Note: Descriptions are shown in the official language in which they were submitted.
CA 02372289 2008-02-28
- 1 -
Fabric Care Treatment Composition and
a Method of Treating Fabric
The present invention relates to a fabric care treatment
composition comprising a novel colour care and stain
treatment system. The present invention also relates to a
method of treating fabric using the novel colour care and
stain treatment system. The present invention further
relates to the use of the novel.colour care and stain
treatment system in fabric care treatment.
Background of the Invention
The present invention is concerned with fabric treatment
that takes place after use of the fabric, in particular to
reverse degradation of fabric that occurs as a result of
that use, for example soiling and staining. Such treatments
are referred to herein as fabric care. Fabric care
treatments include laundering and the application of non-
detergent-based fabric'care products, such as spray-on
products. Considerable attention has been focused on
components for inclusion in fabric care compositions which
are specifically intended for colour care. For example,
these components may comprise dye transfer inhibitors, stain
removers, photofading inhibitors, and fluorescence
inhibitors.
EP 0 786 517 discloses a fabric wash detergent composition in
which a specific polymer system is included to provide stain
removal benefits. International patent application no. PCT/EP
28-08-2001 CA 02372289 2001-10-24 EP0005530
~~~q.3 tC) WO
Amended 22 August 2001
_ 2 _ -~
97/07289 discloses fabric treatment compositions comprising
a sunscreen material for preventing sun damage to colour.
WO 95/13354 discloses compositions comprising polymers such
as PVPNO and N-vinyl pyrollidone/N-vinyl imidazole
copolymers as dye transfer inhibitors. EP-A-0035470
discloses a textile treatment-composition which comprises a
photobleaching component. The photobleach material has some
effect against stains, but can also attack dye.
The present inventors have sought further colour care and
stain treatment components which are suitable for
incorporation into fabric care compositions.
The present inventors have discovered that radical
photoinitiator systems that operate by bond cleavage
mechanism can act as colour care and stain removal
components in fabric care compositions.
WO 96 12785, US-A-3915974 and JP 08 239700A, each disclose
the use of materials which have radical initiating
properties as perfume ingredients. All of these materials
function by a hydrogen-abstraction mechanism rather than a
bond-cleavage mechanism."
Radical photoinitiators themselves are well known and used
in the unrelated fields of polymerisation, polymer cross
linking and curing reactions in materials.
AMENDED SHEET
CA 02372289 2009-05-19
- 2a -
Definition of the Invention
The present invention'accordingly provides a fabric care
composition, comprising a bond-cleavage radical
photoinitiator.
More specifically, the present invention provides a fabric
care composition, chosen from a fabric conditioner composition
or a fabric wash composition comprising a bond-cleavage
radical photoinitiator, wherein the composition being a fabric
wash composition, the composition further comprises fabric
wash detergent, and wherein the composition being a fabric
conditioner composition, the composition further comprises
fabric conditioner.
CA 02372289 2009-05-19
- 3 - ~
The present invention further provides a fabric care
treatment method, comprising treating the fabric with a bond
cleavage radical photoinitiator.
The present invention further provides use of a bond-
cleavage radical photoinitiator in a fabric care treatment
method.
It has also been found that the radical photoinitiators of
the present invention have the advantage that they are
stable in solution if kept in the dark. It is found that
they do not degrade spontaneously on storage.
Further, it has been found that the radical photoinitiators
of the present invention will act on stains without the need
for agitation. This has the advantage that they can be used
in simple application me-thods. Further, damage to fabrics,
such as fibrillation can be avoided.
The radical photoinitiator systems according to the present
invention are found to be soluble or dispersible in other
media than water and can be used on dry-clean only garments.
Finally, it is found that the radical photoinitiators of the
present invention can have a bactericidal effect.
28-08-2001 CA 02372289 2001-10-24 EP0005530
1..3743 (l;) WO Amended 22 August 2001
- 4 - ~
Detailed Description of the Invention
Radical Photoinitiators
Radical photoinitiators suitable for use in the present
invention are components which produce radicals capable of
attacking stains on fabric, on photoexcitation.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
~.. ~~ k %.I) WO
Amended 22 August 2001
- 5 - z
Bond cleavage radical photoinitiators operate according to=
the following reaction:
light k2 = =
y Y* R1 + R2
k(2) is the rate constant of the bond-cleavage reaction.
Preferably, k(2) is greater than 106 s"1 .
Suitable bond cleavage radical initiators may be selected
from the following groups.
(a) alpha amino ketones, particuarly those containing a
benzoyl moiety, otherwise called alpha-amino acetophenones,
for example 2-methyl 1-[4-phenylJ-2-morpholinopropane-l-one
(Irgacure 907, trade mark), (2-benzyl-2-dimethyl amino-l-(4-
morpholinophenyl)-butan-l-one (Irgacure 369, trade mark).
(b) alphahydroxy ketones, particuarly alpha-hydroxy
acetophenones, eg (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-
2-methyl-l-propane-i-one) (Irgacure 2959, trade mark), 1-
hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, trade mark).
(c) phosphorus containing photoinitiators, including
monoacyl and bisacyl phosphine oxide and sulphides, for
AMENDED SHEET
28_08_2001 CA 02372289 2001-10-24
EP0005530
U,sy4.s (C) WO
Amended 22 August 2001
- 6 - T
example 2-4-6-(trimethylbenzoyl)diphenyl-phosphine oxide,
bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (Irgacure
819, trade mark).
(d) dialkoxy acetophenones.
(e) alpha-haloacetophenones.
(f) trisacyl phosphine oxides.
Suitable radical photoinitiators are disclosed in
WO 9607662 (trisacyl phosphine oxides), US 5399782
(phosphine sulphides), US 5410060, EP-A-57474, EP-A-73413
(phosphine oxides), EP-A-088050, EP-A-0117233, EP-A-0138754,
EP-A-0446175 and US 4559371.
Suitable photoinitiators are disclosed for example in EP-A-
0003002 in the name of Ciba Geigy,
EP-A-0446175 in the name of Ciba Geigy, GB 2259704 in the
name of Ciba Geigy (alkyl bisacyl phosphine oxides),
US 4792632 (bisacyl phosphine oxides), US 5554663 in the
name of Ciba Geigy (alpha amino acetophenones) and US
5767169 (alkoxy phenyl substituted bisacyl phosphine
oxides).
Radical photoinitiators are all discussed in A.F.
Cunningham, V. Desorby, K. Di-e-tliker, R. Husler and D.G.
Leppard, Chemia 48 (1994) 423-426.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
~~} WO
Amended 22 August 2001
- 7 - ~
Without wishing to be bound by theory, it is preferred that
the radical photoinitiators all react through their excited
triplet state, to reduce the influence of the cage effect.
The radical photoinitiator suitably undergoes the reactions
set out above when excited by radiation falling generally in
the range 290-800 nm. For example, natural sunlight, which
comprises light in this region, will be suitable for causing
the radical photoinitiator to undergo the reactions
described above. Preferably, the radical photoinitiator has
a maximum extinction coefficient in the ultraviolet range
(290-400 nm) which is greater than 100 mol'1 lcml. Suitably,
the radical photoinitiator is a solid or a liquid at room
temperature.
Suitably, the radical photoinitiator is substantially
colourless and gives non-coloured photo products upon
undergoing one of the reactions set out above.
Preferably, the compositions comprise sensitisers such as
thioxanthones, for example as described in EP-A-0088050, EP-
A-0138754.
Preferred Radical Photoinitiator Systems
The present inventors have discovered that radical
photoinitiators having a spec_i_f.i-ed_hydrophobicity, measured
by their log P value, have a particularly preferred effect.
All materials for the removal -of stains also have a tendency
to attack dye. The preferred radical photoinitiator systems
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
C3943
- 8 -
have a particularly beneficial balance of stain removal
versus dye attack tendency.
Preferably, the radical photoinitiators have a high log P
value, where log P is the octanol-water partition
coefficient. It is preferred that the radical
photoinitiators have a log P measured at 25 C in excess of
2.5 and more preferably in excess of 4Ø
= 10 Fabric Care Compositions
The present invention is suitable for use in industrial or
domestic fabric wash compositions, fabric conditioning
compositions and compositions for both washing and
conditioning fabrics (so-called through the wash conditioner
compositions). The present invention can also be applied to
industrial or domestic non-detergent based fabric care
compositions, for example spray-on compositions.
Fabric Wash Compositions
Fabric wash compositions according to the present invention
may be in any suitable form, for example powdered, tableted
powders, liquid or solid detergent bars.
Fabric wash compositions according to the present invention
comprise a fabric wash detergent-4naterial selected from non-
soap anionic surfactant, nonionic surfactants, soap,
amphoteric surfactants, zwitterionic surfactants and
mixtures thereof.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
.C3943
- 9 -
Suitable anionic surfactants are well known to the person
skilled in the art and include alkyl benzene suiphonate,
primary and secondary alkyl sulphates, particularly C8-C,5
primary alkyl sulphates; alkyl ether sulphates; olefin
sulphonates; alkyl xylene sulphonates, dialkyl
sulphosuccinates; ether carboxylates; isethionates;
sarcosinates; fatty acid ester sulphonates and mixtures
thereof. The sodium salts are generally preferred.
Nonionic surfactants are also well known to the person
skilled in the art and include primary and secondary alcohol
ethoxylates, especially C8-C2Q aliphatic alcohol ethoxylated
with an average of from 1 to 20 moles of ethylene oxide per
mole of alcohol, and more especially the Clo-C15 primary and
secondary aliphatic alcohols ethoxylated with an average of
from 1 to 10 moles of ethylene oxide per mole of alcohol.'
Non-ethoxylated nonionic surfactants include alkyl
polyglycosides, glycerol monoethers and polyhydroxy amides
(glucamide). Mixtures of nonionic surfactant may be used.
Detergent compositions suitable for use in domestic or
industrial automatic fabric washing machines generally
contain anionic non-soap surfactant or nonionic surfactant,
or combinations of the two in suitable ratio, as will be
known to the person skilled in the art, optionally together
with soap.
Many suitable detergent-active compounds are available and
fully described in the literature, for example in,"Surface-
'Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry & Berch.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
C3943
- 10 -
Anionic surfactant is suitably present at a level of from 5
wt% to 50 wt%, preferably 10 wt%-40 wt% based on the fabric
treatment composition. Nonionic surfactant is suitably
present at a level of 1-20 wt%, preferably 5-15 wtt.
The total amount of surfactant present will depend upon the
intended end use and may be as high as 60 wt% for example in
a composition for washing fabrics by hand. In compositions
for machine washing of fabric, an amount of from 5 to 40 wt%
is generally appropriate.
Detergency Builder
The detergent compositions of the invention will generally
also contain one or more detergency builders. The total
amount of detergency builder in the compositions will
suitably range from 5 to 80 wtt, preferably from 10 to 60
wt%.
Inorganic builders that may be present include sodium
carbonate, if desired in combination with a crystallisation
seed for calcium carbonate, as disclosed in GB 1 437,950
(Unilever); crystalline and amorphous aluminosilicates, for
example, zeolites as disclosed in GB 1 473 202 (Henkel) and
mixed crystalline/amorphous aluminosilicates as disclosed in
GB 1 470 250 (Procter & Gamble); and layered silicates as
disclosed in EP 164 514B (Hoeehst-)-: Inorganic phosphate
builders, for example, sodium orthophosphate, pyrophosphate
and .tripolyphosphate are also 'suitable for use with this
invention.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
C3943
- 11 -
The detergent compositions of the invention preferably
contain an alkali metal, preferably sodium, aluminosilicate
builder. Sodium aluminosilicates may generally be
incorporated in amounts of from 10 to 70t by weight
(anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline
or amorphous or mixtures thereof, having the general
: formula:
0. 8-1. 5 Na20. A1203. 0-8-6 S i 02
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 Si02 units (in the formula above). Both the amorphous
and the crystalline materials can be prepared readily be
reaction between sodium silicate and sodium aluminate, as
amply described in the literature.
~ 20
Suitable crystalline sodium aluminosilicate ion-exchange
detergency builders are described, for example, in GB 1 429
143 (Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known
commercially available zeolites A and X, and mixtures
thereof.
The zeolite may be the commercially available zeolite 4A now
widely used in laundry detergent powders. The zeolite
builder incorporated in the compositions of the invention
may be maximum aluminiuin zeolite P (zeolite MAP) as
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 12 -
described and claimed in EP 384 070A (Unilever). Zeolite
MAP is defined as an alkali metal aluminosilicate of the
zeolite P type having a silicon to aluminium ratio not
exceeding 1.33, preferably within the range of from 0.90 to
1.33, and more preferably within the range of from 0.90 to
1.20.
Especially preferred is zeolite MAP having a silicon to
aluminium ratio not exceeding 1.07, more preferably about
1.00. The calcium binding capacity of zeolite MAP is
generally at least 150 mg CaO per g of anhydrous material.
Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers,
and acrylic phosphinates; monomeric polycarboxylates such as
citrates, gluconates, oxydisuccinates, glycerol mono-, di-
and trisuccinates, carboyxmethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates,
hydroyxethyliminodiacetates, alkyl- and alkenylmalonates and
= 20 succinates,; and sulphonated fatty acid salts. This list is
-not intended to be exhaustive.
Especially preferred organic builders are citrates, suitable
used in amounts of from 5 to 30 wtt, preferably from 10 to
25 wt%; and acrylic polymers, more especially acrylic/maleic
copolymers, suitably used in amounts'of from 0.5 to 15 wtt,
preferably from 1 to 10 wt%-. Builders, both inorganic and organic, are
preferably present
in alkali metal salt, especially sodium salt, form.
AMENDED SHEET
28-08-2001 CA 02372289 2001-10-24
EP0005530
C3943
- 13 -
Bleach Components
Detergent compositions according to the invention may also
suitably contain a peroxy bleach system for example,
inorganic persalts or organic peroxyacids, capable of
yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides
, such as urea peroxide, and inorganic persalts such as the
alkali metal perborates, percarbonates, perphosphates,
persilicates and persulphates. Preferred inorganic persalts
are sodium perborate monohydrate and tetrahydrate, and
sodium percarbonate.
Especially preferred is sodium percarbonate having a
protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising
sodium metaborate and sodium silicate is disclosed in
GB 2 123 044B (Kao) .
, 20
The compositions may further comprise a photobleach system
as described, for example, in EP-A-0035470.
Fabric Softening Composition
The fabric treatment composition of the present invention
may be a fabric conditioning_oamposition or it may comprise
fabric conditioner.
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 14 -
Fabric Softening Compound
The fabric softening compound is preferably a cationic
nonionic or anionic fabric softening compound.
The fabric softening compound may be a quaternary ammonium
material comprising a polar head group and one or two
alkyl or alkenyl chains. The fabric softening compound
may also be a nonionic fabric softening compound such as a
fabric softening oil, a fabric softening silicone
composition or a fabric softening ester composition such
as sugar esters.
Particularly preferably, the fabric softening compound has
two long chain alkyl or alkenyl chains with an average
chain length greater than C14, more preferably each chain
has an average chain length greater than C14, more .
preferably at least 50% of each long chain alkyl or
alkenyl group has a chain length of Cls.
. 20
It is preferred if the long chain alkyl or alkenyl groups
of the fabric softening compound are predominantly linear.
It is highly preferred if the fabric softening compounds
are substantially water-insoluble. Substantially
insoluble fabric softening compounds in the context of
this invention are defined as--fabric softening compounds
having a solubility less than 1 x 10-3 wt* in demineralised
water at 20 C, preferably the fabric softening compounds
have a solubility less than 1 x 10'4, most preferably the
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
- C3943
- 15 -
fabric softening compounds have a solubility at 20 C in
demineralised water from 1 x 10'3 to 1 x 10-6.
Well known species of substantially water-insoluble
quaternary ammonium compounds having the formula:
R1 R3
. N +
R2 Ra
wherein R' and R2 represent hydrocarbyl groups having from
12 to 24 carbon atoms; R3 and R4 represent hydrocarbyl
groups containing 1 to 4 carbon atoms; and X is an anion,
preferably selected from halide, methyl sulphate and ethyl
sulphate groups are preferred.
Representative examples of these quaternary softeners
include di(tallow alkyl) dimethyl ammonium methyl
sulphate; dihexadecyl dimethyl ammonium chloride;
di(hydrogenated tallow alkyl) dimethyl ammonium chloride;
dioctadecyl dimethyl ammonium chloride; di(hydrogenated
tallow alkyl) ditnethyl ammonium methyl sulphate;
dihexadecyl diethyl ammonium chloride; di(coconut alkyl)
dimethyl ammonium chloride, ditallow alkyl dimethyl
ammonium chloride and di (hydrtsgerna't-ed tallow alkyl)
dimethyl ammonium chloride (Arquad 2HT Trade Mark).
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 16 -
Other preferred softeners contain esters or amide links,
for example those available under the trade names Accosoft
580, Varisoft 222, and Stepantex.
Particularly preferred fabric softening compounds are
water-insoluble quaternary ammonium materials which
comprise-a compound having two C12_la alkyl or alkenyl
groups connected to the molecule via at least one ester
link. It is more preferred if the quaternary ammonium
material has two ester links present. The preferred
ester-linked quaternary ammonium material for use in the
invention can be represented by the formula:
R1
FZl (CHZ) n-T-R2 X"
(CH2) n-T-RZ
wherein each Rl group is independently selected from Cl-4
alkyl, hydroxyalkyl or Ca_4 alkenyl groups; and wherein
each R2 group is independently selected from Ce_28 alkyl or
alkenyl groups;
0 0
11 11
T is --C-O- or -0-C-; X' is any suitable anion and n is an
integer from 0-5. Particularly preferred is di(ethyl
ester) dimethyl ammonium chloride (DEEDMAC).
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 17 -
A second preferred type of quaternary ammonium material
can be represented by the formula:
OOCR2
1
(RI) aN +- ( CH2 ) a CH X-
CHzO0CR2
i
10- wherein Rt, n, X- and R2 are as def ined above.
It is advantageous for environmental reasons if the
quaternary ammonium material is biologically degradable.
Preferred materials of this class such as 1,2 bis[hardened
tallowoyloxy]-3-trimethylammonium propane chloride and their
methods of preparation are, for example, described in US 4
137 180 (Lever Brothers). Preferably these materials
comprise small amounts of the corresponding monoester as
. 20 described in US 4 137 180 for example 1-hardened
tallowoyloxy-2-hydroxy trimethylamrnonium propane chloride.
The fabric softening agent may also be a polyol ester quat
(PEQ). as described in EP 0 638 639 (Akzo).
Other Ingredients
The compositions of the invention can also contain one or
more optional ingredients, selected from pH buffering
agents, perfume carriers, fluorescers, colorants,
hydrotropes, antifoaming agents, antiredeposition agents,
AMENDED SHEET
_._..~,~.._
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 18 -
enzymes, optical brightening agents, opacifiers, anti-
shrinking agents, anti-wrinkle agents, anti-spotting agents,
germicides, fungicides, anti-corrosion agents, drape
imparting agents, antistatic agents and ironing aids.
The present inverition may be in the form of a dilute or
concentrated aqueous solution or suspension, for example as
described in WO 97/15651, WO 95/27769. Alternatively, the
fabric softening composition may be in the form of a powder
for use in the rinse cycle of an automatic washing machine.
Alternatively, the fabric softening composition may be in
the -form-of a sheet comprising fabric conditioning
compositions for use in a tumble dryer, for example as
disclosed in WO 95/27777. Alternatively, the fabric
conditioning composition may be in the form of a
substantially non-aqueous concentrate as described in
international patent application no. PCT/EP99/00497.
Fabric wash detergent compositions according to the present
~ 20 invention may further include through the wash softening
material, such as-cationic fabric softener.
Non-Detergent-Based Fabric Care Products
The present invention can also be used in non-detergent-
based fabric care products. For example, the product may
comprise the stain removal systenr-as the principal
ingredient. For exainple, non-detergent based compositions
may comprise solutions of the stain removal system of the
present invention in a suitable solvent, such as
isopropanol, alcohol etc. The compositions may comprise
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 19 -
aerosol or spray-on compositions. They may be in the form
of sticks, bars, dab-on compositions, for example absorbed
into sponges for application to the surface etc.
The present invention will be further described by way of
example only with reference to the following examples.
Examples
All quantities are in percent or parts by weight unless
indicated otherwise.
The following radical initiators are used in the present
examples. They-are available commercially under the trade
marks set out below from Ciba Specialty Chemicals.
Irgacure 369 - 1-[4-(2-hydroxy ethoxy)-phenyl]-2-hydroxy-2-
methyl-l-propane-i-one (log P = 2.9, measured at 25 C).
Irgacure 819 - bis(2,4,6-trimethyl benzoyl) - phenyl
phosphine oxide (log P = 5.8, measured at 25 C).
Irgacure 2959 - (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-
methyl-l-propane-l-one (log P 0.84, measured at 25 C).
Example 1
Cloths heavily stained with stains set out in Table 1 were
obtained from a commercial supplier (Equest, stains aged for
three days then sealed). The stained cloths were then
treated with solutions of ethanol containing various radical
AMENDED SHEET
~_ _ _
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 20 -
photoinitiators and then placed in an Atlas S3000
Weatherometer WOM (trade mark) for 12 minutes (at a power
level of 0.35 w/m2 at 340 nm). The results in the change in
reflectance at 460 nm (R(460 nm)) measured using a
Spectraflash SF60 (trade mark) reflectometer are set out in
table 4.
The following treatment regimes were used:
Treatment 1 - no immersion.
Treatment 2 - place stained cloth in ethanol, remove and
dry, wet with water, placed in Weatherometer for 12 minutes.
Treatment 3 - place in ethanol containing 0.20% by weight
Irgacure 2959 (trade mark), remove and dry, wet with water,
place in WOM for 12 minutes.
Treatment 4 - place in ethanol containing 0.20% Irgacure 819
(trade mark), remove and dry, wet with water, place in
Weatherometer for 12 minutes.
The results are shown in Table 1.
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 21 -
Table 1
R(460 nm)
stain 1 2 3 4
chilli 42.7 52.7 61.5 72.6
bolognese. 33.8 40.1 48.2 67.8
curry 43.2 55.9 55.9 84.5
baby food 50.6 71.3 79.9 84.8
P-carotene 23.8 24.5 43.0 87.5
grass 18.8 2=2.4 26.8 32.6
blood 8.1 5.8 6.8 5.7
wine 60.4 59.9 61.2 63.2
In general, the radical initiators lead to an increase in
reflectance at 460 nm for a variety of stains. That is, the
radical initiators effectively bleach the stains from the
fabric.
Example 2
The method of Example 1 was repeated, using treatment 1, 2
and 4 except that the quantity of Irgacure 819 (trade mark)
in the ethanol was varied. The results are shown in Table
2.
Table 2
Stain Treatment
1 2 4
~ Ir acure 0 0 0.01 0.02 0.05 0.1
bolognese 38.3 38.7 48.9 50.3 52.8 55.1
13-carotene 32 30.6 65.3 76 82.1
curry 31 29.1 44.7 50.2 55.4 57.5
The results show that the bleaching of stains can be
obtained at very low on-weight-fabric levels of radical
photoinitiator.
annFNDFD ,SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 22 -
Example 3
The following experiment was conducted to compare the effect
of different radical initiator systems on stains and on dye.
A variety of stained cotton cloths were purchased from
Equest as above. Photoinitiators at various levels on-
weight-fabric (owf) were padded onto the stained cloths from
ethanol. The ethanol was then evaporated, the cloths wetted
with demineralised water and placed in an Atlas S3000
Weatherometer (trade mark) for 12 minutes of irradiation
(power = 0.35W/mz at 340 nm Reflectance at 460 nm was
measured for the stained cloths and for a piece of unstained
fabric to yield.AE values. The values were compared to a
Control where the stains had followed the same treatment,
except that the ethanol contained no radical initiator. It
was found, as in Example 1, that the initiators were
particularly good at bleaching curry, bologonese, b-carotene
and chilli. Table 3 and 4 give the average reduction in AE
above the control found for these four stains for Irgacure
2959 and 819 (trade mark) at various levels on weight of
fabric.
To gauge how badly the initiators damage dyes, the above
experiments were repeated except printed cloth purchased
from Veebee The of Harrogate England,was used instead of
stained fabric. In this case, the AE values represent dye
damage. 16 different dyes were tested and the average dye
damage measured is given in Tables 3 and 4.
The dyes were as follows:
AMENDED SHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 23 -
Dye Level on weight fabric (g/kg)
on dyed side
Procion
Red HE-7B 0.5
Scarlet HE-XL 0.5
Yellow HE-6G 1.0
Red HE-GXL 0.5
Blue HE-GXL 2.0
Turquoise H-A 5.0
Navy HE-XL 1.0
Remazol
Red RB 1.0
Golden Yellow RNL 1.0
Brill Red RBS 2.0
Yellow FG 1.0
Orange FR 2.0
Navy GG 2.0
Turquoise G 2.0
Black B 1.0
The measurement of stain removal was divided by the
measurement of dye damage to give a value of benefit/damage
which is a measure of how specific the initiator is to the
stains rather than the dye. It can be seen that Irgacure
819 (trade mark) which has a log P above 2.5 is much more
stain specific than Irgacure 2953--{=trade mark) which has a
log P below 2.5. This is particularly true at low levels
(0-0.02% owf), where Irgacure 819 (trade mark) give large
stain bleaching benefits but only very small dye damage.
AnnFNnFp PHEET
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 24 -
Table 3
wt% Irgacure 819 average stain average dye benefit
(trade mark) owf removal, DE damage, AE damage
0.01 11.5 0.31 37.1
0.02 14 0.62 22.6
0.05 16.9 1.85 9.1
0.1 18.5 3.53 5.2
0.2 17.4 3.9 4.5
Table 4
wtt Irgacure 2959 average stain average dye benefit
(trade mark) owf removal, AE damage, AE damage
0.05 2.3 3.5 0.66
0.1 3.9 5.3 0.74
0.2 4.9 9.9 0.49
, It should be noted that when the experiments were repeated
using dry cloth much less dye damage was observed. However,
the stain bleaching was also reduced.
Examples 4 and 5
The following base powder was prepared:
linear sodium alkyl-benzene sulphonate (LAS) 23.60%
sodium tripolyphosphate - 19.22%
sodium silicate - 4.81%
sodium sulphate - 28.59%
~AIIFNf1Frl ~HF~T
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 25 -
calcite - 10.30%
minors - 1.08%
water - 12.49%
In Example 4, 1 gram of this base powder was intimately
mixed with 0.024 g of Irgacure 819. The final product
contains 2.3% by weight of Irgacure 819. In Example 5, 1
gram of base powder was intimately mixed with 0.024 g of
Irgacure 369. The final product thus contains 2.3% by
weight Irgacure 369.
In each example, the mixture of base powder and radical
photoinitiator was dissolved in 400 grams water at 40 C.
Three lots of cotton cloth were prepared. Each contained
sheets weighing 16.1 grams in total and brushed cotton
weighing 10 grams in total. All cloth was white. For each
lot, both types of cloth were cut into four pieces. The
lots were then washed in the solution prepared above for 5
minutes. One piece of cotton sheeting and one piece of
brushed cotton was removed and dried. The wash solution was
discarded and the cotton rinsed in 600 grams of cold water.
One piece of the cotton sheeting and brushed cotton was
removed and dried. The first.rinse solution was then
discarded. A second rinse was then conducted with a further
600 grams of water. Again, one piece of cotton sheeting and
one piece of brushed cotton were removed.
The pieces of cotton sheeting and brushed cotton removed at
each step were tested to see how much initiator had
deposited onto the cloth. This was measured by measuring
the reflectance of the dried cloths at 320 nm using a
anncnin~n cN~~-r
CA 02372289 2001-10-24
28-08-2001 EP0005530
U3543
- 26 -
Spectraflash SF60 (trade mark) reflectance spectrometer.
The following results were obtained:
Table 5 - Cloth Sheeting
Wash First Second
rinse Rinse
Powder without radical 39.0 38.5 38.5
photoinitiator
Powder with 2.3% Irgacure 369 35.0 36.0 37.5
(trade mark)
Powder with 2.3% Irgacure 819 34.7 35.5 36.0
(trade mark)
Table 6 - Brushed Cotton
Wash First Second
rinse Rinse
Powder without radical 20.0 16.4 17.3
initiator
. Powder with 2.3% Irgacure 369 17.0 13.5 14.0
(trade mark)
Powder with 2.3* Irgacure 819 14.0 15.0 16.1
(trade mark)
In all cases, the reflectance of the cloth washed with
powder compositions containing radical initiator is lower
than the control composition which contains no radical
initiator. This is because the Irgacure radical initiator
absorbs strongly at 320 nm reducing the reflectance. The
changes in reflectance measured were significantly above the
n nnCnrnCn cl-IC:CT
CA 02372289 2001-10-24
28-08-2001 EP0005530
1.1) 7`1J ~l) WO
Amended 22 August 2001
- 27 - ~
noise level for this type of measurement and confirm the
deposition of the initiators.
Examples 4 and 5 demonstrate that radical photoinitiators
may be deposited onto fabric from a laundry composition.
Example 6
The following rinse conditioner formulation was prepared:
HEQ ~ - 4%
Perfume - 0.3%
Irgacure 819 (trade mark) - 0.66%
Water - to 100%
1 HEQ = 1,2 bis [hardened tallowoyloxy)-3-
trimethylammonium propanechloride, ex Hoechst.
3 grams of this rinse conditiorier were dissolved in 600
grams of cold water. 18 grams of cotton sheeting were
placed in it for 5 minutes. At the end of this time, the
cotton was removed and dried. The reflectance spectrum of
the cotton sheeting was studied at 320 nm using a
Spectraflash SF60 (trade mark) reflectometer.
It was calculated from the reflectance results that
approximately 0.003% of radical photoinitiator (based on the
weight of the cloth) had been delivered.
n n nC~nmcn QUCCT
CA 02372289 2001-10-24
28-08-2001 EP0005530
1.J743 (l'.) WO
Amended 22 August 2001
- 28 - T
Example 8
The following experiment carried out to test the effect of
pH on the effects of radical photoinitiators.
The procedure of Example 7 was repeated except that Irgacure
819 (trade mark) was padded from ethanol onto stained cloths
at 0.1% on-weight-fabric. For each stain, separate samples
were taken and then wetted with buffer solution of varying
pH. The resulting cloths were irradiated for 12 minutes in
the Atlas S3000 (trade mark) Weatherometer. The variation
in average reflectance at 460 nm after treatment is shown in
the table. The average reflectance at 460 nm for the four
A IICN I-'1CI'1 0 I_1CCT
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 29 -
treatments was 46.5. It can be seen that the radical
photoinitiators give a substantial improvement in
reflectance over a wide range of pH.
Table 7
pH
3 5 7 9
~ average R460 77.0 78.8. 76.5 68.4
Example 9
The experiments of example 3 were repeated, using Lucerin
TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, ex
BASF) and, separately Irgacure 184 (1-hydroxy-cyclohexyl-
phenyl-ketone ex Ciba) at 0.02 and 0.2% owf. The results are
shown in table 8 below:-
Table 8
chemical wt% owf average average benefit/
stain dye damage damage
removal
Lucerin 0.02 12.5 1.3 9.6
TPO-L
Lucerin 0.2 15.1 2.0 7.6
TPO-L
Irgacure 0.02 8.0 0.9 8.9
184
Irgacure 0.2 13.3 4.6 2.9
184
n n nrrn I rN rn C+i_J1777 rT
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 30 -
Example 10
Stained white polyester cloth (Veebee Tech) was treated with
Initiators as in previous examples and good cleaning effect
found, above control. Little damage was found on dyed
polyester cloth.
Example 11
An oily tomato stains were created by smearing a tomato
paste ( Traditional Ragu Recipe Van den Bergh foods,
ingredients: Tomatoes, sunflower oil, onion, salt, sugar,
dextrose, garlic powder, basil, parsley, spice extract,
citric acid, basil, parsley, CaCla) onto cotton sheeting and
then ageing in air for 1 day. The stained cloths were washed
in a linitest under the following conditions: each pot
contained 12g cloths, (of which 6g were stained), 240ml of
water, 0.34g Borax, 1.44g of liquid detergent. 40 degrees C,
minutes, and no rinse. Cloths were dried in the tumble
20 drier, then placed in a WOM for 6 minutes.
Liquid detergents were created from, Coco5EO (ex Clariant -
a non ionic surfactant), SDS (sodium dodecyl sulphate - an
anionic surfactant), CTAC (cetyl trimethyl ammonium chloride
-a cationic surfactant), Arquad 2HT (ex Akzo Nobel - a
cationic surfactant), with 0.1* Lucerin TPO-L and 10t
ethanol on weight of formulation; the remainder was water.
The amount of surfactant in each formulation is given in the
table:
A n ncnmcn C+lJCC~'
CA 02372289 2001-10-24
28-08-2001 EP0005530
C3943
- 31 -
ingredients control L1 L2 L3 L4
Coco5E0 15.3 15.3 15.3 0 0
SDS 0 0 0 15.3 0
CTAC 1.7 1.7 0 0 0
Arquad 2HT 0 0 0 0 15.3
Lucerin 0 0.1 0.1 0.1 0.1
TPO-L
The results are shown below, in all cases the samples
containing the initiator gave lower DE values (better stain
removal) than the control.
AE value of stain compared to white
original
control 30.0
L1 16.0
L2 18.7
L3 11.3
L4 12.2
Example 12
Formulation Li of example 11 was made using Irgacure 819
instead of TPO-L. Good stain removal benefits above control
were obtained.
Example 13
A detergent composition was created containing 15.3% of an
anionic surfactant, 10% ethanol, 0.1% Lucerin TPO-L,
remainder water. The anionic surfactants were LAS, and SDS.
nnncn1 t',\ rn 0 UCC-r
CA 02372289 2001-10-24
28-08-2001 EP0005530
tc) WO
Amended 22 August 2001
- 32 - z
They were tested using the wash protocol of example 11, both
showed large increased in stain removal benefit on
irradiation, compared to a control of water only. This
indicated that the initiator was effective from the wash.
Benefits were also found for a(3-carotene and a paprika
stain.
Example 14
Persil liquid was purchased in Ireland and 0.01% on weight
Lucerin TPO-L added to the product. On washing, rinsing and
irradiating cloth stained with (,3-carotene, much greater
stain removal was found when the initiator was present.
Example 15
The initiators, benzoin, dimethoxyphenylacetophenone,
benzoin methyl ether, and benzoin ethyl ether (ex Aldrich)
were seperately applied from ethanol to cotton cloth stained
with P-carotene. All bleached the stain. As expected the
initiators with higher logP value gave less dye damage.
n r. n~T nre~ nT}-'T
