TEPZZ¥Z97_7ZB_T

(19)

(11) EP 3 097 170 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C11D 3/40 (2006.01) C11D 17/00 (2006.01)
03.10.2018 Bulletin 2018/40
(86) International application number:
(21) Application number: 15712059.3 PCT/EP2015/051059

(22) Date of filing: 21.01.2015 (87) International publication number:

WO 2015/110444 (30.07.2015 Gazette 2015/30)

(54) PROCESS TO MANUFACTURE A LIQUID DETERGENT FORMULATION

VERFAHREN ZUR HERSTELLUNG EINER FLÜSSIGREINIGUNGSMITTELFORMULIERUNG
PROCÉDÉ DE PRÉPARATION D’UNE FORMULATION DE DÉTERGENT LIQUIDE

(84) Designated Contracting States: • ELLSON, Karen, Jane

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Wirral
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Merseyside CH63 3JW (GB)
PL PT RO RS SE SI SK SM TR • HUSSEY, Ian, James
Wirral
(30) Priority: 22.01.2014 EP 14152157 Merseyside CH63 3JW (GB)
• NAGARAJU, Mrudula
(43) Date of publication of application: Wirral
30.11.2016 Bulletin 2016/48 Merseyside CH63 3JW (GB)
• SAWBRIDGE, Gareth, John
(73) Proprietors: Stafford
• Unilever PLC Staffordshire ST17 0HJ (GB)
London, Greater London EC4Y 0DY (GB)
Designated Contracting States: (74) Representative: Corsten, Michael Allan
CY GB IE MT Unilever PLC
• Unilever NV Unilever Patent Group
3013 AL Rotterdam (NL) Colworth House
Designated Contracting States: Sharnbrook
AL AT BE BG CH CZ DE DK EE ES FI FR GR HR Bedford MK44 1LQ (GB)
HU IS IT LI LT LU LV MC MK NL NO PL PT RO RS
SE SI SK SM TR (56) References cited:
WO-A1-00/24856 WO-A1-00/66703
(72) Inventors: WO-A1-2009/141172 WO-A1-2010/127919
• BATCHELOR, Stephen, Norman
Wirral
Merseyside CH63 3JW (GB)
EP 3 097 170 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 3 097 170 B1

Description

Technical Field of the Invention

5 [0001] The present invention relates to a process of preparing a liquid detergent formulation comprising shading dyes
and to a liquid detergent formulation comprising a maximum level of chlorine.

Background of the Invention

10 [0002] The repeated washing of garments, towels and linens often leads to discolouration or yellowing. This is partic-
ularly the case for light or white coloured garments for which yellowing is often clearly apparent leading to a reduction
in the aesthetic appeal of for example, garments, towels or sheets.
[0003] In order to overcome discolouration and maintain the original appearance of a light coloured article, white
appearance shading dyes may be used as part of a detergent formulation. The shading dyes are fabric substantive and
15 are employed as part of a main wash of the garment and are preferably blue or violet dyes classified as: acid dyes, direct
dyes or hydrolysed reactive dyes. The use of shading dyes in powder formulations and liquid formulations is known. For
example, EP 2227534 discloses a laundry treatment composition comprising a surfactant, fluorescent agent and DANSA
dye.
[0004] Unfortunately, when using such shading dyes in liquid detergent formulations, the process of preparing the
20 liquid detergent may lead to a breakdown of the shading dye, or discolouration of the shading dye per se, with concomitant
reduced performance of the liquid detergent formulation and hence the increased yellowing of garments washed with
said formulations. This is especially true when the liquid detergent formulations are prepared on a large scale using
chlorinated water as the batch water. WO 00/66703 A1 describes concentrated perfume compositions and manufacture
of fabric softening compositions therefrom. WO 2009/141772 A1 describes a laundry treatment composition comprising
25 a cationic azine dye. WO 2013/044466 A1 describes colour enhancing detergent compositions including a bluing agent,
and methods of producing the same. In an attempt to overcome this problem the inventors have now found that it is
possible to prepare liquid detergent formulations in which the shading dyes do not breakdown, and are not bleached by
chlorinated batch water, but which are still able to meet the demands of vigorous wash cycles whilst avoiding the
troublesome problem of yellowing of garments and linens.
30
Object of the Invention

[0005] It is therefore an object of the present invention to provide an improved process of preparing a liquid detergent
formulation which seeks to overcome one or more of the aforementioned disadvantages of known processes and/or to
35 provide one or more of the aforementioned benefits.

Statement of the Invention

[0006] Therefore, according to a first aspect of the present invention there is provided a process of preparing a liquid
40 detergent formulation comprising the steps of:

(i) mixing together with stirring for at least 5 minutes in the presence of at least 30 weight % chlorinated water,
a surfactant in an amount of 5 to 50 weight %; and
additional ingredients in an amount of 0 to 20 weight %,
45 at a water temperature of between 18 and 50 °C;
followed by,

(ii) the addition of one or more shading dyes.

50 [0007] In the process of preparing a liquid detergent formulation according to the present invention the chlorinated
water comprises 0.2 to 10 ppm chlorine. More preferably the chlorinated water comprises 1 to 5ppm. Most preferably
the chlorinated water comprises 1.5 to 4.5 ppm chlorine. Even more preferably the chlorinated water comprises 1.5 to
4.0 ppm chlorine
[0008] Also in relation to the process of preparing a liquid detergent formulation according to the present invention,
55 the chlorinated water, surfactant and additional ingredients may be mixed together at a water temperature of between
18 and 50 °C to form a homogenous mixture.
[0009] In the process according to the present invention in which the chlorinated water, surfactant and additional
ingredients are preferably mixed together to form a homogenous mixture, it will be appreciated by one skilled in the art

2
 EP 3 097 170 B1

that the time to achieve a homogenous mixture may vary depending upon nature of the surfactant and additional ingre-
dients as well as the temperature of the surrounding. However, it is expected that at a temperature of between 18 °C
and 50 °C the time taken to achieve a homogenous mixture may be between 5 and 200 minutes. More preferably at a
temperature of between 20 °C and 45 °C the time taken to achieve a homogenous mixture may be between 10 and 150
5 minutes. Even more preferably however, at a temperature of between 25 °C and 40 °C the time taken to achieve a
homogenous mixture may be between 20 and 120 minutes.
[0010] As stated above, in relation to the process of preparing a liquid detergent formulation according to the present
invention, the surfactant may be present in an amount of 5 to 50 weight % in the final formulation. More preferably, the
surfactant may be present in an amount of 8 to 40 weight % in the final formulation. Most preferably, the surfactant may
10 be present in an amount of 10 to 30 weight % in the final formulation.
[0011] Also in relation to the process of preparing a liquid detergent formulation according to the present invention, it
may be required to add one or more ingredients selected from the group consisting of:
antimicrobial agents, fluorescers, fragrances, hydrotopes, sequestrants, perfume oils, enzymes and polymers, to the
surfactant and chlorinated water with mixing, prior to the addition of the one or more shading dyes. This may increase
15 or decrease the time taken to achieve a homogenous mixture of ingredients for the detergent formulation, however, it
is preferred that these ingredients are added to the surfactant and chlorinated water with mixing prior to the addition of
one or more shading dyes, with mixing to form a homogenous mixture. In addition, one or more non-shading dyes are
preferably added after the surfactant. Most preferably one or more non-shading dyes are added with the one or more
shading dye.
20 [0012] When forming the liquid detergent formulation using the process of the present invention it is possible to add
one or more shading dyes to the chlorinated water and surfactant. The one or more shading dyes may be added to the
chlorinated water and surfactant at a concentration of 0.0001 to 0.5 weight % in the final formulation. More preferably
the one or more shading dyes may be added to the chlorinated water and surfactant at a concentration of 0.0005 to 0.05
weight %. Most preferably however, the one or more shading dyes are added to the chlorinated water and surfactant at
25 a concentration of 0.001 to 0.1 weight %. The one or more shading dyes may be added as a solid or as an aqueous
solution or slurry. Preferably however, the one or more shading dyes are added to the formulation as an aqueous solution
or slurry. Preferably the aqueous solution or slurry comprises 0.1 to 5 weight % shading dye. Most preferably the aqueous
solution or slurry comprises 0.5 to 2 weight % shading dye. Even more preferably the aqueous solution or slurry comprises
at least 1 weight % shading dye.
30 [0013] In addition, in the process of preparing a liquid detergent formulation according to the present invention the
one or more shading dyes are selected from the group consisting of:
direct dyes, acid dyes, hydrophobic dyes, cationic dyes, reactive dyes, dyes comprising one or more carboxylic acid
groups, and azo dyes comprising one or more carboxylic acid groups.
[0014] If required, two or more shading dyes may be added to the mixture of chlorinated water and surfactant to provide
35 the required visual hue to fabric washed with the liquid detergent formulation. In which case, the two or more shading
dyes may be blended to form an aqueous solution prior to addition to the chlorinated water and surfactant.
[0015] When the liquid detergent formulation comprises two or more shading dyes, the two shading dyes may be
selected from the group consisting of: azo dyes, azine dyes or triphenylmethane dyes.
[0016] Also in relation to the process of preparing a liquid detergent formulation according to the present invention,
40 the surfactants may be selected from the group consisting of group consisting of:
linear alkyl benzene sulfonates, linear and branched alkyl sulfonates, alkyl ethoxylates, linear and branched alklyl ether
sulfates.
[0017] The liquid detergent formulation once prepared may be transferred to a container for either: storage, shipping
or sale.
45 [0018] According to a second aspect of the present invention there is provided a liquid detergent formulation which
may be prepared according to the first aspect of the present invention comprising:

a) at least 30 weight % chlorinated water;

b) at least 5 to 50 weight % surfactant;
50 c) additional ingredients in an amount of 0 to 20 weight %; and
d) at least 0.0001 to 0.5 weight % shading dye, and

wherein the formulation comprises 0.2 to 10 ppm chlorine.

[0019] It will be appreciated by one skilled in the art that in the process of the present invention the two or more shading
55 dyes may be blended together to form an aqueous solution or slurry in water prior to addition to the chlorinated water
and surfactant, or the two or more shading dyes may be added as solid particles to the chlorinated water and surfactant.
However, it is most preferred that the two or more shading dyes are blended together to form an aqueous solution in
water prior to addition to the chlorinated water and surfactant. Blending of the two or more shading dyes is preferably

3
 EP 3 097 170 B1

achieved with or without milling the dyes together in water followed by stirring at a temperature of between 50 °C and
90 °C for 5 to 60 minutes. Most preferably, blending of the two or more shading dyes is achieved by mixing the dyes
together in water followed by stirring at a temperature of between 75 °C and 85 °C for 5 to 60 minutes.

5 Detailed Description of the Invention

Shading Dyes

[0020] Shading dyes deposit to fabric during a wash or rinse step of the washing process providing a visible hue to
10 the fabric.
[0021] Examples of Shading dyes suitable for use in accordance with the present invention are detailed in:
WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO
2006/027086(Unilever), WO2008/017570(Unilever), WO2008/141880(Unilever), WO2009/132870(Unilever),
WO2009/141173 (Unilever), WO2010/099997(Unilever), WO 2010/102861(Unilever), WO2010/148624(Unilever),
15 WO2012/119859 (Unilever), WO2008/087497 (Proctor & Gamble) and WO2011/011799 (Proctor & Gamble), WO
2012/054058(Proctor & Gamble), WO 2012/054835 (Proctor & Gamble), WO 2012/166768 (Proctor & Gamble),
WO2013/142495 (Proctor & Gamble) and WO2013/151970 (Proctor & Gamble).
[0022] The shading of white garments may be done with any colour depending on consumer preference. Blue and
violet shading are particularly preferred shades by consumers and consequently preferred dyes or mixtures of dyes are
20 ones that provide a blue or violet shade on white fabrics. The shading dyes used in the present invention are also
preferably blue or violet. A mixture of shading dyes may be used and indeed are often preferred when treating mixed
fibre textiles. In this regard, preferred dyes provide a blue or violet colour to a white cloth with a hue angle of 240 to
345º. More preferably preferred dyes provide a blue or violet colour to a white cloth with a hue angle of 260 to 320º.
Most preferably however, preferred dyes provide a blue or violet colour to a white cloth with a hue angle of 270 to 300º.
25 A white cloth is used to perform shading tests which is bleached and comprises non-mercerised woven cotton sheeting.
[0023] Preferably the shading dye solution should be prepared at a temperature of 80 ºC and used within 10 minutes
of preparation.
[0024] However, in relation to the process according to the present invention is it essential that the shading dyes are
added after the addition of surfactant. Addition of the shading dyes to the liquid formulation after the addition of surfactant
30 has the benefit of minimising the exposure of the shading dyes to chlorine in the chlorinated water.
[0025] The shading dye chromophore may be selected from the group comprising: mono-azo, bis-azo, triphenylmeth-
ane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably, the shading dye
chromophore is selected from the group consisting of mono-azo, bis-azo, azine and anthraquinone.
[0026] It is also preferred that the shading dye is alkoxylated. More preferably, the shading dye is ethoxylated. Most
35 preferably however, the shading is ethoxylated and comprises at least one alkoxy chain with from 2 to 8 repeating units.
[0027] In addition, the dye is preferably uncharged or negatively charged in aqueous solution at a pH of 7.
[0028] Many examples of shading dyes are found in the classes of basic, solvent, acid, direct and disperse dyes.
[0029] It is preferred that the shading dyes utilized in the present invention are selected from the group consisting of:
direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes, dyes bearing carboxylic acid groups and azo
40 dyes bearing carboxylic acid groups. It is more preferred that shading dyes which are azo dyes and which bear carboxylic
acid groups are used.
[0030] It is also preferred that the shading dye in the detergent formulation according to the present comprises from
0.0001 to 0.1 weight % of the formulation. However, it will be appreciated by a skilled reader that for each shading dye
there is a preferred range depending upon the efficacy of the shading dye, which is dependent on the class and particular
45 efficacy within any particular class. As stated above the shading dye is most preferably a blue or violet shading dye.

Direct Dyes

[0031] In relation to the present invention, direct violet and direct blue dyes are preferred for use. In addition, the dye
50 is also preferably a bis-azo dye. Most preferably, the direct dye is a direct violet dye of the following structures:

55

4
 EP 3 097 170 B1

10
or

15

20

wherein:
25
the ring bearing R3 and R4 may be independently naphthyl or phenyl as shown;
R1 is hydrogen or C1-C4-alkyl, preferably hydrogen;
R2 is hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably
phenyl;
30 R3 and R4 are each independently selected from: hydrogen, a polyalkoxy group linked to a ring via a SO2NH group,
and C1-C 4-alkyl, preferably hydrogen or methyl;
X and Y are each independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X=
methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

35 [0032] Preferred dyes are selected from the group consisting of: direct violet 7, direct violet 9, direct violet 11, direct
violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99, and bis-
azo copper containing dyes such as direct violet 66 may also be used.
[0033] Sulphonated, alkoxylated bis-azo dyes as described in WO2012/054058 are also preferred.
[0034] However, benzidene based dyes are not preferred.
40 [0035] Preferably the direct dye is present in the formulation at a concentration of 0.00001 weight % to 0.0010 weight %.
[0036] In another embodiment the direct dye may be covalently linked to photo-bleach, as described for example in
WO2006/024612 and WO2010/099997, the details in relation to which are incorporated herein by reference.

Acid Dyes
45
[0037] Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes
are blue or violet. Preferred acid dyes which may be used in accordance with the present invention are:

(i) azine dyes, wherein the dye comprises the following core structure:
50

55

5
 EP 3 097 170 B1

10
wherein R a, R b, Rc and R d are each independently selected from: H, a branched or linear C1 to C7-alkyl chain,
benzyl, phenyl, and naphthyl; the dye is substituted with at least one SO3- or COO- group;
ring B does not carry a negatively charged group or salt thereof; and
ring A may be further substituted to form naphthyl;
15 the dye may also be optionally substituted by groups selected from the groups consisting of: amine, methyl, ethyl,
hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I, F, and NO 2.

[0038] Preferred azine dyes for use in the present invention include: acid blue 98, acid violet 50, and acid blue 59 and
dye with CAS-Number 72749-80-5. Preferred non-azine acid dyes include: acid violet 17, acid black 1 and acid blue 29.
20 [0039] Preferably the acid dye is present in the detergent formulation according to the present invention at 0.0005
weight % to 0.01 weight %.

Hydrophobic Dyes

25 [0040] Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may
be selected from the groups consisting of: disperse and solvent dyes.
[0041] The detergent formulation according to the present invention may therefore comprise one or more hydrophobic
dyes selected from the group consisting of: benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, nap-
thoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
30 [0042] Blue and violet anthraquinone and mono-azo dye chromophores are preferred. Preferred hydrophobic dyes
are selected from the group consisting of: solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28,
disperse violet 63 and disperse violet 77.
[0043] The hydrophobic dye may also preferably be an alkoxylated dye. Most preferably the hydrophobic may be an
alkoxylated mono-azo thiophene dye.
35 [0044] Preferably the hydrophobic dye is present in the formulation at 0.0001 weight % to 0.01 weight %.

Cationic Dyes

[0045] Cationic dyes are dyes which possess a cationic charge. Preferred cationic dyes used in accordance with the
40 present invention are selected from the group consisting of: mono-azo, phenazines, triphenyl methane and anthraquinone
dyes. However, cationic mono-azo dye and phenazine dyes are most preferred when used in accordance with the
present invention.
[0046] To avoid hydrolysis for mono-azo and anthraquinone dyes, preferably the cationic charge is present as a
quaternary amine on a pendant chain. The cationic dyes may be alkoxylated; and mono-azo dyes may additionally
45 possess anionically charged groups, preferably also on pendant chains. Mono-azo dyes containing a heterocyclic ring
are particularly preferred, such as thiophenes and preferred cationic phenazine dyes are of the form:

50

55

6
 EP 3 097 170 B1

10

15

wherein:

X3 is selected from: -H, -F, -CH3, -C2H5, -OCH3, and -OC2H5;

20 X4 is selected from: -H, -CH3, -C2H5, -OCH3, and -OC2H5; and
Y2 is selected from: -OH, -OCH2CH2OH, -CH(OH)CH2OH, -OC(O)CH3, and, C(O)OCH 3.

Reactive Dyes

25 [0047] Reactive dyes are dyes which contain an organic group and which are capable of reacting with an aliphatic C-
OH, C-NH2 or C-NH-C group to form a covalent bond. Reactive dyes deposit onto cotton.
[0048] Preferably the reactive group in the dye is hydrolysed, or alternatively, the reactive group is reacted with an
organic species such as for example, a polymer, in order to link the dye to the organic species. Reactive dyes may be
selected from the groups consisting of: reactive violet and reactive blue dyes listed in the Colour Index International.
30 [0049] Preferably the reactive dye is reacted with a polymer containing either NH 2 or NH groups, most preferably a
partially alkoxylated polyethylene imine polymer.
[0050] It will be appreciated by one skilled in the art that in the process of the present invention that two or more
shading dyes may be blended together to form an aqueous solution in water prior to addition to the chlorinated water
and surfactant or the two or more shading dyes may be added as solid particles to the chlorinated water and surfactant.
35 However, it is most preferred that the two or more shading dyes are blended together to form an aqueous solution in
water prior to addition to the chlorinated water and surfactant. Blending of the two or more shading dyes is achieved by
mixing or milling the dyes together in water followed by stirring at a temperature of between 65 °C and 90 °C for 1 to 65
minutes. Most preferably, blending of the two or more shading dyes is achieved by milling or mixing the dyes together
in water followed by stirring at a temperature of between 75 °C and 85 °C for 1 to 10 minutes.
40 [0051] Further examples of shading dyes include:

45

50
and

55

7
 EP 3 097 170 B1

Surfactants

[0052] The formulation prepared by the method of the present invention preferably comprises between 5 to 50 weight
% of a surfactant. Most preferably the formulation prepared by the method of the present invention preferably comprises
5 between 10 to 30 weight %.
[0053] In general, nonionic and anionic surfactants may be chosen from the surfactants described in "Surface Active
Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the
current edition of "McCutcheon’s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or
in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. Preferably the surfactants used are saturated.
10 [0054] Mixtures of synthetic anionic and nonionic surfactants, or a wholly anionic mixed surfactant system or admixtures
of anionic surfactants, nonionic surfactants and amphoteric or zwitterionic surfactants may all be used according to the
choice of the formulator for the required cleaning duty and the required dose of the detergent formulation.
[0055] Anionic surfactants may also further include soap (that is, a salt of fatty acid). A preferred soap employed in
detergent formulations according to the present invention is made by neutralisation of hydrogenated coconut fatty acid,
15 for example Prifac® 5908 (ex Croda). Mixtures of saturated and unsaturated fatty acids may also be used.
[0056] Nonionic detergent surfactants are well-known in the art. A preferred nonionic surfactant is a C12-C18 ethoxylated
alcohol, comprising 3 to 9 ethylene oxide units per molecule. More preferred are C12-C15 primary, linear ethoxylated
alcohols with on average between 5 and 9 ethylene oxide groups. More preferably, linear ethoxylated alcohols with an
average of 7 ethylene oxide groups are employed.
20 [0057] Examples of suitable synthetic anionic surfactants include: sodium lauryl sulphate, sodium lauryl ether sulphate,
ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium cocoyl isethion-
ate, sodium lauroyl isethionate, and sodium N-lauryl sarcosinate. Mostly preferably, the synthetic anionic surfactants
comprise synthetic anionic surfactant linear alkylbenzene sulphonate (LAS) or another synthetic anionic surfactant
sodium alcohol ethoxy-ether sulphate (SAES), most preferably comprising high levels of sodium C12 alcohol ethoxy-
25 ether sulphate (SLES). It is preferred for the detergent composition according to the present invention to comprise linear
alkylbenzene sulphonate LAS.
[0058] A preferred mixed surfactant system comprises synthetic anionic with nonionic detergent active materials and
optionally amphoteric surfactant, including amine oxide.
[0059] Another preferred mixed surfactant system comprises two different anionic surfactants, preferably linear alkyl
30 benzene sulphonate and a sulphate, for example LAS and SLES.
[0060] Synthetic anionic surfactants may be present, for example, in amounts in the range from about 5% to about
70 weight % of the mixed surfactant system.
[0061] The detergent compositions may further comprise an amphoteric surfactant, wherein the amphoteric surfactant
is present in a concentration of 1 to 20 weight %. Preferably the detergent compositions comprise an amphoteric surfactant
35 present in a concentration of 2 to 15 weight %. More preferably the detergent compositions comprise an amphoteric
surfactant present in a concentration of 3 to 12 weight % of the mixed surfactant system. Typical examples of suitable
amphoteric and zwitterionic surfactants include: alkyl betaines, alkylamido betaines, amine oxides, aminopropionates,
aminoglycinates, amphoteric imidazolinium compounds, alkyldimethylbetaines or alkyldipolyethoxybetaines.
[0062] In another aspect which is also preferred the surfactant may be cationic such that the formulation is a fabric
40 conditioner.

Chlorine levels

[0063] Chlorine levels are preferably measured using the (diethylparaphenylene diamine) indicator test, using a com-
45 parator as described by the World Health Organisation (How to measure chlorine residuals, WHO-Technical Notes for
Emergencies, Technical Note No. 11). The method is further described in ISO 7393-2:1985 Water quality -- Determination
of free chlorine and total chlorine -- Part 2: Colorimetric method using N,N-diethyl-1,4-phenylenediamine, for routine
control purposes.
[0064] Chlorine levels refer to free chlorine.
50
Fluorescent Agents

[0065] The detergent formulation according to the present invention may also preferably comprise a fluorescent agent
(optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially.
55 Usually, these fluorescent agents are supplied and used in the form of alkali metal salts, for example, as sodium salts.
The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 weight %. More
preferably 0.01 to 0.1 weight %.

8
 EP 3 097 170 B1

Perfumes

[0066] Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %,
most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and
5 Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals
Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

Optional Ingredients

10 [0067] The compositions may also contain one or more optional ingredients conventionally included in liquid detergent
formulations such as but not limited to: polymeric thickeners; enzymes, particularly: lipase, cellulase, protease, man-
nanase, amylase and pectate lyase; cleaning polymers, including ethoxylated polyethylene imines (EPEI) and polyester
soil release polymers; chelating agents or sequestrants, including HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid)
which is available, for example, as Dequest® 2010 from Thermphos; detergency builders; hydrotropes; neutralising and
15 pH adjusting agents; optical brighteners; antioxidants and other preservatives, such as antimicrobial agents including
Proxel®; other active ingredients, processing aids, dyes or pigments, carriers, fragrances, suds suppressors or suds
boosters, chelating agents, clay soil removal/ anti-redeposition agents, fabric softeners, dye transfer inhibition agents,
and transition metal catalyst in a composition substantially devoid of peroxygen species.
[0068] These and further possible ingredients for inclusion in the present invention are further described in WO
20 2009/153184.

Packaging

[0069] The liquid detergent formulation of the present invention may be packaged in any form of container. Typically
25 a plastic bottle with a detachable closure/pouring spout. The bottle may be rigid or deformable. A deformable bottle
allows the bottle to be squeezed to aid dispensing. If clear bottles are used they may be formed from PET. Polyethylene
or clarified polypropylene may also be used. Preferably the container is clear enough that the liquid, with any visual cues
therein, is visible from the outside. The bottle may be provided with one or more labels, or with a shrink wrap sleeve
which is desirably at least partially transparent. For example an area of 50% of the sleeve may be transparent. Adhesives
30 used to secure any transparent label should however, not adversely affect the transparency.

Experimental Section

[0070] The invention will now be further described with reference to the following nonlimiting examples.
35
Abbreviations

[0071] The following abbreviated names used in these examples have the following meanings:

40 MPG is Monopropylene Glycol (hydrotrope).

NaOH is 47% sodium hydroxide base.
LAS acid is linear alkyl benzene sulphonic acid anionic surfactant.
SLES(3EO) is SLES 3EO anionic surfactant.
Preservative is Proxel GXL™ antimicrobial preservative, 20% solution of 1,2 benzisothiazolin-3-one in dipropylene
45 glycol and water ex Arch Chemicals.
Perfume is free oil perfume.
Kleen is an encapsulated fragrance.

Experimental
50
[0072] The following examples illustrate a method of preparing a liquid laundry treatment composition in accordance
with the present invention and a comparative method of preparing a liquid laundry treatment composition.
[0073] Examples of the invention are denoted by a number and comparative examples are denoted by a letter. Unless
otherwise specified, the amounts and proportions used in the method and compositions are by weight.
55
Examples

[0074] The liquid detergent formulation listed in Table 1 was prepared by mixing the ingredients listed therein using

9
 EP 3 097 170 B1

two procedures. The first procedure known as route A is a standard procedure for preparing a liquid detergent composition.
The second procedure referred to a route 1, follows the procedure according to the present invention.

Table 1
5
INGREDIENTS IN LIQUID DETERGENT FORMULATION WEIGHT %
Linear alkyl benzene sulfonic acid 8.4
Alcohol ethoxylate (C12-C15 primary alcohol with 7 moles of ethoxylate (EO)) 2.1

10 Sodium lauryl ether sulphate (3EO) 10.5

1,2-propanediol 2.0
Sodium chloride 0.5
Fragrance 0.26
15
Citric acid 0.5
Sodium hydroxide 1.22
Triethanolamine 1.5

20 Fluorescer 0.1
Antimicrobial agent (Proxel™ GXL) 0.02
Non-shading dye 0.001
Water remainder
25

Preparation of Shading Dye Mixture

[0075] Prior to preparation of the liquid laundry formulation, a shading dye mixture was prepared by dissolving one or
30 more shading dyes in chlorinated water at 80 °C to obtain a mixture comprising 1 weight % of dye. Preferably the shading
dyes were completely dissolved in the chlorinated water. The shading dyes used have CAS-Number 72749-80-5 and
CAS-Number 6227-14-1.
[0076] The shading dye mixture was added to the liquid detergent formulation at a concentration to achieve an optical
absorbance of 0.55 at 577nm using a 1 cm cell. The optical absorbance is therefore proportional to the shading dye
35 concentration.
[0077] In both procedures described below, chlorinated water was used which contained 4ppm chlorine, and the
formulation was prepared on a 1 kg scale, by the two routes. All mixing steps were performed at room temperature.

Route A: Standard procedure

40
[0078] The chlorinated water was first placed into a mixing vessel at room temperature. The shading dye mixture was
then added to the chlorinated water and components stirred for 2 minutes. The remaining formulation ingredients listed
in the Table 1 where then added to the chlorinated water and shading dye mixture.

45 Route 1 - Procedure according to the present invention

[0079] As with the standard route ’A’ procedure described above, chlorinated water was first placed in a mixing vessel
at room temperature. The formulation ingredients listed in Table 1 were then added to the chlorinated water and the
resultant mixture stirred for 40 minutes ensuring dispersion of all ingredients. The shading dye mixture described above
50 was then added to the detergent formulation with mixing for 1 minute.
[0080] The optical absorbance of the liquid detergent formulations prepared using Route ’A’ and Route 1 was then
measured at 577nm and the results are illustrated in Table 2.

Table 2 - Optical Absorbance measurements for the liquid detergent formulations prepared by Route ’A’ and Route 1
55 OPTICAL ABSORBANCE MEASUREMENT AT 577nm
Route ’A’ 0.20

10
 EP 3 097 170 B1

(continued)

OPTICAL ABSORBANCE MEASUREMENT AT 577nm

Route 1 0.54
5
Colour standard 0.55

[0081] As may be seen from the optical absorbance measurements recorded in Table 2, the preparation of a liquid
detergent formulation using Route ’A’ leads to a reduced optical absorbance at 577nm, which is indicative of a reduction
10 in the amount of shading dye, compared to the optical absorbance measurement recorded for the liquid detergent
formulation prepared by Route 1, which retains substantially all of the shading dye.
[0082] That is, the intensity of the absorbance measured for a formulation with a shading dye added at the start of the
formulation process is reduced compared with the intensity of the absorbance for a formulation prepared using the
process of the present invention, (that is Route 1), in which the shading dye is added after the addition of the other
15 ingredients in the formulation.

Summary

[0083] Therefore, whilst not wishing to be bound by any particular theory, it may be seen that in accordance with the
20 process of the present invention, shading dyes or shading dye mixtures may be added as a blend during the preparation
of a liquid detergent formulation with minimal impact on the colour intensity of the shading dye in the final liquid detergent
formulation.
[0084] Furthermore, also in accordance with the process of the present invention, shading dyes or shading dye mixtures
may be added as a blend during the preparation of a liquid detergent formulation with minimal impact on the colour
25 intensity of the final liquid detergent formulation even when the liquid detergent formulation is prepared using chlorinated
water comprising 4ppm chlorine.
[0085] However, in line with the process of the present invention it is also most preferred that the shading dye or
shading dye mixture is the last ingredient added to the liquid detergent formulation.

30

Claims

1. A process of preparing a liquid detergent formulation comprising the steps of:

35 (i) mixing together with stirring for at least 5 minutes in the presence of at least 30 weight % chlorinated water,
a surfactant in an amount of 5 to 50 weight %; and
additional ingredients in an amount of 0 to 20 weight %,
at a water temperature of between 18 and 50 °C;
followed by,
40 (ii) the addition of one or more shading dyes which are capable of depositing to fabric during a wash or rinse
step of a washing process providing a visible hue to the fabric, and

wherein the chlorinated water comprises 0.2 to 10 ppm chlorine.

45 2. A process of preparing a liquid detergent formulation according to claim 1 wherein the chlorinated water comprises
1.5 to 4.5 ppm chlorine.

3. A process of preparing a liquid detergent formulation according to claims 1 or 2 wherein the chlorinated water,
surfactant and additional ingredients are mixed together at a water temperature of between 20 and 45 °C to form a
50 homogenous mixture.

4. A process of preparing a liquid detergent formulation according to any preceding claim wherein the additional
ingredients are selected from the group consisting of:
antimicrobial agents, fluorescers, fragrances, hydrotopes, sequestrants, perfume oils, enzymes, and are each added
55 to the surfactant and chlorinated water with mixing, prior to the addition of the one or more shading dyes.

5. A processing of preparing a liquid detergent formulation according to any preceding claim wherein the one or more

11
 EP 3 097 170 B1

shading dyes are added to the chlorinated water and surfactant as a solid or in aqueous solution, at a concentration
of 0.0001 to 0.5 weight %.

6. A process of preparing a liquid detergent formulation according to any preceding claim wherein the one or more
5 shading dyes are selected from the group consisting of:
direct dyes, acid dyes, hydrophobic dyes, cationic dyes, reactive dyes, dyes comprising one or more carboxylic acid
groups, and azo dyes comprising one or more carboxylic acid groups.

7. A process of preparing a liquid detergent formulation according to any preceding claim wherein two shading dyes
10 are added to the mixture of chlorinated water and surfactant.

8. A process of preparing a liquid detergent formulation according to claim 7 wherein the two shading dyes are blended
to form an aqueous solution prior to addition to the chlorinated water and surfactant.

15 9. A process of preparing a liquid detergent formulation according to claims 7 or 8 where the two shading dyes are
selected from the group consisting of:
azo dyes, azine dyes or triphenylmethane dyes.

10. A process of preparing a liquid detergent formulation according to any preceding claim wherein the surfactants are
20 selected from the group consisting of group consisting of:
linear alkyl benzene sulfonates, linear and branched alkyl sulfonates, alkyl ethoxylates, linear and branched alkyl
ether sulfates.

11. A process of preparing a liquid detergent formulation according to any preceding claim wherein the chlorinated water
25 used to prepare the formulation comprises 1 to 4ppm chlorine.

Patentansprüche

30 1. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung, umfassend die Schritte:

(i) miteinander Mischen unter Rühren für mindestens 5 Minuten in Anwesenheit von mindestens 30 Gewichts-
% chloriertem Wasser von einem Tensid in einer Menge von 5 bis 50 Gewichts-%; und
zusätzlichen Bestandteilen in einer Menge von 0 bis 20 Gewichts-% bei einer Wassertemperatur zwischen 18
35 und 50 °C;
gefolgt von
(ii) der Zugabe eines oder mehrerer Nuancierfarbstoffe, die sich während eines Wasch- oder Spülschritts eines
Waschvorgangs auf Stoff abscheiden können, wodurch dem Stoff eine sichtbare Tönung verliehen wird, und

40 wobei das chlorierte Wasser 0,2 bis 10 ppm Chlor umfasst.

2. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach Anspruch 1, wobei das chlorierte Was-
ser 1,5 bis 4,5 ppm Chlor umfasst.

45 3. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach den Ansprüchen 1 oder 2, wobei das
chlorierte Wasser, das Tensid und zusätzliche Bestandteile bei einer Wassertemperatur zwischen 20 und 45 °C
miteinander gemischt werden, um eine homogene Mischung zu bilden.

4. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
50 spruch, wobei die zusätzlichen Bestandteile ausgewählt sind aus der Gruppe bestehend aus:
antimikrobiellen Mitteln, Fluoreszenzmitteln, Duftstoffen, Hydrotopen, Sequestriermitteln, Parfümölen, Enzymen
und jeweils dem Tensid und dem chlorierten Wasser unter Mischen zugesetzt werden, bevor der eine oder die
mehreren Nuancierfarbstoffe zugegeben werden.

55 5. Verarbeitung zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
spruch, wobei der eine oder die mehreren Nuancierfarbstoffe dem chlorierten Wasser und dem Tensid als ein
Feststoff oder in wässriger Lösung zugesetzt werden, in einer Konzentration von 0,0001 bis 0,5 Gewichts-%.

12
 EP 3 097 170 B1

6. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
spruch, wobei der eine oder die mehreren Nuancierfarbstoffe ausgewählt sind aus der Gruppe bestehend aus:
Direktfarbstoffen, Säurefarbstoffen, hydrophoben Farbstoffen, kationischen Farbstoffen, Reaktivfarbstoffen, Farb-
stoffen, die eine oder mehrere Carbonsäuregruppen umfassen, und Azofarbstoffen, die eine oder mehrere Carbon-
5 säuregruppen umfassen.

7. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
spruch, wobei zwei Nuancierfarbstoffe zu der Mischung aus chloriertem Wasser und Tensid gegeben werden.

10 8. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach Anspruch 7, wobei die zwei Nuancier-
farbstoffe vor der Zugabe zu dem chlorierten Wasser und dem Tensid gemischt werden, um eine wässrige Lösung
zu bilden.

9. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach den Ansprüchen 7 oder 8, wobei die
15 zwei Nuancierfarbstoffe ausgewählt sind aus der Gruppe bestehend aus: Azofarbstoffen, Azinfarbstoffen oder Tri-
phenylmethanfarbstoffen.

10. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
spruch, wobei die Tenside ausgewählt sind aus der Gruppe bestehend aus:
20 linearen Alkylbenzolsulfonaten, linearen und verzweigten Alkylsulfonaten, Alkylethoxylaten, linearen und verzweig-
ten Alkylethersulfaten.

11. Verfahren zur Herstellung einer flüssigen Reinigungsmittelformulierung nach irgendeinem vorhergehenden An-
spruch, wobei das zur Herstellung der Formulierung verwendete chlorierte Wasser 1 bis 4 ppm Chlor enthält.
25

Revendications

1. Procédé de préparation d’une formulation détergente liquide comprenant les étapes de:
30
(i) mélange ensemble sous agitation pendant au moins 5 minutes en présence d’au moins 30 % en poids d’eau
chlorée,
d’un tensioactif en une quantité de 5 à 50 % en poids; et d’ingrédients supplémentaires en une quantité de 0
à 20 % en poids,
35 à une température de l’eau d’entre 18 et 50°C;
suivi par,
(ii) l’addition d’un ou plusieurs colorants de nuançage qui sont capables de se déposer sur un tissu pendant
une étape de lavage ou de rinçage d’un procédé de lavage en conférant une teinte visible au tissu, et

40 où l’eau chlorée comprend 0,2 à 10 ppm de chlore.

2. Procédé de préparation d’une formulation détergente liquide selon la revendication 1 où l’eau chlorée comprend
1,5 à 4,5 ppm de chlore.

45 3. Procédé de préparation d’une formulation détergente liquide selon les revendications 1 ou 2 où l’eau chlorée, le
tensioactif et les ingrédients supplémentaires sont mélangés ensemble à une température de l’eau d’entre 20 et
45°C pour former un mélange homogène.

4. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
50 où les ingrédients supplémentaires sont choisis dans le groupe consistant en:
les agents antimicrobiens, les agents fluorescents, les parfums, les hydrotropes, les séquestrants, les huiles par-
fumées, les enzymes, et sont ajoutés chacun au tensioactif et à l’eau chlorée sous agitation, avant l’addition des
un ou plusieurs colorants de nuançage.

55 5. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
où les un ou plusieurs colorants de nuançage sont ajoutés à l’eau chlorée et au tensioactif sous forme d’un solide
ou dans une solution aqueuse, à une concentration de 0,0001 à 0,5 % en poids.

13
 EP 3 097 170 B1

6. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
où les un ou plusieurs colorants de nuançage sont choisis dans le groupe consistant en:
les colorants directs, les colorants acides, les colorants hydrophobes, les colorants cationiques, les colorants réactifs,
les colorants comprenant un ou plusieurs groupes acide carboxylique, et les colorants azoïques comprenant un ou
5 plusieurs groupes acide carboxylique.

7. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
où deux colorants de nuançage sont ajoutés au mélange d’eau chlorée et de tensioactif.

10 8. Procédé de préparation d’une formulation détergente liquide selon la revendication 7 où les deux colorants de
nuançage sont mélangés pour former une solution aqueuse avant l’addition à l’eau chlorée et au tensioactif.

9. Procédé de préparation d’une formulation détergente liquide selon les revendications 7 ou 8 où les deux colorants
de nuançage sont choisis dans le groupe consistant en: les colorants azoïques, les colorants de type azine ou les
15 colorants de type triphénylméthane.

10. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
où les tensioactifs sont choisis dans le groupe consistant en:
les alkylbenzènesulfonates linéaires, les alkylsulfonates linéaires et ramifiés, les alkyléthoxylats, les alkyléthersul-
20 fates linéaires et ramifiés.

11. Procédé de préparation d’une formulation détergente liquide selon l’une quelconque des revendications précédentes
où l’eau chlorée utilisée pour préparer la formulation comprend 1 à 4 ppm de chlore.

25

30

35

40

45

50

55

14
 EP 3 097 170 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
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15