DYE POLYMERS
FIELD OF INVENTION
The present invention concerns the provision and use of
laundry shading dye polymers.
BACKGROUND OF THE INVENTION
WO2006/055787 (Procter & Gamble) discloses Laundry
formulations containing a cellulose ether polymer covalently
bound to a reactive dye for whitening cellulosic fabric.
SUMMARY OF THE INVENTION
We have found that reactive dyes bound to water soluble
polyester polymers (RDPET) deposit well to cotton fabrics in
a first wash, without unacceptably large deposition to
polyester, cotton, nylon and elastane after multiple washes.
Anti-soiling benefits are found with the RDPET at
surprisingly low levels which are not observed with the PET
alone .
In one aspect the present invention provides a method for
obtaining a method for obtaining a dye-polymer, the method
comprising the step of reacting a polymer with a reactive
dye to form the dye-polymer, wherein the polymer is
comprised of comonomers of a phenyl dicarboxylate, an
oxyalkyleneoxy and a polyoxyalkyleneoxy and the polymer
comprises at least one free OH group.
The present invention also extends to the dye-polymers
obtainable from the method.
In another aspect the present invention provides a laundry
treatment composition comprising:
(i) from 2 to 70 wt% of a surfactant; and,
(ii) from 0.0001 to 20.0 wt% of the dye-polymer, preferably
0.01 to 5wt%.
In a further aspect the present invention provides a method
of treating a laundry textile, the method comprising the
steps of:
(i) treating a textile with an aqueous solution of the
dye-polymer, the aqueous solution comprising from 10 ppb to
500 ppm of the dye-polymer (preferably 0.1 to 50ppm, most
preferably 0.5 to 20ppm) ; and, from 0.0 g/L to 3 g/L,
preferably 0.3 to 2 g/L, of a surfactant;
(ii) optionally rinsing; and,
(iii) drying the textile.
Preferably the laundry treatment composition is granular and
preferably the granular composition contains sodium
carbonate, with predominately anionic surfactants, most
preferably LAS.
DETAILED DESCRIPTION OF THE INVENTION
POLYMER
Polyesters of terephthalic and other aromatic dicarboxylic
acids having soil release properties are widely disclosed in
the art, in particular, the so-called PET/POET (polyethylene
terephthalate/polyoxyethylene terephthalate) and PET/PEG
(polyethylene terephthalate/polyethylene glycol) polyesters
which are disclosed, for example, in US 3 557 039 (ICI), GB
1 467 098 and EP 1305A (Procter & Gamble) . Other patent
publications disclosing soil release polymers which are
condensation products of aromatic dicarboxylic acids and
dihydric alcohols include EP 185 427A, EP 241 984A, EP 241
985A and EP 272 033A and W092/17523 (Procter & Gamble) and
WO2009/138177 (Clariant) .
The polymer must have at least one mole free OH group per
mole polymer, to allow covalent binding to the reactive
dye(s) . Most preferably the polymer comprises at least two
free OH groups. Preferably the OH groups are the terminal
groups of the polymer.
Preferably, the oxyalkyleneoxy [-0(C¾) tO-] is selected from:
oxy-1 ,2-propyleneoxy [-OC¾CH (Me) 0-]; oxy-1 ,3-propyleneoxy
[0-CH2CH2CH20-] ; and, oxy-1 ,2-ethyleneoxy [-OCH2CH20-] (t is
an interger) . As is evident one or more of the C¾ groups of
the oxyalkyleneoxy may be substituted by C I to C4 alkyl
group (s).
The polyoxyalkyleneoxy facilitates water solubility of the
polymer. Preferably, the polyoxyalkyleneoxy [-0 (CH2)w
_ ]sO- is
selected from: polyoxy-1 ,2-propyleneoxy [-0 (CH2CH (Me) -]sO-;
polyoxy-1 ,3-propyleneoxy [0-CH2CH2CH2-] sO-; and, polyoxy-
1,2-ethyleneoxy [0-CH2CH2- ] sO-; The polyoxyalkyleneoxy may
be a mixture of different oxyalkyleneoxy . Different
polyoxyalkyleneoxy types may present in the polymer, (s and
w are intergers) .
Preferably the phenyl dicarboxylate is a 1,4-phenyl
dicarboxylate. Preferably the phenyl dicarboxylate is of the
form: -OC (0) C6H4C (0) 0- .
Examples of preferred polymers that are reacted with the
reactive dye are a PET/POET (Polyethylene
terephthalate/polyoxyethylene terephthalate) , PEG/POET
(Polyethyleneglycol/ polyoxyethylene terephthalate) or
PET/PEG (Polyethylene terephthalate/ Polyethyleneglycol)
polymer. Most preferable a PET/POET.
The structure of a preferred polymer is found below.
wherein
R2 is selected from H or C¾, preferably H ;
b is 2 or 3 , preferably 2;
y is 2 to 100, preferably 5 to 50;
n and m are independently 1 to 100, preferably 2 to 30; and,
the terminal (end) groups of the polymer are (CH2) OH.
The polymers may be synthesised by a variety of routes, for
example an esterif ication reaction of dimethyl terephthalate
with ethyleneglycol and polyethyleneglycol , this reaction is
discussed in Polymer Bulletin 28, 451-458 (1992) . Another
example would be the direct esterif ication of terephthalic
acid with ethylene glycol and/or propylene glycol and
polypropylene glycol.
A further examples would be a transesterif ication of a
polyethyleneterephthalate with a polyethyleneglycol or
polypropylene glycol.
It is preferred that the number average molecular weight of
the polymer is in the range from 1000 to 50,000, preferably
the average molecular weight of the polymer is in the range
of from 1000 to 15000, more preferably from 2000 to 10000.
REACTIVE DYES
A reactive dye may be considered to be made up of a
chromophore which is linked to a reactive group. Reactive
dyes undergo addition or substitution reactions with -OH, -
SH and -N¾ groups to form covalent bonds . The chromophore
may be linked directly to the reactive group or via a
bridging group. The chromophore serves to provide a colour
and the reactive group covalently binds to a substrate.
Reactive dyes are described in Industrial Dyes (K. Hunger ed,
Wiley VCH 2003) . Many Reactive dyes are listed in the colour
index (Society of Dyers and Colourists and American
Association of Textile Chemists and Colorists) .
Preferred reactive groups of the reactive dyes are
dichlorotriazinyl, dif luorochl oropy rimi dine,
monof luorotrazinyl , dichloroquinoxaline, vinylsulf one,
dif luorotriazine, monochlorotriazinyl , bromoacrlyamide and
trichloropyrimidine .
Most preferred reactive groups are monochlorotriazinyl;
dichlorotriazinyl; and, vinylsulf onyl .
Chromophores are preferably selected from azo,
anthraquinone, phthalocyanine, formazan and
triphendioaxazine . More preferably, azo, anthraquinone,
phthalocyanine, and triphendioaxazine. Most preferably, azo
and anthraquinone.
Reactive dyes are preferably selected from reactive blue,
reactive black, reactive red, reactive violet dyes.
Preferably mixtures of reactive dyes are used to provide
optimum shading effects. Preferred mixtures are selected
from reactive black and reactive red; reactive blue and
reactive red; reactive black and reactive violet; reactive
blue and reactive violet. Preferably the number of blue or
black dye moieties is in excess of the red or violet dye
moieties. Most preferably a combination of a reactive blue
and a reactive red dyes is used.
Examples of reactive red dyes are reactive red 21, reactive
red 23, reactive red 180, reactive red 198, reactive red
239, reactive red 65, reactive red 66, reactive red 84,
reactive red 116, reactive red 136, reactive red 218,
reactive red 228, reactive red 238. reactive red 245,
reactive red 264, reactive red 267, reactive red 268,
reactive red 269, reactive red 270, reactive red 271,
reactive red 272, reactive red 274, reactive red 275,
reactive red 277, reactive red 278, reactive red 280,
reactive red 281, reactive red 282
Examples of reactive black azo dyes are reactive black 5 ,
reactive black 31, reactive black 47, reactive black 49
Examples of reactive blue azo dyes are reactive blue 59,
reactive blue 238, reactive blue 260, reactive blue 265,
reactive blue 267, reactive blue 270, reactive blue 271,
reactive blue 275. Reactive blue azo dyes are preferably
bis-azo .
Examples of reactive blue triphenodioxazine dyes are
reactive blue 266, reactive blue 268, reactive blue 269
Examples of reactive blue formazan dyes are reactive blue
220 and reactive blue 235.
Examples of preferred reactive blue phthalocyanine dyes are
reactive blue 7 , reactive blue 11, reactive blue 14,
reactive blue 15, reactive blue 17, reactive blue 18,
reactive blue 21, reactive blue 23, reactive blue 25,
reactive blue 30, reactive blue 35, reactive blue 38,
reactive blue 41, reactive blue 71, reactive blue 72
Preferably, the reactive blue anthraquinone dye is of the
following form:
wherein R is an organic groups which contains a reactive
group. Preferably, R is selected from: monochlorotriazinyl ;
dichlorotriazinyl ; and, vinylsulf onyl .
Preferred reactive blue dyes are selected from: Reactive
Blue 2 ; Reactive Blue 4 ; Reactive Blue 5 ; Reactive Blue 19;
Reactive Blue 27; Reactive Blue 29; Reactive Blue 36;
Reactive Blue 49; Reactive Blue 50; and, Reactive Blue 224.
Preferably, the reactive red azo dye is a reactive red monoazo
dye and preferred reactive red mono-azo dye is of the
follo
wherein the A ring is unsubstituted or substituted by a
sulphonate group or a reactive group. Preferably, the A ring
is napthyl and is substituted by two sulphonate groups.
Preferably, R is an organic groups which contains a reactive
group. Preferred reactive groups are monochlorotriazinyl ;
dichlorotriazinyl ; and, vinylsulf onyl .
Preferred reactive red dyes are selected from: Reactive Red
1 ; Reactive Red 2 ; Reactive Red 3 ; Reactive Red 12; Reactive
Red 17; Reactive Red 24; Reactive Red 29; Reactive Red 83;
Reactive Red 88; Reactive Red 120; Reactive Red 125;
Reactive Red 194; Reactive Red 189; Reactive Red 198;
Reactive Red 219; Reactive Red 220; Reactive Red 227;
Reactive Red 241; Reactive Red 261; and, Reactive Red 253.
The dye polymer has a water solubility at 2 0 °C of at least
0.1 mg/L
OTHER DYES
In a preferred embodiment of the invention, other shading
colourants may be present. They are preferably selected from
blue and violet pigment such as pigment violet 23, solvent
and disperse dyes such as solvent violet 13, disperse violet
28, bis-azo direct dyes such as direct violet 9 , 35, 51 and
99, and triphenodioxazine direct dyes such as direct violet
54 .
Even more preferred is the presence of acid azine dyes as
described in WO 2008/017570; the level of the acid azine
dyes should be in the range from 0.0001 to 0.1 wt%. The acid
azine dyes provide benefit predominately to the pure cotton
garments and the cationic phenazine dyes to the polycotton
garments. Preferred acid azine dyes are acid violet 50, acid
blue 59 and acid blue 98. Blue and Violet cationic phenazine
dyes may also be present.
Photobleaches such as sulphonated Zn/Al phthalocyanins may
be present.
SURFACTANT
The laundry composition comprises between 2 to 70 wt percent
of a surfactant, most preferably 10 to 30 wt % . In general,
the nonionic and anionic surfactants of the surfactant
system may be chosen from the surfactants described "Surface
Active Agents" Vol. 1 , by Schwartz & Perry, Interscience
1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958,
in the current edition of "McCutcheon 's Emulsifiers and
Detergents" published by Manufacturing Confectioners Company
or in "Tenside-Taschenbuch" , H . Stache, 2nd Edn., Carl
Hauser Verlag, 1981. Preferably the surfactants used are
saturated.
Suitable nonionic detergent compounds which may be used
include, in particular, the reaction products of compounds
having a hydrophobic group and a reactive hydrogen atom, for
example, aliphatic alcohols, acids, amides or alkyl phenols
with alkylene oxides, especially ethylene oxide either alone
or with propylene oxide. Specific nonionic detergent
compounds are C to C22 alkyl phenol-ethylene oxide
condensates, generally 5 to 25 EO, i.e. 5 to 25 units of
ethylene oxide per molecule, and the condensation products
of aliphatic C to C primary or secondary linear or
branched alcohols with ethylene oxide, generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are
usually water-soluble alkali metal salts of organic
sulphates and sulphonates having alkyl radicals containing
from about 8 to about 22 carbon atoms, the term alkyl being
used to include the alkyl portion of higher acyl radicals.
Examples of suitable synthetic anionic detergent compounds
are sodium and potassium alkyl sulphates, especially those
obtained by sulphating higher C to C alcohols, produced
for example from tallow or coconut oil, sodium and potassium
alkyl C to C 2 0 benzene sulphonates, particularly sodium
linear secondary alkyl C 10 to C15 benzene sulphonates; and
sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or coconut
oil and synthetic alcohols derived from petroleum. The
preferred anionic detergent compounds are sodium C to C15
alkyl benzene sulphonates and sodium C12 to C i s alkyl
sulphates. Also applicable are surfactants such as those
described in EP-A-328 177 (Unilever) , which show resistance
to salting-out, the alkyl polyglycoside surfactants
described in EP-A-070 074, and alkyl monoglycosides .
Preferred surfactant systems are mixtures of anionic with
nonionic detergent active materials, in particular the
groups and examples of anionic and nonionic surfactants
pointed out in EP-A-346 995 (Unilever). Especially preferred
is surfactant system that is a mixture of an alkali metal
salt of a C i6 to C i s primary alcohol sulphate together with a
C12 to Cis primary alcohol 3 to 7 EO ethoxylate.
The nonionic detergent is preferably present in amounts less
than 50wt%, most preferably less than 20wt% of the
surfactant system. Anionic surfactants can be present for
example in amounts in the range from about 50% to 100 wt %
of the surfactant system.
In another aspect which is also preferred the surfactant may
be a cationic such that the formulation is a fabric
conditioner .
CATIONIC COMPOUND
When the present invention is used as a fabric conditioner
it needs to contain a cationic compound.
Most preferred are quaternary ammonium compounds.
It is advantageous if the quaternary ammonium compound is a
quaternary ammonium compound having at least one C 12 to C22
alkyl chain.
It is preferred if the quaternary ammonium compound has the
following formula:
R2
R 1-N-R3 X I
R4
in which R is a C 12 to C22 alkyl or alkenyl chain; R2, R3 and
R4 are independently selected from C i to C alkyl chains and
X is a compatible anion. A preferred compound of this type
is the quaternary ammonium compound cetyl trimethyl
quaternary ammonium bromide.
A second class of materials for use with the present
invention are the quaternary ammonium of the above structure
in which R and R2 are independently selected from C 12 to C22
alkyl or alkenyl chain; R3 and R4 are independently selected
from C i to C alkyl chains and X is a compatible anion.
A detergent composition according to claim 1 in which the
ratio of (ii) cationic material to (iv) anionic surfactant
is at least 2:1.
Other suitable quaternary ammonium compounds are disclosed
in EP 0 239 910 (Proctor and Gamble) .
It is preferred if the ratio of cationic to nonionic
surfactant is from 1:100 to 50:50, more preferably 1:50 to
20:50.
The cationic compound may be present from 1.5 wt % to 50 wt
% of the total weight of the composition. Preferably the
cationic compound may be present from 2 wt % to 25 wt % , a
more preferred composition range is from 5 wt % to 2 0 wt % .
The softening material is preferably present in an amount of
from 2 to 60% by weight of the total composition, more
preferably from 2 to 40%, most preferably from 3 to 30% by
weight .
The composition optionally comprises a silicone.
BUILDERS OR COMPLEXING AGENTS
Builder materials may be selected from 1 ) calcium
sequestrant materials, 2 ) precipitating materials,
3 ) calcium ion-exchange materials and 4 ) mixtures thereof.
Examples of calcium sequestrant builder materials include
alkali metal polyphosphates, such as sodium tripolyphosphate
and organic sequestrants , such as ethylene diamine tetraacetic
acid.
Examples of precipitating builder materials include sodium
orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include
the various types of water-insoluble crystalline or
amorphous aluminosilicates , of which zeolites are the best
known representatives, e.g. zeolite A , zeolite B (also known
as zeolite P ) , zeolite C , zeolite X , zeolite Y and also the
zeolite P-type as described in EP-A-0, 384, 070 .
The composition may also contain 0-65 % of a builder or
complexing agent such as ethylenediaminetetraacetic acid,
diethylenetriamine-pentaacetic acid, alkyl- or
alkenylsuccinic acid, nitrilotriacetic acid or the other
builders mentioned below. Many builders are also bleachstabilising
agents by virtue of their ability to complex
metal ions.
Zeolite and carbonate (carbonate (including bicarbonate and
sesquicarbonate) are preferred builders.
The composition may contain as builder a crystalline
aluminosilicate, preferably an alkali metal aluminosilicate,
more preferably a sodium aluminosilicate. This is typically
present at a level of less than 15%w. Aluminosilicates are
materials having the general formula:
0.8-1.5 M20 . A1203. 0.8-6 Si02
where M is a monovalent cation, preferably sodium. These
materials contain some bound water and are required to have
a calcium ion exchange capacity of at least 50 mg CaO/g.
The preferred sodium aluminosilicates contain 1.5-3.5 S1O 2
units in the formula above. They can be prepared readily by
reaction between sodium silicate and sodium aluminate, as
amply described in the literature. The ratio of surfactants
to alumuminosilicate (where present) is preferably greater
than 5:2, more preferably greater than 3:1.
Alternatively, or additionally to the aluminosilicate
builders, phosphate builders may be used. In this art the
term phosphate' embraces diphosphate, triphosphate, and
phosphonate species. Other forms of builder include
silicates, such as soluble silicates, metasilicates , layered
silicates (e.g. SKS-6 from Hoechst) .
Preferably the laundry detergent formulation is a nonphosphate
built laundry detergent formulation, i.e.,
contains less than 1 wt% of phosphate. Preferably the
laundry detergent formulation is carbonate built.
FLUORESCENT AGENT
The composition preferably comprises a fluorescent agent
(optical brightener) . Fluorescent agents are well known and
many such fluorescent agents are available commercially.
Usually, these fluorescent agents are supplied and used in
the form of their alkali metal salts, for example, the
sodium salts. The total amount of the fluorescent agent or
agents used in the composition is generally from 0.005 to 2
wt % , more preferably 0.01 to 0.1 wt % . Preferred classes of
fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal
(Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid
compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade
Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
Preferred fluorescers are: sodium 2 (4-styryl-3-
sulf ophenyl )-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-anil ino- 6-morpholino-l ,3,5-triazin-2-yl) ]amino }
stilbene-2-2' disulfonate, and disodium 4 ,4 '-bis (2-
sulf ostyryl) biphenyl .
It is preferred that the aqueous solution used in the method
has a fluorescer present. When a fluorescer is present in
the aqueous solution used in the method it is preferably in
the range from 0.0001 g/1 to 0.1 g/1, preferably 0.001 to
0.02 g/1.
PERFUME
Preferably the composition comprises a perfume. The perfume
is preferably in the range from 0.001 to 3 wt % , most
preferably 0.1 to 1 wt % . Many suitable examples of perfumes
are provided in the CTFA (Cosmetic, Toiletry and Fragrance
Association) 1992 International Buyers Guide, published by
CFTA Publications and OPD 1993 Chemicals Buyers Directory
80th Annual Edition, published by Schnell Publishing Co.
It is commonplace for a plurality of perfume components to
be present in a formulation. In the compositions of the
present invention it is envisaged that there will be four or
more, preferably five or more, more preferably six or more
or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt% are top notes.
Top notes are defined by Poucher (Journal of the Society of
Cosmetic Chemists 6(2): 80 [1955]). Preferred top-notes are
selected from citrus oils, linalool, linalyl acetate,
lavender, dihydromyrcenol , rose oxide and cis-3-hexanol .
Perfume and top note may be used to cue the whiteness
benefit of the invention.
It is preferred that the laundry treatment composition does
not contain a peroxygen bleach, e.g., sodium percarbonate,
sodium perborate, and peracid.
OTHER POLYMERS
The composition may comprise one or more further polymers.
Examples are carboxymethylcellulose, poly (ethylene glycol) ,
poly (vinyl alcohol), polycarboxylates such as polyacrylates ,
maleic/acrylic acid copolymers and lauryl
methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition, for example
poly (vinylpyrrolidone) , poly (vinylpyridine-N-oxide) , and
poly (vinylimidazole) , are preferably absent from the
formulation .
ENZYMES
One or more enzymes are preferred present in a composition
of the invention and when practicing a method of the
invention .
Preferably the level of each enzyme is from 0.0001 wt% to
0.1 wt% protein.
Especially contemplated enzymes include proteases, alphaamylases,
cellulases, lipases, peroxidases/oxidases, pectate
lyases, and mannanases, or mixtures thereof.
Suitable lipases include those of bacterial or fungal
origin. Chemically modified or protein engineered mutants
are included. Examples of useful lipases include lipases
from Humicola (synonym Thermomyces) , e.g. from H . lanuginosa
(T. lanuginosus) as described in EP 258 068 and EP 305 216
or from H . insolens as described in WO 96/13580, a
Pseudomonas lipase, 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), a Bacillus lipase, 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) .
Other examples are lipase variants such as those described
in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, WO
95/35381, WO 96/00292, WO 95/30744, WO 94/25578,
WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO
00/60063.
Preferred commercially available lipase enzymes include
Lipolase™ and Lipolase Ultra™, Lipex™ (Novozymes A/S).
The method of the invention may be carried out in the
presence of phospholipase classified as EC 3.1.1.4 and/or
EC 3.1.1.32. As used herein, the term phospholipase is an
enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine,
consist of glycerol esterified with two fatty acids in an
outer (sn-1) and the middle (sn-2) positions and esterified
with phosphoric acid in the third position; the phosphoric
acid, in turn, may be esterified to an amino-alcohol .
Phospholipases are enzymes which participate in the
hydrolysis of phospholipids. Several types of phospholipase
activity can be distinguished, including phospholipases i
and A 2 which hydrolyze one fatty acyl group (in the sn-1 and
sn-2 position, respectively) to form lysophospholipid; and
lysophospholipase (or phospholipase B ) which can hydrolyze
the remaining fatty acyl group in lysophospholipid.
Phospholipase C and phospholipase D (phosphodiesterases)
release diacyl glycerol or phosphatidic acid respectively.
The enzyme and the shading dye may show some interaction and
should be chosen such that this interaction is not negative.
Some negative interactions may be avoided by encapsulation
of one or other of enzyme or shading dye and/or other
segregation within the product.
Suitable proteases include those of animal, vegetable or
microbial origin. Microbial origin is preferred. Chemically
modified or protein engineered mutants are included. The
protease may be a serine protease or a metallo protease,
preferably an alkaline microbial protease or a trypsin-like
protease. Preferred commercially available protease enzymes
include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™,
Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes
A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™,
Purafect OxP™, FN2™, and F 3™ (Genencor International Inc.).
The method of the invention may be carried out in the
presence of cutinase. classified in EC 3.1.1.74. The
cutinase used according to the invention may be of any
origin. Preferably cutinases are of microbial origin, in
particular of bacterial, of fungal or of yeast origin.
Suitable amylases (alpha and/or beta) include those of
bacterial or fungal origin. Chemically modified or protein
engineered mutants are included. Amylases include, for
example, alpha-amylases obtained from Bacillus, e.g. a
special strain of B . lichen! formis , described in more detail
in GB 1,296,839, or the Bacillus sp . strains disclosed in WO
95/026397 or WO 00/060060. Commercially available amylases
are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™,
Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S) , Rapidase™
and Purastar™ (from Genencor International Inc.).
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 , Thielavia terrestris , Myceliophthora
thermophila , and Fusarium oxysporum disclosed in US
4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO
89/09259, WO 96/029397, and WO 98/012307. Commercially
available cellulases include Celluzyme™, Carezyme™,
Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax
HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao
Corporation) .
Suitable peroxidases/oxidases include those of plant,
bacterial or fungal origin. Chemically modified or protein
engineered mutants are included. Examples of useful
peroxidases include peroxidases from Coprinus, e.g. from C .
cinereus , and variants thereof as those described in WO
93/24618, WO 95/10602, and WO 98/15257. Commercially
available peroxidases include Guardzyme™ and Novozym™ 51004
(Novozymes A/S) .
ENZYME STABILIZERS
Any enzyme present in the composition may be stabilized
using conventional stabilizing agents, e.g., a polyol such
as propylene glycol or glycerol, a sugar or sugar alcohol,
lactic acid, boric acid, or a boric acid derivative, e.g.,
an aromatic borate ester, or a phenyl boronic acid
derivative such as 4-formylphenyl boronic acid, and the
composition may be formulated as described in e.g. WO
92/19709 and WO 92/19708.
Where alkyl groups are sufficiently long to form branched or
cyclic chains, the alkyl groups encompass branched, cyclic
and linear alkyl chains. The alkyl groups are preferably
linear or branched, most preferably linear. The indefinite
article "a" or "an" and its corresponding definite article
"the" as used herein means at least one, or one or more,
unless specified otherwise.
Experimental
Example 1: Dye-polymer Synthesis
A PET/POET polymer was synthesized with a number average
molecular weight of 4,900 and a ratio of PET to POET of 1:2.
0.5g of the PET POET polymer, 0 .5g Na2C03 and 0 .lg of
reactive dye were mixed together in 35ml of demineralised
water and heated at 80°C for 5 hours.
Following the reaction the product was dialyzed against
water (COMW=3500) for 72 hours. Water was then removed by
rotary evaporation. The resultant polymer was dried in
vacuum .
Example 2 : Wash Performance
Woven Cotton, polyester and nylon-elastane fabrics were
washed in an aqueous wash solution (demineralised water)
containing lg/L Linear Alkyl benzene sulfonate, lg/L sodium
carbonate and lg/L sodium chloride at a liquor to cloth
ratio of 30:1. To the wash solution shading were added the
polymers of example 1 such that the wash solution contained
5ppm of polymer. After 30 minutes of agitation the clothes
were removed rinsed and dried. Washes were then repeated
until 4 wash cycles had been accomplished. After the 2nd and
4th wash the reflectance spectra of the cloth were measured
on a reflectometer and the colour expressed as CIE L * a * b *
values .
The increased in whiteness of the cloth was expressed as the
change in blue:
Ab b Ontrol bdye-polymer •
The results are given in the table below
The PET POET dye polymer show good deposition to cotton and
also polyester.
Example 3 : dye polymer with reactive blue and reactive red
dye
0.07g of reactive blue 4 and 0.03g of reactive red 3 were
mixed with lg of a PET POET polymer, TexCare SRN-300 (ex
Clariant) in a manner analogous to example 1 , except the
reaction was conducted at 65°C for 6 hours.
Washes were conducted with the dye-polymer following the
protocol of example 2 and the results are given in the table
below :
The dye polymer shows good deposition to cotton fabrics.
Example : soil anti-redeposition benefits
4 woven and 4 knitted white cotton fabric squares (15x15cm)
were washed at a Liquoricloth 25:1 in a Tergotometer in 26°FH
water with 4g/L of a laundry detergent powder which
contained 15% Linear Alkyl benzene sulfonate (LAS)
surfactant, 30% N a2C C 3 , 40% NaCl, remainder minors included
calcite and fluorescer and moisture. To the wash liquor lppm
of the required polymer was added.
The cloth were dried then the washes repeated four time,
with the addition of fresh soil test strips for each wash.
The soil strips used were 4 x SBL 2004 Soil Ballast Fabrics
(ex wfk Testgewebe GmbH Germany) and 2 x multimix soil
ballast fabric (ex CFT Holland) . All soil strips were
7.5x15cm pieces on cotton.
After the washes the refelectance at 740nm of the initially
white cottons were measured on a reflectometer .
The values are shown in the table below:
The white cotton washed in the dye-polymer has significantly
higher reflectance than the control or those washed in the
polymer without dye. This is because the soil released from
the soil strips deposits less to the white cotton due to the
dye-polymer .
The dye polymer is effective at preventing soil redeposition
at low levels in the wash.
We Claim:
1 . A method for obtaining a dye-polymer, the method
comprising the step of reacting a polymer with a reactive
dye to form the dye-polymer, wherein the polymer is
comprised of comonomers of a phenyl dicarboxylate, an
oxyalkyleneoxy and a polyoxyalkyleneoxy and the polymer
comprises at least one free OH group.
2 . A method for obtaining a dye-polymer wherein the
polymer comprises at least two free OH groups.
3 . A method for obtaining a dye-polymer according to claim
1 or 2 , wherein the oxyalkyleneoxy is selected from: oxy-
1,2-propyleneoxy ; oxy-1 ,3-propyleneoxy; and, oxy-1,2-
ethyleneoxy .
. A method for obtaining a dye-polymer according to any one
of claims 1 to 3 , wherein the polyoxyalkyleneoxy is selected
from: polyoxy-1 ,2-propyleneoxy; polyoxy-1 ,3-propyleneoxy;
and, polyoxy-1, 2-ethyleneoxy.
5 . A method for obtaining a dye-polymer according to any
one of the preceding claims, wherein the phenyl
dicarboxylate is a 1,4-phenyl dicarboxylate.
6 . A method for obtaining a dye-polymer according to claim
5 , wherein the polymer is polyethylene terephthalatepolyoxyethylene
terephthalate .
7 . A method for obtaining a dye-polymer according to claim
wherein ¾ is selected from H or C¾;
b is 2 or 3 ;
y is from 2 to 100;
n and m are independently selected from 1 to 100; and,
terminal groups of the polymer are (CH2)b H .
8 . A method for obtaining a dye-polymer according to claim
1 , wherein the reactive group of the reactive dye is
selected from: dichlorotriazinyl ; dif luorochloropyrimidine ;
monof luorotrazinyl ; dichloroquinoxaline ; vinylsulf one ;
dif luorotriazine ; monochlorotriazinyl ; bromoacrlyamide, and
trichloropyrimidine .
9 . A method for obtaining a dye-polymer according to claim
1 , wherein the chromophore of the reactive dye is selected
from: azo; anthraquinone ; phthalocyanine ; formazan; and,
triphendioaxazine .
10. A method for obtaining a dye-polymer according to claim
1 , wherein the chromophores of the reactive dye is selected
from: azo; and, anthraquinone.
11. A method for obtaining a dye-polymer according to any
one of claims 2 to 10, wherein the polymer is reacted with
reactive red dye and a blue reactive dye, wherein when the
weight ratio of the blue dye: the red dye is from 10:1 to
10:4.
12. A dye-polymer obtainable from the method as defined in
any one of the preceding claim.
13. A laundry treatment composition comprising:
(i) from 2 to 70 wt% of a surfactant; and,
(ii) from 0.0001 to 20.0 wt% of the dye-polymer as defined
claim 12 .
14. A laundry treatment composition according to claim 13,
wherein the laundry treatment is granular.
15. A method of treating a laundry textile, the method
comprising the steps of:
(i) treating a textile with an aqueous solution of the
dye-polymer as defined in claim 12, the aqueous solution
comprising from 10 ppb to 500 ppm of the dye-polymer and,
from 0.0 g/L to 3 g/L of a surfactant;
(ii) optionally rinsing; and,
(iii) drying the textile.