AU2019204219B2 - Detergent composition - Google Patents

Abstract

A liquid hard surface detergent composition comprising a 5 liquid mixed alkoxylate fatty alcohol non-ionic surfac tant comprising a greater number of the lower higher alkoxylate group than the higher alkoxylate group in the molecule and a builder. The compositions provide good shine/anti-spotting characteristics on hard surfaces and 10 are especially suitable for use as automatic dishwashing compositions.

Description

DETERGENT COMPOSITION

Technical field

The present invention relates to hard surface detergent

compositions such as dishwashing detergent compositions,

in particular automatic dishwashing compositions. It al

so relates to a process of preparing these compositions.

In particular the present invention relates to such com

positions comprising particular types of non-ionic sur

factants and which demonstrate good anti-spotting/shine

properties on articles cleansed therewith.

Background of the invention

It is well known to use detergent compositions in the

cleansing of hard surfaces such as cleaning falls and

walls and in dishwashing such as automatic dishwashing.

However it is well known that washing hard surfaces with

detergent compositions can lead to the cleansed items

suffering from spotting due to mineral deposits being

left behind once the cleansing operation has been com

pleted. These mineral deposits can be seen as spots on

the items and also reduce the shine of the item which has

been treated. In dishwashing operations, as well as other

cleaning operations the appearance of a shiny surface is

tremendously important to consumers as it is perceived as

showing thorough and hygienic cleaning results.

The shine of a hard surface is determined mainly by the

builder, the polymer and the surfactant system used in the detergent used to clean the surface in question.

Typically such detergent compositions are formulated to

contain a builder. Builder such as the phosphate build

ers can bind calcium and magnesium ions, act as alkalini

ty source for the detergent and are used to buffer the

wash liquor in a dishwasher at pH 9 and above sometimes

together with other chemicals such as disilicate, meta

silicates and soda. Phosphates are also able to disperse

existing calcium carbonate in the wash liquor to prevent

spotting on glasses as for the aforementioned reasons

this is seen as undesirable by the consumer. Thus, phos

phates in a detergent have at least four different func

tions in an alkaline detergent; (1) Providing alkalinity;

(2) buffering capacity, (3) complexing of magnesium and

calcium ions; and (4) dispersing capacity of calcium car

bonate. However, often the use of builders alone is not

sufficient to prevent the appearance of spotting on hard

surfaces.

Accordingly there is a need in the art to provide deter

gent compositions for hard surfaces such as kitchenware,

walls and floors, which show good anti-spotting proper

ties and which retain the shine on the surface of the

item being cleansed. This is especially important for

items such as glassware cleaned in a dishwashing opera

tion such as in an automatic dishwashing machine.

It is an object of the present invention to address one

or more of the above-mentioned problems.

In particular, it is an object of the present invention

to provide detergent compositions for hard surfaces, and in particular and (automatic) dishwashing detergent com positions which provide effective shine/anti-spotting properties on the surfaces it is used to cleanse.

Statement of invention

It has surprisingly been found that one or more of the

above problems are addressed by the compositions of the

present invention.

According to a first aspect the invention provides a liq

uid automatic dishwashing detergent composition compris

ing;

a. liquid mixed ethoxylate/propoxylate fatty alcohol non

ionic surfactant having 7 or 8 moles of the ethoxylate

group and 4 or 5 moles of the propoxylate group in the

molecule, and

b. a builder.

Preferably, the composition is a gel.

Preferably the mixed ethoxylate/propoxylate fatty alcohol

non-ionic surfactant comprises 4 moles of PO and 8 moles

of EO.

Preferably the mixed ethoxylate/propoxylate fatty alcohol

non-ionic surfactant is from a linear chain fatty alcohol

having 12-18 carbon atoms.

Preferably said surfactant is from a linear chain fatty

alcohol having 12 - 15 carbon atoms.

Preferably said surfactant has at least 10 moles of al

kylene oxide per mole of alcohol.

Preferably the detergent composition comprises at least 2

wt % of the mixed ethoxylate/propoxylate fatty alcohol

non-ionic surfactant.

Preferably the detergent compositioncomprises 2 to 30 %wt

of the mixed ethoxylate / propoxylate fatty alcohol non

ionic surfactant.

Preferably the total amount of builder present in the

composition is at least 10 wt %.

Preferably the builder is selected from phosphate

containing builders, polycarboxylic acids and their salts

and amino acid based builders.

Preferably the builder is selected from tripolyphos

phates, citrates, MGDA and GLDA and salts or derivatives

and mixtures thereof.

Preferably the detergent composition further comprises a

polymer.

preferably the polymer is a sulphonated polymer.

Preferably the sulphonated polymer comprises monomers of

a carboxylic acid or a salt thereof and a sulphonated

monomer.

Preferably the composition further comprises additional

non-ionic surfactant.

Preferably any solvent included in the composition is

present in an amount of no more than 10 wt %.

According to a second aspect the invention provides a

method of preparing a detergent composition according to

the first aspect wherein the detergent composition is

prepared at a temperature in the range of from 25- 800C.

Preferably the detergent composition is prepared at a

temperature in the range of from 30-500C.

According to a third aspect the invention provides a unit

dose detergent composition comprising a liquid automatic

dishwashing detergent composition according to the first

aspect enveloped in a water soluble or water dispersible

package.

Preferably the water soluble or water dispersible package

has a plurality of compartments.

Preferably the water soluble or water dispersible package

comprises polymeric packaging material.

Preferably the polymeric packaging material is selected

from polyvinyl alcohol, celluloses and cellulose deriva tives, starches, gelatine, polyglycolides, gelatine and polylactides copolymers or a mixture or co-polymer there of.

According to a fourth aspect the invention provides a

method of reducing spotting on a hard surface by contact

ing a hard surface with a composition according to the

first aspect or a unit dose composition according to the

third aspect, wherein the method is carried out in an au

tomatic dishwashing machine.

Surprisingly, it has been found that the detergent compo

sitions according to the present invention exhibit good

anti-spotting and shine properties upon hard surfaces,

especially in dishwashing applications such as in auto

matic dishwashers.

Unless stated otherwise, all amounts herein are given as

the percentage by weight of active ingredient based upon

the weight of the total composition.

Unless the context clearly requires otherwise, throughout

the description and the claims, the words "comprise", "comprising", and the like are to be construed in an in

clusive sense as opposed to an exclusive or exhaustive

sense; that is to say, in the sense of "including, but

not limited to".

The term 'substantially free of' as used herein means

less than 0.5%wt of the material in question based on the

total weight of that material in the detergent composi

tion.

By the term 'water soluble or water dispersible packag

ing' as used herein is meant a package which at least

partially dissolves in water or disperses in water at

20°C within 10 minutes to allow for egress of the con

tents of the package into the surrounding water.

By the term 'higher alkoxylate' it is meant the alkox

ylate group having the greatest number of carbon atoms in

that alkoxylate group. By the term 'lower alkoxylate' it

is meant the alkoxylate group having the lowest number of

carbon atoms in that alkoxylate group. Thus for a mixed

alkoxylate fatty alcohol comprising ethoxylate (EO) and

propoxylate (PO) groups the EO is the lower alkoxylate

and the PO is the higher alkoxylate. Thus the detergent

compositions of the invention comprise mixed alkoxylate

fatty alcohols comprising a greater number of EO groups

than PO groups. The same applies to other mixed alkox

ylates such as those containing EO and butoxylate (BO) or

even PO and BO groups.

By the term 'liquid surfactant' as used herein is meant a

surfactant which is liquid at 21°C.

A 'liquid composition' as used herein refers coherent

composition which shows a tendency to flow as a coherent

mass. It includes liquids, gels and pastes. For the

avoidance of doubt it does not include solid bodies,

granules or powders.

Detailed description

The present invention will now be described in further

detail.

a) detergent composition format

The composition of the invention may be type of hard sur

face detergent compositions such as a floor or wall

cleaning composition. However it is preferred that the

composition of the invention is a dishwashing composition

and in particular an automatic dishwashing composition.

The detergent compositions of the present invention are

in liquid form as herein defined. According to a pre

ferred aspect of the present invention the dishwashing

composition is a gel.

Preferably the detergent compositions of the invention

are alkaline, more preferably having a pH in the range of

9-12 as a 1%wt solution at 20 0 C, most preferably 9.5

11.5. However in some applications it is possible to use

less alkaline detergents e.g. those with a pH in the

range of from 6.5 to 9, especially from 7 to 8.5 as a

1%wt solution at 20 0 C.

The detergent compositions of the present invention may

be made by any suitable method as well known to the per

son skilled in the art. However, it is preferred that

when the detergent composition is according to the second

aspect of the invention.

b) Liquid mixed alkoxylate fatty alcohol nonionic surfac

tant

Non-ionic surfactants are preferred for automatic dish

washing and some other hard surface cleaning operations

as they are considered to be low foaming surfactants.

The standard non-ionic surfactant structure is based on a

fatty alcohol with a carbon C8 to C20 chain, wherein the

fatty alcohol has been ethoxylated or propoxylated. The

degree of ethoxylation is described by the number of eth

ylene oxide units (EO), and the degree of propoxylation

is described by the number of propylene oxide units (PO).

Surfactants may also comprise butylene oxide units (BO)

as a result of butoxylation of the fatty alcohol. Prefer

ably, this will be a mix with PO and EO units. The sur

factant chain can be terminated with a butyl (Bu) moiety.

The length of the fatty alcohol and the degree of ethoxy

lation/ propoxylation determines if the surfactant struc

ture has a melting point below room temperature or in

other words if is a liquid or a solid at room tempera

ture. It is believed that the mixed alkoxylate fatty al

cohol non-ionic surfactant of the present invention pro

vide their advantages for spotting inhibition and shine

at least partly because they are liquid at room tempera

ture.

It is preferred that the mixed alkoxylate fatty alcohol

nonionic surfactant have a fast wetting properties on

glass, plastic and metal surfaces such that at least 90%

of the surface is wetted in less than 30 seconds.

The compositions of the invention comprise a liquid mixed

alkoxylate fatty alcohol non-ionic surfactant comprising

a greater number of moles of the lower higher alkoxylate group than of the higher alkoxylate group in the mole cule.

It is especially preferred that the mixed alkoxylate fat

ty alcohol nonionic surfactant comprises at least two of

EO, PO or BO groups and especially a mixture of EO and PO

groups, preferably EO and PO groups only.

It is most preferred that the mole ratio of the lower

alkoxylate group to the higher alkoxylate group is at

least 1.1:1, more preferably at least 1.5:1, and most

preferably at least 1.8:1, such as at least 2:1 or even

at least 3:1.

An especially preferred mixed alkoxylate fatty alcohol

nonionic surfactant according to the present invention

comprises between 3 to 5 moles of the higher alkoxylate

group and between 6 to 10 moles the higher lower group.

Especially preferred are mixed alkoxylate fatty alcohol

nonionic surfactants having 4 or 5 moles of the higher

alkoxylate group and 7 or 8 moles of the lower alkoxylate

group. According to one aspect of the invention a mixed

alkoxylate fatty alcohol nonionic surfactant having 4 or

5 PO moles and 7 or 8 EO moles is especially preferred

and good results have been obtained with for surfactants

with 4 PO moles and 8 EO moles. In an especially pre

ferred embodiment the mixed alkoxylate fatty alcohol

nonionic surfactant is C12-15 8EO/4PO.

Surfactants of the above type which are ethoxylated mono

hydroxy alkanols or alkylphenols which additionally com

prise poly-oxyethylene-polyoxypropylene block copolymer units may be used. The alcohol or alkylphenol portion of such surfactants constitutes more than 30%, preferably more than 50%, more preferably more than 70% by weight of the overall molecular weight of the non-ionic surfactant.

The mixed alkoxylate fatty alcohol non-ionic surfactants

used in the compositions of the invention may be prepared

by the reaction of suitable monohydroxy alkanols or al

kylphenols with 6 to 20 carbon atoms. Preferably the

surfactants have at least 8 moles, particularly preferred

at least 10 moles of alkylene oxide per mole of alcohol

or alkylphenol.

Particularly preferred liquid mixed alkoxylate fatty al

cohol non-ionic surfactants are those from a linear chain

fatty alcohol with 12-18 carbon atoms, preferably 12 to

15 carbon atoms and at least 10 moles, particularly pre

ferred at least 12 moles of alkylene oxide per mole of

alcohol.

When PO units are used they preferably constitute up to

25% by weight, preferably up to 20% by weight and still

more preferably up to 15% by weight of the overall molec

ular weight of the non-ionic surfactant.

Suitable liquid mixed alkoxylate fatty alcohol non-ionic

surfactants can be found in the class of reverse block

copolymers of polyoxyethylene and poly-oxypropylene and

block copolymers of polyoxyethylene and polyoxypropylene

initiated with trimethylolpropane.

Suitable types can also be described by the formula:

RiO[CH 2 CH(CH 3 )0]x [CH 2 CH 2 0]y [CH 2 CH(OH)R 2]

where RI represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof, R2 represents a linear or branched chain ali phatic hydrocarbon rest with 2-26 carbon atoms or mix tures thereof, x is a value between 0.5 and 1.5 and y is a value of at least 15.

Another group of suitable liquid mixed alkoxylate fatty alcohol non-ionic surfactants can be found in the end capped polyoxyalkylated non-ionics of formula:

R1O [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] jOR2

where Ri and R2 represent linear or branched chain, satu

rated or unsaturated, aliphatic or aromatic hydrocarbon

groups with 1-30 carbon atoms, R3 represents a hydrogen

atom or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x is a value between 1 and 30 and, k and j are values between 1 and 12, prefera bly between 1 and 5 with the proviso that the molecule contains more of the lower alkoxylate than of the higher

alkoxylate. When the value of x is >2 each R3 in the for

mula above can be different. Ri and R2 are preferably

linear or branched chain, saturated or unsaturated, ali phatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where group with 8 to 18 carbon atoms are particu

larly preferred. For the group R3 = H, methyl or ethyl are particularly preferred. Particularly preferred values for x are comprised between 1 and 20, preferably between

6 and 15.

As described above, in case x>2, each R3 in the formula

can be different. For instance, when x=3, the group R3

could be chosen to build ethylene oxide (R3 = H) or pro

pylene oxide (R3 = methyl) units which can be used in

every single order for instance (PO)(EO)(EO),

(EO)(PO)(EO), (EO)(EO)(PO), (PO) (EO)(PO) and

(PO)(PO) (EO) . Only the mixed alkoxylates having compris

ing more of the lower alkoxylate than of the higher

alkoxylate are suitable as the claimed mixed alkoxylate

fatty alcohol nonionic surfactant. The value 3 for x is

only an example and bigger values can be chosen whereby a

higher number of variations of (EO) or (PO) units would

arise.

Particularly preferred end-capped polyoxyalkylated alco

hols of the above formula are those where k=l and j=1

originating molecules of simplified formula:

R 1 0 [CH2CH (R3) 0] xCH2CH (OH) CH20R2

Other suitable surfactants are disclosed in WO 95/01416,

to the contents of which express reference is hereby

made.

In a particularly preferred embodiment of the present in

vention the mixed alkoxylate fatty alcohol non-ionic sur

factants have the general formula;

Ri-[EO]n-[POlm-[BO1p-BUq

wherein:

Ri is an alkyl group of between C8 and C20;

EO is ethylene oxide;

PO is propylene oxide;

BO is butylene oxide;

Bu is butylene

n and m are integers from 1 to 15;

p is an integer from 0 to 15; and

q is 0 or 1.

Examples of especially preferred mixed alkoxylate fatty

alcohol non-ionic surfactants can be found in the Plu

rafacTM , LutensolTM and PluronicTM ranges from BASF and

the GenapolTM series from Clariant.

The claimed mixed alkoxylate fatty alcohol non-ionic sur

factants, and especially the C12-15 fatty alcohol 8EO,4PO

surfactant (commercially available as Genapol EP 2584 ex

Clariant, Germany) exhibit;

• Excellent wetting of plastic, glass, ceramic and

stainless steel

• Excellent temperature stability up to 900C for pro

cessing

• Good compatibility with thickeners typically used in

the liquid detergent compositions (e.g. PEG)

• Stability in alkaline conditions.

The use of a mixture of any of the aforementioned

nonionic surfactants is suitable in compositions of the

present invention, e.g. mixtures of alkoxylated alcohols

and hydroxy group containing alkoxylated alcohols, pro

vided that they are liquid and have a greater number of

moles of the lower higher alkoxylate group than of the

higher alkoxylate group in the molecule.

It is preferred that the liquid detergent compositions of

the invention comprise 2-30%wt of the liquid mixed alkox

ylate fatty alcohol nonionic surfactant more preferably

3-25%wt such as 5-20%wt. If the composition of the inven

tion are present as part of a multi-phase unit dose com

position then preferably the claimed non-ionic surfac

tants are present an amount of from 0.1 %wt to 15 %wt,

more preferably 0.5%wt to 10 %wt, such as 0.5 to 7.5%wt

based on the total unit dose composition.

Without wishing to be bound by theory it is believed that

the film of the surfactant molecules covering the surface

of the tableware and the dishwasher prevents the deposi

tion of calcium carbonate on the surfaces and so aids the

reduction in spotting and improves the shine of the sur

faces being treated. A second and unexpected beneficial

effect is an increased "carry over" of surfactant from

the main washing cycle into the rinse cycle in the auto

matic dishwashing machine due to the high concentration

of surfactant. This is important for multi-benefit deter

gents, because they are used without adding extra rinse

aid into the reservoir provided in the dishwasher.

Many technological processes require control of liquid

spreading over solid surfaces. When a drop is placed on a

surface, it can completely wet, partially wet, or not wet

the surface. Wetting can be defined in terms of the con

tact angle 0 of a liquid droplet on a particular surface,

with a smaller contact angle signifying greater wetting;

a contact angle of between 00 and 900 is defined as

highly wettable, with 00 being defined as totally wetta

ble.

By reducing the surface tension with the claimed

surfactants non-wetting material for water can be made to

become partially or completely wetting. Surfactants are

absorbed onto the liquid-vapor, solid-liquid, and solid

vapor interfaces, which modify the wetting behavior of

hydrophobic materials to reduce the free energy. When

surfactants are absorbed onto a hydrophobic surface, the

polar head groups face into the solution with the tail

pointing outward. In more hydrophobic surfaces, surfac

tants may form a bilayer on the solid, causing it to be

come more hydrophilic. As the surfactants are absorbed,

the solid-vapor surface tension increases and the edges

of the drop become hydrophilic. As a result, the drop

spreads and the appearance of spotting is reduced.

This process is time dependent, and the dynamic drop ra

dius can be characterized as the drop begins to spread.

The contact angle changes are based on the following

equation:

Cos (t) Cos%+(Cos0"- Cos%)(1

S80 is the initial contact angle

E). is the final contact angle

• T is the surfactant transfer time scale

The wetting properties of a surfactant are therefore key

to its performance in detergent compositions used on hard

surfaces, such as dishwashing compositions as they regu

lating the amount of spots left on surfaces as a result

of drying of unevenly spread water droplets.

c) builders

The compositions of the invention comprise a builder. A

builder may also be included in any additional detergent

composition used in a multi-phase unit dose composition

with the composition of the invention. The detergent com

positions may comprise conventional amounts of detergent

builders which may be either phosphorous based or non

phosphorous based, or a combination of both types. Suit

able builders are well known in the art.

If phosphorous containing builders are to be used then it

is preferred that mono-phosphates, di-phosphates, tri

polyphosphates, polyphosphonates or oligomeric

poylphosphates are used. The alkali metal salts of these

agents are preferred, in particular the sodium salts. An

especially preferred phosphorous containing builder is

sodium tripolyphosphate (STPP). Conventional amounts of

the phosphorous-containing builders may be used in the

solid detergent compositions, typically in the range of

from 15%wt to 80%wt, such as 20%wt to 75%wt, more prefer

ably 25%wt to 60%wt.

The non-phosphorous containing builder may be organic

molecules with carboxylic group(s), amino acid based com

pounds, a succinate based compound or a mixture thereof.

The term 'succinate based compound' and 'succinic acid

based compound' are used interchangeably herein and these

compounds are further described below.

Builder compounds which are organic molecules selected

from water-soluble monomeric polycarboxylic acids and/or

their acid forms may be used according to the invention.

Suitable polycarboxylic acids include acyclic, alicyclic,

heterocyclic and aromatic carboxylic acids. Suitable

examples of such compounds include citric acid, fumaric

acid, tartaric acid, maleic acid, lactic acid, (ethylene

dioxy)diacetic acid, tartronic acid, lactic acid, glycol

ic acid, malonic acid, diglycolic acid and fumaric acid

and salts and derivatives thereof, especially the water

soluble salts thereof. Preferred salts of the abovemen

tioned compounds are the ammonium and/or alkali or alka

line earth metal salts, e.g. the ammonium, lithium, sodi

um, potassium or calcium salts, and particularly pre

ferred salts are the sodium salts. These acids may be

used in their monomeric or oligomeric form. An especially

preferred builder is sodium citrate.

Preferred examples of amino acid based compounds accord

ing to the invention are MGDA (methyl-glycine-diacetic

acid, and salts and derivatives thereof) and GLDA (glu

tamic-N,N-diacetic acid) and salts and derivatives there

of. Other suitable builders are described in US 6,426,229

which is incorporated by reference herein. A preferred

MGDA compound is a salt of methyl glycine diacetic acid.

Suitable salts include the triammonium salt, the tripo

tassium salt and, preferably, the trisodium salt. A pre ferred GLDA compound is a salt of glutamic diacetic acid.

Suitable salts include the tetraammonium salt, the tetra

potassium salt and, preferably, the tetrasodium salt. Es

pecially preferred are the sodium salts thereof.

In particular suitable builders include; for example,

aspartic acid-N-monoacetic acid (ASMA), aspartic acid

N,N-diacetic acid (ASDA), iminodisuccinic acid (IDA), as

partic acid-N- monopropionic acid (ASMP), N-(2

sulfomethyl) aspartic acid (SMAS), N- (2

sulfoethyl)aspartic acid (SEAS), N- (2

sulfomethyl)glutamic acid (SMGL), N-(2- sul

foethyl)glutamic acid (SEGL), N- methyliminodiacetic acid

(MIDA), a- alanine-N,N-diacetic acid (a-ALDA), I-alanine

N,N-diacetic acid (P-ALDA), serine-N,N-diacetic acid

(SEDA), isoserine-N,N-diacetic acid (ISDA), phenylala

nine-N,N-diacetic acid (PHDA), anthranilic acid-N,N- di

acetic acid (ANDA), sulphanilic acid-N,N-diacetic acid

(SLDA), taurine-N, N-diacetic acid (TUDA) and sulphome

thyl-N,N-diacetic acid (SMDA) and alkali metal salts or

ammonium salts thereof.

Preferred succinate compounds are described in US-A

5,977,053 and have the formula;

O 0 R R

R40 OR 2

R 50 OR 3 N H O 0

in which R, R', independently of one another, denote H or

OH, R2 , R3 , R4 , R5 , independently of one another, denote

a cation, hydrogen, alkali metal ions and ammonium ions,

ammonium ions having the general formula R 6 R 7 R 8 R 9 N+ and

R6 , R , R 8 , R , independently of one another, denoting

hydrogen, alkyl radicals having 1 to 12 C atoms or hy

droxyl-substituted alkyl radicals having 2 to 3 C atoms.

Iminodisuccinic acid (IDS) and (hydroxy)iminodisuccinic

acid (HIDS) and alkali metal salts or ammonium salts

thereof are especially preferred succinate based builder

salts. Especially preferred are the sodium salts there

of.

MGDA, GLDA, IDS and HIDS are especially preferred amino

acid based and succinate based builders according to the

present invention and mixtures thereof may also be used.

Any suitable form of the amino acid and succinate based

compounds in the preceding paragraphs may be used.

Conventional amounts of these phosphorous free builders

may be used, typically with an amount in the range of

from 20%wt to 80%wt, such as 25 or 30%wt to 60 or 70%wt

being used.

According to one aspect of the present invention a mix

ture of a phosphorous containing builder such as STPP and

a non-phosphorous containing builder such as MGDA, GLDA,

IDS, HIDS and/or citrates may be used. The weight pro

portions of each builder can be selected according to the

needs of the formulator.

Preferably the total amount of builder present in the

composition is at least 10 wt%, and most preferably at

least 15 wt%, preferably in an amount of up to 80wt%,

preferably up to 65wt%, more preferably up to 60wt%. The

actual amount used in the compositions will depend upon

the nature of the builder used.

d) optional ingredients

The detergent compositions of the invention may also com

prise additional optional ingredients in addition to the

claimed surfactant. These ingredients may also be present

in any other detergent composition used in conjunction

with the composition of the invention to form a multi

phase unit dose detergent composition. Where reference is

made below to a weight percentage based it is to the

weight percentage of the composition comprising that in

gredient. For the composition of the invention this is

based simply upon the weight of that composition. Where

the composition forms part of a multi-phase unit dose de

tergent composition the amount is stated as based upon

the weight of that part of the multi-phase unit dose com

position which contains the specified ingredient.

In addition to the particular liquid mixed alkoxylated

fatty alcohol surfactants described above which are an essential component of the detergent compositions of the invention, they may also comprise one or more further surfactants. Any other detergent compositions used with the compositions of the invention in the multi-phase unit dose compositions of the invention may also comprise sur factant as described herein.

If any further surfactant is present it may be any of

nonionic, anionic, cationic, amphoteric or zwitterionic

surface active agents or mixtures thereof although cati

onic surfactants are less preferred. Many such suitable

surfactants are described in Kirk Othmer's Encyclopedia

of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379,

"Surfactants and Detersive Systems", incorporated by ref

erence herein.

For automatic dishwashing compositions according to the

present invention non-ionic surfactants are especially

preferred. For other cleaning applications, such as

floors and walls, other surfactants such as anionic sur

factants may also be included and suitable types are well

known in the art.

The additional nonionic surfactants which may be used in

clude any solid nonionic surfactant and any nonionic sur

factants which do not contain more of the lower alkox

ylate than of the higher alkoxylate.

Additional nonionic surfactants which may be used (ex

cluding any falling into the essential liquid mixed

alkoxylate fatty alcohol non-ionic surfactants class

above) include ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkylphenol with 6 to 20 carbon atoms which are not liquid or which do not contain more of the lower alkoxylate than of the higher alkoxylate.

Preferably the surfactants have at least 12 moles partic

ularly preferred at least 16 moles, and still more pre

ferred at least 20 moles, such as at least 25 moles of

ethylene oxide per mole of alcohol or alkylphenol. Par

ticularly preferred non-ionic surfactants suitable for

use as the additional nonionic surfactants are those from

a linear chain fatty alcohol with 16-20 carbon atoms and

at least 12 moles, particularly preferred at least 16 and

still more preferred at least 20 moles, of ethylene oxide

per mole of alcohol.

The additional fatty alcohol non-ionic surfactants may be

prepared as described above for the mixed alkoxylate fat

ty alcohol nonionic surfactants.

The use of mixtures of different nonionic surfactants is

suitable in the context of the present invention for in

stance mixtures of alkoxylated alcohols and hydroxy group

containing alkoxylated alcohols.

Preferably the total amount of non-ionic surfactants is

in an amount of from 0.1 %wt to 20 %wt, more preferably

0.5%wt to 15 %wt, such as 1 to 10%wt based on the weight

of the composition(s) comprising the surfactant.

An especially preferred optional ingredient in the deter

gent compositions of the invention is a polymer. Suitable polymers include those comprising polycarboxylic groups such as polyacrylate homopolymers and copolymers and the salts thereof. Copolymers of polycarboxylic acids such as acrylic acids with sulphonated monomers are especially preferred according to the present invention as it has been found that the combination of a sulphonated polymer with the claimed surfactant system provides significant benefits in shine and anti-spotting properties of the de tergent composition.

Preferred examples of the sulphonated polymers include

copolymers of CH2=CR -CR 2 R 3 -O-C4H3R 4 -SO3X wherein R , R2

R 3 , R 4 are independently 1 to 6 carbon alkyl or hydrogen,

and X is hydrogen or alkali with any suitable other mono

mer units including modified acrylic, fumaric, maleic,

itaconic, aconitic, mesaconic, citraconic and meth

ylenemalonic acid or their salts, maleic anhydride,

acrylamide, alkylene, vinylmethyl ether, styrene and any

mixtures thereof. Other suitable sulfonated monomers for

incorporation in sulfonated (co)polymers are 2

acrylamido-2-methyl-1-propanesulphonic acid, 2

methacrylamido-2-methyl-1-propanesulphonic acid, 3

methacrylamido-2-hydroxy-propanesulphonic acid, allysul

phonic acid, methallysulphonic acid, 2-hydroxy-3-(2

propenyloxy)propanesulphonic acid, 2-methyl-2-propenen-1

sulphonic acid, styrenesulphonic acid, vinylsulphonic ac

id, 3-sulphopropyl acrylate, 3-sulphopropylmethacrylate,

sulphomethylacrylamide, sulphomethylmethacrylamide and

water soluble salts thereof. Suitable sulphonated poly

mers are also described in US 5308532 and in WO

2005/090541.

It is especially preferred that the sulphonated polymer

comprises monomers of a carboxylic acid and a sulphonated

monomer, especially acrylic acid and/or 2-acrylamido-2

methyl-1-propanesulphonic acid (AMPS). It is most pre

ferred that the sulphonated polymer is a copolymer of

acrylic acid and AMPS, especially in a weight ratio (of

the monomers) of 50:50 to 90:10, such as 70:30 to 80:20.

When a sulfonated polymer is present, it is preferably

present in the detergent composition of the invention in

an amount of at least 0.5 wt%, preferably at least 1 wt%,

more preferably at least 2 wt%, and most preferably at

least 3 wt%, up to 40wt%, preferably up to 30wt%, more

preferably up to 20wt%, and most preferably up to 15 wt%.

In one embodiment of the invention for a multi-phase unit

dose composition it is preferred that a sulphonated poly

mer is present in the detergent composition of the inven

tion and in at least one further detergent composition

forming at least one further phase of the multi-phase

unit dose composition.

It is also possible to include a polymer which is a poly

aspartic acid derivative of formula (I):

O 0 0a oR

N O N 0 OM a

(I)

wherein:

M is selected from the group H, alkali metals, ammonium,

optionally substituted alkylammonium or a mixture there

of;

X is selected from the group NR1 , 0 and S or a mixture

thereof, wherein R1 is H or C1-20 hydrocarbyl optionally

substituted with hydroxy or C1-8 alkyl

Z is R 2 Yn, wherein:

R2 is selected from the group comprising:

linear or branched Ci-C 2 0 alkyl, C5-20 aralkyl, each op

tionally substituted with C1-8 alkyl or cyclic C3-10 al

kyl, wherein the aralkyl may contain one or more heteroa

toms selected from N, 0 and S; and

3 linear and branched -R -( R 3 0)p or -R5-(N(R )R5)

wherein R3 and R5 are selected from linear or branched

Ci-C10 alkyl and wherein R4 is selected from the same

group as Ri and p and q are integers from 1 to 100;

each Y is independently selected from the group of hydro

philic substituents containing OH; OR10; SO3M; SO2M; S03

R ; SO2R12; OSO3M; OSO2M; OSO3R ; OSO2R12; PO3M; PO2M,

2 PO3R"; PO2R1 2 ; OPO3M; OPO2M, OPO3R"; OPO2R1 ; COOM;

COOR 1 3 wherein R1 0 , R , R 2 and R1 3 are each selected in

dependently from each other from the group defined for

R 6 ; and/or the group of hydrophobic substituents contain

ing NR 1 4 R1 5 and NR1 4 R 1 5 R1 6 wherein R'4 , R1 5 and R are

each independently selected from linear or branched Ci

C20 alkyl, cyclic C3-10 alkyl or C5-20 aralkyl, each op

tionally substituted with C1-8 alkyl or cyclic C3-10 al

kyl, wherein the aralkyl may contain one or more heteroa

toms selected from N, 0 and S;

R8 is H or is selected from the same group as R2

provided that when X is NR , then Y is not SO3M, SO2M,

S03 R , SO2R12 , OSO3M, OSO2M, OSO3R" or OS02R1 2 .

n is an integer from 1 to 20;

k, 1 are each independently integers from 0 to 860; and

m is an integer from 1 to 860.

According to a further embodiment of the first aspect of

the present invention, there is provided a composition comprising a compound of formula (I) as hereinbefore de scribed wherein:

M is selected from the group H, alkali metals, ammonium, optionally substituted alkylammonium or a mixture there

of;

X is selected from the group NR1 , 0 and S or a mixture

thereof, wherein R1 is H or C1-20 hydrocarbyl optionally

substituted with hydroxy or C1-8 alkyl ;

Z is R 2 Yn, wherein

R2 is selected from the group comprising:

linear or branched Ci-C20 alkyl, C5-20 aralkyl, each op

tionally substituted with C1-8 alkyl or cyclic C3-10 al

kyl, wherein the aralkyl may contain one or more heteroa

toms selected from N, 0 and S; and

linear and branched -R 3 -( R 3 0)p or -R 5 -(N(R 4 )R 5 ) q wherein

R 3 and R 5 are selected from linear or branched Ci-C10 al

kyl and wherein R4 is selected from the same group as Ri

and p and q are integers from 1 to 100;

each Y is independently selected from the group of hydro

philic substituents containing OH; OR10; SO3M; SO2M; S03

R11; SO2R 1 2 ; OSO3M; OSO2M; OSO3R ; OSO2R 1 2 ; PO3M; PO2M,

PO3R"; P02R 1 2 ; OPO3M; OPO2M, OPO3R1; OP02R 1 2 ; COOM;

COOR1 3 wherein R1 0 , R'1 , R 1 2 and R 1 3 are each selected in

dependently from each other from the group defined for

R6 ; and/or the group of hydrophobic substituents con training H, NR1 4 R1 5 and NR1 4 R1 5 R 1 6 wherein R 1 4 , R15 and R16 are each independently selected from linear or branched

Ci-C20 alkyl, cyclic C3-10 alkyl or C5-20 aralkyl, each

optionally substituted with C1-8 alkyl or cyclic C3-10

alkyl, wherein the aralkyl may contain one or more het

eroatoms selected from N, 0 and S;

R8 is H or is selected from the same group as R2

provided that the molar ratio of hydrophobic:hydrophilic

substituents is from 1:1.1 to 1:1000.

n is an integer from 1 to 20;

k, 1 are each independently integers from 0 to 860; and

m is an integer from 1 to 860.

The polyaspartic acid derivatives may be included in the

compositions of the invention in amounts 0.1-40%wt, such

as 5-30%wt.

The compositions of the invention may also comprise one

or more thickeners to control the viscosity thereof. Any

suitable thickeners as known in the art may be used with

gums, polymers and gels being preferred. For example,

polyethylene glycols, e.g. PEG with a molecular weight in

the range of 5000 to 15,000 may be used as a thickener.

Thickeners are typically present in amounts of up to

2%wt.

The detergent composition of the invention may also com

prise one or more foam control agents and indeed this is

preferred. Suitable foam control agents for this purpose are all those conventionally used in this field, such as, for example, silicones and their derivatives and paraffin oil. The foam control agents are preferably present in the composition in amounts of 0.5% by weight or less of the total weight of the composition.

The detergent compositions of the invention may also com

prise minor, conventional, amounts of preservatives,

dyes, colurants and perfume as desired. Such ingredients

are typically present in amounts of up to 2%wt.

Solvents may also be included in the liquid detergent

compositions of the invention, for example glycols such

as 1,2 propylene glycol. Typically solvents, if used are

present in amounts of up to 10%wt, preferably in amounts

of up to 5%wt.

The detergent compositions of invention may comprise

bleaching compounds although generally they will be sub

stantially free of bleaching compounds. The detergent

composition of the invention may also be used as part of

a multi-phase unit dose detergent composition. In this

case the other detergent compositions making up the mul

ti-phase unit dose detergent composition may comprise a

bleaching compound and preferably they do so.

Any conventional bleaching compound can be used in any

conventional amount in either the composition of the in

vention or in any other detergent composition forming

part of the multi-phase unit dose detergent composition.

When a bleach is present, it is preferably present in the

relevant composition in an amount of at least 1 wt%, more

preferably at least 2 wt%, more preferably at least 4

wt%. Preferably it is present in the relevant composition

in an amount of up to 30wt%, more preferably up to 20wt%,

and most preferably up to 15wt%. Amounts of 1% to 30%wt

of bleach component are especially preferred.

Most preferably the bleach is selected from inorganic

peroxy-compounds and organic peracids and the salts de

rived therefrom.

Examples of inorganic perhydrates include persulfates

such as peroxymonopersulfate (KMPS), perborates or per

carbonates. The inorganic perhydrates are normally alkali

metal salts, such as lithium, sodium or potassium salts,

in particular sodium salts. The inorganic perhydrates

may be present in the detergent as crystalline solids

without further protection. For certain perhydrates, it

is however advantageous to use them as granular composi

tions provided with a coating which gives the granular

products a longer shelf life.

The preferred percarbonate is sodium percarbonate of the

formula 2Na2CO3.3H202. A percarbonate, when present, is

preferably used in a coated form to increase its stabil

ity.

Organic peracids include all organic peracids tradition

ally used as bleaches, including, for example, perbenzoic

acid and peroxycarboxylic acids such as mono- or diperox

yphthalic acid, 2-octyldiperoxysuccinic acid, diperoxy dodecanedicarboxylic acid, diperoxy-azelaic acid and im idoperoxycarboxylic acid and, optionally, the salts thereof. Especially preferred is phthalimidoperhexanoic acid (PAP).

When a composition of the invention, or a unit dose com

position comprising a composition of the invention, com

prises a bleach it may also comprise one or more bleach

activators or bleach catalysts depending upon the nature

of the bleaching compound. Any suitable bleach activator

may be included for example TAED. Any suitable bleach

catalyst may be used for example manganese acetate or di

nuclear manganese complexes such as those described in

EP-A-1,741,774. Conventional amounts may be used e.g. in

amounts of from 1 to 30t%, more preferred of from 5 to 25

wt% and most preferred of from 10 to 20wt% based on the

weight of the part of the composition comprising the

bleach.

The detergent compositions of the invention, or other de

tergent compositions included in the multi-phase unit

dose compositions, may comprise one or more anti

corrosion agents especially when the detergent composi

tions are for use in automatic dishwashing operations.

These anti-corrosion agents may provide benefits against

corrosion of glass and/or metal and the term encompasses

agents that are intended to prevent or reduce the tar

nishing of non-ferrous metals, in particular of silver

and copper. It may be desirable to include more than one

type of anti-corrosion agent to provide protection

against corrosion of glass and metals.

Organophosphoric acids are often used as corrosion inhib

itors. Diphosphoric acids and their salts are preferred

according to the present invention with the tetrasodium

and disodium salts being especially preferred. 1, hy

droxy, ethylidene 1,1- diphosphoric acid (HEDP) and it

tetrasodium or disodium salts is especially preferred.

The organophosphoric acid is preferably used in an amount

of from 0.05 to 10%wt, such as 0.1 to 7.5%wt based on the

weight of the composition in which it is present.

It is known to include a source of multivalent ions in

detergent compositions, and in particular in automatic

dishwashing compositions, for anti-corrosion benefits.

For example, multivalent ions and especially zinc, bis

muth and/or manganese ions have been included for their

ability to inhibit such corrosion. Organic and inorganic

redox-active substances which are known as suitable for

use as silver/copper corrosion inhibitors are mentioned

in WO 94/26860 and WO 94/26859. Suitable inorganic re

dox-active substances are, for example, metal salts

and/or metal complexes chosen from the group consisting

of zinc, bismuth, manganese, titanium, zirconium, hafni

um, vanadium, cobalt and cerium salts and/or complexes,

the metals being in one of the oxidation states II, III,

IV, V or VI. Particularly suitable metal salts and/or

metal complexes are chosen from the group consisting of

MnSO4, Mn(II) citrate, Mn(II) stearate, Mn(II) acety

lacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate],

V205, V204, V02, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(N03)2

and Ce(N03)3. Any suitable source of multivalent ions

may be used, with the source preferably being chosen from sulphates, carbonates, acetates, gluconates and metal protein compounds. Zinc salts are specially preferred corrosion inhibitors.

Preferred silver/copper anti-corrosion agents are ben

zotriazole (BTA) or bis-benzotriazole and substituted de

rivatives thereof. Other suitable agents are organic

and/or inorganic redox-active substances and paraffin

oil. Benzotriazole derivatives are those compounds in

which the available substitution sites on the aromatic

ring are partially or completely substituted. Suitable

substituents are linear or branch-chain C1-20 alkyl

groups and hydroxyl, thio, phenyl or halogen such as flu

orine, chlorine, bromine and iodine. A preferred substi

tuted benzotriazole is tolyltriazole (TTA).

Therefore, an especially preferred optional ingredient

according to the present invention is a source of multi

valent ions such as those mentioned in the immediately

preceding paragraphs and in particular compounds com

prising zinc, bismuth and/or manganese ions and/or ben

zotriazole, including substituted benzotriazoles. In

particular a source of zinc ions and unsubstituted ben

zotriazole are preferred as anti-corrosion agents and a

mixture of these two ingredients is especially preferred

according to the invention.

Any conventional amount of the anti-corrosion agents may

be included in the solid detergent compositions of the

invention. However, it is preferred that they are pre

sent in an total amount of from 0.01%wt to 5%wt, prefera

bly 0.05%wt to 3%wt, more preferably 0.1 to 2.5%wt, such as 0.2%wt to 2%wt based on the total weight of the compo sition. If more than one anti-corrosion agent is used, the individual amounts may be within the preceding amounts given but the preferred total amounts still ap ply.

The compositions of the invention may optionally comprise

one or more enzymes. Any type of enzyme typically used in

detergent compositions may be included in the composi

tions of the present invention. It is preferred that the

enzyme(s) is/are selected from proteases, lipases, amyl

ases, cellulases laccases, catalases and peroxidases. It

is most preferred that protease and/or amylase enzymes

are included in the compositions according to the inven

tion as such enzymes are especially effective in dish

washing detergent compositions. Any suitable species of

these enzymes may be used as desired. Conventional

amounts of such enzymes may be used.

The compositions according to the invention, and/or any

detergent composition used therewith in a multi-phase

unit dose composition, may also comprise a source of

acidity or a source of alkalinity (to obtain the desired

pH on dissolution) especially if the composition is to be

used in an automatic dishwashing application.

A source of alkalinity may suitably be any suitable basic

compound for example any salt of a strong base and a weak

acid. When an alkaline composition is desired silicates

are amongst the suitable sources of alkalinity. Preferred

silicates are sodium silicates such as sodium disilicate,

sodium metasilicate and crystalline phyllosilicates. Oth er suitable sources of alkalinity may be a carbonate or bicarbonate (such as the alkali metal or alkaline earth metal salts with sodium carbonate being especially pre ferred). A source of acidity may suitably be any suita ble acidic compound for example a polycarboxylic acid.

Conventional amounts of the alkalinity or acidity source

may be used.

The detergent compositions can be prepared by any suita

ble method. However, it has been found that they exhibit

especially good stability if they are produced by mixing

the ingredients together at a temperature in the range of

from 25-50°C, preferably of from 30-40°C. This has been

found to result in liquid compositions which typically

show good stability for at least three months at room

temperature.

The present invention also provides a method of improving

shine and/or inhibiting spotting on hard surfaces such as

kitchenware and especially glassware. In particular the

method is carried out by treating kitchenware items in an

automatic dishwasher by the step of contacting a deter

gent composition according to either the first or second

aspect of the invention with kitchenware items during a

dishwashing cycle. Suitable conditions to effect the re

moval are employed in the method and will typically in

volve contact under aqueous conditions and usually at a

temperature in the range of from 15-70°C, such as 30

70°C.

According to third aspect of the invention it is pre

ferred that the detergent composition of the invention

forms a part of an overall dishwashing composition such

as a multi-phase unit dose composition. A unit dose de

tergent composition is designed to be used as a single

portion of detergent composition in a single washing op

eration. Of course, one or more of such single portions

may be used in a cleaning operation if desired. The addi

tional detergent may be of any physical form e.g. liquid,

powder, granules, shaped body etc.

One type of preferred unit dose composition according to

the present invention comprises the detergent composition

of the invention at least partially enveloped by a water

soluble or water dispersible package. Thus this is a unit

dose detergent composition intended to be consumed in a

single washing operation. It is preferred that the water

soluble or water dispersible packaging material fully en

velopes the detergent composition. In this aspect the de

tergent composition of the invention may be present with

in the water soluble or dispersible package either on its

own (e.g. as a gel encased in a water soluble single com

partment package) or it may form a part of a water solu

ble package containing two or more different detergent

compositions. In this latter arrangement it is preferred

that the water soluble package is a multi-compartment

package with each compartment containing one or more de

tergent compositions.

It is preferred according to one embodiment of the inven

tion that the water soluble or water dispersible package

comprises a plurality of compartments, typically 2 to 5 compartments. This has the advantage of allowing incom patible ingredients of the overall formulation to be physically separated from each other which can increase the stability of the overall composition.

The water soluble or water dispersible package comprising

the detergent of the invention may be of any suitable

form e.g. flexible pouch or a self-supporting body such

as one with a substantially planar base and upstanding

side walls which container is typically closed with a

film lid. In some embodiments of the invention it may

comprise a partially pre-formed container. Preferred ex

amples of such containers include gelatin capsules, such

as those employed in medicament applications. When gela

tin is used it will be appreciated that the formulation

and the physical nature of the gelatin may wary widely.

For example the gelatin may be a hard gelatin or a soft

gelatin (having a plasticiser component such as water,

glycerine, mono-propylene glycol or polyethylene glycol).

As stated above the water soluble or water dispersible

package may be in the form of a self supporting body.

Preferably this is a self-supporting body with a substan

tially planar base and upstanding side walls which is

typically closed with a film lid. Such a body may be of

any shape but will typically be of a substantially square

or rectangular cross section. The package may also not

be in the form of a walled container but instead a shape,

which is substantially self supporting (optionally with

pores / apertures). The self supporting body preferably

comprises a matrix. The matrix may be formed of the ma

terial used for the film of the package or alternatively the matrix may comprise a second material. Preferred ma trix forming materials include gelatin, especially in an admixture with glycerine, optionally with water. A fur ther preferred matrix forming material is polyethylene glycol (PEG) having a molecular mass of 3000 or above, e.g. such as 6000, 8000, 20000, 35000 or 8 million.

Generally the package has a maximum dimension in at least

one plane of between 5 and 60mm, preferably between 10

and 50mm, such as between 20 and 45mm. It will be appre

ciated that the size of the package will vary in accord

ance with desires of the unit dose detergent product for

mulator and the intended use of the package. It is espe

cially preferred that the package has this dimension in

at least two planes and most preferably in three planes.

The package may be formed by any suitable method, for ex

ample the method described in WO 2004/081161 which method

is incorporated by reference herein. If the package is a

self supporting body produced by injection moulding then

it can be made according to the process disclosed in EP

A-1232100 which is incorporated by reference herein.

When the package comprising the detergent composition is

a flexible pouch, the method may comprise the step of en

veloping the detergent composition with at least one

sheet of the material used to form the packaging, espe

cially a flexible sheet of the packaging material.

One way of producing the water soluble or water dispersi

ble package in the form of a pouch containing the deter

gent composition of the invention is to form a cavity in a first sheet of the packaging material used to form the pouch and add the detergent composition thereto prior to the packaging material being sealed to produce the water soluble or water dispersible packaging pouch. The package may be sealed by the addition of a second sheet of the packaging material over the cavity containing the deter gent composition and sealing it to the first sheet of the packaging material. The first and second sheets of the packaging material may comprise the same or different wa ter soluble or dispersible packaging material however the two sheets preferably comprise the same packaging materi al.

The water soluble or water dispersible package may be

formed by any suitable conventional method, for example,

vacuum forming, thermoforming or injection moulding de

pending upon the type of packaging to be produced e.g.

flexible pouch or self supporting container. For exam

ple, in a thermoforming process the film may be drawn

down or blown down into a mould. Thus, for example, the

film is heated to the thermoforming temperature using a

thermoforming heater plate assembly, and then drawn down

under vacuum or blown down under pressure into the mould.

Plug-assisted thermoforming and pre-stretching the film,

for example by blowing the film away from the mould be

fore thermoforming, may, if desired, be used. One

skilled in the art can choose an appropriate temperature,

pressure or vacuum and dwell time to achieve an appropri

ate package. The amount of vacuum or pressure and the

thermoforming temperature used depend on the thickness

and porosity of the film and on the polymer or mixture of polymers being used. Thermoforming of PVOH films is known and described in, for example, WO 00/55045.

Polyvinyl alcohol is one suitable material from which to

form the water dispersible or water soluble package (see

further details below). A suitable forming temperature

for PVOH or ethoxylated PVOH is, for example, from 90 to

1300C, especially 90 to 1200C. A suitable forming pres

sure is, for example, 69 to 138kPa (10 to 20 p.s.i.), es

pecially 83 to 117 kPa (12 to 17 p.s.i.). A suitable

forming vacuum is 0 to 4 kPa (0 to 40 mbar), especially 0

to 2 kPa (0 to 20 mbar). A suitable dwell time is, for

example, 0.4 to 2.5 seconds, especially 2 to 2.5 seconds.

The packaging material used to produce the water soluble

or water dispersible package is preferably polymeric and

is preferably selected from polyvinyl alcohol, celluloses

(including cellulose derivatives), starches, gelatine,

polyglycolides, gelatine and polylactides copolymers or a

mixture or co-polymer thereof. Polyvinyl alcohol is espe

cially preferred as the packaging material. Preferred

cellulose derivatives include hydroxyproppyl cellulose

ether (HMPC). The polymeric material may be a photopoly

mer or a co-polymer of any suitable monomers such as

those of the aforementioned types.

The water soluble or water dispersible polymeric material

may, for example, be formed of a film. The film may be a

single film, or a laminated film as disclosed in GB-A

2,244,258. While a single film may have pinholes, the

two or more layers in a laminate are unlikely to have

pinholes which coincide.

The thickness of at least one, and preferably all, of the

external walls of the water soluble or water dispersible

package may be up to 2mm, more preferably up to 1mm, more

preferably 10 to 300 tm, more preferably 20 to 200 tm,

especially 25 to 160 pum, more especially 30 to 150 pm and

most especially 30 to 150 pm.

The packaging material, e.g. film, may be produced by any

process, for example by extrusion and blowing or by cast

ing. The film may be unoriented, monoaxially oriented or

biaxially oriented. If the layers in the film are ori

ented, they usually have the same orientation, although

their planes of orientation may be different if desired.

The layers in a laminate may be the same or different.

Thus they may each comprise the same polymer or a differ

ent polymer.

Examples of the water-soluble or dispersible polymeric

material which may be used in a single layer film or in

one or more layers of a laminate or which may be used for

injection moulding or blow moulding are poly(vinyl alco

hol) (PVOH), cellulose derivatives such as hydroxypropyl

methyl cellulose (HPMC) and gelatin. An example of a

suitable PVOH is ethoxylated PVOH. The PVOH may be par

tially or fully alcoholised or hydrolysed. For example

it may be from 40 to 100%, preferably from 70 to 92%,

more preferably about 88% or about 92%, alcoholised or

hydrolysed. The degree of hydrolysis is known to influ

ence the temperature at which the PVOH starts to dissolve

in water. 88% hydrolysis corresponds to a film soluble

in cold (i.e. room temperature) water, whereas 92% hy drolysis corresponds to a film soluble in warm water.

Therefore the water soluble characteristics of the film

can be controlled.

The invention is further described with reference to the

following non-limiting Examples. Further examples within

the scope of the invention will be apparent to the person

skilled in the art.

Examples

Example 1

Two multi-phase unit dose automatic dishwashing composi

tions having the formulations as shown below in Table 1

were prepared as described below. The compositions com

prise a gel according to the invention and also two addi

tional powder compositions herein designated as powder 1

and powder 2. The gel composition and the two powder

compositions are placed into separate compartments of a

water soluble injection moulded pre-formed polyvinyl

alcohol container having three compartments to form the

multi-phase unit dose composition. All percentages are

given as %wt based on the total weight of the composi

tion.

Formulation 1 comprises a gel detergent composition ac

cording to the invention. Formulation 2 is a comparative

example comprising gel detergent composition an ethox

ylated fatty alcohol non-ionic surfactant which is not

according to the present invention.

Powder 1 is formed by mixing together the given amounts

of sodium carbonate, sodium percarbonate and sodium

tripolyphosphate.

Powder 2 is formed by mixing together the given amounts

of TAED, Protease granules, Amylase granules, Manganese

acetate and the sulfonated copolymer.

The gel composition is formed by mixing the liquid

nonionic surfactant, the two thickeners (PEG 6000 and the

EO/PO thickener) with the sodium tripolyphosphate (for

use in gel) in an Ystral X50/10 mixer at room temperature

for 20 minutes at a speed or 1000 revolutions per minute

until it yielded a fine dispersion of solids and liquids

which formed a gel. This dispersion did not show any ap

preciable phase separation after three months storage at

room temperature.

Table 1; Formulation 1

Formula Formula- tion tn2 2 Component in wt%Foml- tion 1 (compara tive) Powder 1

Sodium carbonate 8.0 8.0

Sodium percarbonate 15.0 15.0

Sodium Tripolyphosphate (STPP) 45.0 45.0

Powder 2

TAED 5.0 5.0

Protease granules 1.0 1.0

Amylase granules 0.5 0.5

Managanese acetate 0.5 0.5

Sulfonated co-polymer*l 8.0 8.0 Gel composition of the inven tion Liquid nonionic surfactant 5.0 0.0 (C11-E05 -P0 5 ), Liquid nonionic surfactant 0.0 5.0 (C12-C15-EO8-PO4), Sodium Tripolyphosphate (STPP) 10.0 10.0 for gel PEG 6000 as thickener 1.5 1.5 Statistical EO-PO thickener with mole ratio 4:1 and Mw 0.5 0.5 1200Og/mol. Total %wt 100.0 100.0 pH measured lwt% in water at 9.8 9.8 20oC

*1 Available ex Rohm and Haas, a copolymer of Acrylic ac

id and AMPS in a wt ratio of 74:26.

For both formulations, 8.5g of Powder 1 was placed into a

first compartment of the polyvinyl alcohol water soluble

capsule. 4.5g of Powder 2 was placed into a second com

partment of the polyvinyl alcohol water soluble capsule.

3.Og of the gel composition of the invention was placed

into a third compartment of the polyvinyl alcohol water

soluble capsule. The water soluble filled capsule was

then sealed with a Polyvinyl alcohol water soluble film

(Monosol PT 75). The capsule weight was 2.5 g. Thus the

total filled capsule weight was 18.5g.

Example 2

Formulation 1 and Formulation 2 were tested for their

shine profile/anti-spotting properties in a Bosch

SGS058M02EU/36 dishwashing machine using the Eco 500C

+ Vario Speed (no 3-in-1 function) program following the

Rinse Performance method as described below.

A capsule according to Formulation 1 or Formulation 2 was

added into the dosing chamber of the dishwasher and the

machine was run on the above dishwashing program. The

dishwasher was loaded with glassware (long drink glasses)

as described below. The water hardness was 210GH. This

test is repeated 5 times for each formulation.

Spotting/filming on the long drink glassware after 5 dish

washing cycles was assessed by viewing the glasses in a

lit black box. The results are given in Table 2 and are

expressed on a scale of 1 to 10 (1 being worst with ex

treme spotting and filming and 10 being best with no visi

ble spotting and filming).

Table 2: Rinse Performance

Formulation 1 Formulation 2

(comparative)

Spotting 3.0 6.0

Filming 7.0 7.0

The rinse performance results above demonstrate that the

compositions of the invention exhibit better anti

spotting properties that the comparative example. This

also results in a better perception of shine on the

glasses by the consumer.

Claims (23)

Claims

1. A liquid automatic dishwashing detergent composition comprising; a) liquid mixed ethoxylate/propoxylate fatty alco hol non-ionic surfactant having 7 or 8 moles of the ethoxylate group and 4 or 5 moles of the propoxylate group in the molecule, and b) a builder.

2. A detergent composition according to claim 1, where in the composition is a gel.

3.A detergent composition according to claim 1 or claim 2, wherein the mixed ethoxylate/propoxylate fatty alcohol non-ionic surfactant comprises 4 moles of PO and 8 moles of EO.

4. A detergent composition according to any one of the preceding claims, wherein the mixed ethox ylate/propoxylate fatty alcohol non-ionic surfactant is from a linear chain fatty alcohol having 12-18 carbon atoms.

5.A detergent composition according to claim 4, where in said surfactant is from a linear chain fatty al cohol having 12 - 15 carbon atoms.

6.A detergent composition according to any one of the preceding claims, wherein said surfactant has at least 10 moles of alkylene oxide per mole of alco hol.

7. A detergent composition according to any one of the

preceding claims, which comprises at least 2 wt % of

the mixed ethoxylate/propoxylate fatty alcohol non

ionic surfactant.

8.A detergent composition according to claim 7, which

comprises 2 to 30 %wt of the mixed ethoxylate

/ propoxylate fatty alcohol non-ionic surfactant.

9.A detergent composition according to any one of the

preceding claims, wherein the total amount of build

er present in the composition is at least 10 wt %.

10. A detergent composition according to any one of

the preceding claims, wherein the builder is select

ed from phosphate-containing builders, polycarbox

ylic acids and their salts and amino acid based

builders.

11. A detergent composition according Claim 10,

wherein the builder is selected from tripolyphos

phates, citrates, MGDA and GLDA and salts or deriva

tives and mixtures thereof.

12. A detergent composition according to any one of

the preceding claims, wherein the detergent composi

tion further comprises a polymer.

13. A detergent composition according Claim 12,

wherein the polymer is a sulphonated polymer.

14. A detergent composition according Claim 13,

wherein the sulphonated polymer comprises monomers

of a carboxylic acid or a salt thereof and a sulpho

nated monomer.

15. A detergent composition according to any one of

the preceding claims, wherein the composition fur

ther comprises additional non-ionic surfactant.

16. A detergent composition according to any one of

the preceding claims, wherein any solvent included

in the composition is present in an amount of no

more than 10 wt %.

17. A method of preparing a detergent composition

according to any one of the preceding claims, where

in the detergent composition is prepared at a tem

perature in the range of from 25- 800C.

18. A method of preparing a detergent composition

according to Claim 17, wherein the detergent compo

sition is prepared at a temperature in the range of

from 30-50 0 C.

19. A unit dose detergent composition comprising a

liquid automatic dishwashing detergent composition

according to any one of claims 1 to 16 enveloped in

a water soluble or water dispersible package.

20. A unit dose detergent composition according to

Claim 19, wherein the water soluble or water dis

persible package has a plurality of compartments.

21. A unit dose detergent composition according to

either of Claims 19 or 20, wherein the water soluble

or water dispersible package comprises polymeric

packaging material.

22. A unit dose detergent composition according to

any one of Claims 19 to 21, wherein the polymeric

packaging material is selected from polyvinyl alco

hol, celluloses and cellulose derivatives, starches,

gelatine, polyglycolides, gelatine and polylactides

copolymers or a mixture or co-polymer thereof.

23. A method of reducing spotting on a hard surface

by contacting a hard surface with a composition ac

cording to any one of Claims 1 to 16 or a unit dose

composition according to any one of Claims 19 to 22,

wherein the method is carried out in an automatic

dishwashing machine.