Benzoyl

Preferred perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

Figure imgf000020_0003

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

Figure imgf000021_0001

Perbenzoic acid derivative precursors

Suitable perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.

Other preferred precursors include derivatives or benzene sulfonates, preferably sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS).

Preformed organic peroxyacid

The oxygen releasing bleach system may contain, in addition to, or as an alternative to a, preferably hydrophobic organic peroxyacid bleach precursor compound, a preformed, preferably hydrophobic organic, peroxyacid Such a preformed peroxyacid is typically present at a level of from 0.05% to 20%> by weight, more preferably from 1% to 10%> by weight of the composition.

A preferred class of hydrophobic organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R1 — C — N — R2 — C — OOH

|; jj

O R5 O or

R1 — N — C — R2 C — OOH

R5 O O

wherein Ri is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R- is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Ri preferably contains from about 6 to 12 carbon atoms. R- preferably contains from about 4 to 8 carbon atoms. Ri may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R-. R^ can include alkyl, aryl, wherein said R- may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. Ri and R^ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Suitable examples of this class of agents include (6-octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. 4,483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0,170,386. A preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is monononylamido peroxycarboxylic acid.

Other suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA), diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid (PAP), nonanoylamido peroxo-adipic acid (NAPAA) and hexane sulphenoyl peroxypropionic acid and are also suitable herein.

Other suitable organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 03275, with the following general formula:

O O O O

MOCR-^ N^-C (NR2)n' ~R3HR2N)m—c (NR1)m-RCOOM wherein:

R is selected from the group consisting of Cj-C^ alkylene, C5-C12 cycloalkylene,

Cg-Cι 2 arylene and radical combinations thereof;

Ri and R- are independently selected from the group consisting of H, Ci -Cjg alkyl and Cg-Ci2 aryl radicals and a radical that can form a C3-C12 ring together with and both nitrogens; R^ is selected from the group consisting of Cj-C^ alkylene,

C5-C12 cycloalkylene and Cg-Cj2 arylene radicals; n and n' each are an integer chosen such that the sum thereof is 1 ; m and m' each are an integer chosen such that the sum thereof is 1 ; and

M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.

Other suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:

X— Ar-CO — NY — R(Z) — CO — OOH

in which X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH2)n in which n = 2 or 3, and Y and Z each represent independently a substituent selected from hydrogen or an alkyl or aryl or alkaryl group or an aryl group substituted by a compatible substituent provided that at least one of Y and Z is not hydrogen if n = 3. The substituent X on the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group comprising halogen, typically chlorine atom, or some other non-released non-interfering species such as an alkyl group, conveniently up to C6 for example a methyl, ethyl or propyl group. Alternatively, X can represent a second amido-percarboxylic acid substituent of formula:-

CO — NY — R(Z) — CO — OOH

in which R, Y, Z and n are as defined above.

MOOC-R1 CO-NR2-R3-NR4-CO-R5COOOM

wherein R^is selected from the group consisting of C1-C12 alkylene, C5-C12 cycloalkylene, Cg-Cj2 arylene and radical combinations thereof; R

It may be found to be particularly useful to mix the pre-formed peroxyacid or the peroxyacid precursor with the cationic surfactant, prior to incorporation with any other components of the detergent composition. Additional components

The detergent compositions or components thereof in accordance with the present invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component thereof, and the precise nature of the washing operation for which it is to be used.

The compositions or components thereof, of the invention preferably contain one or more additional detergent components selected from additional surfactants, builders, sequestrants, chlorine-based bleach, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.

Additional surfactant

The compositions or components thereof in accordance with the invention preferably contain an additional surfactant selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

The total amount of surfactants is preferably of from 1% to 95%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition. Anionic surfactant

The composition or components of the present invention can comprise one or more anionic surfactants. Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, «-C1 s monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cfi-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

The anionic surfactant is preferably present at a level of 0.5% to 60%, preferably at a level of from 3% to 50%, more preferably of from 5%> to 35%, most preferably from 6% to 20%) by weight of the composition.

The ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to 1 :3, more preferably from 15: 1 to 1 : 1. most preferably from 10: 1 to 1 : 1.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C9-C22 alkyl sulfates, more preferably the C^ 1-C15 branched chain alkyl sulfates and the C\ 2-C1 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CjQ-Cig alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C\ i-Cjg, most preferably Cj \-C - alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C -C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

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

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)x CH2C00"M+ wherein R is a Cg to C^g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 %> and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-O)χ-R3 wherein R is a Cg to C\~ alkyl group, x is from 1 to 25, R^ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2- propyl-1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R- CON (Ri) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Ri is a C1 -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

The nonionic surfactant is preferably present at a ratio to the anionic surfactants of the invention of from 10:1 to 1 :10, more preferably from 5:1 to 1:10, even more preferably from 1 :1 to 1:10.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxylated alcohol surfactant

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms, more preferably form 9 to 15 carbon atoms, with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONR^Z wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C\ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactants include those having the formula:

R6C0N(R7)2 wherein R^ is an alkyl group containing from 7 to 21, preferably from

9 to 17 carbon atoms and each R' is selected from the group consisting of hydrogen,

C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)xH, where x is in the range of from l to 3.

Nonionic alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R2θ(CnH2nO)t(glycosyl)x

wherein R- is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3(OR4)xNθ(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C\ Q-C\ g alkyl dimethylamine oxide, and CJO-18 acylamido alkyl dimethylamine oxide.

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

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N+R2COO" wherein R is a Cg-Cj hydrocarbyl group, each R is typically C1-C3 alkyl, and R~ is a C1-C5 hydrocarbyl group. Preferred betaines are Ci2-lg dimethyl-ammonio hexanoate and the C^Q-lg acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Additional Cationic surfactants

A suitable group of cationic surfactants which can be used in the compositions or components thereof of the invention are cationic ester surfactants.

The cationic ester surfactant is a compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.

Preferred cationic ester surfactants are water dispersible.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents Nos. 4228042, 4239660 and 4260529. Other additional cationic surfactants are mono- or bis -alkoxylated amine surfactant, the mono-alkoxylated surfactants are of the general formula:

Figure imgf000030_0001

wherein Ri is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms; R- and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.

When used in granular detergent compositions cationic mono-alkoxylated amine surfactants wherein the hydrocarbyl substituent Ri is Cg-Cj \, especially C^Q, are preferred, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.

Cationic bis-alkoxylated amine surfactants which are useful as additional cationic surfactants which have preferably the general formula:

Figure imgf000030_0002

wherein S is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms; R- is an alkyl group containing from one to three carbon atoms, preferably methyl; R- and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

The levels of the cationic mono or bis—alkoxylated amine surfactants used in detergent compositions or components of the invention can range from 0.1% to 20%>, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.

Acid Source

In particular the solid compositions or components thereof, which can be preferred compositions or components of the invention, preferably comprise an acid source, such that the acid source is capable of reacting with an alkalinity system, in the presence of water to produce a gas.

The acid source is preferably present at a level of from 0.1%) to 50%, more preferably from 0.5% to 25%, even more preferably from 1% to 12%, even more preferably from 1% to 7%, most preferably from 2% to 5% by weight of the composition. It can be preferred that the source of acidity is present in the range of about 1% to about 3%, most preferably about 3% by weight of the composition.

The acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source may be a mono-, bi- or tri- protonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, a monohydrate acidic source can be useful herein. Organic acids and their derivatives are preferred. The acid is preferably water-soluble. Suitable acids include citric, glutaric, tartaric acid, succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred. Metal containing bleach catalyst

The compositions or components thereof, of the invention can contain a metal containing bleach catalyst. Preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese containing bleach catalyst and most preferably a bi-nuclear complex of manganese or manganese gluconate.

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn^2(u"0)3(l'4,7-trimethyl-l,4,7-triazacyclononane)2- (PFg)2, Mnιπ2(u-O) 1 (u-O Ac)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)2, MnIV4(u-O)g(l,4,7-triazacyclononane)4-(Clθ4)2, MnmMnIV4(u-O)ι(u-OAc)2_ (l,4,7-trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- 1,4,7- triazacyclononane)(OCH3)3 _(PFg) .

Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:

R2 R3

R1-N=C-B-C=N-R4

wherein Rl, R-, R , and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 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), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis- (2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N- dentate ligands, including

Figure imgf000033_0001
[Bipy2MnIH(u- O)2MnIVbipy2]-(Clθ4)3.

Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)

Canadian 866,191 (transition metal-containing salts) and U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations).

Highly preferred catalyst are describedU.S. 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a peroxyacid bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.

Alkalinity

In the compositions or components of the present invention preferably an alkalinity system is present to achieve optimal cationic surfactant performance. The alkalinity system comprises components capable of providing alkalinity species in solution. Examples of alkalinity species include carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perphosphates, persulfate and persilicate. Such alkalinity species can be formed for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and percarbonate, perborates, perphosphates, persulfate and persilicate salts and any mixtures thereof are dissolved in water. Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Suitable silicates include the water soluble sodium silicates with an SiO2:NA2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2:Na2O ratio of 2.0 is the most preferred silicate.

Preferred crystalline layered silicates for use herein have the general formula

NaMSixO2χ+ι .yH2O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A- 0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE- A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na2Si2θ5, available from Hoechst AG as NaSKS-6.

Water-soluble builder compound

The compositions or components in accordance with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1%> to 80% by weight, preferably from 10%) to 70% by weight, most preferably from 20% to 60% by weight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric poly carboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Poly carboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 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 sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound

The compositions or components thereof, of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1% to 80%) by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60%> weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%), more preferably from 18%> to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na 12 [(AlO2) 12 (Siθ2)i2l. *H2O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(AlO2)gg(SiO2)i06]- 2 6 H2O.

Another preferred aluminosilicate zeolite is zeolite MAP builder.

The zeolite MAP can be present at a level of from 1%> to 80%>, more preferably from 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5ø value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A.

Heavy metal ion sequestrant

The compositions or components thereof in accordance with the present invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%>, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 - hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine terra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate. Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3 -sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N- monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-l,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'- disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzymes

The compositions or components thereof of the present invention may comprise one or more enzymes.

Preferred additional enzymatic materials include the commercially available enzymes. Said enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes in a composition according to the present invention comprises a mixture of conventional applicable enzymes such as lipase, protease, amylase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes. Suitable enzymes are exemplified in US Patents 3,519,570 and 3,533,139.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. Suitable is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 13, 1994.

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

One or a mixture of proteolytic enzymes may be incorporated in the compositions of the present invention, generally at a level of from 0.0001%> to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1 %> pure enzyme by weight of the composition.

If present in the detergent compositions of the present invention, the lipolytic enzyme component is generally present at levels of from 0.00005% to 2% of active enzyme by weight of the detergent composition, preferably 0.001% to 1% by weight, most preferably from 0.0002%) to 0.05% by weight active enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention include those produced by micro-organisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-section with the antibody of the lipase produced by the microorganism Pseudomonas Hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as Ml Lipase^- and LipomaχR (Gist-Brocades) and Lipolase^ and Lipolase Ultra^-(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use in the present invention.

Another preferred lipase for use in the present invention is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 is used.

By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 in which the native lipase ex Humicola lanuginosa has the aspartic acid (D) residue at position 96 changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L. To determine the activity of the enzyme D96L the standard LU assay may be used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity is assayed at pH 7 using pH stat. method.

The detergent compositions of the invention may also contain one or a mixture of more than one amylase enzyme (α and/or β). WO94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A S, published April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β -amylases. α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).

Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases : α-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other preferred amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostabihty and a higher activity level are described in WO95/35382.

The amylolytic enzymes if present are generally incorporated in the compositions of the present invention a level of from 0.0001% to 2%>, preferably from 0.00018% to 0.06%), more preferably from 0.00024%) to 0.048% pure enzyme by weight of the composition.

The detergent compositions of the invention may additionally incorporate one or more cellulase enzymes. Suitable cellulases include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.

Peroxidase enzymes may also be incorporated into the detergent compositions of the invention. Peroxidasis are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

Preferred enhancers are substituted phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said cellulases and/or peroxidases, if present, are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Said additional enzymes, when present, are normally incorporated in the composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition. The additional enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).

Organic polymeric compound

Organic polymeric compounds are preferred additional components of the compositions or components thereof of the present invention, and are preferably present as components of any particulate component of the detergent composition where they may act such as to bind the particulate component together. By organic polymeric compound is meant any polymeric organic compound commonly used as dispersants, anti-redeposition or soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Such an organic polymeric compound is generally incorporated in the compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB- A- 1,596,756. Examples of such salts are polyacrylic acid or polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000. Polymaleates or polymaleic acid polymers and salts thereof are also suitable examples.

Polyamino compounds useful herein include those derived from aspartic acid including polyaspartic acid and such as those disclosed in EP-A-305282, EP-A- 305283 and EP-A-351629. Terpolymers containing monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, particularly those having an average molecular weight of from 1,000 to 30,000, preferably 3,000 to 10,000, are also suitable for incoφoration into the compositions of the present invention.

Other organic polymeric compounds suitable for incoφoration in the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000 to 10000, more particularly 2000 to 8000 and most preferably about 4000.

Cationic soil removal/anti-redeposition compounds

The composition or components thereof of the invention may comprise water- soluble cationic ethoxylated amine compounds with particulate soil/clay-soi! removal and/or anti-redeposition properties. These cationic compounds are described in more detail in EP-B-111965, US 4659802 and US 4664848. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines. Especially preferred are the ethoxylated cationic monoamines, diamines and triamines of the formula:

Figure imgf000046_0001

wherein X is a nonionic group selected from the group consisting of H, -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 2, 1 or 0; for cationic monoamines (b=0), n is preferably at least 16, with a typical range of from 20 to 35; for cationic diamines or triamines, n is preferably at least about 12 with a typical range of from about 12 to about 42.

These compounds where present in the composition, are generally present in an amount of from 0.01 to 30% by weight, preferably 0.05 to 10% by weight.

Suds suppressing system

The compositions of the invention are preferably substantially free of any suds suppressing agents where high foaming is desired. It can be preferred that the composition require low-sudsing, and that thus incoφoration of suds suppressant for foam control are desirable. They are preferably present in amounts no greater than 2.5% and most preferably in amounts no greater than 1.5% or even no greater than 0.5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci g-C4o ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) poly dimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incoφorated at a level of from 5% to 50%, preferably 10%> to 40%> by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544; (c) an inert carrier fluid compound, most preferably comprising a C \ g-C \ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.

Polymeric dye transfer inhibiting agents

The compositions herein may also comprise from 0.01%> to 10 %, preferably from

0.05%) to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be cross-linked polymers.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :

(I) Ax

R

wherein P is a polymerisable unit, and

O R1 R1 © O O R1

A is-C-N- , -N-C - , CO, C, -O- , — S - , -N- ; x is 0 or l; Ri is H or Cj.g linear or branched alkyl; or may form a heterocyclic group with R; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures :

O

A

O

Figure imgf000050_0001
-(R1)x

wherein RI, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, N-substituted pyrrole, imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, N-substituted pyrrole, imidazole and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone having a preferred average molecular weight range of from 5,000 to 100,000, or 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Coφoration, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K- 15 is also available from ISP Coφoration. Other suitable polyvinylpyrrolidones which are commercially available from BASF Coφoration include Sokalan HP 165 and Sokalan HP 12.

d Polyvinyloxazolidone

The compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener

The compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. Hydrophilic optical brighteners useful herein include those having the structural formula:

Figure imgf000052_0001

wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R\ is anilino, R is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R\ is anilino, R is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, Rj is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions or components. If utilized, SRA's will generally comprise from 0.01%> to 10.0%, typically from 0.1 % to 5%>, preferably from 0.2%) to 3.0%> by weight, of the compositions.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric or polymeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1 ,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400. SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

Near neutral wash pH detergent formulation

While the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH, i.e. an initial pH of from about 7.0 to about 10.5 at a concentration of from about 0.1 to about 2% by weight in water at 20°C. Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.

Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83.200688.6, filed May 16, 1983, J.H.M. Wertz and P.C.E. Goffinet.

Highly preferred compositions of this type also preferably contain from about 2 to about 10%) by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti- oxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incoφorated by reference).

In a preferred aspect of the invention the cationic surfactant is present in a solid detergent composition in granules which additionally contain an acidic component such as a carboxylic acid, such as citric or tartaric acid. In this way, near neutral to acid conditions may be present in the vicinity of the cationic surfactant for at least part of the delivery and wash process.

Form of the compositions

The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, flake, pastille and bar and liquid forms. Liquids may be aqueous or non-aqueous and may be in the form of a gel. The compositions may be pre-treatment compositions or may be conventional washing detergents. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

Such granular detergent compositions or components thereof in accordance with the present invention can be made via a variety of methods, including spray-drying, dry- mixing, extrusion, agglomerating and granulation. The cationic quaternised surfactant can be added to the other detergent components by mixing, agglomeration (preferably combined with a carrier material), granulation or as a spray-dried component.

The compositions in accordance with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

In one aspect of the invention the mean particle size of the components of granular compositions in accordance with the invention, should preferably be such that no more than 15% of the particles are greater than 1.8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter. Preferably the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm in diameter. The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

In a further aspect of the invention at last 80%>, preferably at least 90% by weight of the composition comprises particles of mean particle size at least 0.8 mm, more preferably at least 1.0 mm and most preferably from 1.0, or 1.5 to 2.5 mm. Most preferably at least 95%> of the particles will have such a mean particle size. Such particles are preferably prepared by an extrusion process.

Compacted solids may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting. Preferably tablets for use in dish washing processes, are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm^, more preferably from 5 to 1 lKN/cm^ so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.

Laundry washing method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Dosage is dependent upon the particular conditions such as water hardness and degree of soiling of the soiled laundry.

The detergent composition may be dispensed for example, from the drawer dispenser of a washing machine or may be sprinkled over the soiled laundry placed in the machine. In one use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

The dispensing device containing the detergent product is placed inside the drum before the commencement of the wash, before, simultaneously with or after the washing machine has been loaded with laundry. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562. Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent egress of wetted, imdissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Machine dishwashing method

Any suitable methods for machine dishwashing or cleaning soiled tableware, particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods. Packaging for the compositions

Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No. 94921505.7.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear Cj χ_j3 alkyl benzene sulfonate

TAS Sodium tallow alkyl sulfate

CxyAS Sodium Cjx - Cjy alkyl sulfate

C46SAS Sodium Cj4 - Cjg secondary (2,3) alkyl sulfate

CxyEzS Sodium Cιx-C] v alkyl sulfate condensed with z moles of ethylene oxide

CxyEz Clχ-Civ predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide PAS Salt of R, N+ (CH3)2 R2, wherein R, is C2-C3 hydroxyalkyl and R2 is primary ethylene amine or primary propylene amine

PAS, Salt of R, N+ (CH3)2 R2 wherein R, is C5-C8 alkyl and R2 is primary ethylene amine or primary propylene amine

QAS R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14 QAS 1 R2.N+(CH3)2(C2H4OH) with R2 = Cg - Ci i APA Cg - CJO amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an

80/20 mixture of tallow and coconut fatty acids

STS Sodium toluene sulphonate

CFAA Cl2"Cl4 (coco) alkyl N-methyl glucamide

TFAA Cjg-Cjg alkyl N-methyl glucamide

TPKFA Cj_2-Cl4 topped whole cut fatty acids

STPP Anhydrous sodium tripolyphosphate

TSPP Tetrasodium pyrophosphate

Zeolite A Hydrated sodium aluminosilicate of formula

Nai2(AlO2SiO2)i2-2 H2O having a primary particle size in the range from 0.1 to 10 micrometers

(weight expressed on an anhydrous basis)

NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2θ5 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous sodium silicate (SiO2:Na2O = 2.0:1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850μm

MA AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000

MA AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000

AA Sodium polyacrylate polymer of average molecular weight 4,500

CMC Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu

Chemicals

Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A S under the tradename Savinase

Protease I Proteolytic enzyme, having 4%> by weight of active enzyme, as described in WO 95/10591, sold by

Genencor Int. Inc.

Alcalase Proteolytic enzyme, having 5.3%> by weight of active enzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23%) by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme

Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T Lipase Lipolytic enzyme, having 2.0%> by weight of active enzyme, sold by NOVO Industries A S under the tradename Lipolase

Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra

Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A S

PB4 Sodium perborate tetrahydrate of nominal formula

NaBO2.3H2O.H2O2

PB1 Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O

Percarbonate Sodium percarbonate of nominal formula

2Na2CO3.3H2O2

DOBS Decanoyl oxybenzene sulphonate in the form of the sodium salt

DDOBS Dodecanoyl oxybenzene sulphonate in the form of the sodium salt

NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt

NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate TAED Tetraacetylethylenediamine DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest

2060

EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach

(1) dextrin soluble polymer

Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer

Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-l .3.5- triazin-2-yl)amino) stilbene-2 :2'-disulfonate

HEDP 1,1-hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x

(typically 4,000)

PEO Polyethylene oxide, with an average molecular weight of 50,000

TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl imidosole, with an average molecular weight of 20,000

PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60,000

PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000

PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of

20,000

QEA bis((C2H5θ)(C2H4θ)n)(CH3) -N+-CgHι2-N+-

(CH3) bis((C2H5O)-(C2H4O))n, wherein n = from

20 to 30

SRPl Anionically end capped poly esters

SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen

Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1

Opacifier Water based monostyrene latex mixture, sold by

BASF Aktiengesellschaft under the tradename Lytron

621

Wax Paraffin wax

In the following examples all levels are quoted as %> by weight of the composition: Example 1

The following high density granular laundry detergent compositions A to F were prepared in accord with the invention:

A B C D E F

LAS 8.0 8.0 8.0 2.0 6.0 6.0

TAS - 0.5 - 0.5 1.0 0.1

C46(S)AS 2.0 2.5 - - - -

C25AS - - - 7.0 4.5 5.5

C68AS 2.0 5.0 7.0 - - -

C25E5 - - 3.4 10.0 4.6 4.6

C25E7 3.4 3.4 1.0 - - -

C25E3S - - - 2.0 5.0 4.5

QAS - 0.8 - - - -

PAS/PAS! 2.0 0.8 1.0 4.0 0.5 1.0

QAS (I) - - - - 0.5 0.5

Zeolite A 18.1 18.0 14.1 18.1 20.0 18.

Citric acid - - - 2.5 - 2.5

Carbonate 13.0 13.0 27.0 10.0 10.0 13.ι

SKS-6 10.0 10.0 Silicate 1.4 1.4 3.0 0.3 0.5 0.3

Citrate - 1.0 - 3.0

Sulfate 26.1 26.1 26.1 6.0

Mg sulfate 0.3 - - 0.2 - 0.2

MA AA 0.3 0.3 0.3 4.0 1.0 1.0

CMC 0.2 0.2 0.2 0.2 0.4 0.4

PB4/PB, 9.0 9.0 5.0 -

Percarbonate - - - 15.0 18.0 18.0

TAED 1.5 0.4 1.5 - 3.9 4.2

NAC-OBS - 2.0 1.0 -

NOBS/DDOBS 2.0

DTPMP 0.25 0.25 0.25 0.25

SRP I 0.2 0.2

EDDS - 0.25 0.4 - 0.5 0.5

CFAA - 1.0 - 2.0 -

HEDP 0.3 0.3 0.3 0.3 0.4 0.4

QEA - - - 0.2 - 0.5

Protease I - - 0.26 1.0 Protease 0.26 0.26 - - 1.5 1.0

Cellulase 0.3 - - 0.3 0.3 0.3

Amylase 0.1 0.1 0.1 0.4 0.5 0.5

Lipase (1) 0.3 - - 0.5 0.5 0.5

Photoactivated 15 ppm 15 ppm 15 ppm - 20 ppm 20 ppm bleach (ppm)

PVNO/PVPVI - - - 0.1 -

Brightener 1 0.09 0.09 0.09 - 0.09 0.09

Perfume 0.3 0.3 0.3 0.4 0.4 0.4

Silicone antifoam 0.5 0.5 0.5 - 0.3 0.3

Misc/minors to

100%

Density in g/litre 850 850 850 850 850 850

Example 2

The following granular laundry detergent compositions G to L of particular utility under European machine wash conditions were prepared in accord with the invention:

G H I J K L

LAS 5.5 7.5 5.0 5.0 6.0 7.0

TAS 1.25 1.86 - 0.8 0.4 0.3

C24AS/C25AS - 2.24 5.0 5.0 5.0 2.2

C25E3S - 0.76 1.0 1.5 3.0 1.0

C45E7 3.25 - - - - 3.0

TFAA - - 2.0 - - -

C25E5 - 5.5 - - - -

QAS 0.8 - - - - -

QAS II - - - 0.5 - 0.7

PAS/PAS, 0.7 1.2 1.0 4.0 1.0 0.5

STPP 19.7 - - - - -

Zeolite A 19.5 25.0 19.5 20.0 17. 0

NaSKS-6/citric 10.6 - 10.6 - - acid (79:21)

NaSKS-6 - 9.0 - 10.0 10 0 Carbonate 6.1 21.4 9.0 10.0 10.0 18.

0

Bicarbonate - 2.0 7.0 5.0 - 2.0

Silicate 6.8 - - 0.3 0.5

Citrate - - 4.0 4.0

Sulfate 39.8 - - 5.0 - 12.

0

Mg sulfate - - 0.1 0.2 0.2

MA/AA 0.5 1.6 3.0 4.0 1.0 1.0

CMC 0.2 0.4 1.0 1.0 0.4 0.4

PB4 5.0 12.7 - - - -

PB, - - 15.0

Percarbonate - - - 15.0 18.0 15.

0

TAED 0.5 3.1 4.0 - 5.0

NAC-OBS 1.0 3.5 - - - 2.5

NOBS/DOBS - - 2.0 3.0 -

DTPMP 0.25 0.2 0.3 0.4 - 0.2

HEDP - 0.3 - 0.3 0.3 0.3

QEA - - 1.0 1.0 1.0 -

Protease I - - - 0.5 1.2 - Protease 0.26 0.85 0.9 1.0 - 0.7

Lipase (1) 0.15 0.15 0.3 0.3 0.3 0.2

Cellulase 0.28 0.28 0.2 0.2 0.3 0.3

Amylase 0.1 0.1 0.4 0.4 0.6 0.2

PVNO/PVPVI - - 0.2 0.2

PVP 0.9 1.3 - - - 0.9

SRP l - - 0.2 0.2 0.2

Photoactivated 15 27 - - 20 20 bleach (1) (ppm) ppm ppm ppm pp m

Photoactivated 15 - - - - - bleach (2) (ppm) ppm

Brightener 1 0.08 0.19 - - 0.09 0.1

5 Brightener 2 - 0.04 -

Perfume 0.3 0.3 0.4 0.3 0.4 0.3

Silicone antifoam 0.5 2.4 0.3 0.5 0.3 2.0

Minors/misc to 100%

Density in g/litre 750 750 750 750 750 75

0 Example 3

The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.

M N O

Blown powder

LAS 6.0 5.0 11.0 6.0

TAS 2.0 - - 2.0

PAS/PAS , - - 1.0 -

Zeolite A 24.0 - - 20.0

STPP - 27.0 24.0 -

Sulfate 4.0 6.0 13.0 -

MA/AA 1.0 4.0 6.0 2.0

Silicate 1.0 7.0 3.0 3.0

CMC 1.0 1.0 0.5 0.6

Brightener 1 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 on

Brightener 0.02 - - 0.02

C45E7 - - - 5.0

C45E2 2.5 2.5 2.0 -

C45E3 2.6 2.5 2.0 -

Perfume 0.5 0.3 0.5 0.2

Silicone antifoam 0.3 0.3 0.3 -

Dry additives

QEA - - - 1.0

EDDS 0.3 - - -

Sulfate 2.0 3.0 5.0 10.0

Carbonate 6.0 13.0 15.0 14.0

Citric acid 2.5 - - 2.0

QAS II 0.5 - - 0.5

PAS/PAS! 2.0 1.0 - 0.7

SKS-6 10.0 - - -

Percarbonate 18.5 - _ _ PB4 - 18.0 10.0 21.5

TAED 2.0 2.0 - 2.0

DDOBS/NAC-OBS 3.0 2.0 4.0 -

Protease 1.0 1.0 1.0 1.0

Lipase - 0.4 - 0.2

Lipase (1) 0.4 - 0.4 -

Amylase 0.2 0.2 0.2 0.4

Brightener 1 0.05 - - 0.05 isc/minor to 100%

Example 4

The following granular detergent formulations were prepared in accord with the invention.

Q R S T U V

Blown powder

LAS 23.0 8.0 7.0 9.0 7.0 7.0

TAS - - - - 1.0 -

C45AS 6.0 6.0 5.0 8.0 - -

C45AES - 1.0 1.0 1.0 - -

C45E35 - - - - 2.0 4.0

Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0

MA AA - 0.5 - - - 2.0

MA/AA (1) 7.0 - - - - -

AA - 3.0 3.0 2.0 3.0 3.0

Sulfate 5.0 6.3 14.3 11.0 15.0 19.3

Silicate 10.0 1.0 1.0 1.0 1.0 1.0

Carbonate 15.0 20.0 10.0 20.7 8.0 6.0

PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0

DTPA - 0.9 0.5 - - 0.5

Brightener 2 0.3 0.2 0.3 - 0.1 0.3

Spray on

C45E7 - 2.0 - - 2.0 2.0

C25E9 3.0 - - - - -

C23E9 - - 1.5 2.0 - 2.0

Perfume 0.3 0.3 0.3 2.0 0.3 0.3

Agglomerates

C45AS - 5.0 5.0 2.0 - 5.0

LAS - 2.0 2.0 - - 2.0

Zeolite A - 7.5 7.5 8.0 - 7.5

Carbonate - 4.0 4.0 5.0 - 4.0

PEG 4000 - 0.5 0.5 - - 0.5

Misc (water etc) - 2.0 2.0 2.0 - 2.0

Dry additives

QAS (I) - - - - 1.0 - PAS/PAS! 0.7 1.0 2.0 4.0 1.0 0.8

Citric acid - - - 2.0 -

PB4 - - - 4.0 12.0 -

PB1 4.0 1.0 3.0

Percarbonate - - - 2.0 10.0

Carbonate - 5.3 1.8 4.0 4.0

TAED 4.0 2.0 - 5.0 _

DDOBS/NOBS 4.0 - 3.0 0.6

Methyl cellulose 0.2 - -

SKS-6 8.0 - -

STS - - 2.0 1.0

Cumene sulfonic acid - 1.0 - - 2.0

Lipase 0.2 - 0.2 0.2 0.4

Cellulase 0.2 0.2 0.2 0.3 0.2 0.2

Amylase 0.2 - 0.1 0.2 -

Protease 0.5 0.5 0.5 0.3 0.5 0.5

PVPVI - - - 0.5 0.1

PVP - - - 0.5 -

PVNO - - 0.5 0.3

QEA - - - 1.0 _

SRP1 0.2 0.5 0.3 0.2 -

Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -

Mg sulfate - - 0.2 0.2 _

Misc/minors to 100%>

Example 5

The following detergent formulations of particular use in the washing of coloured clothing, according to the present invention were prepared:

W

Blown Powder

Zeolite A 15.0 15.0 -

Sulfate 0.0 5.0 -

PAS/PAS j - 1.0 1.0

LAS 3.0 3.0 -

DTPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA AA 4.0 4.0 -

Agglomerates

C45AS - - 11.0

LAS 6.0 5.0 -

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

PAS/PAS . - - -

Zeolite A 10.0 15.0 13.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.0 7.0 7.0

Spray On

Perfume 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0

Dry additives

MA AA - - 3.0

PAS/PAS ! 1.0 - -

NaSKS-6 - - 12.0

Citrate 10.0 - 8.0

TAED 4.0 2.0 4.0

Carbonate/Bicarbonate 10.0 10.0 15.0

Percarbonate 18.0 15.0 10.0

PVPVI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.9

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 additives

Sulfate 0.0 9.0 0.0 Misc/minors to 100% 100.0 100.0 100.0

Density (g/litre) 700 700 700

Example 6

The following granular detergent formulations were prepared in accord with the invention.

AA BB CC

Base granule

Zeolite A 30.0 22.0 24.0 10.0

Sulfate 10.0 5.0 10.0 7.0

MA/AA 3.0 - - -

AA - 1.6 2.0 -

MA AA (1) - 12.0 - 6.0

LAS 14.0 10.0 9.0 20.0

C45AS 8.0 7.0 9.0 7.0

C45AES - 1.0 1.0 -

Silicate - 1.0 0.5 10.0

Soap - 2.0 - -

Brightener 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 10.0 10.0

PEG 4000 - 1.0 1.5 -

DTPA - 0.4 - -

Spray on

C25E9 - - - 5.0

C45E7 1.0 1.0 - -

C23E9 - 1.0 2.5 -

Perfume 0.2 0.3 0.3 -

Dry additives

PAS/PAS! 2.0 1.0 5.0 0.7

Carbonate 5.0 10.0 18.0 8.0

PVPVI/PVNO 0.5 - 0.3 -

Protease 1.0 1.0 1.0 0.5

Lipase 0.4 - - 0.4

Amylase 0.1 - - 0.1

Cellulase 0.1 0.2 0.2 0.1

DDOBS/NOBS - 4.0 - 4.5

TAED - 1.0 2.0 -

PB1 1.0 5.0 1.5 6.0

Sulfate 4.0 5.0 - 5.0

SRPI - 0.4 - -

Sud supressor - 0.5 0.5 -

Misc/minor to 100%) Example 7

The following granular detergent compositions were prepared in accord with the invention.

DD EE FF

Blown powder

Zeolite A 20.0 - 15.0

STPP - 20.0 -

Sulphate - - 5.0

Carbonate - - 5.0

TAS - - 1.0

LAS 6.0 6.0 6.0

C68AS 2.0 2.0 -

Silicate 3.0 8.0 -

MA/AA 4.0 2.0 2.0

CMC 0.6 0.6 0.2

Brightener 1 0.2 0.2 0.1

DTPMP 0.4 0.4 0.1

STS - - 1.0

Spray on

C45E7 5.0 5.0 4.0

Silicone antifoam 0.3 0.3 0.1

Perfume 0.2 0.2 0.3

Dry additives

QEA - - 1.0

Carbonate 14.0 9.0 10.0

PB1 1.5 2.0 -

PB4 18.5 13.0 13.0

TAED 2.0 2.0 2.0

NAC-OBS - - 2.0

DDOBS/NOBS - 2.0 -

PAS/PAS! 1.0 2.0 1.0

Photoactivated bleach 15 ppm 15 ppm 15ppm

SKS-6 - - 3.0

Protease 1.0 1.0 0.2 Lipase 0.2 0.2 0.2

Amylase 0.4 0.4 0.2

Cellulase 0.1 0.1 0.2

Sulfate 10.0 20.0 5.0 isc/minors to 100%

Density (g/litre) 700 700 700

Example 8

The following detergent compositions, according to the present invention were prepared:

GG HH II

Blown Powder

Zeolite A 15.0 15.0 15.0

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

EDDS - 0.4 0.2

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

PAS/PAS! 2.0 - -

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Spray On

Perfume 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - -

Dry additives

Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

PAS/PAS. - 1.0 1.0

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

DDOBS/NAC-OBS - 2.0 -

PB1 14.0 7.0 10.0

PEO - - 0.2

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 additives

Sodium sulfate 0.0 3.0 0.0 Misc/minors to 100% 100.0 100.0 100.0

Density (g/litre) 850 850 850

Example 9

The following detergent formulations, according to the present invention were prepared:

JJ KK LL MM

LAS 18.0 14.0 24.0 20.0

QAS 0.7 - - 0.7

PAS/PAS! 2.0 5.0 1.0 0.8

TFAA - 1.0 - -

C23E56.5 - - 1.0 -

C45E7 - 1.0 - -

C45E3S 1.0 2.5 1.0 -

STPP 32.0 18.0 30.0 22.0

Silicate 9.0 5.0 9.0 8.0

Carbonate 11.0 7.5 10.0 5.0

Bicarbonate - 7.5 - -

PB1 3.0 1.0 - -

PB4 - 1.0 - -

NOBS/DOBS 2.0 1.0 - -

Percarbonate - - 5.0 10.0

TAED - 2.0 2.0 2.0

DTPMP - 1.0 - -

DTPA 0.5 - 0.2 0.3

SRP 1 0.3 0.2 - 0.1

MA/AA 1.0 1.5 2.0 0.5

CMC 0.8 0.4 0.4 0.2

PEI - - 0.4 -

Sodium sulfate 20.0 10.0 20.0 30.0

Mg sulfate 0.2 - 0.4 0.9

Protease 0.8 1.0 0.5 0.5

Amylase 0.5 0.4 - 0.25

Lipase 0.2 - 0.1 -

Cellulase 0.15 - - 0.05

Photoactivated 30ppm 20ppm - lOppm bleach (ppm)

Perfume 0.3 0.3 0.1 0.2

Brightener 1/2 0.05 0.2 0.08 0.1

Misc/minors to

100% Example 10

The following liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):

NN OO PP QQ RR SS TT UU

LAS 10.0 13.0 9.0 - 25.0 - - -

C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0

C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0

C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0

TFAA - - - 4.5 - 6.0 8.0 8.0

APA - 1.4 - - 3.0 1.0 2.0 -

TPKFA 2.0 - 13.0 7.0 - 15.0 11.0 11.0

Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0

Dodecenyl/tetradecenyl 12.0 10.0 - - 15.0 - - - succinic acid

Rape seed fatty acid 4.0 2.0 1.0 - 1.0 - 3.5 -

Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0

1 ,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0

Monoethanolamine - - - 5.0 - - 9.0 9.0

Triethanolamine - - 8.0 - - - - -

TEPAE 0.5 - 0.5 0.2 - - 0.4 0.3

DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 -

Protease 0.5 0.5 0.4 0.25 - 0.5 0.3 0.6

Alcalase - - - - 1.5 - - -

Lipase - 0.10 - 0.01 - - 0.15 0.15

Amylase 0.25 0.25 0.6 0.5 0.25 0.9 0.6 0.6

Cellulase - - - 0.05 - - 0.15 0.15

Endolase - - - 0.10 - - 0.07 -

SRP2 0.3 - 0.3 0.1 - - 0.2 0.1

Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 2.5

Calcium chloride - 0.02 - 0.01 - - - -

Bentonite clay - - - - 4.0 4.0 - -

Brightener 1 - 0.4 - - 0.1 0.2 0.3 -

Sud supressor 0.1 0.3 - 0.1 0.4 - - -

Opacifier 0.5 0.4 - 0.3 0.8 0.7 - -

Water/minors

NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2

PB, 12.0 10.0 5.0 3.0 2.0 4.0 2.0 11.0

TAED 2.0 2.0 2.0 - - 1.0 2.0 5.0

DDOBS/NAC-OBS - - - 2.0 2.0 2.0 - -

PAS/PAS! 1.0 2.0 3.5 0.7 1.5 1.0 5.5 2.0 Example 11

The following laundry detergent compositions are in accord with the invention:

W ww XX YY

MB AS 16.5, 1.8 22 - - 5.5

C45 AS 8 10 11 4

C45E1S 4 3 - 1

LAS 8 14 - 4

PAS/PAS, 1.0 1.5 0.5 3.5

C16 SAS - - 3 -

MES - - 12 -

C23E6.5 1.5 1.5 1.5 1.5

Zeolite A 17.8 20.8 20.8 27.8

AA 2.3 2.3 2.3 2.3

Carbonate 27.3 27.3 27.3 27.3

Silicate 0.6 0.6 0.6 0.6

Perborate 1.0 1.0 1.0 1.0

Protease 0.3 0.3 0.3 0.3

Cellulase 0.3 0.3 0.3 0.3

SRP1 0.4 0.4 0.4 0.4

Brightener 0.2 0.2 0.2 0.2

PEG 1.6 1.6 1.6 1.6

PB1 16.0 6.0 - -

NOBS/DDOBS 2.4 4.5 0.8 3.5

PC - - 8.0 15.0

Sulfate 5.5 5.5 5.5 5.5

Silicone Antifoam 0.42 0.42 0.42 0.42

TAED 0.5 4.5 8.0 2.0

Moisture & Minors - -Balance —

Density (g/L) 660 660 660 660 Example 12

The following laundry detergent compositions are in accord with the invention:

ZZ AB AC AD AE

MB AS 16.5, 1.7 14.8 - - 8.2 -

C45 AS 5 7 6 4 12

C45 E3S 2 - 4 - 5

LAS 14 8 - 18 5

PAS/PAS , 2.0 1.0 3.0 0.5 0.7

C16 SAS - - 1 - 1

MES - - 10 - -

TFAA 1.6 - - - -

C24E3 4.9 4.9 4.9 4.9 4.9

Zeolite A 15 15 15 15 15

QAS 1.0 1.5 - - 1.0

NaSKS-6 11 11 11 11 11

Citrate/citric 1.0 2.0 3 3 -

MA/AA 4.8 4.8 4.8 4.8 4.8

HEDP 0.5 0.5 0.5 0.5 0.5

Carbonate 8.5 8.5 8.5 8.5 8.5

Protease 0.9 0.9 0.9 0.9 0.9

Lipase 0.15 0.15 0.15 0.15 0.15

Cellulase 0.26 0.26 0.26 0.26 0.26

Amylase 0.36 0.36 0.36 0.36 0.36

NOBS - - - 4.0 5.0

NACA-OBS 4.0 2.0 6.0 - -

TAED 4.0 - 2.0 1.0 0.5

PB1 - - 14.0 - 8.0

Percarbonate 20.0 14.0 - 22.0 -

SRP1 0.2 0.2 0.2 0.2 0.2

QEA1 1.0 1.5 - - -

Brightener 0.2 0.2 0.2 0.2 0.2

Sulfate 2.3 2.3 2.3 2.3 2.3

Silicone Antifoam 0.4 0.4 0.4 0.4 0.4

Moisture & Minors — Balance — Density (g/L) 850 850 850 850

Example 13

The following laundry detergent compositions are prepared in accord with the invention:

AF AG AH Al AJ AK

MB AS 16.5, 1.7 - 32 - - - 8

C45 AS 5 - 6 12 2 -

C45E1S 1 - - 1 5 2

LAS - 20 8 23 12 16

C16 SAS 1 4 - - - -

MES 14 - - - - -

PAS/PAS, 1.0 4.0 0.7 1.0 1.5 1.2

C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6

QAS - 0.5 - - 0.5 -

Zeolite A 9.0 9.0 9.0 9.0 9.0 9.0

Polycarboxylate 7.0 7.0 7.0 7.0 7.0 7.0

Carbonate 18.4 18.4 18.4 18.4 18.4 18.4

Silicate 11.3 11.3 11.3 11.3 11.3 11.3

PB1 - - 3.9 10.0 3.9 15.0

TAED 2.0 5.0 - - 6.0 2.0

Percarbonate 7.0 7.0 - - - -

NOBS/DDOBS 4.1 4.1 4.1 4.1 - 4.1

Protease 0.9 0.9 0.9 0.9 0.9 0.9

SRP1 0.5 0.5 0.5 0.5 0.5 0.5

Brightener 0.3 0.3 0.3 0.3 0.3 0.3

PEG 0.2 0.2 0.2 0.2 0.2 0.2

Sulfate 5.1 5.1 5.1 5.1 5.1 5.1

Silicone Antifoam 0.2 0.2 0.2 0.2 0.2 0.2

Moistures & Minors — Balance —

Density (g/L) 810 810 810 810 810 810

Claims

What is claimed is:
1 A detergent or cleaning composition or component thereof comprising:
(a) at least 0.01% by weight of the composition or component, one or more cationic surfactants, comprising at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.
(b) at least 0.05% by weight of the composition or component, an oxygen - releasing bleach
2. A composition or component according to claim 1 wherein the cationic surfactant is a cationic surfactant of the general formula
Figure imgf000087_0001
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from
R2-
Figure imgf000087_0002
╬╕
B -N- and
M"
R^
C~~ = -N-
R 8
wherein R\, R2, R3, R4, R5, Rg, R7 and Rg are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of R\, R2, R3, R4, R5, Rg, R7 or Rg can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, Rjand R2 and R3, R4 and R5 or Rg and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R7 is not present and Rg is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, Ri. or R2 or R and or R5 form together with the nitrogen atoms of A and D part of a ring structure; M" is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of R\, R2 or R3 is hydrogen, or at least one B is present in which neither Rg nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.
3. A composition or component according to claim 2 wherein the cationic surfactant is a cationic surfactant of the general formula
Figure imgf000088_0001
wherein L is a linking unit, and each L is independently selected from the group consisting of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B or D units; x is a number from 0 to 10; and wherein the unit A is
R ╬╕
R. -N I -
M"
R.
R
0
BΓÇö = N-
M"
R~
and -D comprises a primary amine group and wherein R , R2, R3, R4 or R5 are independently selected from the group consisting of C1-C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of R\, R2, R3, R4 or R- can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R\ and R2, Rjand R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R\ or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M" is one or more counterions.
3. A composition or component according to claim 2 comprising a cationic surfactant wherein x=0.
4. A composition or component according to claim 2 or 3 comprising a cationic surfactant wherein R4 and R- are, independently from each other, C1 -Cg alkyl or (poly) hydroxyalkyl group or hydrogen atom.
5. A composition or component according to any of claims 2 to 4 comprising a cationic surfactant, wherein L is a C2-C4 linear or branched alkyl or hydroxyalkyl group.
6. A composition according to any preceding claim in which the cationic surfactant is present in an amount of from 0.01% to 20% by weight, preferably of from 0.05%> to 5% by weight of the composition.
7. A composition or component thereof according to any preceding claim wherein said oxygen-releasing bleach system a hydrogen peroxide source and a peroxyacid precursor.
8. A composition or component according to claim 7 wherein said precursor is an alkyl fatty peroxyacid precursor, preferably TAED.
9. A composition or component according to claim 7 wherein said precursor is a hydrophobic organic peroxyacid precursor, preferably an amide substituted alkyl peroxyacid precursor compound selected from the group consisting of
R ! N ΓÇö R' R N R' C L
1 ~ " ! !
O R^ and R5 O O
wherein L can be essentially any leaving group, R is an aryl or alkaryl group with from 1 to 14 carbon atoms, R- is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that R* and R in total not contain more than 18 carbon; or preferably benzenesulfonate derivatives, preferably 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS).
10. A composition according to claim 7 in which the is precursor is present in an amount of from 0.5% to 20% by weight, preferably of from 1% to 15%) by weight of the composition.
11. A composition or component thereof according to claim7 wherein the hydrogen peroxide source is a sodium or potassium salt of percarbonate or perborate.
PCT/US1998/002461 1997-02-11 1998-02-11 A cleaning composition WO1998035005A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB9702731.2 1997-02-11
GB9702731A GB9702731D0 (en) 1997-02-11 1997-02-11 Detergent compound
GB9726895.7 1997-12-20
GB9726895A GB9726895D0 (en) 1997-12-20 1997-12-20 A cleaning composition

Publications (1)

Publication Number Publication Date
WO1998035005A1 true true WO1998035005A1 (en) 1998-08-13

Family

ID=26310964

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/002461 WO1998035005A1 (en) 1997-02-11 1998-02-11 A cleaning composition

Country Status (1)

Country Link
WO (1) WO1998035005A1 (en)

Cited By (162)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015750A1 (en) * 1998-09-15 2000-03-23 The Procter & Gamble Company Sanitising compositions and methods
US6551975B1 (en) 1998-09-15 2003-04-22 The Procter & Gamble Company Sanitizing compositions and methods
WO2006088980A1 (en) 2005-02-17 2006-08-24 The Procter & Gamble Company Fabric care composition
WO2008059013A1 (en) 2006-11-17 2008-05-22 Ciba Holding Inc. Premoistened cleaning disposable substrate
WO2008109384A2 (en) 2007-03-05 2008-09-12 Celanese Acetate Llc Method of making a bale of cellulose acetate tow
WO2009010911A2 (en) 2007-07-19 2009-01-22 The Procter & Gamble Company Detergent composition containing suds boosting co-surfactant and suds stabilizing surface active polymer
EP2071017A1 (en) 2007-12-04 2009-06-17 The Procter and Gamble Company Detergent composition
EP2083065A1 (en) 2008-01-22 2009-07-29 The Procter and Gamble Company Colour-Care Composition
EP2103676A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company A laundry detergent composition comprising the magnesium salt of ethylene diamine-n'n' -disuccinic acid
EP2103675A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising cellulosic polymer
EP2103678A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising a co-polyester of dicarboxylic acids and diols
EP2135932A1 (en) 2008-06-20 2009-12-23 The Procter and Gamble Company Laundry composition
EP2135933A1 (en) 2008-06-20 2009-12-23 The Procter and Gamble Company Laundry composition
EP2135931A1 (en) 2008-06-16 2009-12-23 The Procter and Gamble Company Use of soil release polymer in fabric treatment compositions
EP2154235A1 (en) 2008-07-28 2010-02-17 The Procter and Gamble Company Process for preparing a detergent composition
EP2163608A1 (en) 2008-09-12 2010-03-17 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye and fatty acid soap
EP2166077A1 (en) 2008-09-12 2010-03-24 The Procter and Gamble Company Particles comprising a hueing dye
EP2166078A1 (en) 2008-09-12 2010-03-24 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye
EP2210520A1 (en) 2009-01-22 2010-07-28 The Procter and Gamble Company Package comprising an adhesive perfume delivery material
WO2010151906A2 (en) 2010-10-22 2010-12-29 Milliken & Company Bis-azo colorants for use as bluing agents
WO2011005813A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005804A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
WO2011005730A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005911A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
WO2011005910A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005913A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005623A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of bleach
WO2011005912A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric
WO2011005830A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of sulphate
WO2011005630A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005844A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005904A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Detergent composition
WO2011005917A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
WO2011017719A2 (en) 2010-11-12 2011-02-10 Milliken & Company Thiophene azo dyes and laundry care compositions containing the same
WO2011016958A2 (en) 2009-07-27 2011-02-10 The Procter & Gamble Company Detergent composition
WO2011025615A2 (en) 2009-08-13 2011-03-03 The Procter & Gamble Company Method of laundering fabrics at low temperature
WO2011031599A1 (en) 2009-09-08 2011-03-17 The Procter & Gamble Company A laundry detergent composition comprising a highly water-soluble carboxymethyl cellulose particle
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition
WO2011038078A1 (en) 2009-09-23 2011-03-31 The Procter & Gamble Company Process for preparing spray-dried particles
WO2011044305A1 (en) 2009-10-07 2011-04-14 The Procter & Gamble Company Detergent composition
US7928054B2 (en) 2007-05-17 2011-04-19 The Procter & Gamble Company Detergent additive extrudates containing alkyl benzene sulphonate
WO2011075352A1 (en) 2009-12-18 2011-06-23 The Procter & Gamble Company Cleaning composition containing hemicellulose
WO2011094374A1 (en) 2010-01-29 2011-08-04 The Procter & Gamble Company Novel linear polydimethylsiloxane-polyether copolymers with amino and/or quaternary ammonium groups and use thereof
US7994369B2 (en) 2008-09-22 2011-08-09 The Procter & Gamble Company Specific polybranched polyaldehydes, polyalcohols, and surfactants, and consumer products based thereon
WO2011100411A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising polyglycerol esters
WO2011100667A1 (en) 2010-02-14 2011-08-18 Ls9, Inc. Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011100405A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising crosslinked polyglycerol esters
WO2011100420A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising crosslinked polyglycerol esters
WO2011100500A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising polyglycerol esters
WO2011109322A1 (en) 2010-03-04 2011-09-09 The Procter & Gamble Company Detergent composition
EP2380960A1 (en) 2010-04-19 2011-10-26 The Procter and Gamble Company Detergent composition
WO2011133371A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
WO2011133372A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company Detergent composition
WO2011133456A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company A liquid laundry detergent composition comprising a source of peracid and having a ph profile that is controlled with respect to the pka of the source of peracid
WO2011133380A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company A laundry detergent composition comprising bleach particles that are suspended within a continuous liquid phase
WO2011146602A2 (en) 2010-05-18 2011-11-24 Milliken & Company Optical brighteners and compositions comprising the same
WO2011146604A2 (en) 2010-05-18 2011-11-24 Milliken & Company Optical brighteners and compositions comprising the same
WO2011149871A1 (en) 2010-05-28 2011-12-01 Milliken & Company Colored speckles having delayed release properties
WO2011149870A1 (en) 2010-05-28 2011-12-01 Milliken & Company Colored speckles for use in granular detergents
WO2011149907A1 (en) 2010-05-24 2011-12-01 University Of Utah Research Foundation Reinforced adhesive complex coacervates and methods of making and using thereof
EP2395070A1 (en) 2010-06-10 2011-12-14 The Procter and Gamble Company Liquid laundry detergent composition comprising lipase of bacterial origin
WO2011163457A1 (en) 2010-06-23 2011-12-29 The Procter & Gamble Company Product for pre-treatment and laundering of stained fabric
WO2012003316A1 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Process for making films from nonwoven webs
WO2012003367A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Method for delivering an active agent
WO2012003360A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Detergent product and method for making same
WO2012003365A1 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising an ingestible active agent nonwoven webs and methods for making same
WO2012003319A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
WO2012003300A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising a non-perfume active agent nonwoven webs and methods for making same
WO2012009660A2 (en) 2010-07-15 2012-01-19 The Procter & Gamble Company Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
WO2012040130A1 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Non-fluoropolymer surface protection composition
WO2012040131A2 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Fabric care formulations and methods
WO2012040171A1 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Non-fluoropolymer surface protection composition
WO2012054835A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US8232431B2 (en) 2008-09-22 2012-07-31 The Procter & Gamble Company Specific branched surfactants and consumer products
US8247364B2 (en) 2007-01-19 2012-08-21 The Procter & Gamble Company Whitening agents for cellulosic substrates
WO2012112741A1 (en) 2011-02-16 2012-08-23 The Procter & Gamble Company Compositions and methods of bleaching
WO2012116014A1 (en) 2011-02-25 2012-08-30 Milliken & Company Capsules and compositions comprising the same
WO2012145062A1 (en) 2011-02-16 2012-10-26 The Procter & Gamble Company Liquid cleaning compositions
US8299010B2 (en) 2006-01-23 2012-10-30 The Procter & Gamble Company Laundry care compositions with thiazolium dye
WO2012166584A1 (en) 2011-06-03 2012-12-06 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
WO2012177709A1 (en) 2011-06-23 2012-12-27 The Procter & Gamble Company Product for pre-treatment and laundering of stained fabric
WO2013002786A1 (en) 2011-06-29 2013-01-03 Solae Baked food compositions comprising soy whey proteins that have been isolated from processing streams
WO2013016371A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergents having acceptable color
WO2013025742A1 (en) 2011-08-15 2013-02-21 The Procter & Gamble Company Detergent compositions containing pyridinol-n-oxide compounds
WO2013043805A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants
WO2013043857A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
WO2013043803A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
EP2581438A1 (en) 2011-10-12 2013-04-17 The Procter and Gamble Company Detergent composition
WO2013070559A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Surface treatment compositions including shielding salts
WO2013109671A1 (en) 2012-01-18 2013-07-25 The Procter & Gamble Company Acidic laundry detergent compositions
WO2013126550A2 (en) 2012-02-22 2013-08-29 Kci Licensing, Inc. New compositions, the preparation and use thereof
WO2013128431A2 (en) 2012-02-27 2013-09-06 The Procter & Gamble Company Methods for producing liquid detergent products
WO2013134269A2 (en) 2012-03-06 2013-09-12 Kci Licensing, Inc. New compositions, the preparation and use thereof
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
WO2014018309A1 (en) 2012-07-26 2014-01-30 The Procter & Gamble Company Low ph liquid cleaning compositions with enzymes
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
WO2014123665A1 (en) 2013-02-06 2014-08-14 Kci Licensing, Inc. Polymers, preparation and use thereof
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
WO2014150171A1 (en) 2013-03-15 2014-09-25 The Procter & Gamble Company Specific unsaturated and branched functional materials for use in consumer products
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US8957009B2 (en) 2010-01-29 2015-02-17 Evonik Degussa Gmbh Linear polydimethylsiloxane-polyether copolymers having amino and/or quaternary ammonium groups and use thereof
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
WO2015084813A1 (en) 2013-12-04 2015-06-11 The Procter & Gamble Company Furan-based composition
WO2015088826A1 (en) 2013-12-09 2015-06-18 The Procter & Gamble Company Fibrous structures including an active agent and having a graphic printed thereon
WO2015112671A1 (en) 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer product compositions
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
WO2016003699A1 (en) 2014-06-30 2016-01-07 The Procter & Gamble Company Laundry detergent composition
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
WO2016123347A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company Amino silicone nanoemulsion
WO2016123349A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company A method of making an amino silicone nanoemulsion
WO2016123002A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company Silicone nanoemulsion comprising c3-c6 alkylene glycol alkyl ether
WO2016130521A1 (en) 2015-02-10 2016-08-18 The Procter & Gamble Company Liquid laundry cleaning composition
WO2017065977A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017066337A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017066343A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017065979A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017066334A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017065978A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017112016A1 (en) 2015-12-22 2017-06-29 Milliken & Company Occult particles for use in granular laundry care compositions
WO2017127258A1 (en) 2016-01-21 2017-07-27 The Procter & Gamble Company Fibrous elements comprising polyethylene oxide
WO2017132003A1 (en) 2016-01-29 2017-08-03 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
WO2018052725A1 (en) 2016-09-13 2018-03-22 The Procter & Gamble Company Stable violet-blue to blue imidazolium compounds
WO2018085308A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085380A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085301A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco triphenylmethane colorants as bluing agents in laundry care compositions
WO2018085313A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
WO2018085305A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085303A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085382A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085391A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085388A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085309A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085311A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085378A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085304A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085306A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085302A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085386A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085394A1 (en) 2016-11-01 2018-05-11 Milliken & Company Reactive leuco compounds and compositions comprising the same
WO2018085300A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
WO2018085312A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
WO2018085389A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085372A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085314A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Reactive leuco compounds and compositions comprising the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248827A (en) * 1978-06-12 1981-02-03 The Procter & Gamble Company Method for sanitizing toilets
JPH01113500A (en) * 1987-10-28 1989-05-02 Dainichiseika Color & Chem Mfg Co Ltd Bleaching agent composition
US4960526A (en) * 1985-07-25 1990-10-02 Colgate-Polmolive Company Diammonium compound containing fabric softening and antistatic detergent composition
USH1313H (en) * 1991-08-30 1994-05-03 Minnesota Mining And Manufacturing Company Process of making poly(glycidyl azide) product and compounds useful therein
JPH06123071A (en) * 1992-10-08 1994-05-06 Kao Corp Softening, finishing agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248827A (en) * 1978-06-12 1981-02-03 The Procter & Gamble Company Method for sanitizing toilets
US4960526A (en) * 1985-07-25 1990-10-02 Colgate-Polmolive Company Diammonium compound containing fabric softening and antistatic detergent composition
JPH01113500A (en) * 1987-10-28 1989-05-02 Dainichiseika Color & Chem Mfg Co Ltd Bleaching agent composition
USH1313H (en) * 1991-08-30 1994-05-03 Minnesota Mining And Manufacturing Company Process of making poly(glycidyl azide) product and compounds useful therein
JPH06123071A (en) * 1992-10-08 1994-05-06 Kao Corp Softening, finishing agent

Cited By (194)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015750A1 (en) * 1998-09-15 2000-03-23 The Procter & Gamble Company Sanitising compositions and methods
US6551975B1 (en) 1998-09-15 2003-04-22 The Procter & Gamble Company Sanitizing compositions and methods
WO2006088980A1 (en) 2005-02-17 2006-08-24 The Procter & Gamble Company Fabric care composition
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US8299010B2 (en) 2006-01-23 2012-10-30 The Procter & Gamble Company Laundry care compositions with thiazolium dye
WO2008059013A1 (en) 2006-11-17 2008-05-22 Ciba Holding Inc. Premoistened cleaning disposable substrate
US8247364B2 (en) 2007-01-19 2012-08-21 The Procter & Gamble Company Whitening agents for cellulosic substrates
US8367598B2 (en) 2007-01-19 2013-02-05 The Procter & Gamble Company Whitening agents for cellulosic subtrates
US8703688B2 (en) 2007-01-19 2014-04-22 The Procter & Gamble Company Whitening agents for cellulosic substrates
WO2008109384A2 (en) 2007-03-05 2008-09-12 Celanese Acetate Llc Method of making a bale of cellulose acetate tow
US7928054B2 (en) 2007-05-17 2011-04-19 The Procter & Gamble Company Detergent additive extrudates containing alkyl benzene sulphonate
WO2009010911A2 (en) 2007-07-19 2009-01-22 The Procter & Gamble Company Detergent composition containing suds boosting co-surfactant and suds stabilizing surface active polymer
US7854770B2 (en) 2007-12-04 2010-12-21 The Procter & Gamble Company Detergent composition comprising a surfactant system and a pyrophosphate
EP2071017A1 (en) 2007-12-04 2009-06-17 The Procter and Gamble Company Detergent composition
EP2083065A1 (en) 2008-01-22 2009-07-29 The Procter and Gamble Company Colour-Care Composition
EP2103678A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising a co-polyester of dicarboxylic acids and diols
EP2103675A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company Detergent composition comprising cellulosic polymer
EP2103676A1 (en) 2008-03-18 2009-09-23 The Procter and Gamble Company A laundry detergent composition comprising the magnesium salt of ethylene diamine-n'n' -disuccinic acid
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
US7910538B2 (en) 2008-06-04 2011-03-22 The Procter & Gamble Company Detergent composition
EP2135931A1 (en) 2008-06-16 2009-12-23 The Procter and Gamble Company Use of soil release polymer in fabric treatment compositions
EP2272941A2 (en) 2008-06-20 2011-01-12 The Procter and Gamble Company Laundry composition
EP2135932A1 (en) 2008-06-20 2009-12-23 The Procter and Gamble Company Laundry composition
EP2135933A1 (en) 2008-06-20 2009-12-23 The Procter and Gamble Company Laundry composition
EP2154235A1 (en) 2008-07-28 2010-02-17 The Procter and Gamble Company Process for preparing a detergent composition
US8058222B2 (en) 2008-07-28 2011-11-15 The Procter & Gamble Company Process for manufacturing extruded alkyl sulfate particles
EP2166077A1 (en) 2008-09-12 2010-03-24 The Procter and Gamble Company Particles comprising a hueing dye
US8153579B2 (en) 2008-09-12 2012-04-10 The Procter & Gamble Company Laundry composition
EP2163608A1 (en) 2008-09-12 2010-03-17 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye and fatty acid soap
EP2166078A1 (en) 2008-09-12 2010-03-24 The Procter & Gamble Company Laundry particle made by extrusion comprising a hueing dye
US8183197B2 (en) 2008-09-12 2012-05-22 The Procter & Gamble Company Particles comprising a hueing dye
US7994369B2 (en) 2008-09-22 2011-08-09 The Procter & Gamble Company Specific polybranched polyaldehydes, polyalcohols, and surfactants, and consumer products based thereon
EP2650280A1 (en) 2008-09-22 2013-10-16 The Procter and Gamble Company Specific polybranched surfactants and consumer products based thereon
US8044249B2 (en) 2008-09-22 2011-10-25 The Procter & Gamble Company Specific branched aldehydes, alcohols, surfactants, and consumer products based thereon
EP2650275A1 (en) 2008-09-22 2013-10-16 The Procter and Gamble Company Specific polybranched alcohols and consumer products based thereon
US8299308B2 (en) 2008-09-22 2012-10-30 The Procter & Gamble Company Specific branched aldehydes, alcohols, surfactants, and consumer products based thereon
US8232432B2 (en) 2008-09-22 2012-07-31 The Procter & Gamble Company Specific branched aldehydes, alcohols, surfactants, and consumer products based thereon
US8232431B2 (en) 2008-09-22 2012-07-31 The Procter & Gamble Company Specific branched surfactants and consumer products
EP2210520A1 (en) 2009-01-22 2010-07-28 The Procter and Gamble Company Package comprising an adhesive perfume delivery material
WO2010085471A1 (en) 2009-01-22 2010-07-29 The Procter & Gamble Company Package comprising an adhesive perfume delivery material
WO2011005910A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005813A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005730A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005904A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Detergent composition
WO2011005844A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005630A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005830A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of sulphate
WO2011005804A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
WO2011005912A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric
WO2011005623A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of bleach
WO2011005913A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005911A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
WO2011005917A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a liquid laundry detergent composition
WO2011016958A2 (en) 2009-07-27 2011-02-10 The Procter & Gamble Company Detergent composition
WO2011025615A2 (en) 2009-08-13 2011-03-03 The Procter & Gamble Company Method of laundering fabrics at low temperature
EP2292725A1 (en) 2009-08-13 2011-03-09 The Procter and Gamble Company Method of laundering fabrics at low temperature
EP2302025A1 (en) 2009-09-08 2011-03-30 The Procter and Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
WO2011031599A1 (en) 2009-09-08 2011-03-17 The Procter & Gamble Company A laundry detergent composition comprising a highly water-soluble carboxymethyl cellulose particle
WO2011038078A1 (en) 2009-09-23 2011-03-31 The Procter & Gamble Company Process for preparing spray-dried particles
WO2011044305A1 (en) 2009-10-07 2011-04-14 The Procter & Gamble Company Detergent composition
WO2011075352A1 (en) 2009-12-18 2011-06-23 The Procter & Gamble Company Cleaning composition containing hemicellulose
US8957009B2 (en) 2010-01-29 2015-02-17 Evonik Degussa Gmbh Linear polydimethylsiloxane-polyether copolymers having amino and/or quaternary ammonium groups and use thereof
US8158572B2 (en) 2010-01-29 2012-04-17 The Procter & Gamble Company Linear polydimethylsiloxane-polyether copolymers with amino and/or quaternary ammonium groups and use thereof
WO2011094374A1 (en) 2010-01-29 2011-08-04 The Procter & Gamble Company Novel linear polydimethylsiloxane-polyether copolymers with amino and/or quaternary ammonium groups and use thereof
WO2011100405A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising crosslinked polyglycerol esters
WO2011100420A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising crosslinked polyglycerol esters
WO2011100411A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising polyglycerol esters
WO2011100500A1 (en) 2010-02-12 2011-08-18 The Procter & Gamble Company Benefit compositions comprising polyglycerol esters
WO2011100667A1 (en) 2010-02-14 2011-08-18 Ls9, Inc. Surfactant and cleaning compositions comprising microbially produced branched fatty alcohols
WO2011109322A1 (en) 2010-03-04 2011-09-09 The Procter & Gamble Company Detergent composition
WO2011133382A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company Detergent composition
WO2011133380A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company A laundry detergent composition comprising bleach particles that are suspended within a continuous liquid phase
EP2380960A1 (en) 2010-04-19 2011-10-26 The Procter and Gamble Company Detergent composition
WO2011133371A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
WO2011133372A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company Detergent composition
WO2011133456A1 (en) 2010-04-19 2011-10-27 The Procter & Gamble Company A liquid laundry detergent composition comprising a source of peracid and having a ph profile that is controlled with respect to the pka of the source of peracid
WO2011146602A2 (en) 2010-05-18 2011-11-24 Milliken & Company Optical brighteners and compositions comprising the same
EP3020768A1 (en) 2010-05-18 2016-05-18 Milliken & Company Optical brighteners and compositions comprising the same
WO2011146604A2 (en) 2010-05-18 2011-11-24 Milliken & Company Optical brighteners and compositions comprising the same
WO2011149907A1 (en) 2010-05-24 2011-12-01 University Of Utah Research Foundation Reinforced adhesive complex coacervates and methods of making and using thereof
WO2011149870A1 (en) 2010-05-28 2011-12-01 Milliken & Company Colored speckles for use in granular detergents
WO2011149871A1 (en) 2010-05-28 2011-12-01 Milliken & Company Colored speckles having delayed release properties
WO2011156297A2 (en) 2010-06-10 2011-12-15 The Procter & Gamble Company Compacted liquid laundry detergent composition comprising lipase of bacterial origin
EP2395070A1 (en) 2010-06-10 2011-12-14 The Procter and Gamble Company Liquid laundry detergent composition comprising lipase of bacterial origin
WO2011163457A1 (en) 2010-06-23 2011-12-29 The Procter & Gamble Company Product for pre-treatment and laundering of stained fabric
WO2012003365A1 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising an ingestible active agent nonwoven webs and methods for making same
WO2012003360A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Detergent product and method for making same
WO2012003316A1 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Process for making films from nonwoven webs
WO2012003300A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising a non-perfume active agent nonwoven webs and methods for making same
WO2012003351A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Web material and method for making same
WO2012003319A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Filaments comprising an active agent nonwoven webs and methods for making same
WO2012003367A2 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Method for delivering an active agent
WO2012009660A2 (en) 2010-07-15 2012-01-19 The Procter & Gamble Company Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
WO2012040130A1 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Non-fluoropolymer surface protection composition
US8637442B2 (en) 2010-09-20 2014-01-28 The Procter & Gamble Company Non-fluoropolymer surface protection composition comprising a polyorganosiloxane-silicone resin mixture
US8633146B2 (en) 2010-09-20 2014-01-21 The Procter & Gamble Company Non-fluoropolymer surface protection composition comprising a polyorganosiloxane-silicone resin mixture
WO2012040171A1 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Non-fluoropolymer surface protection composition
WO2012040131A2 (en) 2010-09-20 2012-03-29 The Procter & Gamble Company Fabric care formulations and methods
WO2012054835A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
WO2010151906A2 (en) 2010-10-22 2010-12-29 Milliken & Company Bis-azo colorants for use as bluing agents
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
WO2011017719A2 (en) 2010-11-12 2011-02-10 Milliken & Company Thiophene azo dyes and laundry care compositions containing the same
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
WO2012112741A1 (en) 2011-02-16 2012-08-23 The Procter & Gamble Company Compositions and methods of bleaching
WO2012145062A1 (en) 2011-02-16 2012-10-26 The Procter & Gamble Company Liquid cleaning compositions
WO2012116023A1 (en) 2011-02-25 2012-08-30 Milliken & Company Capsules and compositions comprising the same
WO2012116021A1 (en) 2011-02-25 2012-08-30 Milliken & Company Capsules and compositions comprising the same
WO2012116014A1 (en) 2011-02-25 2012-08-30 Milliken & Company Capsules and compositions comprising the same
WO2012166584A1 (en) 2011-06-03 2012-12-06 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
WO2012177709A1 (en) 2011-06-23 2012-12-27 The Procter & Gamble Company Product for pre-treatment and laundering of stained fabric
WO2013002786A1 (en) 2011-06-29 2013-01-03 Solae Baked food compositions comprising soy whey proteins that have been isolated from processing streams
WO2013016371A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergents having acceptable color
US9309490B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer compositon and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
WO2013025742A1 (en) 2011-08-15 2013-02-21 The Procter & Gamble Company Detergent compositions containing pyridinol-n-oxide compounds
WO2013043857A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
WO2013043803A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
WO2013043805A1 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid - based surfactants
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013055903A1 (en) 2011-10-12 2013-04-18 The Procter & Gamble Company Detergent composition
EP2581438A1 (en) 2011-10-12 2013-04-17 The Procter and Gamble Company Detergent composition
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9988526B2 (en) 2011-11-04 2018-06-05 Akzo Nobel Chemicals International B.V. Hybrid dendrite copolymers, compositions thereof and methods for producing the same
WO2013070559A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Surface treatment compositions including shielding salts
WO2013070560A1 (en) 2011-11-11 2013-05-16 The Procter & Gamble Company Surface treatment compositions including shielding salts
WO2013109671A1 (en) 2012-01-18 2013-07-25 The Procter & Gamble Company Acidic laundry detergent compositions
WO2013126550A2 (en) 2012-02-22 2013-08-29 Kci Licensing, Inc. New compositions, the preparation and use thereof
WO2013128431A2 (en) 2012-02-27 2013-09-06 The Procter & Gamble Company Methods for producing liquid detergent products
WO2013134269A2 (en) 2012-03-06 2013-09-12 Kci Licensing, Inc. New compositions, the preparation and use thereof
WO2014018309A1 (en) 2012-07-26 2014-01-30 The Procter & Gamble Company Low ph liquid cleaning compositions with enzymes
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
WO2014123665A1 (en) 2013-02-06 2014-08-14 Kci Licensing, Inc. Polymers, preparation and use thereof
WO2014150171A1 (en) 2013-03-15 2014-09-25 The Procter & Gamble Company Specific unsaturated and branched functional materials for use in consumer products
WO2014160820A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2015084813A1 (en) 2013-12-04 2015-06-11 The Procter & Gamble Company Furan-based composition
WO2015088826A1 (en) 2013-12-09 2015-06-18 The Procter & Gamble Company Fibrous structures including an active agent and having a graphic printed thereon
WO2015112671A1 (en) 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer product compositions
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10053652B2 (en) 2014-05-15 2018-08-21 Ecolab Usa Inc. Bio-based pot and pan pre-soak
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
WO2016003699A1 (en) 2014-06-30 2016-01-07 The Procter & Gamble Company Laundry detergent composition
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
WO2016123349A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company A method of making an amino silicone nanoemulsion
WO2016123347A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company Amino silicone nanoemulsion
WO2016123002A1 (en) 2015-01-28 2016-08-04 The Procter & Gamble Company Silicone nanoemulsion comprising c3-c6 alkylene glycol alkyl ether
WO2016130521A1 (en) 2015-02-10 2016-08-18 The Procter & Gamble Company Liquid laundry cleaning composition
WO2017065977A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017065979A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017066334A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017065978A1 (en) 2015-10-13 2017-04-20 The Procter & Gamble Company Laundry care compositions comprising whitening agents for cellulosic substrates
WO2017066413A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017066343A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017066337A1 (en) 2015-10-13 2017-04-20 Milliken & Company Novel whitening agents for cellulosic substrates
WO2017112016A1 (en) 2015-12-22 2017-06-29 Milliken & Company Occult particles for use in granular laundry care compositions
WO2017127258A1 (en) 2016-01-21 2017-07-27 The Procter & Gamble Company Fibrous elements comprising polyethylene oxide
WO2017132003A1 (en) 2016-01-29 2017-08-03 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
WO2018052725A1 (en) 2016-09-13 2018-03-22 The Procter & Gamble Company Stable violet-blue to blue imidazolium compounds
WO2018085391A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085313A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
WO2018085301A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco triphenylmethane colorants as bluing agents in laundry care compositions
WO2018085303A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085382A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085380A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085388A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085309A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085311A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085308A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085304A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085306A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085302A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions
WO2018085386A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085394A1 (en) 2016-11-01 2018-05-11 Milliken & Company Reactive leuco compounds and compositions comprising the same
WO2018085300A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Methods of using leuco colorants as bluing agents in laundry care compositions
WO2018085312A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco colorants as bluing agents in laundry care compositions
WO2018085389A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085372A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085314A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Reactive leuco compounds and compositions comprising the same
WO2018085378A1 (en) 2016-11-01 2018-05-11 Milliken & Company Leuco polymers as bluing agents in laundry care compositions
WO2018085305A1 (en) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco polymers as bluing agents in laundry care compositions

Similar Documents

Publication Publication Date Title
US6022844A (en) Cationic detergent compounds
US6610312B2 (en) Cosmetic effervescent cleansing pillow
US6579840B1 (en) Detergent compositions or components comprising hydrophobically modified cellulosic polymers
US6472364B1 (en) Detergent compositions or components
US6482789B1 (en) Detergent composition comprising mid-chain branched surfactants
US6444634B1 (en) Bleaching compositions
US6191100B1 (en) Detergent composition having effervescent generating ingredients
US6207632B1 (en) Detergent composition comprising a cationic surfactant and a hydrophobic peroxyacid bleaching system
US6046149A (en) Detergent compositions
US6689732B1 (en) Detergent compositions having a specific hydrophobic peroxyacid bleaching system and anionic surfactant
WO1997043366A1 (en) Detergent composition
US6313086B1 (en) Detergent compositions containing and effervescent
WO1996014384A1 (en) Laundry washing method using a dispensing means for a solid bleaching detergent
US6339055B1 (en) Cleaning compositions
US6103685A (en) Detergent compositions
WO1997044417A1 (en) Detergent composition
WO1998046714A1 (en) Detergent particle
WO1998035004A1 (en) Solid detergent compositions
EP0710714A2 (en) Bleaching compositions
WO1998017767A1 (en) Detergent compositions
WO2000018859A1 (en) Solid detergent compositions
WO1998035002A1 (en) Cleaning compositions
WO1995028469A1 (en) Detergents containing a builder and a delayed release enzyme
US6689739B1 (en) Detergent compositions
WO2000034422A2 (en) Effervescence components

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase in:

Ref country code: JP

Ref document number: 1998534973

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase