FIELD OF THE INVENTION
[0001] The present invention relates to methods of laundering fabrics.
BACKGROUND OF THE INVENTION
[0002] Fabric care compositions are often added by consumers to the rinse step of a fabric
washing operation. Fabric care compositions impart a number of sensorial benefits
that consumers enjoy, including softness and freshness. Most frequently, softness
is provided by esterified cationic surfactants or silicones. It is also known to add
cellulase enzymes into such compositions for example as described in
WO95/005442.
[0003] Laundry detergent compositions are used to provide fabric cleaning benefits in the
wash step of a laundry operation. There is a further need for a means to improve cleaning
particularly at low wash temperatures and also at short wash cycles.
[0004] The present invention alleviates this problem.
SUMMARY OF THE INVENTION
[0005] The present invention is to a method of laundering a fabric, comprising the steps
of;
- i) contacting a fabric with an aqueous wash liquor comprising a detergent composition,
the detergent composition comprising a surfactant and wherein the wash liquor comprises
from 0.05 to 4g/l of a surfactant; and
- ii) in a first rinse step, contacting the fabric from step (i) with a first rinse
liquor;
- iii) in a second rinse step, contacting the fabric from step (ii) with a second rinse
liquor comprising a lipid esterase;
- iv) drying the fabric;
- v) contacting the fabric from step (iv) with a soil;
- vi) contacting the fabric from step (v) with an aqueous wash liquor of a detergent
composition wherein the detergent composition comprises a surfactant, the wash liquor
comprising from 0.05 to 4g/l of a surfactant.
[0006] Typically the first and second rinse liquors are aqueous. Preferably the rinse liquor,
in particular the second rinse liquor additionally comprises a soil release polymer.
DETAILED DESCRIPTION OF THE INVENTION
[0007] The method of the present invention comprises the steps of:
- i) contacting a fabric with an aqueous wash liquor comprising a detergent composition,
the detergent composition comprising a surfactant and wherein the wash liquor comprises
from 0.05 to 4g/l of a surfactant; and
- ii) in a first rinse step, contacting the fabric from step (i) with an aqueous rinse
liquor;
- iii) in a second rinse step, contacting the fabric from step (ii) with a second aqueous
rinse liquor comprising a lipid esterase;
- iv) drying the fabric;
- v) contacting the fabric from step (iv) with a soil;
- vi) contacting the fabric from step (v) with an aqueous wash liquor of a detergent
composition wherein the detergent composition comprises a surfactant, the wash liquor
comprising from 0.05 to 4g/l of a surfactant. In step (i) and/or step (vi) it may
be preferred for the ratio of surfactant to fabric on a weight to weight basis to
be from 1:150 to 1:500 in step (i) and/or step (iii).
[0008] In the method of the present invention, in step (i) the fabric may be washed in a
conventional wash step in which an aqueous wash liquor is formed by the addition of
a detergent composition to water. The surfactant concentration in the aqueous wash
liquor is from 0.05 to 4g/l. In step (ii) the fabric undergoes a rinse step of a wash
operation, to substantially remove the wash liquor from the fabric. In step (iii)
a further rinse step is provided in which the fabric is contacted with a lipid esterase.
The fabric is then dried in step (iv) and undergoes soiling in step (v), i.e. the
fabric may then be worn by a consumer or used in another way for its intended use.
Following use of the fabric, the fabric may then be contacted with a further aqueous
wash liquor in step (vi). Without wishing to be bound by theory, it is believed that
the lipid esterase contacted to the fabric in step (iii) acts 'out of the wash' to
hydrolyse the soils/stains which contact the fabric during the soiling step (v). This
leads to good soil removal in a subsequent wash step (vi) and effective stripping
of soil from the fabric in step (vi). This can also be used to enable a reduction
in the amount of surfactant used to provide effective cleaning.
Step (i)
[0009] The method of the present invention comprises a step (i) of contacting the fabric
with an aqueous wash liquor. The aqueous wash liquor is formed by the addition of
a laundry detergent composition to water. The detergent composition added to water
to form the aqueous wash liquor may be in any suitable form including granular, liquid
or unitized dose. When in unitized dose form, it is preferred that the composition
is enclosed within a water-soluble film, for example a polyvinyl alcohol-based film.
The fabric may be contacted with the composition in a hand washing step or even a
wash liquor in a machine wash cycle.
[0010] The laundry detergent composition typically comprises from 1 to 70 wt%, or from 2
to 50 wt% or from 5 to 40 wt%, based on the total weight of the laundry detergent
composition, of a surfactant. The concentration of the surfactant in the wash liquor
is from 0.05 to 5g/l, or from 0.1 to 4g/l.
[0011] The detersive surfactant may be an anionic, cationic, non-ionic, zwitterionic, amphoteric
surfactant or a combination thereof. The surfactant composition may comprise one surfactant
or typically mixtures of more than one surfactant.
[0012] Preferred anionic detersive surfactants are alkyl benzene sulfonates, alkoxylated
anionic surfactant, or a combination thereof. Suitable anionic detersive surfactants
include sulphate and sulphonate detersive surfactants.
[0013] Particularly preferred alkyl benzene sulphonates are linear alkylbenzene sulphonates,
particularly those having a carbon chain length of C8-15, or C
10-13 alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable,
or even obtained, by sulphonating commercially available linear alkyl benzene (LAB);
suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the
tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other
suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the
tradename Hyblene®. Another suitable anionic detersive surfactant is alkyl benzene
sulphonate that is obtained by DETAL catalyzed process, preferably having 8 to 15
carbon atoms. Other synthesis routes, such as HF, may also be suitable.
[0014] Suitable sulphate detersive surfactants include alkyl sulphate, such as C
8-18 alkyl sulphate, or predominantly C
12 alkyl sulphate. The alkyl sulphate may be derived from natural sources, such as coco
and/or tallow. Alternatively, the alkyl sulphate may be derived from synthetic sources
such as C
12-15 alkyl sulphate.
[0015] It may be preferred for the surfactant composition to comprise in addition an alkyl
alkoxylated sulphate, such as alkyl ethoxylated sulphate, or a C
8-18 alkyl alkoxylated sulphate, or a C
8-18 alkyl ethoxylated sulphate. Preferably the alkyl chain length may be from 12 to 16
carbon atoms. The alkyl alkoxylated sulphate may have an average degree of alkoxylation
of from 0.5 to 20, or from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5 or from 0.5
to 3. Examples include predominantly C12 sodium lauryl ether sulphate ethoxylated
with an average of 3 moles of ethylene oxide per mole.
[0016] The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may
be linear or branched, substituted or un-substituted.
[0017] The anionic detersive surfactant may be a mid-chain branched anionic detersive surfactant,
such as a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene
sulphonate. The mid-chain branches are typically C
1-4 alkyl groups, such as methyl and/or ethyl groups.
[0018] Another suitable anionic detersive surfactant is alkyl ethoxy carboxylate.
[0019] The anionic surfactants are typically present in their salt form, typically being
complexed with a suitable cation. Suitable counter-ions include Na
+ and K
+, substituted ammonium such as C
1-C
6 alkanolammnonium such as mono-ethanolamine (MEA) tri-ethanolamine (TEA), diethanolamine
(DEA), and any mixture thereof.
[0020] Preferably the surfactant composition comprises a non-ionic detersive surfactant
in addition to the anionic surfactant. Preferred nonionic surfactants are primary
and secondary alcohol alkoxylates, especially ethoxylates. Suitable non-ionic detersive
surfactants include alkyl alkoxylated alcohols, such as C
8-18 alkyl alkoxylated alcohol, or a C
8-18 alkyl ethoxylated alcohol. The alkyl alkoxylated alcohol may have an average degree
of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to 20, or from 1 to
10. The alkyl alkoxylated alcohol may be a C
8-18 alkyl ethoxylated alcohol, typically having an average degree of ethoxylation of
from 1 to 10, or from 1 to 7, or from 1 to 5, or from 3 to 7. The alkyl alkoxylated
alcohol can be linear or branched, and substituted or un-substituted.
[0021] Suitable examples of nonionic surfactants include those selected from the group consisting
of: C
8-C
18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C
6-C
12 alkyl phenol alkoxylates wherein optionally the alkoxylate units are ethyleneoxy
units, propyleneoxy units or a mixture thereof; C
12-C
18 alcohol and C
6-C
12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such
as Pluronic® from BASF; C
14-C
22 mid-chain branched alcohols; C
14-C
22 mid-chain branched alkyl alkoxylates, typically having an average degree of alkoxylation
of from 1 to 30; alkylpolysaccharides, such as alkylpolyglycosides; polyhydroxy fatty
acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
Suitable non-ionic detersive surfactants are also alkyl polyglucoside and/or an alkyl
alkoxylated alcohol.
[0022] Suitable nonionic detersive surfactants include secondary alcohol-based detersive
surfactants having the formula:

wherein R
1 = linear or branched, substituted or unsubstituted, saturated or unsaturated C
2-8 alkyl; wherein R
2 = linear or branched, substituted or unsubstituted, saturated or unsaturated C
2-8 alkyl, wherein the total number of carbon atoms present in R
1 + R
2 moieties is in the range of from 7 to 13; wherein EO/PO are alkoxy moieties selected
from ethoxy, propoxy, or mixtures thereof, optionally the EO/PO alkoxyl moieties are
in random or block configuration; wherein n is the average degree of alkoxylation
and is in the range of from 4 to 10.
[0023] Other suitable non-ionic detersive surfactants include EO/PO block co-polymer surfactants,
such as the Plurafac
® series of surfactants available from BASF, and sugar-derived surfactants such as
alkyl N-methyl glucose amide.
[0024] The ratio of anionic surfactant to nonionic surfactant may be from 2:1 to 1:2, or
even from 1:1 to 1:3 or from greater than 1:1 to 1:2.
[0025] The composition may also comprise an amine oxide preferably in amounts up to 10 wt%
of the surfactant composition. Suitable amine oxides are described in
WO2014/114570, a particularly preferred amine oxide comprising lauryl dimethylamine oxide. The
composition may also comprise a zwitterionic surfactant. A preferred zwitterionic
surfactant is a betaine surfactant, for example a carbobetaine, such as Empigen® from
Huntsman. Where amine oxide and/or betaine surfactant is present, the weight ratio
of anionic and/or nonionic surfactant to amine oxide and/or betaine is typically from
10:1 1 to 20:1.
[0026] The laundry detergent composition may comprise a lipid esterase. The lipid esterase
can be any lipid esterase. The lipid esterase may be a lipase, or a cutinase, or a
combination thereof.
[0027] The lipid esterase may be selected from the following:
- (1) Triacylglycerol lipases (E.C. 3.1.1.3)
- (2) Carboxylic ester hydrolase (E.C. 3.1.1.1)
- (3) Cutinase (E.C. 3.1.1.74)
- (4) Sterol esterase (E.C. 3.1.1.13)
- (5) Wax-ester hydrolase (E.C. 3.1.1.50)
[0028] Suitable triacylglycerol lipases can be selected from variants of the
Humicola lanuginosa (
Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of
Pseudomonas lipases, e.g., from
P. alcaligenes or
P. pseudoalcaligenes (
EP 218 272),
P. cepacia (
EP 331 376),
P. stutzeri (
GB 1,372,034),
P. fluorescens, Pseudomonas sp. strain SD 705 (
WO 95/06720 and
WO 96/27002),
P. wisconsinensis (
WO 96/12012),
Bacillus lipases, e.g., from
B. subtilis (
Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360),
B. stearothermophilus (
JP 64/744992) or
B. pumilus (
WO 91/16422).
[0029] Suitable carboxylic ester hydrolases can be selected from wild-types or variants
of carboxylic ester hydrolases endogenous to
B. gladioli, P. fluorescens, P. putida, B. acidocaldarius, B. subtilis, B. stearothermophilus,
Streptomyces chrysomallus, S. diastatochromogenes and Saccaromyces cerevisiae.
[0030] Suitable cutinases can be selected from wild-types or variants of cutinases endogenous
to strains of
Aspergillus, in particular
Aspergillus oryzae, a strain of
Alternaria, in particular
Alternaria brassiciola, a strain of
Fusarium, in particular
Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa,
Fusarium roseum culmorum, or
Fusarium roseum sambucium, a strain of
Helminthosporum, in particular
Helminthosporum sativum, a strain of
Humicola, in particular
Humicola insolens, a strain of
Pseudomonas, in particular
Pseudomonas mendocina, or
Pseudomonas putida, a strain of
Rhizoctonia, in particular
Rhizoctonia solani, a strain of
Streptomyces, in particular
Streptomyces scabies, a strain of
Coprinopsis, in particular
Coprinopsis cinerea, a strain of
Thermobifida, in particular
Thermobifida fusca, a strain of
Magnaporthe, in particular
Magnaporthe grisea, or a strain of
Ulocladium, in particular
Ulocladium consortiale.
[0031] In a preferred embodiment, the cutinase is selected from variants of the
Pseudomonas mendocina cutinase described in
WO 2003/076580 (Genencor), such as the variant with three substitutions at I178M, F180V, and S205G.
[0033] In another preferred embodiment, the cutinase is a wild-type or variant of the two
cutinases endogenous to
Trichoderma reesei described in
WO2009007510 (VTT).
[0034] In a most preferred embodiment the cutinase is derived from a strain of
Humicola insolens, in particular the strain
Humicola insolens DSM 1800.
Humicola insolens cutinase is described in
WO 96/13580 which is hereby incorporated by reference. The cutinase may be a variant, such as
one of the variants disclosed in
WO 00/34450 and
WO 01/92502. Preferred cutinase variants include variants listed in Example 2 of
WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes,
Bagsvaerd, Denmark).
[0035] Suitable sterol esterases may be derived from a strain of
Ophiostoma, for example
Ophiostoma piceae, a strain of
Pseudomonas, for example
Pseudomonas aeruginosa, or a strain of
Melanocarpus, for example
Melanocarpus albomyces.
[0037] Suitable wax-ester hydrolases may be derived from
Simmondsia chinensis.
The lipid esterase may be selected from an enzyme in E.C. class 3.1 or 3.2 or a combination
thereof. The lipid esterase may be selected from an enzyme in E.C. class 3.1.1.1 or
3.1.1.3 or a combination thereof.
[0038] The detergent composition from step (i) optionally contains one or more additional
detergent ingredients as described below.
[0039] The fabric may be any suitable fabric. The fabric may comprise natural or synthetic
materials or a combination thereof. The fabric may comprise cotton, polycotton, polyester,
or a combination thereof. The fabric may comprise cotton.
Step (ii)
[0040] In step (ii) the washed fabric from step (i) undergoes a rinse step, typically using
an aqueous rinse liquor. This can be a hand rinsing step in which fabric from step
(i) is placed into rinse liquor, that is substantially free from the detergent composition
present in step (i), or a rinse step in a washing machine. Typically, subsequently
rinse liquor is removed from the fabric by conventional means. Step (ii) may include
two or more separate rinse stages in which fresh rinse liquor is provided in respective
stages. Although rinsing does not remove all of the laundry detergent composition
from a wash step, step (ii) aims to at least partially, preferably substantially,
remove the laundry detergent composition from step (i) from the fabric.
Step (iii)
[0041] The method of the present invention comprises a second rinse step (iii) in which
the fabric is contacted with a second rinse liquor comprising a lipid esterase.
[0042] The lipid esterase may be any suitable lipid esterase. The lipid esterase may comprise
at least a first and a second lipid esterase. The lipid esterase may comprise more
than two lipid esterases. The lipid esterase may be a lipase, or a cutinase, or a
combination thereof.
[0043] The lipid esterase may be selected from the following:
- (1) Triacylglycerol lipases (E.C. 3.1.1.3)
- (2) Carboxylic ester hydrolase (E.C. 3.1.1.1)
- (3) Cutinase (E.C. 3.1.1.74)
- (4) Sterol esterase (E.C. 3.1.1.13)
- (5) Wax-ester hydrolase (E.C. 3.1.1.50)
[0044] By 'E.C. class' we herein mean the Enzyme Commission class. The Enzyme Commission
class is an international recognized enzyme classification scheme based on chemical
reactions that the enzymes catalyse.
[0045] Suitable triacylglycerol lipases can be selected from variants of the
Humicola lanuginosa (
Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of
Pseudomonas lipases, e.g., from
P. alcaligenes or
P. pseudoalcaligenes (
EP 218 272),
P. cepacia (
EP 331 376),
P. stutzeri (
GB 1,372,034),
P. fluorescens, Pseudomonas sp. strain SD 705 (
WO 95/06720 and
WO 96/27002),
P. wisconsinensis (
WO 96/12012),
Bacillus lipases, e.g., from
B. subtilis (
Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360),
B. stearothermophilus (
JP 64/744992) or
B. pumilus (
WO 91/16422).
[0046] Suitable carboxylic ester hydrolases can be selected from wild-types or variants
of carboxylic ester hydrolases endogenous to
B. gladioli, P. fluorescens, P. putida, B. acidocaldarius, B. subtilis, B. stearothermophilus,
Streptomyces chrysomallus, S. diastatochromogenes and Saccaromyces cerevisiae.
[0047] Suitable cutinases can be selected from wild-types or variants of cutinases endogenous
to strains of
Aspergillus, in particular
Aspergillus oryzae, a strain of
Alternaria, in particular
Alternaria brassiciola, a strain of
Fusarium, in particular
Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa,
Fusarium roseum culmorum, or
Fusarium roseum sambucium, a strain of
Helminthosporum, in particular
Helminthosporum sativum, a strain of
Humicola, in particular
Humicola insolens, a strain of
Pseudomonas, in particular
Pseudomonas mendocina, or
Pseudomonas putida, a strain of
Rhizoctonia, in particular
Rhizoctonia solani, a strain of
Streptomyces, in particular
Streptomyces scabies, a strain of
Coprinopsis, in particular
Coprinopsis cinerea, a strain of
Thermobifida, in particular
Thermobifida fusca, a strain of
Magnaporthe, in particular
Magnaporthe grisea, or a strain of
Ulocladium, in particular
Ulocladium consortiale.
[0048] In a preferred embodiment, the cutinase is selected from variants of the
Pseudomonas mendocina cutinase described in
WO 2003/076580 (Genencor), such as the variant with three substitutions at I178M, F180V, and S205G.
[0050] In another preferred embodiment, the cutinase is a wild-type or variant of the two
cutinases endogenous to
Trichoderma reesei described in
WO2009007510 (VTT).
[0051] In a most preferred embodiment the cutinase is derived from a strain of
Humicola insolens, in particular the strain
Humicola insolens DSM 1800.
Humicola insolens cutinase is described in
WO 96/13580 which is hereby incorporated by reference. The cutinase may be a variant, such as
one of the variants disclosed in
WO 00/34450 and
WO 01/92502. Preferred cutinase variants include variants listed in Example 2 of
WO 01/92502.
[0052] Suitable sterol esterases may be derived from a strain of
Ophiostoma, for example
Ophiostoma piceae, a strain of
Pseudomonas, for example
Pseudomonas aeruginosa, or a strain of
Melanocarpus, for example
Melanocarpus albomyces.
[0054] Suitable wax-ester hydrolases may be derived from
Simmondsia chinensis.
[0055] The lipid esterase may be selected from an enzyme in E.C. class 3.1 or 3.2 or a combination
thereof. The lipid esterase may comprise an enzyme selected from E.C. class 3.1.1.1
or 3.1.1.3 or 3.1.1.74 or a combination thereof. The preferred lipid esterase may
comprise an enzyme selected from E.C. class 3.1.1.3. The lipid esterase may comprise
a variant having at least 90% sequence identity to wild-type lipase from
Thermomyces lanuginosus and having sequence substitutions T231R and N233R, or a variant corresponding to
Claim 5, part (u) of
EP1290150B1, or a combination thereof. The lipid esterase may comprise a variant having at least
90% sequence identity to wild-type lipase from
Thermomyces lanuginosus and having sequence substitutions T231R and N233R.
[0056] The fabric may be contacted with a lipid esterase at a concentration of between 30
and 55,000 ng enzyme/g fabric. The fabric may be contacted with a lipid esterase at
a concentration of between 30 and 2000 ng enzyme/g fabric. The fabric may be contacted
with a lipid esterase at a concentration of between 50 and 1700ng enzyme/g fabric,
or even 80 and 1600ng enzyme/g fabric. The fabric may be contacted with a lipid esterase
at a concentration of between 100 and 3000 ng enzyme/g fabric, or even 125 and 2500
ng enzyme/g fabric. The fabric may be contacted with the lipid esterase at a concentration
of between 100 and 35,000 ng enzyme/g fabric, or even between 500 and 30,000 ng enzyme/g
fabric. Without wishing to be bound by theory, it is believed that these concentrations
are optimal for soil removal from the fabrics.
[0057] In step (ii) the fabric from step (ii) is contacted with the lipid esterase in a
second rinse step. This can be a hand rinsing step in which fabric from step (ii)
is placed into rinse water, that is substantially free from the detergent composition
present in step (i), or a rinse step in a washing machine. Step (iii) contacts the
fabric with lipid esterase thereby depositing the lipid esterase onto the fabric.
[0058] The rinse liquor of the second rinse step may comprise optional additional rinse-added
ingredients, such as fabric softening ingredients, such as quaternary ammonium surfactants
or silicones and optionally other ingredients useful in the rinse stage, such as perfumes,
dyes, polymers, surfactants.
[0059] Preferably the aqueous rinse liquor from the second rinse step (iii) comprises a
soil release polymer. The soil release polymer may be present in the aqueous rinse
liquor in amounts from 0.00001 to 3g/l in the rinse liquor, or from 0.0001 to 2g/l
or up to 1g/l or 0.5g/l. The rinse liquor may be provided by adding a fabric softening
composition to water to for the aqueous rinse liquor. The soil release polymer may
be added via the fabric softening composition. In such fabric softening composition,
the soil release polymer may be present in amounts from about 0.01% to about 10.0%,
typically from about 0.1% to about 5%, in some aspects from about 0.2% to about 3.0%,
by weight of the composition, of a soil release polymer (also known as a polymeric
soil release agents or "SRA").
[0060] Suitable soil release polymers typically have hydrophilic segments to hydrophilize
the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments
to deposit on hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This may enable stains occurring subsequent to treatment with a soil release agent
to be more easily cleaned in later washing procedures.
[0061] Soil release agents may include a variety of charged, e.g., anionic or cationic (see,
e.g.,
U.S. Pat. No. 4,956,447), as well as non-charged monomer units. The structure of the soil release agent may
be linear, branched, or star-shaped. The soil release polymer may include a capping
moiety, which is especially effective in controlling the molecular weight of the polymer
or altering the physical or surface-active properties of the polymer. The structure
and charge distribution of the soil release polymer may be tailored for application
to different fibers or textile types and for formulation in different detergent or
detergent additive products. Suitable polyester soil release polymers have a structure
as defined by one of the following structures (III), (IV) or (V):
- [(OCHR1-CHR2)a-O-OC-Ar-CO-]d (III)
- [(OCHR3CHR4)b-O-OC-sAr-CO]e (IV)
- [(OCHR5-CHR6), OR7]f (V)
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50;
Ar is a 1,4-substituted phenylene;
sAr is 1,3 -substituted phenylene substituted in position 5 with SO3Me;
Me is H, Na, Li, K, Mg+2, Ca+2, Al+3, ammonium, mono-, di-, tri-, or tetra-alkylammonium
wherein the alkyl groups are C1-C18 alkyl or C2-C10 hydroxyalkyl, or any mixture thereof;
R1, R2, R3, R4, R5 and R6 are independently selected from H or C,-C18 n- or iso- alkyl; and R7 is a linear or branched C1-C18 alkyl, or a linear or branched C2-C30 alkenyl, or
a cycloalkyl group with 5 to 9 carbon atoms, or a C6-C30 aryl group, or a C6-C30 arylalkyl
group.
[0062] Suitable polyester soil release polymers are terephthalate polymers having the structure
(III) or (IV) above. Other suitable soil release polymers may include, for example
sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped.
Examples of suitable polyester soil release polymers are the REPEL-O-TEX® line of
polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2. Other
suitable soil release polymers include TexCare® polymers, including TexCare® SRA-100,
TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare® SRN-300,
and TexCare® SRN-325, all supplied by Clariant. Especially useful soil release polymers
are the sulphonated non-end-capped polyesters described in
WO 95/32997A (Rhodia Chimie) Other suitable soil release polymers are Marloquest® polymers, such
as Marloquest® SL supplied by Sasol. Examples of SRAs are described in
U.S. Pat. Nos. 4,968,451;
4,711,730;
4,721,580;
4,702,857;
4,877,896;
3,959,230;
3,893,929;
4,000,093;
5,415,807;
4,201,824;
4,240,918;
4,525,524;
4,201,824;
4,579,681; and
4,787,989; European Patent Application
0 219 048;
279,134 A;
457,205 A; and
DE 2,335,044; and
WO201419792;
WO2012104156/57/58,
WO201419658;
WO20141965;
WO201429479.
[0063] Optionally the second rinse liquor additionally comprises a fabric softener active
selected from the group comprising, diester quaternary ammonium compounds, dialkyl
quaternary ammonium compounds, imidazolinium quaternary compounds, cationic starch,
sucrose ester-based fabric care materials, and mixtures thereof. In one aspect, said
ester quat fabric softener active, monoester, diester, and triester quat fabric softener
active and ion pair fabric softener actives are selected from the group consisting
of:
- a) materials having Formula (1) below

wherein:
- (i) R1 and R2 are each independently a C5 - C23 hydrocarbon;
- (ii) R3 and R4 are each independently selected from the group consisting of C1-C4 hydrocarbon, C1-C4 hydroxy substituted hydrocarbon, benzyl, -(C2H4O)yH where y is an integer from 1 to 10;
- (iii) L is selected from the group consisting of -C(O)O-, -OC(O)-,;
- (iv) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4
- (v) X- is a softener-compatible anion;
- b) materials having Formula (2) below

wherein
- (i) R5 is a C5 - C23 hydrocarbon;
- (ii) each R6 is independently selected from the group consisting of C1-C4 hydrocarbon, C1-C4 hydroxy substituted hydrocarbon, benzyl, -(C2H4O)yH where y is an integer from 1 to 10;
- (iii) L is selected from the group consisting of -C(O)O-, -O-(O)C-,
- (iv) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
- (v) X- is a softener-compatible anion;
- c) materials having Formula (3) below

wherein
- (i) R5 is a C5 - C23 hydrocarbon;
- (ii) each R6 is independently selected from the group consisting of C1-C4 hydrocarbon, C1-C4 hydroxy substituted hydrocarbon, benzyl, -(C2H4O)yH where y is an integer from 1 to 10;
- (iii) L is selected from the group consisting of -C(O)O-, -O-(O)C-,
- (iv) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
- (v) X- is an anionic surfactant comprising a C6-C24 hydrocarbon.
- d) materials having Formula (4) below

wherein:
(i) R7, R8 and R9 are each independently a C5 - C23 hydrocarbon;
(i) R10 is selected from the group consisting of C1-C4 hydrocarbon, C1-C4 hydroxy substituted hydrocarbon, benzyl, -(C2H4O)yH where y is an integer from 1 to 10;
(ii) L is selected from the group consisting of -C(O)O-, -O-(O)C-;
(iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
(iv) X- is a softener-compatible anion;
[0064] In one aspect, said di-tail fabric softener active, mono-tail fabric softener active
and ion pair fabric softener actives are selected from the group consisting of:
- a) materials having Formula (1) below

wherein:
- (i) R1 and R2 are each independently a C11 - C17 hydrocarbon;
- (ii) R3 and R4 are each independently selected from the group consisting of C1-C2 hydrocarbon, C1-C2 hydroxy substituted hydrocarbon;
- (iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 2;
- (iv) L is selected from the group consisting of -C(O)O-, , -O-(O)C-;
- (v) X- is a softener-compatible anion, selected from the group consisting of halides,
sulfonates, sulfates, and nitrates.
- b) materials having Formula (2) below

wherein
- (i) R5 is a C11) - C17 hydrocarbon;
- (ii) each R6 is independently selected from the group consisting of C1-C2 hydrocarbon, C1-C2 hydroxy substituted hydrocarbon;
- (iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
- (iv) L is selected from the group consisting of -C(O)O-, -O-(O)C-;
- (v) X- is a softener-compatible anion, selected from the group consisting of halides, sulfonates,
sulfates, and nitrates;
- c) materials having Formula (3) below

wherein
- (i) R5 is a C11 - C17 hydrocarbon;
- (ii) each R6 is independently selected from the group consisting of C1-C4 hydrocarbon, C1-C4 hydroxy substituted hydrocarbon, benzyl, -(C2H4O)yH where y is an integer from 1 to 10;
- (iii) L is selected from the group consisting of -C(O)O-, -O-(O)C-,;
- (iv) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
- (v) X- is an anionic surfactant comprising a C6-C24 hydrocarbon.
[0065] In one aspect, said di-tail fabric softener active, mono-tail fabric softener active
and ion pair fabric softener actives are selected from the group consisting of:
b) materials having Formula (1) below

wherein:
- (i) R1 and R2 are each independently a C11 - C17 hydrocarbon;
- (ii) R3 and R4 are each independently selected from the group consisting of C1-C2 hydrocarbon, C1-C2 hydroxy substituted hydrocarbon;
- (iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 2;
- (iv) L is selected from the group consisting of -C(O)O-, -O-(O)C-;
- (v) X- is a softener-compatible anion, selected from the group consisting of chloride, bromide,
methylsulfate, ethylsulfate, and methyl sulfonate.
b) materials having Formula (2) below

wherein
(i) R5 is a C11 - C17 hydrocarbon;
(ii) each R6 is independently selected from the group consisting of C1-C2 hydrocarbon, C1-C2 hydroxy substituted hydrocarbon;
(iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
(iv) L is selected from the group consisting of -C(O)O-, -O-(O)C-;
(v) X- is a softener-compatible anion, selected from the group consisting of chloride,
bromide, methylsulfate, ethylsulfate, and methyl sulfonate or anionic surfactant comprising
a C6-C18 hydrocarbon
c) materials having Formula (3) below

wherein
- (i) R5 is a C11 - C17 hydrocarbon;
- (ii) each R6 is independently selected from the group consisting of C1-C2 hydrocarbon, C1-C2 hydroxy substituted hydrocarbon;
- (iii) Z is selected from the group consisting of -(CH2)n, -CH2C(CH3)H- where each n is independently an integer from 1 to 4;
- (iv) L is selected from the group consisting of -C(O)O-" -O-(O)C-;
- (v) X- is a softener-compatible anion, selected from the group consisting of chloride,
bromide, methylsulfate, ethylsulfate, and methyl sulfonate or anionic surfactant comprising
a C6-C18 hydrocarbon.
[0066] In one aspect, for Formula 2, X- is a C
6-C
24 hydrocarbon that is an anionic surfactant.
[0067] In one aspect, said fabric care active comprises a fabric softening active selected
from the group consisting of N,N-di(hydrogenated tallowoyloxyethyl)-N,N-dimethylammonium
chloride; N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride; N,N-di(hydrogenated
tallowoyloxyisopropyl)-N,N-dimethylammonium chloride; N,N-di(tallowoyloxyisopropyl)-N,N-dimethylammonium
chloride; N,N-di(stearoyloxyisopropyl)-N,N-dimethylammonium chloride; N,N-di(palmoyloxyisopropyl)-N,N-dimethylammonium
chloride; bis-(2-hydroxypropyl)-dimethylammonium chloride stearic acid diester; partially
hydrogenated bis-(2-hydroxypropyl)-dimethylammonium chloride palmitic acid diester;
and mixtures thereof.
[0068] In the cationic nitrogenous salts herein, the anion A
- , which is any softener compatible anion, provides electrical neutrality. Most often,
the anion used to provide electrical neutrality in these salts is from a strong acid,
especially a halide, such as chloride, bromide, or iodide. However, other anions can
be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate,
and the like. Chloride and methylsulfate are preferred herein as anion A. The anion
can also, but less preferably, carry a double charge in which case A
- represents half a group.
Step (iv)
[0069] In step (iv) the fabric is dried. This can be by any conventional drying means such
as air-drying or mechanically drying in a conventional laundry drying machine.
Step (v)
[0070] The method of the present invention comprises a step (v) of contacting the fabric
from step (iv) with a soil. By 'soil' we mean herein any organic or inorganic material
that is deposited onto the fabric that the consumer perceives as dirtying the fabric.
The soil could be a stain, for example a greasy or oily food stain, or body soils
such as sweat or blood. Other common stains include red food stains, clay-based stains
and grass stains. Alternatively, the soil could be atmospheric soil such as chemical
pollutants, dust or soot. The soil may be water-soluble or water-insoluble. These
are non-limiting examples. Those skilled in the art would know what is meant by 'soil'
in the context of the present invention. Contact of the fabric with a soil takes place
in the normal use of the fabric article, for example by wearing fabric garments or
typical consumer use of other fabric articles.
Step (vi)
[0071] In step (vi), the fabric from step (v) is contacted with an aqueous wash liquor of
a detergent composition wherein the detergent composition comprises a surfactant,
the wash liquor comprising from 0.05 to 4g/l of a surfactant. Step (vi) is independent
from, but as described in step (i) above.
[0072] The fabric may be contacted with the respective liquor in any of steps (i), (ii),
(iii) and/or (vi) at a temperature of 60°C or less, or even 40°C or less. In particular,
the fabric may be contacted with the respective wash liquors of steps (i) and/or (vi)
at a temperature of between 5°C and 50°C, preferably between 10°C and 30°C. The fabric
may be contacted at these temperatures in the wash cycle of a domestic washing machine.
In particular the present invention enables good stain/soil removal in step (vi) even
at low wash temperatures such as between 10 and 30 °C.
[0073] The fabric may be contacted with a laundry detergent composition in step (i) and/or
step (vi) in a wash cycle of an automatic washing machine and the length of the wash
cycle may be at least 30 seconds, or even at least 3 mins, or even at least 6 mins,
but no more than 30 mins, or even no more than 45 mins, or even no more than 1 hour.
Other ingredients
[0074] The laundry detergent composition of step (iii) may comprise further laundry detergent
ingredients. The laundry detergent composition of step (iii) may comprise a hueing
agent, a polymer or a combination thereof. Suitable detergent ingredients include:
hueing agent; detersive surfactants including anionic detersive surfactants, non-ionic
detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants,
amphoteric detersive surfactants, and any combination thereof; polymers including
carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers
such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer
inhibition polymers, dye lock polymers such as a condensation oligomer produced by
condensation of imidazole and epichlorhydrin, optionally in ratio of 1:4:1, hexamethylenediamine
derivative polymers, and any combination thereof; builders including zeolites, phosphates,
citrate, and any combination thereof; buffers and alkalinity sources including carbonate
salts and/or silicate salts; fillers including sulphate salts and bio-filler materials;
bleach including bleach activators, sources of available oxygen, preformed peracids,
bleach catalysts, reducing bleach, and any combination thereof; chelants; photobleach;
hueing agents; brighteners; enzymes including proteases, amylases, cellulases, lipases,
xylogucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and any combination
thereof; fabric softeners including clay, silicones, quaternary ammonium fabric-softening
agents, and any combination thereof; flocculants such as polyethylene oxide; perfume
including starch encapsulated perfume accords, perfume microcapsules, perfume loaded
zeolites, schif base reaction products of ketone perfume raw materials and polyamines,
blooming perfumes, and any combination thereof; aesthetics including soap rings, lamellar
aesthetic particles, geltin beads, carbonate and/or sulphate salt speckles, coloured
clay, and any combination thereof: and any combination thereof.
[0075] Fabric Hueing Agents - The composition may comprise a fabric hueing agent (sometimes referred to as shading,
bluing or whitening agents). Typically the hueing agent provides a blue or violet
shade to fabric. Hueing agents can be used either alone or in combination to create
a specific shade of hueing and/or to shade different fabric types. This may be provided
for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing
agents may be selected from any known chemical class of dye, including but not limited
to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo,
disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifurane
and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane,
formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and
nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane,
xanthenes and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay
conjugates, and organic and inorganic pigments. Suitable dyes include small molecule
dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes
selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications
of Acid, Direct, Basic, Reactive or hydrolysed Reactive, Solvent or Disperse dyes
for example that are classified as Blue, Violet, Red, Green or Black, and provide
the desired shade either alone or in combination. In another aspect, suitable small
molecule dyes include small molecule dyes selected from the group consisting of Colour
Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet dyes such
as 9, 35, 48, 51, 66, and 99, Direct Blue dyes such as 1, 71, 80 and 279, Acid Red
dyes such as 17, 73, 52, 88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and
50, Acid Blue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, Acid Black
dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35, Basic Blue dyes such
as 3, 16, 22, 47, 66, 75 and 159, Disperse or Solvent dyes such as those described
in
US 2008/034511 A1 or
US 8,268,016 B2, or dyes as disclosed in
US 7,208,459 B2, and mixtures thereof. In another aspect, suitable small molecule dyes include small
molecule dyes selected from the group consisting of C. I. numbers Acid Violet 17,
Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue
29, Acid Blue 113 or mixtures thereof.
[0076] Preferred dyes include dye polymers, wherein a dye group is bound to a polymeric
group, optionally via a linking group. Suitable polymeric groups include (1) alkoxylated
polyethyleneimine (for example as disclosed in
WO2012119859), (2) polyvinyl alcohol (for example as disclosed in
WO2012130492), or (3) diamine derivative of an alkylene oxide capped polyethylene glycol (for
example as disclosed in
WO2012126665, especially figure 24), or polyalkoxylated alcohol, for example as described in
WO2011/011799,
WO2012/054058,
WO2012/166699 or
WO2012/166768. One preferred class of dye polymers is obtainable by reacting a blue or violet dye
containing an NH2 group with a polymer to form a covalent bond via the reacted NH2
group of the blue or violet dye and the dye polymer has an average of from 0 to 30,
preferably 2 to 20, most preferably 2 to 15 repeating same units. In a preferred embodiment
the monomeric units are selected from alkylene oxides, preferably ethylene oxides.
Typically dye polymers will be in the form of a mixture of dye polymers in which there
is a mixture of molecules having a distribution of number of monomer groups in the
polymer chains, such as the mixture directly produced by the appropriate organic synthesis
route, for example in the case of alkylene oxide polymers, the result of an alkoxylation
reaction. Such dye polymers are typically blue or violet in colour, to give to the
cloth a hue angle of 230 to 345, more preferably 250 to 330, most preferably 270 to
300. In the synthesis of dye polymers unbound blue or violet organic dyes may be present
in a mixture with the final dye-polymer product. The chromophore of the blue or violet
dye is preferably selected from the group consisting of: azo; anthraquinone; phthalocyanine;
triphendioxazine; and, triphenylmethane. In one aspect the dye polymer is obtainable
by reacting a dye containing an NH[2] group with a polymer or suitable monomer that
forms a polymer in situ. Preferably the NH[2] is covalently bound to an aromatic ring
of the dye. Unbound dye is formed when the dye does not react with polymer. Preferred
dyes containing -NH[2] groups for such reactions are selected from: acid violet 1
; acid violet 3; acid violet 6; acid violet 1 1 ; acid violet 13; acid violet 14;
acid violet 19; acid violet 20; acid violet 36; acid violet 36:1 ; acid violet 41
; acid violet 42; acid violet 43; acid violet 50; acid violet 51 ; acid violet 63;
acid violet 48; acid blue 25; acid blue 40; acid blue 40:1; acid blue 41 ; acid blue
45; acid blue 47; acid blue 49; acid blue 51 ; acid blue 53; acid blue 56; acid blue
61 ; acid blue 61 :1 ; acid blue 62; acid blue 69; acid blue 78; acid blue 81 :1 ;
acid blue 92; acid blue 96; acid blue 108; acid blue 1 1 1 ; acid blue 215; acid blue
230; acid blue 277; acid blue 344; acid blue 1 17; acid blue 124; acid blue 129; acid
blue 129:1 ; acid blue 138; acid blue 145; direct violet 99; direct violet 5; direct
violet 72; direct violet 16; direct violet 78; direct violet 77; direct violet 83;
food black 2; direct blue 33; direct blue 41 ; direct blue 22; direct blue 71 ; direct
blue 72; direct blue 74; direct blue 75; direct blue 82; direct blue 96; direct blue
1 10; direct blue 1 1 1 ; direct blue 120; direct blue 120:1 ; direct blue 121 ; direct
blue 122; direct blue 123; direct blue 124; direct blue 126; direct blue 127; direct
blue 128; direct blue 129; direct blue 130; direct blue 132; direct blue 133; direct
blue 135; direct blue 138; direct blue 140; direct blue 145; direct blue 148; direct
blue 149; direct blue 159; direct blue 162; direct blue 163; food black 2; food black
1 wherein the acid amide group is replaced by NH[2]; Basic Violet 2; Basic Violet
5; Basic Violet 12; Basic Violet 14; Basic Violet 8; Basic Blue 12; Basic Blue 16;
Basic Blue 17; Basic Blue 47; Basic Blue 99; disperse blue 1 ; disperse blue 5; disperse
blue 6; disperse blue 9; disperse blue 1 1 ; disperse blue 19; disperse blue 20; disperse
blue 28; disperse blue 40; disperse blue 56; disperse blue 60; disperse blue 81 ;
disperse blue 83; disperse blue 87; disperse blue 104; disperse blue 1 18; disperse
violet 1 ; disperse violet 4, disperse violet 8, disperse violet 17, disperse violet
26; disperse violet 28; solvent violet 26; solvent blue 12; solvent blue 13; solvent
blue 18; solvent blue 68. Further preferred dyes are selected from mono-azo dyes which
contain a phenyl group directly attached to the azo group, wherein the phenyl group
has an NH[2] groups covalent bound to it. For example a mono-azo thiophene dye. The
polymer chain may be selected from polyalkylene oxides. The polymer chain andf/or
the dye chromophore group may optionally carry anionic or cationic groups. Examples
of polyoxyalkylene oxide chains include ethylene oxide, propylene oxide, glycidol
oxide, butylene oxide and mixtures thereof.
[0077] Suitable polymeric dyes include polymeric dyes selected from the group consisting
of polymers containing covalently bound (sometimes referred to as conjugated) chromogens,
(dye-polymer conjugates), for example polymers with chromogens co-polymerized into
the backbone of the polymer and mixtures thereof. Polymeric dyes include those described
in
WO2011/98355,
US 2012/225803 A1,
US 2012/090102 A1,
US 7,686,892 B2, and
WO2010/142503.
[0078] In another aspect, suitable polymeric dyes include polymeric dyes selected from the
group consisting of fabric-substantive colorants sold under the name of Liquitint®
(Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at
least one reactive dye and a polymer selected from the group consisting of polymers
comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary
amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still
another aspect, suitable polymeric dyes include polymeric dyes selected from the group
consisting of Liquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound
to a reactive blue, reactive violet or reactive red dye such as CMC conjugated with
C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE,
product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated
thiophene polymeric colourants, and mixtures thereof.
[0080] Suitable dye clay conjugates include dye clay conjugates selected from the group
comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof.
In another aspect, suitable dye clay conjugates include dye clay conjugates selected
from the group consisting of one cationic/basic dye selected from the group consisting
of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red
1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I.
Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through
11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite
clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay
conjugates include dye clay conjugates selected from the group consisting of:
Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9
C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite
Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate,
Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,
Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555
conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I.
45160 conjugate, Hectorite C.I.
Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic
Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite
Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite
C.I. Basic Black 2 conjugate and mixtures thereof.
[0081] Suitable pigments include pigments selected from the group consisting of flavanthrone,
indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone,
dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone,
perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted
or substituted by C1-C3 -alkyl or a phenyl or heterocyclic radical, and wherein the
phenyl and heterocyclic radicals may additionally carry substituents which do not
confer solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone,
isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to
2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper
phthalocyanine containing up to 14 bromine atoms per molecule and mixtures thereof.
[0082] In another aspect, suitable pigments include pigments selected from the group consisting
of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment Violet
15) and mixtures thereof.
[0083] The aforementioned fabric hueing agents can be used in combination (any mixture of
fabric hueing agents can be used).
[0084] Polymer: Suitable polymers include carboxylate polymers, polyethylene glycol polymers,
polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic
polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation
oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio
of 1:4:1, hexamethylenediamine derivative polymers, and any combination thereof.
[0085] Carboxylate polymer: Suitable carboxylate polymers include maleate/acrylate random copolymer or polyacrylate
homopolymer. The carboxylate polymer may be a polyacrylate homopolymer having a molecular
weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000 Da. Other suitable
carboxylate polymers are co-polymers of maleic acid and acrylic acid, and may have
a molecular weight in the range of from 4,000 Da to 90,000 Da.
[0086] Other suitable carboxylate polymers are co-polymers comprising: (i) from 50 to less
than 98 wt% structural units derived from one or more monomers comprising carboxyl
groups; (ii) from 1 to less than 49 wt% structural units derived from one or more
monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt% structural units
derived from one or more types of monomers selected from ether bond-containing monomers
represented by formulas (I) and (II):

wherein in formula (I), R
0 represents a hydrogen atom or CH
3 group, R represents a CH
2 group, CH
2CH
2 group or single bond, X represents a number 0-5 provided X represents a number 1-5
when R is a single bond, and R
1 is a hydrogen atom or C
1 to C
20 organic group;

in formula (II), R
0 represents a hydrogen atom or CH
3 group, R represents a CH
2 group, CH
2CH
2 group or single bond, X represents a number 0-5, and R
1 is a hydrogen atom or C
1 to C
20 organic group.
[0087] Polyethylene glycol polymer: Suitable polyethylene glycol polymers include random
graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol;
and (ii) hydrophobic side chain(s) selected from the group consisting of: C
4-C
25 alkyl group, polypropylene, polybutylene, vinyl ester of a saturated C
1-C
6 mono-carboxylic acid, C
1-C
6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene
glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl
acetate side chains. The average molecular weight of the polyethylene glycol backbone
can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da. The
molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate
side chains can be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2. The average
number of graft sites per ethylene oxide units can be less than 1, or less than 0.8,
the average number of graft sites per ethylene oxide units can be in the range of
from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can
be in the range of from 0.1 to 0.5, or from 0.2 to 0.4. A suitable polyethylene glycol
polymer is Sokalan HP22.
[0088] Polyester soil release polymers: Suitable polyester soil release polymers have a structure as defined by one of the
following structures (I), (II) or (III):
(I) -[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(II) -[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(III) -[(OCHRs-CHR6)c-OR7]f
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50;
Ar is a 1,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted in position 5 with SO3Me;
Me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium
wherein the alkyl groups are C1-C18 alkyl or C2-C10 hydroxyalkyl, or any mixture thereof;
R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n- or iso-alkyl; and
R7 is a linear or branched C1-C18 alkyl, or a linear or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group. Suitable polyester soil release polymers are terephthalate polymers
having the structure of formula (I) or (II) above.
[0089] Suitable polyester soil release polymers include the Repel-o-tex series of polymers
such as Repel-o-tex SF2 (Rhodia) and/or the Texcare series of polymers such as Texcare
SRA300 (Clariant).
[0090] Amine polymer: Suitable amine polymers include polyethylene imine polymers, such as alkoxylated
polyalkyleneimines, optionally comprising a polyethylene and/or polypropylene oxide
block.
[0091] Cellulosic polymer: The composition can comprise cellulosic polymers, such as polymers selected from
alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl,
and any combination thereof. Suitable cellulosic polymers are selected from carboxymethyl
cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose,
and mixtures thereof. The carboxymethyl cellulose can have a degree of carboxymethyl
substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da.
Another suitable cellulosic polymer is hydrophobically modified carboxymethyl cellulose,
such as Finnfix SH-1 (CP Kelco).
[0092] Other suitable cellulosic polymers may have a degree of substitution (DS) of from
0.01 to 0.99 and a degree of blockiness (DB) such that either DS+DB is of at least
1.00 or DB+2DS-DS
2 is at least 1.20. The substituted cellulosic polymer can have a degree of substitution
(DS) of at least 0.55. The substituted cellulosic polymer can have a degree of blockiness
(DB) of at least 0.35. The substituted cellulosic polymer can have a DS + DB, of from
1.05 to 2.00. A suitable substituted cellulosic polymer is carboxymethylcellulose.
[0093] Another suitable cellulosic polymer is cationically modified hydroxyethyl cellulose.
[0094] Dye transfer inhibitor (DTI) polymer: The laundry detergent compositions may comprise DTI polymers. Suitable DTIs include
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures
thereof. The DTI polymers discussed above are well known in the art and commercially
available, for example PVP-K15 and K30 (Ashland), Sokalan HP165, HP50, HP53, HP59,
HP56K, HP56, HP66 (BASF), Chromabond S-400, S403E and S-100 (Ashland), and Polyquart
FDI (Cognis).
[0095] Builder: Suitable builders include zeolites, phosphates, citrates, and any combination thereof.
[0096] Zeolite builder: The composition may be substantially free of zeolite builder. Substantially free
of zeolite builder typically means comprises from 0wt% to 10wt%, zeolite builder,
or to 8wt%, or to 6wt%, or to 4wt%, or to 3wt%, or to 2wt%, or even to 1wt% zeolite
builder. Substantially free of zeolite builder preferably means "no deliberately added"
zeolite builder. Typical zeolite builders include zeolite A, zeolite P, zeolite MAP,
zeolite X and zeolite Y.
[0097] Phosphate builder: The composition may be substantially free of phosphate builder. Substantially free
of phosphate builder typically means comprises from 0wt% to 10wt% phosphate builder,
or to 8wt%, or to 6wt%, or to 4wt%, or to 3wt%, or to 2wt%, or even to 1wt% phosphate
builder. Substantially free of zeolite builder preferably preferably means "no deliberately
added" phosphate builder. A typical phosphate builder is sodium tri-polyphosphate
(STPP).
[0098] Citrate: A suitable citrate is sodium citrate. However, citric acid may also be incorporated
into the composition, which can form citrate in the wash liquor.
[0099] Buffer and alkalinity source: Suitable buffers and alkalinity sources include carbonate salts and/or silicate salts
and/or double salts such as burkeitte.
[0100] Carbonate salt: A suitable carbonate salt is sodium carbonate and/or sodium bicarbonate. The carbonate
salt may have a weight average mean particle size of from 100 to 500 micrometers.
Alternatively, the carbonate salt may have a weight average mean particle size of
from 10 to 25 micrometers.
[0101] Silicate salt: The silicate can be crystalline or amorphous. Suitable crystalline silicates include
crystalline layered silicate, such as SKS-6. Other suitable silicates include 1.6R
silicate and/or 2.0R silicate. A suitable silicate salt is sodium silicate. Another
suitable silicate salt is sodium metasilicate.
[0102] Sulphate salt: A suitable sulphate salt is sodium sulphate. The sulphate salt may have a weight
average mean particle size of from 100 to 500 micrometers, alternatively, the sulphate
salt may have a weight average mean particle size of from 10 to 45 micrometers.
[0103] Bleach activator: Suitable bleach activators include: tetraacetylethylenediamine (TAED); oxybenzene
sulphonates such as nonanoyl oxybenzene sulphonate (NOBS), caprylamidononanoyl oxybenzene
sulphonate (NACA-OBS), 3,5,5-trimethyl hexanoyloxybenzene sulphonate (Iso-NOBS), dodecyl
oxybenzene sulphonate (LOBS), and any mixture thereof; caprolactams; pentaacetate
glucose (PAG); nitrile quaternary ammonium; imide bleach activators, such as N-nonanoyl-N-methyl
acetamide; and any mixture thereof.
[0104] Source of available oxygen: A suitable source of available oxygen (AvOx) is a source of hydrogen peroxide, such
as percarbonate salts and/or perborate salts, such as sodium percarbonate. The source
of peroxygen may be at least partially coated, or even completely coated, by a coating
ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate,
or any mixture thereof, including mixed salts thereof. Suitable percarbonate salts
can be prepared by a fluid bed process or by a crystallization process. Suitable perborate
salts include sodium perborate mono-hydrate (PB1), sodium perborate tetra-hydrate
(PB4), and anhydrous sodium perborate which is also known as fizzing sodium perborate.
Other suitable sources of AvOx include persulphate, such as oxone. Another suitable
source of AvOx is hydrogen peroxide.
[0105] Pre-formed peracid: A suitable pre-formed peracid is N,N-pthaloylamino peroxycaproic acid (PAP).
[0106] Bleach catalyst: Suitable bleach catalysts include oxaziridinium-based bleach catalysts, transition
metal bleach catalysts and bleaching enzymes.
[0107] Oxaziridinium-based bleach catalyst: A suitable oxaziridinium-based bleach catalyst has the formula:

wherein: R
1 is selected from the group consisting of: H, a branched alkyl group containing from
3 to 24 carbons, and a linear alkyl group containing from 1 to 24 carbons; R' can
be a branched alkyl group comprising from 6 to 18 carbons, or a linear alkyl group
comprising from 5 to 18 carbons, R' can be selected from the group consisting of:
2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl
and iso-pentadecyl; R
2 is independently selected from the group consisting of: H, a branched alkyl group
comprising from 3 to 12 carbons, and a linear alkyl group comprising from 1 to 12
carbons; optionally R
2 is independently selected from H and methyl groups; and n is an integer from 0 to
1.
[0108] Transition metal bleach catalyst: The composition may include transition metal bleach catalyst, typically comprising
copper, iron, titanium, ruthenium, tungsten, molybdenum, and/or manganese cations.
Suitable transition metal bleach catalysts are manganese-based transition metal bleach
catalysts.
[0109] Reducing bleach: The composition may comprise a reducing bleach. However, the composition
may be substantially free of reducing bleach; substantially free means "no deliberately
added". Suitable reducing bleach include sodium sulphite and/or thiourea dioxide (TDO).
[0110] Co-bleach particle: The composition may comprise a co-bleach particle. Typically, the co-bleach particle
comprises a bleach activator and a source of peroxide. It may be highly suitable for
a large amount of bleach activator relative to the source of hydrogen peroxide to
be present in the co-bleach particle. The weight ratio of bleach activator to source
of hydrogen peroxide present in the co-bleach particle can be at least 0.3:1, or at
least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least
1.0:1.0, or even at least 1.2:1 1 or higher.
[0111] The co-bleach particle can comprise: (i) bleach activator, such as TAED; and (ii)
a source of hydrogen peroxide, such as sodium percarbonate. The bleach activator may
at least partially, or even completely, enclose the source of hydrogen peroxide.
[0112] The co-bleach particle may comprise a binder. Suitable binders are carboxylate polymers
such as polyacrylate polymers, and/or surfactants including non-ionic detersive surfactants
and/or anionic detersive surfactants such as linear C
11-C
13 alkyl benzene sulphonate.
[0113] The co-bleach particle may comprise bleach catalyst, such as an oxaziridium-based
bleach catalyst.
[0114] Chelant: Suitable chelants are selected from: diethylene triamine pentaacetate, diethylene
triamine penta(methyl phosphonic acid), ethylene diamine-N'N'-disuccinic acid, ethylene
diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid), hydroxyethane
di(methylene phosphonic acid), and any combination thereof. A suitable chelant is
ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid
(HEDP). The laundry detergent composition may comprise ethylene diamine-N'N'- disuccinic
acid or salt thereof. The ethylene diamine-N'N'-disuccinic acid may be in S,S enantiomeric
form. The composition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid disodium
salt. Suitable chelants may also be calcium crystal growth inhibitors.
[0115] Calcium carbonate crystal growth inhibitor: The composition may comprise a calcium carbonate crystal growth inhibitor, such as
one selected from the group consisting of: 1-hydroxyethanediphosphonic acid (HEDP)
and salts thereof; N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof;
2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and any combination
thereof.
[0116] Photobleach: Suitable photobleaches are zinc and/or aluminium sulphonated phthalocyanines.
[0117] Brightener: The laundry detergent composition may comprise fluorescent brightener. Preferred
classes of fluorescent brightener are: Di-styryl biphenyl compounds, e.g. Tinopal
™ CBS-X, Di-amino stilbene di-sulfonic acid compounds, e.g. Tinopal
™ DMS pure Xtra and Blankophor
™ HRH, and Pyrazoline compounds, e.g. Blankophor
™ SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole,
disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino 1 ,3,5- triazin-2-yl)];amino}stilbene-2-2'
disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'
disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
[0118] A particularly preferred fluorescent brightener is C.I. Fluorescent Brightener 260
having the following structure. For solid detergent compositions, this brightener
may be used in its beta or alpha crystalline forms, or a mixture of these forms.

[0119] Enzyme: Suitable enzymes include proteases, amylases, cellulases, lipases, xylogucanases,
pectate lyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof.
[0120] For the enzymes, accession numbers and IDs shown in parentheses refer to the entry
numbers in the databases Genbank, EMBL and/or Swiss-Prot. For any mutations, standard
1-letter amino acid codes are used with a * representing a deletion. Accession numbers
prefixed with DSM refer to micro-organisms deposited at Deutsche Sammlung von Mikroorganismen
und Zellkulturen GmbH, Mascheroder Weg 1b, 38124 Brunswick (DSMZ).
[0121] Protease. The composition may comprise a protease. Suitable proteases include metalloproteases
and/or serine proteases, including neutral or alkaline microbial serine proteases,
such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable
or microbial origin. In one aspect, such suitable protease may be of microbial origin.
The suitable proteases include chemically or genetically modified mutants of the aforementioned
suitable proteases. In one aspect, the suitable protease may be a serine protease,
such as an alkaline microbial protease or/and a trypsin-type protease. Examples of
suitable neutral or alkaline proteases include:
- (a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO), Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM), Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391).
- (b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g. of porcine
or bovine origin), including the Fusarium protease and the chymotrypsin proteases
derived from Cellumonas (A2RQE2).
- (c) metalloproteases, including those derived from Bacillus amyloliquefaciens (P06832, NPRE_BACAM).
[0122] Suitable proteases include those derived from
Bacillus gibsonii or
Bacillus Lentus such as subtilisin
309 (P29600) and/or DSM 5483 (P29599).
[0123] Suitable commercially available protease enzymes include: those sold under the trade
names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®,
Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by
Novozymes A/S (Denmark); those sold under the tradename Maxatase®, Maxacal®, Maxapem®,
Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect
OXP® by Genencor International; those sold under the tradename Opticlean® and Optimase®
by Solvay Enzymes; those available from Henkel/Kemira, namely BLAP (P29599 having
the following mutations S99D + S101 R + S103A + V104I + G159S), and variants thereof
including BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with
S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V2051 + L217D)
all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V
+ S256G + S259N) from Kao.
[0124] Other suitable protease enzymes are fungal serine proteases. Suitable enzymes are
variants or wild-types of the fungal serine proteases endogenous to
Trichoderma reesei strain QM9414,
Malbranchea cinnamomea strain ALK04122,
Fusarium graminearum strain ALK01726,
Fusarium equiseti strain CBS 119568 and
Fusarium acuminatum strain CBS 124084. Examples of commercially available fungal serine proteases are
Biotouch ROC and Biotouch Novia, both supplied by AB Enzymes, Darmstadt, Germany.
[0125] Amylase: Suitable amylases are alpha-amylases, including those of bacterial or fungal
origin. Chemically or genetically modified mutants (variants) are included. A suitable
alkaline alpha-amylase is derived from a strain of
Bacillus, such as
Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus
subtilis, or other
Bacillus sp., such as
Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSMZ no. 12649,
KSM AP1378, KSM K36 or KSM K38. Suitable amylases include:
- (a) alpha-amylase derived from Bacillus licheniformis (P06278, AMY_BACLI), and variants thereof, especially the variants with substitutions
in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156,
181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.
- (b) AA560 amylase (CBU30457, HD066534) and variants thereof, especially the variants
with one or more substitutions in the following positions: 26, 30, 33, 82, 37, 106,
118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269,
270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345,
361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, optionally
that also contain the deletions of D183* and G184*.
- (c) variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus SP722 (CBU30453, HD066526), especially variants with deletions in the 183 and 184 positions.
[0126] Suitable commercially available alpha-amylases are Duramyl®, Liquezyme® Termamyl®,
Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, Stainzyme Plus®, Fungamyl® and
BAN® (Novozymes A/S), Bioamylase® and variants thereof (Biocon India Ltd.), Kemzym®
AT 9000 (Biozym Ges. m.b.H, Austria), Rapidase®, Purastar®, Optisize HT Plus®, Enzysize®,
Powerase® and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM® (KAO,
Japan). Suitable amylases are Natalase®, Stainzyme® and Stainzyme Plus®.
[0127] Cellulase: The composition may comprise a cellulase. Suitable cellulases include those of bacterial
or fungal origin. Chemically modified or protein engineered mutants are included.
Suitable cellulases include cellulases from the genera
Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from
Humicola insolens, Myceliophthora thermophila and
Fusarium oxysporum.
[0128] Commercially available cellulases include Celluzyme®, and Carezyme® (Novozymes A/S),
Clazinase®, and Puradax HAS (Genencor International Inc.), and KAC-500(B)® (Kao Corporation).
[0129] The cellulase can include microbial-derived endoglucanases exhibiting endo-beta-1,4-glucanase
activity (E.C. 3.2.1.4), including a bacterial polypeptide endogenous to a member
of the genus
Bacillus sp. AA349 and mixtures thereof. Suitable endoglucanases are sold under the tradenames Celluclean®
and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
[0130] The composition may comprise a cleaning cellulase belonging to Glycosyl Hydrolase
family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases
sold under the tradename Biotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
[0131] Suitable cellulases may also exhibit xyloglucanase activity, such as Whitezyme®.
[0132] Xyloglucanase: Suitable xyloglucanase enzymes may have enzymatic activity towards both xyloglucan
and amorphous cellulose substrates. The enzyme may be a glycosyl hydrolase (GH) selected
from GH families 5, 12, 44 or 74. The glycosyl hydrolase selected from GH family 44
is particularly suitable. Suitable glycosyl hydrolases from GH family 44 are the XYG1006
glycosyl hydrolase from
Paenibacillus polyxyma (ATCC 832) and variants thereof.
[0133] Pectate lyase: Suitable pectate lyases are either wild-types or variants of Bacillus-derived pectate
lyases (CAF05441, AAU25568) sold under the tradenames Pectawash®, Pectaway® and X-Pect®
(from Novozymes A/S, Bagsvaerd, Denmark).
[0134] Mannanase: Suitable mannanases are sold under the tradenames Mannaway® (from Novozymes A/S,
Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).
[0135] Bleaching enzyme: Suitable bleach enzymes include oxidoreductases, for example oxidases such as glucose,
choline or carbohydrate oxidases, oxygenases, catalases, peroxidases, like halo-,
chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases
(phenoloxidases, polyphenoloxidases). Suitable commercial products are sold under
the Guardzyme® and Denilie® ranges from Novozymes. It may be advantageous for additional
organic compounds, especially aromatic compounds, to be incorporated with the bleaching
enzyme; these compounds interact with the bleaching enzyme to enhance the activity
of the oxidoreductase (enhancer) or to facilitate the electron flow (mediator) between
the oxidizing enzyme and the stain typically over strongly different redox potentials.
[0136] Other suitable bleaching enzymes include perhydrolases, which catalyse the formation
of peracids from an ester substrate and peroxygen source. Suitable perhydrolases include
variants of the Mycobacterium smegmatis perhydrolase, variants of so-called CE-7 perhydrolases,
and variants of wild-type subtilisin Carlsberg possessing perhydrolase activity.
[0137] Identity. The relativity between two amino acid sequences is described by the parameter "identity".
For purposes of the present invention, the alignment of two amino acid sequences is
determined by using the Needle program from the EMBOSS package (http://emboss.org)
version 2.8.0. The Needle program implements the global alignment algorithm described
in
Needleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. The substitution matrix used is BLOSUM62, gap opening penalty is 10, and gap extension
penalty is 0.5.
[0138] Fabric-softener: Suitable fabric-softening agents include clay, silicone and/or quaternary ammonium
compounds. Suitable clays include montmorillonite clay, hectorite clay and/or laponite
clay. A suitable clay is montmorillonite clay. Suitable silicones include amino-silicones
and/or polydimethylsiloxane (PDMS). A suitable fabric softener is a particle comprising
clay and silicone, such as a particle comprising montmorillonite clay and PDMS.
[0139] Flocculant: Suitable flocculants include polyethylene oxide; for example having an average molecular
weight of from 300,000 Da to 900,000 Da.
[0140] Suds suppressor: Suitable suds suppressors include silicone and/or fatty acid such as stearic acid.
[0141] Perfume: Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery
systems including Schiff base perfume/polymer complexes, starch-encapsulated perfume
accords, perfume-loaded zeolites, blooming perfume accords, and any combination thereof.
A suitable perfume microcapsule is melamine formaldehyde based, typically comprising
perfume that is encapsulated by a shell comprising melamine formaldehyde. It may be
highly suitable for such perfume microcapsules to comprise cationic and/or cationic
precursor material in the shell, such as polyvinyl formamide (PVF) and/or cationically
modified hydroxyethyl cellulose (catHEC).
[0142] Aesthetic: Suitable aesthetic particles include soap rings, lamellar aesthetic particles, geltin
beads, carbonate and/or sulphate salt speckles, coloured clay particles, and any combination
thereof.
EXAMPLES
Example 1
[0143] The improved soil removal benefit of the method of the present invention was demonstrated
in the following experiment.
[0144] A composition was prepared comprising a Western European liquid detergent detailed
in table 1. This composition was labeled pre-condition composition 1.
[0145] A second pre-condition composition was prepared which was identical to pre-condition
composition 1, but which was also used in conjunction with a rinse additive detailed
in table 2.
[0146] A third pre-condition composition was prepared which was identical to pre-condition
composition 2, but which also comprised a variant having at least 90% sequence identity
to wild-type lipase from
Thermomyces lanuginosus and having sequence substitutions T231R and N233R.
[0147] A fourth pre-condition composition was prepared which was identical to pre-condition
composition 2, but which was also used in conjunction with a Soil Release Polymer
(SRP).
[0148] A fifth pre-condition composition was prepared which was identical to pre-condition
composition 4, but which also comprised a variant having at least 90% sequence identity
to wild-type lipase from
Thermomyces lanuginosus and having sequence substitutions T231R and N233R.
[0149] To summarise;
- 1. pre-condition composition only
- 2. pre-condition composition in conjunction with rinse additive
- 3. pre-condition composition comprising Lipex® in conjunction with rinse additive
- 4. pre-condition composition comprising SRP in conjunction with rinse additive
- 5. pre-condition composition comprising SRP and Lipex® in conjunction with rinse additive
[0150] Standard fabric swatches TF7436-M polycotton (25x20cm swatches) and Dacron 64 polyester
(25 x20cm swatches) were obtained from Westlairds. Two of each of these were added
to a washing machine together with 2.5kg of cotton sheets and cotton towels supplied
by Test Fabrics added as additional ballast.
[0151] The swatches were then washed on the 'short cotton cycle' (30°C) at 1600rpm together
with the detergent composition detailed in table 1 such that the 13 litre wash liquor
comprised 2692ppm of the detergent. A 30g dose of the rinse additive detailed in table
2 was added to the rinse compartment in the drawer of the washing machine to be added
during the rinse step of the washing machine cycle. The lipid esterase was added to
the rinse compartment in the drawer of the washing machine such that the concentration
of 1ppm active enzyme protein would be delivered during the rinse step of the washing
machine cycle. The soil release polymer was added at a level of 0.2% w/w to the rinse
compartment in the drawer of the washing machine to be delivered during the rinse
step of the washing machine cycle. The order of addition to the rinse compartment
was rinse additive, then lipid esterase, then soil release polymer. After the wash
cycle was complete, the fabrics were then dried on a line. This was repeated so that
all swatches had been washed four times together with the same pre-condition treatment
composition during the wash and rinse additive, lipid esterase and soil release polymer
added through the rinse.
[0152] 5x5cm swatches of TF7436-M and Dacron 64 from each pre-condition treatment were prepared
and stained with 200 µL of SV13-dyed lard (Asda lard batch 130R7, SV13 %, batch SPt001013)
and were stored at 32°C/80%rh overnight.
[0153] The stained swatches were then washed in a Tergotometer (0.8L pot) in the presence
of a Western European liquid detergent detailed in table 1 at a total concentration
of 2692ppm. Ballast fabric made up of knitted cotton fabric was also added, with an
overall fabric load of 26.7g. Wash conditions in the Tergotometer were 200rpm, wash
time 20 minutes at 30°C and rinse time of five minutes. Fabrics were then air dried
overnight on metal racks.
Table 1: Detergent Composition |
(wt%) |
1,2-Propanediol |
17.3 |
Linear alkylbenzene sulfonate |
14.8 |
C12-14 alkyl -7-ethoxylate |
13.0 |
C12-18 fatty acid |
12.7 |
Sodium C12-14 alkyl ethoxy 3 sulfate |
11.1 |
Monoethanolamine |
7.5 |
Glycerol |
6.2 |
Ethoxylated polyethylenepolyamine |
4.0 |
1-hydroxyethyidene-1,1-diphosphonic acid |
1.2 |
Citric acid |
0.6 |
Tinopal® CBS-X B49 |
0.2 |
Magnesium chloride |
0.2 |
Sodium hydroxide |
0.1 |
Water, aesthetics, (dyes, perfumes) and minors (solvents and structurants) |
Balance to 100% |
Table 2: Rinse Additive Composition |
(wt%) |
Silicone HC306 |
12.0 |
Poly(acrylamide-methacrylamidopropyltrimethyl ammonium |
0.2 |
chloride (PAMMAPTAC) |
|
Tallow alkyl ethoxylated alcohol with an average degree of ethoxylation of 80. (TAE80) |
0.1 |
Proxel™ GXL |
0.02 |
Perfume Best B |
1.0 |
Water |
86.68 |
[0154] Lipid esterase was added to the rinse liquor at a concentration of 1ppm (active enzyme
protein) Soil release polymer Texcare® SRA300 was added at 0.2% w/w.
[0155] Stain removal was quantified using commercially available Digieye software to calculate
percentage stain removal from L*a*b* values. The software generates the L value, the
a value and the b value, and percentage stain removal was calculated using the following
equation;
Subscript 'b' denotes data for the stain before washing
Subscript 'a' denotes data for the stain after washing
Subscript 'c' denotes data for the unstained fabric
[0156] Thus, L*a*b* values are taken of the unstained fabric, of the stained fabric before
washing and of the stained fabric after washing.
Results can be seen in table 3
[0157]
Table 3
Pre-condition composition |
TF7436-M |
Dacron 64 |
%SR |
Standard Error |
%SR |
Standard Error |
1 |
69 |
3 |
51 |
3 |
2 |
80 |
3 |
57 |
6 |
3 |
86 |
1 |
89 |
1 |
4 |
81 |
4 |
67 |
8 |
5 |
91 |
1 |
91 |
1 |
[0158] (Standard error was calculated as SE = SD/√n where SD = standard deviation and n
= number of external replicates)
[0159] The data clearly show that the addition of a rinse additive or a soil release polymer
i.e. pre-condition compositions 2 and 4 respectively, significantly improves percentage
soil removal. Further to this, with the addition of a lipid esterase in combination
with either the rinse additive or soil release polymer i.e. pre-condition compositions
3 and 5 respectively result in higher percentage soil removal still. Thus, the inclusion
of a lipid esterase in combination with either a rinse additive or soil release polymer
during the rinse step of the pre-condition according to the present invention showed
a surprising improvement in percentage soil reduction as compared to fabrics pre-conditioned
without a lipid esterase.
Examples 3-8;
[0160] The following examples are of rinse additive compositions suitable for use in step
(i);
|
3 (wt%) |
4 (wt%) |
5 (wt%) |
6 (wt%) |
7 (wt%) |
8 (wt%) |
Silicone HC306 |
6.0 |
6.0 |
3.0 |
4.0 |
8.0 |
12.0 |
PAMMAPTAC |
0.1 |
0.1 |
0.1 |
0.4 |
0.4 |
0.2 |
Butyl carbitol |
3.0 |
3.0 |
4.0 |
0.0 |
0.0 |
0.0 |
TAE80 |
0.1 |
0.05 |
0.05 |
0.1 |
0.1 |
0.1 |
Proxel™ GXL |
0.02 |
0.02 |
0.02 |
0.02 |
0.02 |
0.02 |
Perfume Best B |
0.5 |
0.5 |
0.5 |
0.4 |
0.4 |
0.4 |
Water |
90.28 |
90.33 |
92.33 |
95.08 |
93.08 |
87.28 |
Examples 9-27;
[0161] The following examples are of laundry detergent compositions suitable for use in
step (i) and (iii);
Examples 9-14
[0162] Granular laundry detergent compositions designed for hand washing or top-loading
washing machines may be added to sufficient water to form a paste for direct contact
with the surface to be treated, forming a concentrated cleaning composition.
|
(wt %) |
(wt %) |
(wt %) |
(wt %) |
(wt %) |
(wt %) |
Linear alkylbenzenesulfonate |
20 |
22 |
20 |
15 |
20 |
20 |
C12-14 Dimethylhydroxyethyl ammonium chloride |
0.7 |
0.2 |
1 |
0.6 |
0.0 |
0 |
AE3S |
0.9 |
1 |
0.9 |
0.0 |
0.5 |
0.9 |
AE7 |
0.0 |
0.0 |
0.0 |
1 |
0.0 |
3 |
Sodium tripolyphosphate |
5 |
0.0 |
4 |
9 |
2 |
0.0 |
Zeolite A |
0.0 |
1 |
0.0 |
1 |
4 |
1 |
1.6R Silicate (SiO2:Na2O at ratio 1.6:1) |
7 |
5 |
2 |
3 |
3 |
5 |
Sodium carbonate |
25 |
20 |
25 |
17 |
18 |
19 |
Polyacrylate MW 4500 |
1 |
0.6 |
1 |
1 |
1.5 |
1 |
Random graft copolymer1 |
0.1 |
0.2 |
0.0 |
0.0 |
0.0 |
0.0 |
Carboxymethyl cellulose |
1 |
0.3 |
1 |
1 |
1 |
1 |
Stainzyme® (20 mg active/g) |
0.1 |
0.2 |
0.1 |
0.2 |
0.1 |
0.1 |
Bacterial protease (Savinase®, 32.89 mg active/g) |
0.1 |
0.1 |
0.1 |
0.1 |
|
0.1 |
Natalase® (8.65 mg active /g) |
0.1 |
0.0 |
0.1 |
0.0 |
0.1 |
0.1 |
Lipex® (18 mg active /g) |
0.03 |
0.07 |
0.3 |
0.1 |
0.07 |
0.4 |
Biotouch® ROC (20mg active/g) |
0.1 |
0.2 |
0.2 |
0.2 |
0.1 |
0.4 |
Fluorescent Brightener 1 |
0.06 |
0.0 |
0.06 |
0.18 |
0.06 |
0.06 |
Fluorescent Brightener 2 |
0.1 |
0.06 |
0.1 |
0.0 |
0.1 |
0.1 |
DTPA |
0.6 |
0.8 |
0.6 |
0.25 |
0.6 |
0.6 |
MgSO4 |
1 |
1 |
1 |
0.5 |
1 |
1 |
Sodium Percarbonate |
0.0 |
5.2 |
0.1 |
0.0 |
0.0 |
0.0 |
Sodium Perborate Monohydrate |
4.4 |
0.0 |
3.85 |
2.09 |
0.78 |
3.63 |
NOBS |
1.9 |
0.0 |
1.66 |
0.0 |
0.33 |
0.75 |
TAED |
0.58 |
1.2 |
0.51 |
0.0 |
0.015 |
0.28 |
Sulphonated zinc |
0.0030 |
0.0 |
0.0012 |
0.0030 |
0.0021 |
0.0 |
phthalocyanine |
|
|
|
|
|
|
S-ACMC |
0.1 |
0.0 |
0.0 |
0.0 |
0.06 |
0.0 |
Direct Violet 9 |
0.0 |
0.0 |
0.0003 |
0.0005 |
0.0003 |
0.0 |
Acid Blue 29 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0003 |
Sulfate/Moisture |
Balance |
Examples 15-20
[0163] Granular laundry detergent compositions designed for front-loading automatic washing
machines may be added to sufficient water to form a paste for direct contact with
the surface to be treated, forming a concentrated cleaning compostion.
|
15 (wt%) |
16 (wt%) |
17 (wt%) |
18 (wt%) |
19 (wt%) |
20 (wt%) |
Linear alkylbenzenesulfonate |
8 |
7.1 |
7 |
6.5 |
7.5 |
7.5 |
AE3S |
0 |
4.8 |
0 |
5.2 |
4 |
4 |
C12-14 Alkylsulfate |
1 |
0 |
1 |
0 |
0 |
0 |
AE7 |
2.2 |
0 |
3.2 |
0 |
0 |
0 |
C10-12 Dimethyl hydroxyethylammonium chloride |
0.75 |
0.94 |
0.98 |
0.98 |
0 |
0 |
Crystalline layered silicate (δ-Na2Si2O5 |
4.1 |
0 |
4.8 |
0 |
0 |
0 |
Zeolite A |
5 |
0 |
5 |
0 |
2 |
2 |
Citric Acid |
3 |
5 |
3 |
4 |
2.5 |
3 |
Sodium Carbonate |
15 |
20 |
14 |
20 |
23 |
23 |
Silicate 2R (SiO2:Na2O at ratio 2:1) |
0.08 |
0 |
0.11 |
0 |
0 |
0 |
Soil release agent |
0.75 |
0.72 |
0.71 |
0.72 |
0 |
0 |
Acrylic Acid/Maleic Acid Copolymer |
1.1 |
3.7 |
1.0 |
3.7 |
2.6 |
3.8 |
Carboxymethylcellulose |
0.15 |
1.4 |
0.2 |
1.4 |
1 |
0.5 |
Bacterial protease (84 mg active/g) |
0.2 |
0.2 |
0.3 |
0.15 |
0.12 |
0.13 |
Stainzyme® (20 mg active/g) |
0.2 |
0.15 |
0.2 |
0.3 |
0.15 |
0.15 |
Lipex® (18.00 mg active/g) |
0.05 |
0.15 |
0.1 |
0 |
0 |
0 |
Natalase® (8.65 mg active/g) |
0.1 |
0.2 |
0 |
0 |
0.15 |
0.15 |
Celluclean™ (15.6 mg active/g) |
0 |
0 |
0 |
0 |
0.1 |
0.1 |
Biotouch® ROC (20mg active/g) |
0.2 |
0.1 |
0.2 |
0.2 |
0.2 |
0.2 |
TAED |
3.6 |
4.0 |
3.6 |
4.0 |
2.2 |
1.4 |
Percarbonate |
13 |
13.2 |
13 |
13.2 |
16 |
14 |
Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
Hydroxyethane di phosphonate (HEDP) |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
MgSO4 |
0.42 |
0.42 |
0.42 |
0.42 |
0.4 |
0.4 |
Perfume |
0.5 |
0.6 |
0.5 |
0.6 |
0.6 |
0.6 |
Suds suppressor agglomerate |
0.05 |
0.1 |
0.05 |
0.1 |
0.06 |
0.05 |
Soap |
0.45 |
0.45 |
0.45 |
0.45 |
0 |
0 |
Sulphonated zinc phthalocyanine (active) |
0.0007 |
0.0012 |
0.0007 |
0 |
0 |
0 |
S-ACMC |
0.01 |
0.01 |
0 |
0.01 |
0 |
0 |
Direct Violet 9 (active) |
0 |
0 |
0.0001 |
0.0001 |
0 |
0 |
Sulfate/ Water & Miscellaneous |
Balance |
[0164] Any of the above compositions is used to launder fabrics in the second step at a
concentration of 7000 to 10000 ppm in water, 20-90 °C, and a 5:1 water:cloth ratio.
The typical pH is about 10. The fabrics are then dried. In one aspect, the fabrics
are actively dried using a dryer. In one aspect, the fabrics are actively dried using
an iron. In another aspect, the fabrics are merely allowed to dry on a line wherein
they are exposed to air and optionally sunlight.
Examples 21-26 Heavy Duty Liquid laundry detergent compositions
[0165]
|
21 (wt%) |
22 (wt%) |
23 (wt%) |
24 (wt%) |
25 (wt%) |
26 (wt%) |
AES C12-15 alkyl ethoxy (1.8) sulfate |
11 |
10 |
4 |
6.32 |
0 |
0 |
AE3S |
0 |
0 |
0 |
0 |
2.4 |
0 |
Linear alkyl benzene sulfonate |
1.4 |
4 |
8 |
3.3 |
5 |
8 |
HSAS |
3 |
5.1 |
3 |
0 |
0 |
0 |
Sodium formate |
1.6 |
0.09 |
1.2 |
0.04 |
1.6 |
1.2 |
Sodium hydroxide |
2.3 |
3.8 |
1.7 |
1.9 |
1.7 |
2.5 |
Monoethanolamine |
1.4 |
1.49 |
1.0 |
0.7 |
0 |
0 |
Diethylene glycol |
5.5 |
0.0 |
4.1 |
0.0 |
0 |
0 |
AE9 |
0.4 |
0.6 |
0.3 |
0.3 |
0 |
0 |
AE7 |
0 |
0 |
0 |
0 |
2.4 |
6 |
Chelant |
0.15 |
0.15 |
0.11 |
0.07 |
0.5 |
0.11 |
Citric Acid |
2.5 |
3.96 |
1.88 |
1.98 |
0.9 |
2.5 |
C12-14 dimethyl Amine Oxide |
0.3 |
0.73 |
0.23 |
0.37 |
0 |
0 |
C12-18 Fatty Acid |
0.8 |
1.9 |
0.6 |
0.99 |
1.2 |
0 |
4-formyl-phenylboronic acid |
0 |
0 |
0 |
0 |
0.05 |
0.02 |
Borax |
1.43 |
1.5 |
1.1 |
0.75 |
0 |
1.07 |
Ethanol |
1.54 |
1.77 |
1.15 |
0.89 |
0 |
3 |
Ethoxylated (EO15) tetraethylene pentamine |
0.3 |
0.33 |
0.23 |
0.17 |
0.0 |
0.0 |
Ethoxylated hexamethylene diamine |
0.8 |
0.81 |
0.6 |
0.4 |
1 |
1 |
1,2-Propanediol |
0.0 |
6.6 |
0.0 |
3.3 |
0.5 |
2 |
Bacterial protease (40.6 mg active/g) |
0.8 |
0.6 |
0.7 |
0.9 |
0.7 |
0.6 |
Mannaway® (25 mg active/g) |
0.07 |
0.05 |
0.045 |
0.06 |
0.04 |
0.045 |
Stainzyme® (15 mg active/g) |
0.3 |
0.2 |
0.3 |
0.1 |
0.2 |
0.4 |
Natalase® (29 mg |
0 |
0.2 |
0.1 |
0.15 |
0.07 |
0 |
active/g) |
|
|
|
|
|
|
Lipex® (18 mg active/g) |
0.4 |
0.2 |
0.3 |
0.1 |
0.2 |
0 |
Biotouch® ROC (20mg active/g) |
0.2 |
0.1 |
0.2 |
0.2 |
0.1 |
0.1 |
Liquitint® Violet CT (active) |
0.006 |
0.002 |
0 |
0 |
0 |
0.002 |
S-ACMC |
- |
- |
0.01 |
0.05 |
0.01 |
0.02 |
Water, perfume, dyes & other components |
Balance |
Example 27
[0166] This composition may be enclosed in a polyvinyl alcohol pouch.
|
27 |
|
(wt%) |
Alkylbenzene sulfonic acid |
21.0 |
C14-15 alkyl 8-ethoxylate |
18.0 |
C12-18 Fatty acid |
15.0 |
Bacterial protease (40.6 mg active/g) |
1.5 |
Natalase® (29 mg active/g) |
0.2 |
Mannanase (Mannaway®, 11mg active/g) |
0.1 |
Xyloglucanase (Whitezyme®, 20mg active/g) |
0.2 |
Biotouch® ROC (20mg active/g) |
0.2 |
A compound having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N+-CXH2x-N+-(CH3)-bis((C2H5O)(C2H4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated
variants thereof |
2.0 |
Ethoxylated Polyethylenimine2 |
0.8 |
Hydroxyethane diphosphonate (HEDP) |
0.8 |
Fluorescent Brightener 1 |
0.2 |
Solvents (1,2 propanediol, ethanol), stabilizers |
15.0 |
Hydrogenated castor oil derivative structurant |
0.1 |
Perfume |
1.6 |
Core Shell Melamine-formaldehyde encapsulate of perfume |
0.10 |
Ethoxylated thiophene Hueing Dye |
0.004 |
Buffers (sodium hydroxide, Monoethanolamine) |
To pH 8.2 |
Water* and minors (antifoam, aesthetics) |
To 100% |
* Based on total cleaning and/or treatment composition weight, a total of no more
than 7% water
1 Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer
having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The
molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio
of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than
1 grafting point per 50 ethylene oxide units.
2 Polyethyleneimine (MW = 600) with 20 ethoxylate groups per -NH.
* Remark: all enzyme levels expressed as % enzyme raw material |
Raw Materials and Notes For Composition Examples 3-8
[0167] Silicone HC306 supplied by Wacker Chemical Corporation, Adrian, Michigan, USA Poly(acrylamide-methacrylamidopropyltrimethyl
ammonium chloride (PAMMAPTAC) supplied by
Butyl carbitol, supplied by
Tallow alkyl ethoxylated alcohol with an average degree of ethoxylation of 80 supplied
by Proxel™ GXL supplied by
Perfume Best B supplied by
Raw Materials and Notes For Composition Examples 9-27
[0168] Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C
11-C
12 supplied by Stepan, Northfield, Illinois, USA
C
12-14 Dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH, Sulzbach, Germany
AE3S is C
12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA
AE7 is C
12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman,
Salt Lake City, Utah, USA
AE9 is C
12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman,
Salt Lake City, Utah, USA
HSAS is a mid-branched primary alkyl sulfate with carbon chain length of about 16-17
Sodium tripolyphosphate is supplied by Rhodia, Paris, France
Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK
1.6R Silicate is supplied by Koma, Nestemica, Czech Republic
Sodium Carbonate is supplied by Solvay, Houston, Texas, USA
Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany
Carboxymethyl cellulose is Finnfix® V supplied by CP Kelco, Arnhem, Netherlands Suitable
chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by
Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied
by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark
Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean
™, Mannaway® and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.
Biotouch® ROC is a product of AB Enzymes, Darmstadt, Germany.
Bacterial protease (examples 8-13) described in
US 6,312,936 B1 supplied by Genencor International, Palo Alto, California, USA
Bacterial protease (examples 14-20) described in
US 4,760,025 is supplied by Genencor International, Palo Alto, California, USA
Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X,
Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol® Violet BN-Z all supplied
by Ciba Specialty Chemicals, Basel, Switzerland
Sodium percarbonate supplied by Solvay, Houston, Texas, USA
Sodium perborate is supplied by Degussa, Hanau, Germany
NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville,
Arkansas, USA
TAED is tetraacetylethylenediamine, supplied under the Peractive® brand name by Clariant
GmbH, Sulzbach, Germany
S-ACMC is carboxymethylcellulose conjugated with C.I. Reactive Blue 19, sold by Megazyme,
Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code
S-ACMC.
Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France
Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate
ratio 70:30, supplied by BASF, Ludwigshafen, Germany
Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) is supplied by
Octel, Ellesmere Port, UK
Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan,
USA
Suds suppressor agglomerate is supplied by Dow Coming, Midland, Michigan, USA
HSAS is mid-branched alkyl sulfate as disclosed in
US 6,020,303 and
US 6,060,443
C
12-14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals, Cincinnati, Ohio,
USA
Liquitint® Violet CT is supplied by Milliken, Spartanburg, South Carolina, USA.
[0169] The dimensions and values disclosed herein are not to be understood as being strictly
limited to the exact numerical values recited. Instead, unless otherwise specified,
each such dimension is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension disclosed as "40
mm" is intended to mean "about 40 mm."
[0170] Every document cited herein, including any cross referenced or related patent or
application, is hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise limited. The citation of any document is not an admission that
it is prior art with respect to any invention disclosed or claimed herein or that
it alone, or in any combination with any other reference or references, teaches, suggests
or discloses any such invention. Further, to the extent that any meaning or definition
of a term in this document conflicts with any meaning or definition of the same term
in a document incorporated by reference, the meaning or definition assigned to that
term in this document shall govern.
[0171] While particular embodiments of the present invention have been illustrated and described,
it would be obvious to those skilled in the art that various other changes and modifications
can be made without departing from the spirit and scope of the invention. It is therefore
intended to cover in the appended claims all such changes and modifications that are
within the scope of this invention.