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BLEACHING COMPOSITIONS
Field of the invention
The present invention relates to a fabric protective system for use in
bleaching
compositions, which can be used to bleach fabrics, e.g., clothes, carpets and
the
like.
Background of the invention
Bleach-containing compositions for bleaching fabrics, are well known in the
art.
Amongst the different bleaching compositions available, those relying on
bleaching by hypohalite bleach, such as hypochlorite; and those relying on
peroxygen bleach, such as hydrogen peroxide,. are often preferred, mainly for
bleaching performance reasons.
However, a drawback associated with the use of bleach-containing
compositions, e.g., hypochlorite-based compositions, is that said compositions
may potentially damage andlor cause yeifowin<~ of the fabrics being bleached.
During the bleaching operation, a liquid hypochlorite-containing composition
for
example, can be applied onto the fabric in neat or in diluted form. The
hypochforite bleach can be present in various foiTrls, including hypochlorous
acid
and in the form of various molecule fragments resulting from its decomposition
pathways. Hypochlorous acid and these molecules fragments are reactive with
fabrics and may cause damage and/or yellowing of fabrics being bleached.
Therefore, bleaching compositions are often fomnulated comprising bleach and a
fabric protective system. Compositions comprising bleach and one of various
fabric protective systems are well-known in the art. An example is a bleaching
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composition based on hypohalite bleach or peroxygen bleach comprising a
polymer and a borate as a fabric protective system (EP-A-0 824 147}, or
bleaching compositions based on hypochlorite comprising a metaborate as a
fabric protective system (EP-A-0 781 480}.
However, there are some limitations to the convenience of said bleaches
comprising a fabric protective system. In particular, it is well-known from
consumes research that said compositions may still damage andlor yellow the
fabrics which are being bleached, although said compositions comprise a fabric
protective system.
It is therefore an object of the present invention to provide a bleach-
containing
composition, suitable for use in laundry applications, whereby the fabric
yellowing-prevention is further improved.
It is a further object of the present invention to provide a bleaching
composition,
suitable for use in laundry application, whereby fabric safety is further
improved.
Fabrics made of cotton andlor synthetic materials have free hydroxyl groups.
It
is believed that fabric damage andlor fabric yellowing occurs due to the
oxidation of the hydroxyl groups by the bleach. The oxidation of the hydroxyl
groups is believed to be further emphasised at lower pHs. Indeed, low pH
shifts
the chemical equilibrium between hypochlorite and hypochlorous acid in favor
of
the latter. Hypochlorous acid is a more aggressive bleach, which has been
found to further contribute to fabric yellowing and fabric damage. Moreover,
it is
further believed that the hydroxyl groups of the fabric are more easily
oxidised at
lower pHs.
It has been found that fabric protection can be achieved using a combination
of
a borate andJor boric acid and a surfactant as a fabric protective system in
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bleach-containing compositions. The use of a combination of a borate andlor
boric acid and a surfactant in bleach-containing compositions provides further
improved fabric yellowing-prevention and/or further improved fabric safety on
fabrics bleached therewith, as compared to bleaching compositions comprising
other fabric protective systems, e.g., a metaborate alone, or bleaching
compositions comprising no fabric protective system. It is believed that the
hydroxyl groups of a fabric are protected by the fabric protective system
according to the present invention from oxidation by a bleach, especially a
hypochlorite bleach, thus, providing fabric safety andlor fabric yellowing-
prevention.
Advantageously, the bleaching composition as described herein are suitable for
various laundry bleaching applications both when used in diluted conditions;
e.g., as a detergent additive or a fully formulated laundry detergent
composition,
and when used in neat condition, e.g., as a liquid pretreater (spotter).
A further advantage of the bleaching composiliions according to the present
invention is that they are able to perform in a variety of conditions, i.e.,
in hard
and soft water as well as when used neat or diluted.
Yet another advantage of the use of a borate and/or boric acid and a
surfactant
as a fabric protective system in a bleaching composition as described herein
is
that said bleaching compositions are suitable for the bleaching of different
types
of fabrics. More particularly, the compositions of the present invention are
suitable for bleaching any type of fabrics including natural fabrics (e.g.,
fabrics
made of cotton, viscose, linen, silk and wool), synthetic fabrics such as
those
made of polymeric fibers of synthetic origin a;> well as those made of both
natural and synthetic fibers. Indeed, the compositions of the present
invention
may be used on synthetic fibers despite a standing prejudice against the use
of
hypohalite bleaches, especially hypochiorite bleaches, on synthetic fibers, as
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evidenced by warning on labels of commercially available hypochiorite bleaches
and clothes.
Background art
Bleach-containing compositions based on hypochlorite bleach or peroxygen
bleach suitable for bleaching fabrics have been described in the art.
EP-A-622 451 discloses compositions comprising hypochlorite, sodium
hydroxide, a bleach stable perfume and a buffering system whereby the pH of
the diluted composition is buffered to a constant value throughout use,
comprising carbonate andlor silicate. However, the use of a borate andlor
boric
acid and a surfactant, as described herein, is not disclosed.
EP-A-0 824 147 discloses liquid bleaching compositions comprising a hypohaiite
bleach and a polymer. The composition may further comprise a boron salt as pH
buffering component. However, the use of a borate and/or boric acid and a
surfactant, as described herein, is not disclosed.
EP-A-0 781 840 discloses composition comprising hypochlorite and a
metaborate as a pH buffering means. However, the use of a combination of a
borate andlor boric acid and a surfactant, as described herein, is not
disclosed.
Summary of the invention
The present invention encompasses the use of a borate andlor boric acid and a
surfactant as a fabric protective system in a bleaching composition to treat
fabrics, whereby good fabric yellowing-prevention performance andlor good
fabric safety is achieved.
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In a preferred embodiment of the present invention the surfactant is selected
from the group consisting of alkyl afkoxyiated sulphate surfactants, alkyl
alkoxylated sulphonate surfactants, alkyl alko>cyiated carboxylate
surfactants,
alkoxylated nonionic surfactants, fatty acid surfactants, amineoxide
surfactants,
betaine surfactants and quaternary ammonium surfactants, or a mixture thereof.
Detailed description of the invention
The fabric protective system as described herein is used in a bleaching
composition. Said fabric protective system may be added to said bleaching
composition just prior to the use of said bleaching composition or at the time
of
manufacture of said bleaching composition.
The bleaching compositions may be formulated either as solids or liquids.
In the case where the bleaching compositions are formulated as solids, for
example as granules, tablets or powders, they are preferably applied on the
fabrics to be bleached according to the present invention in a liquid form,
i.e.,
solid compositions are used in combination with an appropriate solvent,
typically
water.
In the case where the bleaching compositions are formulated as liquids
including
gel and paste form, the bleaching compo:;itions are preferably but not
necessarily formulated as aqueous composition;>. Liquid bleaching compositions
are preferred herein for convenience of u;>e. Preferred liquid bleaching
compositions of the present invention are aqueous and therefore, preferably
comprise water in an amount of from 60% to 98%, more preferably of from 80%
to 97% and most preferably 85% to 97% by weight of the total composition.
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Bleach
The fabric protective system of the present invention is used in a composition
comprising a bleach. Any bleach known to those skilled in the art may be
suitable for use herein. Preferred bleaches include any hypohalite bleach, as
well as any peroxygen bleach.
Suitable hypohalite bleaches may be provided by a variety of sources,
including
bleaches that lead to the formation of positive halide ions and/or hypohalite
ions,
as well as bleaches that are organic based sources of halides such as
chloroisocyanurates.
Suitable hypohalite bleaches for use herein include the alkali metal and
alkaline
earth metal hypochlorites, hypobromites; hypoiodites, chlorinated trisodium
phosphate dodecahydrates, potassium and sodium dichioroisocyanurates,
potassium and sodium trichiorocyanurates, N-chioroimides, N-chloroamides, N-
chloroamines and chlorohydantoins.
For the bleaching compositions herein, the preferred hypohaiite bleaches among
those described above are the alkali metal or alkaline earth metal
hypochlorites
selected from the group consisting of sodium, potassium, magnesium, lithium
and calcium hypochlorites, and mixtures thereof. Sodium hypochlorite is the
most preferred hypohaiite bleach.
Suitable peroxygen bleaches to be used herein are hydrogen peroxide, water
soluble sources thereof, or mixtures thereof. A hydrogen peroxide source
refers
to any compound that produces perhydroxyl ions when said compound is in
contact with water.
Suitable water-soluble sources of hydrogen peroxide for use herein include:
percarbonates; persilicates; persulphates, such as monopersulfate; perborates;
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peroxyacids, such as diperoxydodecandioic acid (DPDA), magnesium perphtalic
acid, periauric acid, perbenzoic and alkyiperbenzoic acids, hydroperoxides,
aliphatic and aromatic diacyi peroxides; and mixtures thereof. .Preferred
peroxygen bleaches herein are hydrogen peroxide, hydroperoxide andlor diacyl
peroxide. Hydrogen peroxide is the most preferred peroxygen bleach herein.
Suitable hydroperoxides for use herein are t~ert-butyl hydroperoxide, cumyl
hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-
monohydroperoxide, tart-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-
dihydroperoxide.
Suitable aliphatic diacyi peroxides for use herein are dilauroyl peroxide,
didecanoyl peroxide, dimyristoyl peroxide, or mixfures thereof. Suitable
aromatic
diacyi peroxide for use herein is for example dibenzoyf peroxide.
Accordingly, the bleaching compositions according to the present invention may
typically comprise from 0.01 % to 20%, preferably from 0.25% to 15%, more
preferably from 0.5% to 8% and most preferably 'From 1 % to 6% by weight of
the
total composition of a bleach.
Borate andlor boric acid
The first essential ingredient of the fabric protective system of the present
invention for use in a bleaching composition is a borate or boric acid or a
mixture
thereof.
Suitable borates include alkali metal salts of borates, and mixtures thereof.
Suitable alkali metal salts of borates include alkali metal salts of
metaborate,
tetraborate, octoborate, pentaborate, dodecaborate, borontrifluoride and alkyl
borates containing from 1 to 12, preferably from 1 to 4 carbon atoms.
Preferred
alkyl borate includes methyl borate, ethyl borate and propyi borate.
Particularly
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preferred herein are the alkali metal salts of metaborate, such as sodium
metaborate, potassium metaborate, or mixtures thereof.
Borates like sodium metaborate and sodium tetraborate are commercially
available from Borax and Societa Chimica Larderello under the name sodium
metaborate and Borax.
The bleaching compositions according to the present invention preferably
comprise from 0.01 % to 10%, more preferably from 0.1 % to 5%, even more
preferably from 0.5% to 3%, and most preferably from 0.5% to 1.5% by weight of
the total composition of said borate or boric acid or a mixture thereof.
Surfactant
The second essential ingredient of the fabric protective system of the present
invention for use in a bleaching composition is a surfactant.
Preferred surfactants are selected from the group consisting of alkyl
alkoxylated
sulphate surfactants, alkyl aikoxylated suiphonate surfactants, alkyl
alkoxylated
carboxylate surfactants, alkoxylated nonionic surfactants, tatty acid
surfactants,
amineoxide surfactants, betaine surfactants and quaternary ammonium
surfactants, or a mixture thereof.
Suitable alkyl alkoxyiated sulphate surfactants for use herein are according
to
the formula RO{A)mS03M wherein R is an unsubstituted Cg-C2p alkyl or
hydroxyalkyl group having a Cg-C20 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1 g alkyl or hydroxyalkyl, A is an
ethoxy or propoxy or butoxy unit, m is greater than zero, typically between
0.5
and 6, more preferably between 0.5 and 3, and M is H or a cation which can be,
for example, a metal cation (e.g., sodium, potassium, lithium, calcium,
magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
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ethoxyiated sulfates as well as alkyl propoxyi<~ted sulfates are contemplated
herein. Specific examples of substituted ammonium cations include methyl-,
dimethyl-, trimethyl-ammonium and quaternary' ammonium cations, such as
tetramethyl-ammonium, dimethyl piperdinium and cations derived from
alkanoiamines such as ethylamine, diethyiamine, triethylamine, mixtures
thereof,
and the like. Exemplary surfactants are C12-~Clg alkyl polyethoxylate (1.0)
sulfate, C12-ClgE(1.0)M}, C12-Clg alkyl poly~ethoxylate (2.25) sulfate, C12-
CIgE(2.25)M), C12-C1g alkyl poiyethoxylate (3.0) sulfate C12-CIgE(3.0), and
C12-Clg alkyl poiyethoxylate (4.0) sulfate C12-C~gE(4.0)M, wherein M is
conveniently selected from sodium and potassium.
Suitable alkyl aikoxyfated sulphonate surfactants. for use herein are
according to
the formula R(A)mS03M wherein R is an unsubstituted Cg-C2p alkyl or
hydroxyalkyl group having a Cg-C20 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1~; alkyl or hydroxyalkyl, A is an
ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6,
more
preferably between 0.5 and 3, and M is H or a cation which can be, for
example,
a metal cation (e.g., sodium, potassium, lithium, calcium; magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxyiated suiphonates as
well as alkyl propoxylated sulphonates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium cations, ;>uch as tetramethyl-ammonium,
dimethyl piperdinium and cations derived ifrom aikanoiamines such as
ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
Exemplary surfactants are C12-C1g alkyl polyetlhoxyiate (1.0) sulphonate, C12-
CIgE(1.0)M}, C12-C1g alkyl polyethoxyiate (2.25) sulphonate, C12-
CIgE(2.25)M), C12-C1g alkyl polyethoxylate (3~.0) sulphonate C12-CIgE(3.0},
and C12-C1g alkyl polyethoxyiate (4.0) sulphortate C12-CIgE(4.0}M), wherein
M is conveniently selected from sodium and potassium.
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Suitable alkyl alkoxyiated carboxyiate surfactants for use herein are
according to
the formula RO(A)mC02M wherein R is an unsubstituted Cg-C20 alkyl or
hydroxyaikyl group having a Cg-C20 alkyl component, preferably a C12-C20
alkyl or hydroxyalkyl, more preferably C12-C1g alkyl or hydroxyalkyl, A is an
ethoxy or propoxy or butoxy unit, m is greater than zero, typically between
0.5
and 6, more preferably between 0.5 and 3, and M is H or a ration which can be,
for example, a metal ration (e.g., sodium, potassium, lithium, calcium,
magnesium, etc.), ammonium or substituted-ammonium ration. Alkyl
ethoxylated carboxyiates as well as alkyl propoxyiated carboxylates are
contemplated herein. Specific examples of substituted ammonium rations
include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium
rations, such as tetramethyl-ammonium, dimethyl piperdinium and rations
derived from aikanolamines such as ethylamine, diethylamine, triethylamine,
mixtures thereof, and the like. Exemplary surfactants are C12-C1g alkyl
polyethoxylate { 1.0) carboxylate, C' 2-C1 gE( 1.0)M), C 12-C1 g alkyl
polyethoxylate (2.25) carboxyiate, C12-CIgE(2.25)M), C12-C1g alkyl
polyethoxyiate {3.0) carboxylate C12-CIgE(3.0), and C12-C1g alkyl
polyethoxylate (4:0) carboxyiate C12-CIgE(4.0)M), wherein M is conveniently
selected from sodium and potassium.
Suitable alkoxylated nonionic surfactants for use herein include capped and
non-capped alkoxylated nonionic surfactants. Suitable non-capped aikoxyiated
nonionic surfactants are non-capped ethoxylated nonionic surfactants according
to the formula RO-(C2H40)nH, wherein R is a C6 to C22, preferably a Cg to
C22 alkyl chain or a Cg to C2g alkyl benzene chain, and wherein n is from 0 to
20, preferably from 1 to 15 and, more preferably from 2 to 15 and most
preferably from 2 to 12. The preferred R chains for use herein are the Cg to
C22
alkyl chains. Propoxylated, butoxylated, ethoxylbutoxyiated,
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ethoxylpropoxylated, butoxy/propoxyiated and ethoxylbutoxylpropoxylated
nonionic surfactants may also be used herein instead of the ethoxylated
nonionic surfactants as defined herein above or together with said
surfactants.
Accordingly suitable non-capped ethoxylated nonionic surfactants for use
herein
are DobanolO 91-2.5 (HLB= 8.1; R is a mixture of Cg and C11 alkyl chains, n is
2.5), or Lutensoi~ T03 (HLB=8; R is a C13 alkyl chains, n is 3), or Lutensol~
A03 (HLB=8; R is a mixture of C13 and C15 alkyl chains, n is 3), or Tergitol0
25L3 (HLB= 7.7; R is in the range of C12 to C15 alkyl chain length, n is 3),
or
Dobanol~ 23-3 (HLB=8.1; R is a mixture of C12 and C13 alkyl chains, n is 3},
or
DobanolC~ 23-2 (HLB=6.2; R is a mixture of C12 and C13 alkyl chains, n is 2),
or
Dobanol~ 45-7 (HLB=11.6; R is a mixture of C14 and C15 alkyl chains, n is 7}
Dobanol~ 23-6.5 (HLB=11.9; R is a mixture of C12 and C13 alkyl chains, n is
6.5), or Dobanol~ 25-7 (HLB=12; R is a mixture' of C12 and C15 alkyl chains, n
is 7), or Dobanol~ 91-5 (HLB=11.6; R is a mixture of Cg and C11 alkyl chains,
n
is 5}, or Dobanol~ 91-6 (HLB=12.5 ; R is a mixture of Cg and C11 alkyl chains,
n
is 6), or DobanolC~ 91-8 (HLB=13.7 ; R is a mixture of Cg and C11 alkyl
chains, n
is 8), DobanolO 91-10 (HLB=14.2 ; R is a mixture of Cg to C11 alkyl chains, n
is
10), Dobanol~ 91-12 (HLB=14.5 ; R is a mixture of Cg to C11 alkyl chains, n is
12), or mixtures thereof. Preferred herein are Lutensol~ T03, or Lutensoi~
A03,
or Tergitol~ 25L3, or Dobanol~ 23-3, or Dobanol~ 23-6.5, or DobanolO 45-7,
Dobanol~ 91-8, or Dobanol~ 91-10, or Dobanoi~ 91-12, or mixtures thereof.
These DobanolO surfactants are commercially available from SHELL. These
Lutensol4 surfactants are commercially av~ulable from BASF and these
Tergitol~ surfactants are commercially available from UNION CARBIDE.
Suitable capped alkoxylated non-ionic surfactants, having the terminal
hydroxyl
group capped, are according to the formula : R:(A)n-O-R1 where R and R1 are
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independently a Cg to C22, preferably a Cg to C22 alkyl chain or a Cg to C2g
alkyl benzene chain; A is an ethoxy or propoxy or butoxy unit; and n is from 0
to
20, preferably from 1 to 15 and, more preferably from 2 to 15 and most
preferably from 2 to 12.
Suitable chemical' processes for preparing the alkoxyiated nonionic
surfactants
for use herein include condensation of corresponding aicohois with aikylene
oxide, in the desired proportions. Such processes are well-known to the person
skilled in the art and have been extensively described in the art.
Suitable fatty acid surfactants to be used herein are according to the formula
R-CH2COOM; with R being a linear or branched C1-C30, preferably C12-C16
group; M being H or a metal ion, preferably an alkaline earth ion, more
preferably Sodium or Potassium. An exemplary fatty acid surfactant is Prifac4,
which is a C12/C14/C1g fatty acid available from Unichema.
Suitable amine oxides to be used herein are according to the following formula
R1R2R3N0 wherein each of R1, R2 and R3 is independently a saturated
substituted or unsubstituted, linear or branched hydrocarbon chains of from 1
to
30 carbon atoms. Preferred amine oxide surfactants to be used according to the
present invention are amine oxides having the following formula : R1 R2R3N0
wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms,
preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8
to
12; and wherein R2 and R3 are independently substituted or unsubstituted,
linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms,
preferably from 1 to 3 carbon atoms, and more preferably are methyl groups. R1
may be a saturated substituted or unsubstituted linear or branched hydrocarbon
chain. Suitable amine oxides for use herein are for instance natural blend Cg-
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C1p amine oxides as well as C12-C16 amine oxides commercially available from
Hoechst.
A generic formula for betaine surfactants for use herein {i.e., betaine andlor
sulfobetaine) is
R1-N+~R2){R3)R4X_
wherein R1 is a hydrophobic group; R2 is hydrogen, C1-Cg alkyl, hydroxy alkyl
or other substituted C1-Cg alkyl group; R3 is C1-Cg alkyl, hydroxy alkyl or
other
substituted C1-Cg alkyl group which can also be joined to R2 to form ring
structures with the N, or a C1-C6 carboxylic acid group or a C1-Cg sulfonate
group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic
group
and is typically an alkylene, hydroxy alkjrlene, or polyalkoxy group
containing
from 1 to 10 carbon atoms; and X is the hydrophilic group which is a
carboxylate
or sulfonate group, preferably sulfonate group.
Preferred hydrophobic groups R1 are aliphatic or aromatic, saturated or
unsaturated, substituted or unsubstituted hydrocarbon chains that can contain
linking groups such as amido groups, ester groups. More preferred R1 is an
alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 7 8,
and
more preferably from 10 to 16. These simple alH;yl groups are preferred for
cost
and stability reasons. However, the hydrophobic group R1 can also be an amido
radical of the formula : Ra-C{O)-NRb-{C{Rc)2)n~, wherein Ra is an aliphatic or
aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon
chain containing from 8 up to 20 carbon atoms, preferably an alkyl group
containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably
up to 18; Rb is either a hydrogen a short chain alkyl or substituted alkyl
containing from 1 to 4 carbon atoms, preferably a group selected from the
group
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consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and
mixtures thereof, more preferably methyl or hydrogen; Rc is selected from the
group consisting of hydrogen and hydroxy groups, and m is from 1 to 4,
preferably from 2 to 3, more preferably 3, with no more than one hydroxy group
in any (C(Rc)2) moiety.
Preferred R2 is hydrogen, or an alkyl or substituted alkyl containing from 1
to 4
carbon atoms, preferably a group selected from the group consisting of methyl,
ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more
preferably methyl. Preferred Rg is a C1-C4 carboxylic acid group, a C1-C4
suifonate group, or an alkyl or substituted alkyl containing from 1 to 4
carbon
atoms, preferably a group selected from the group consisting of methyl, ethyl,
propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more
preferably
methyl. Preferred R4 is (CH2)n wherein n is an integer from 1 to 10,
preferably
from 1 to 6, more preferably is from 1 to 3.
Some common examples of betainelsufphobetaine are described in U.S. Pat.
Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
Examples of particularly suitable alkyldimethyl betaines include coconut-
dimethyl
betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-
dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyf
dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl
dimethyl betaine. For example Coconut dimethyl betaine is commercially
available from Seppic under the trade name of Amonyi 2fi5~. Lauryl betaine is
commercially available from Albright 8~ Wilson under the trade name Empigen
BB/L~.
A further example of betaine is Lauryl-immino-dipropionate commercially
available from Rhone-Poufenc under the trade name Mirataine H2C-HA ~.
~,.
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Examples of particularly suitable suifobetaine surfactants include tallow
bis(hydroxyethyi) suiphobetaine, cocoamido propyl hydroxy sulfobetaines which
are commercially available from Rhone Poulenc and Witco, under the trade
name of Mirataine CBS~ and Rewoteric AM CAS 15~ respectively.
Further examples of amidobetaineslamidosulfobetaine include
cocoamidoethylbetaine, cocoamidopropyl betaine or C1 p-C14 fatty
acylamidopropylene(hydropropylene}suifobetaine. For example C1p-C14 fatty
acyiamidopropylene(hydropropylene)sulfobetaine is commercially available from
Sherex Company under the trade name "Varion CAS~ sulfobetaine".
Suitable quaternary ammonium surfactants for use herein are according to the
formula : R1 R2R3R4N+ X-, wherein X is a counteranion such as halogen,
methyl sulphate, methyl sulphonate, or hydroxide; R1 is a saturated or
unsaturated, substituted or unsubstituted, li~~ear or branched alley! group
containing from 1 to 30 carbon atoms, preferably from 12 to 20, more
preferably
from 8 to 20; and R2, R3 and R4 are independently hydrogen, or saturated or
unsaturated, substituted or unsubstituted, linear or branched alkyl groups
containing from 1 to 4 carbon atoms, preferably from 1 to 3 and more
preferably
methyl. In highly preferred quaternary ammonium surfactants herein R1 is a
C1p-C1g hydrocarbon chain, most preferably C12, C14,,,or Clg; and R2, R3
and R4 are ail three methyl, and X is halogen, preferably bromide or chloride,
most preferably bromide.
Examples of quaternary ammonium surfactants are myristyl trimethylammonium
methyl sulphate, cetyl trimethylammonium methyl sulphate, lauryi trimethyl
ammonium bromide, stearyl trimethyl ammonium bromide (STAB), cetyt trimethyl
ammonium bromide (CTAB) and myristyl trimethyl ammonium bromide (MTAB).
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Highly preferred herein are lauryl trimethyl ammonium salts. Such trimethyl
quaternary ammonium surfactants may be commercially available from Hoechst,
or from Albright & Wilson under the trade name Empigen CM~.
The bleaching compositions according to the present invention preferably
comprise from 0.01 % to 50%, more preferably from 0.03% to 40%, even more
preferably from 0.07% to 20%, and most preferably from 0.1 % to 10% by weight
of the total composition of said surfactant.
Cotton fabrics contain cellulose (i.e., (CgH1005)n)- When a bleach-containing
composition, e.g., a hypochlorite-containing composition, is used to bleach a
cotton fabric, the bleach may react with the hydroxyl substituents of
cellulose in
position 6, 2, 3 and 5 of the cellulosic ring and thus may introduce new
functional groups like carbonyfic, aldehydic and/or carboxylic groups.
Synthetic
fabrics may be made of various synthetic materials like polyamide-elasthane
that
also comprise hydroxyl groups capable of being oxidized by bleach.
It has now been found that a borate and/or boric acid and a surfactant as
described herein act together as a fabric protective agent for use in a
bleaching
composition. Compared to a bleach-containing composition comprising a fabric
protective system other than that described by the present invention or no
fabric
protective system at all, the fabric yellowing-prevention performance and/or
the
fabric safety performance is further improved.
Whilst not wishing to be bound by theory, it is believed that the fabric
protective
system consisting of a borate andlor boric acid and a surfactant as described
herein, for use in a bleaching composition is capable of protecting, i.e.,
esterifying and/or complexing, the hydroxyl groups present on the fibers of a
treated fabric. Otherwise, said hydroxyl groups would be subject to oxidation
by
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17
the bleach, e.g., hypochlorite bleach, which leads to fabric yellowing andlor
fabric damages.
The fabric yellowing-prevention and/or fabric safety performance beneft can be
achieved when using the fabric protective systf;m of the present invention in
a
liquid bleaching composition which is applied in a neat form, e.g., as a
pretreater, as well as in a solid or liquid bleaching composition which is
applied
in a diluted form, e.g., typical dilution with wafer in conventional washing
conditions.
indeed, the yellowing-prevention effect and/or safety effect of the present
invention can be evaluated by comparing the' composition according to the
present invention to a bleach-containing composition comprising a fabric
protective system other than that claimed by the present invention.
By "further improved fabric yellowing-prevention", it is meant herein that the
yellowing of fabrics, i.e., the appearance of a yellowish tone of said
fabrics, that
occurs by using the bleach-containing compo:;itions of the present invention
(e.g., those containing a hypohaiite bleach, e.g., hypochlorite) is reduced,
compared to the yellowing that occurs by using a bleach-containing composition
comprising a fabric protective system other than that described by the present
invention.
The degree of yellowing can be determined by both visual and instrumental
grading. Visually, the difference in yellowing betrNeen items treated with
different
compositions can be determined by a team of expert panelists. Instrumentally,
the assessment can be determined with the help of Colorimeters such as Ganz
Griesser~ instruments (e.g., Datacoior~ SpectrafiashC~ SF 500, Machbet White-
eye~ 500) or a ZEISS ELREPHO~ or others which are available for instance
from Hunterlab~ or Gardnert~.
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18
By "further improved fabric safety", it is meant herein that the damage caused
on
fabric by using the bleach-containing compositions of the present invention
(e.g.,
those containing a hypohalite bleach, e.g., hypochlorite) is reduced, compared
to the damage caused by using a bleach-containing composition comprising a
fabric protective system other than that described by the present invention.
Fabric safety may be evaluated by different test methods including the degree
of
polymerisation test method according to UNI (Ente Nazionale Italiano di
Unificazione} official method UNI 8282-Determinazione delta viscosity
intrinseca
in soluzione di cuprietilendiammina (CED).
The fabric protective system as described herein may be used in liquid
bleaching compositions, having a pH of from 0 to 14. The borate may also act
as
a pH buffering means.
(n a preferred embodiment of the present invention wherein the bleaching
composition herein is a composition comprising an alkali metal hypochlorite as
the bleach, the boron salt provides a prolonged through-the-bleach buffering
action, i.e., maintains the pH of the bleaching solution at a pH at least 8,
preferably at least 8.5, more preferably at least 9.5 for a longer period of
time,
throughout the treatment, e.g., at a dilution level of 200:1
(water:composition),
as compared to the buffering action obtained with the same composition without
said boron salt.
It has been found that the buffering action of the boron salt also affects the
hypochloritel hypochlorous acid such that the shift of hypochlorite into
hypochlorous acid is reduced. It is believed that by controlling this
equilibrium,
fabric damage and/or fabric yellowing can be reduced.
i ~'
CA 02341188 2001-02-19
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19
In an embodiment, wherein the bleaching compositions herein are liquid and
comprise a hypohalite bleach, typically an alkali metal hypochlorite, the
recommended pH range of the ,bleaching composition is from 8 to 14, preferably
from 8.5 to 14, more preferably from 9 to 13.5, and even more preferably from
9.5 to 13.5. It is in this alkaline pH range that the optimum stability and
performance of the hypohalite bleach, e.g., hypo~chlorite, is obtained.
if appropriate, the compositions of the present invention may comprise an
alkalinity source to adjust the pH of said composition. The bleaching
compositions herein may comprise up to 10%, preferably of from 0.04% to 5%
and more preferably of from 0.1 % to 2% by wE:ight of the total composition of
said alkalinity source.
Suitable alkalinity sources for use herein are they caustic alkalis, such as
sodium
hydroxide, potassium hydroxide andlor lithium hydroxide, andlor the alkali
metal
oxides such, as sodium andlor potassium oxide or mixtures thereof. A preferred
alkalinity source is a caustic alkali, more preferably sodium hydroxide andlor
potassium hydroxide.
Other suitable alkalinity sources include ammonia, ammonium carbonate and
hydrogen carbonate.
In an embodiment, wherein the bleaching compositions herein are liquid and
comprise a peroxygen bleach, the recommended pH range of the bleaching
composition to achieve good stability is from 1 to 9, preferably between pH 1
and 8, more preferably between pH 1 and 7 and most preferably between pH 1
and 6.
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If appropriate, the bleaching compositions herein may further comprise an acid
to adjust the pH of said composition. The bleaching compositions of the
present
invention may comprise up to 10%, preferably of from 0.04% to 5% and more
preferably of from 0.1 % to 2% by weight of the total composition of said
acid.
Suitable acids for use herein may be organic acids, inorganic acids, or
mixtures
thereof. Preferred organic acids are citric, malefic, oxalic succinic,
tartaric acids
or mixtures thereof. A preferred inorganic acid is sulphuric acid.
Optional pH bufferinct components
The bleaching compositions according to the present invention may further
comprise as an optional, but preferred ingredient, a pH buffering component in
addition to the pH buffering action that the borate may have. Particularly
useful
are alkali metal salts of carbonates, polycarbonates, sesquicarbonates,
silicates,
polysilicates, phosphonates, stannates, alluminates or mixtures thereof. The
preferred alkali metal salts to be used herein are sodium and potassium salts.
Particularly preferred are alkali metal salts of carbonate. The preferred
alkali
metal salt of carbonate is sodium carbonate.
The bleaching compositions of the present invention may comprise up to 5%,
preferably from 0.01 % to 4% and more preferably from 0.02% to 3% by weight
of the total composition of a pH buffering component.
Other optional ingredients
The bleaching compositions according to the present invention may further
comprise other optional ingredients, such as bleach-stable surfactants,
pigments, enzymes, dyes, optical brighteners, solvents, polymers, stabilizing
agents, chelating agents, radical scavengers, bleach activators, hydrotropes
and
the like.
I ill
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21
Bleach activators
!n an embodiment of the present invention where the bleaching compositions
herein comprise a peroxygen bleach, said compositions may comprise a bleach
activator up to a level of 10% by weight of the total composition. Suitable
bleach
activators to be used herein include those belonging to the class of esters,
amides, imides, or anhydrides. Examples of suitable compounds of this type are
disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for
their formation into a prilled form is described in European Published Patent
Application EP-A-62 523. Suitable examples of such compounds to be used
herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl
hexanoyloxybenzene suiphonate; diperoxy dodlecanoic acid as described for
instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for
instance in US 4 259 201 and n-nonanoyloxybe~nzenesulphonate (NOBS). Also
suitable are N-acyl caprolactams selected from the group consisting of
substituted or unsubstituted benzoyi caprol;actam, octanoyl caprolactam,
nonanoyl caprolactam, hexanoyl caprolacilam, decanoyi caprolactam,
undecenoyl caprolactam, focmyl caprolactam, acetyl caprolactam, propanoyl
caproiactam, butanoyi caprolactam pentanoyi ca~prolactam or mixtures thereof.
A
particular family of bleach activators of interest was disclosed in EP 624
154,
and particularly preferred in that family is aceiyi methyl citrate (ATC).
Acetyl
triethyl citrate has the advantage that it is environmental friendly as it
eventually
degrades into citric acid and alcohol. Furthermore, acetyl triethyi citrate
has a
good hydrolytical stability in the product upon storage and it is an efficient
bleach
activator.
Stabilizing agents
The bleaching compositions of the present invention may further comprise a
stabilizing agent, preferably a radical scavenger, a chelating agent or a
mixture
thereof. Naturally, for the purpose of the invention, the stabilizing agents
have to
be stable to the hypohalite bleach. In an embodiment wherein the bleaching
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22
compositions according to the present invention comprise a hypohalite bleach
said stabilizing agents are highly preferred.
Highly preferred stabilizing agents are radical scavengers atone, or in
combination with a chelating agent.
Suitable radical scavengers for use herein include aromatic radical scavengers
comprising an unsaturated ring system of from 3 to 20, preferably of from 3 to
18
and more preferably of from 5 to 14 carbon atoms and having a double bond set
comprising a total of 4n+2 electrons, wherein n is an integer of from 0 to 4,
preferably of from 1 to 3. Indeed said aromatic radical scavengers include
benzene derivatives, naphthalene derivatives, annulene derivatives,
cyciopentadiene derivatives, cyclopropene derivatives and the like, especially
aryl carboxylates and/or aryl sulfonates.
Particularly suitable radical scavengers (aryl carboxylates, aryl sulphonate
and
derivatives thereof) for use in the present invention have one of the
following
formulas:
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23
(a)
Y
X
Z ~ ' C:00- M+
(b)
Y
X
Z ~ ~ ~ ~>03- M+
c)
X C~Z_M+
Y~ J
Z
d)
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24
X S~3_M+
Y-t~-% )
Z
wherein each X, Y, and Z are -M, -COO-M+, -CI, -Br, -SOg-M+, -N02, -OCH3, or
a C~ to Cep primary and secondary alkyl groups and M is H or an alkali metal,
or mixtures thereof. Examples of these components include pyromellitic acid,
i.e.
where X, Y and Z are -COO-H+; hemimeilitic acid, trimellitic acid, i.e. where
X
and Y are -COO-H+ and Z is H. Preferred to be used in the present invention as
radical scavengers are phthalic acid; sulfophthalic acid; other mono-
substituted
phthalic acids; di-substituted benzoic acids; alkyl-, chloro-, bromo-, sulfo-,
nitro-
and alkoxy- benzoic acids, i.e. where Y and Z are -H and X is a C~ to C~0
primary and secondary alkyl groups, -CI, -Br, -SOg-H+, -N02 or -OCH3 (anisic
acid) respectively and substituted sulfonic acids. Highly preferred examples
of
the radical scavengers useful in the present invention are benzoic acid,
toiuic
acid, 4-toluene sulfonic acid, 3-nitro benzoic acid, 2 n-octyl benzoic acid, 2
n-
octyl sulfonic acid, anisic acid or mixtures thereof. Most preferred herein
are n-
anisic acid, benzoic acid, methoxy benzoic acid andlor 3-nitrobenzoic acid.
The radical scavengers described above are the acidic form of these species,
i.e., M is H. it is intended that the present invention also covers the salt
derivatives of these species, i.e., M is an alkali metal, preferably sodium or
potassium. Ln fact, where the pH of the bleaching compositions of the present
invention is in the alkaline range, the radical scavengers of the present
invention
exist primarily as the ionized salt in the aqueous composition herein. The
anhydrous derivatives of certain species described herein above can also be
f~
CA 02341188 2001-02-19
WO 00/15744 PCTlUS99121588
used in the present invention, e.g., pyromellitic dianhydride, phthalic
anhydride,
suiphthalic anhydride and the like.
Suitable cheiating agents for use herein may be any of those known to those
skilled in the art such as the ones selectf:d from the group comprising
phosphonate chelating agents, phosphate chelating agents, poiyfunctionally-
substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids,
or
mixtures fhereof.
Suitable phosphonate chelating agents to be used herein may include alkali
metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene
phosphonate), as well as amino phosphonate compounds, including amino
aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates
(NTP), ethylene diamine tetra methylene phosplhonates, and diethylene triamine
yenta methylene phosphonates (DTPMP). Then phosphonate compounds may
be present either in their acid form or as salts of different cations on some
or all
of their acid functionaiities. Preferred phosphonate chelating agents to be
used
herein are diethylene triamine yenta methylene phosphonate (DTPMP) and
ethane 1-hydroxy diphosphonate (HEDP). Suclh phosphonate chelating agents
are commercially available from Monsanto under the trade name DEQUEST~~
Suitable phosphate chelating agents are as follows: Phosphonic acid can be
condensed in the reaction
0 0 0 0
II II Il II
HO-P-OH + OH-P-OH ----= HO-P-O-P-HO+2H20
I I I I
OH OH HO HO
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26
The reaction can be repeated with any of the reactive OH groups, and
phosphate ingredients are obtained which can be
- linear or branched polyphosphates of structure
O O
MO P O P OM
n
MO OR
-when R is M or
O
il
O P OM
m
OR
- when M is a counterion, preferably alkali metal;
- when 0 <_ n+m < 500 (if n+m = 0 then the compound is phosphonic acid)
- cyclic polyphosphates (also referred to as metaphosphates), of structure
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27
O O
P O p O
n
OM OR
-when R is M or
O
O P OM
m
OR
-if R is
0
O P OM
m
OR
the phosphate compound contains both cycles and branched chain, and can be
referred to as an ultraphosphate.)
- where M is a counte~ion, preferably an alkali metal
- where 0 <_ n+m < 500
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28
All such phosphate ingredients are suitable for use herein, and preferred are
linear phosphate ingredients (i.e., R is M) where n is 1 (pyrophosphate) and n
is
2 {tripolyphosphate {STPP)), most preferably where n is 2. The most commonly
available form of this phosphate is where M is Sodium.
Phytic acid, which is a chefating agent particularly suitable for use herein,
is a
hexa-phosphoric acid that occurs naturally in the seeds of many cereal grains,
generally in the form of the insoluble calcium-magnesium salt. It may also be
derived from corn steep liquor. Commercial grade phytic acid is commercially
available from J.T.Baker Co., e.g., as a 40% aqueous solution. It is intended
that
the present invention covers the acidic form of phytic acid as well as alkali
metal
salt derivatives thereof, particularly sodium or potassium salts thereof.
Sodium
phytate is available from Jonas Chemical Co (Brooklyn, N.Y.). In fact since
the
typical pH of the compositions of the present invention are in the alkaline pH
range, the phytic acid component exists primarily as the ionized salt in the
liquid
compositions herein even if it is added in its acidic form. Mixtures of such
salts of
phytic acid are also covered.
Polyfunctionaily-substituted aromatic chelating agents may also be useful in
the
compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to
Connor et al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine
N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or
substitutes
ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic
acids, especially the {S,S) isomer have been extensively described in US
patent
4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine N, N'-
disuccinic acids is, for instance, commercially available under the tradename
ssEDDS~ from Palmer Research Laboratories.
i'
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29
Particularly preferred chelating agents for use herein are phosphate chelating
agents like sodium tripoiyphosphate, sodium pyrophosphate, phytic acid, and
mixtures thereof.
Typically, the bleaching compositions according to the present invention may
comprise from 0.01 % to 10%, preferably from 0.01 % to 8% by weight, more
preferably from 0.1 % to 5%, and most preferably from 0.2% to 3% by weight of
the total composition of a stabilising agent.
Optional surfactants
The bleaching compositions of the present invention may further comprise
another surfactant in addition to the surfactants which are part of the fabric
protective system. Said surfactant may be present in the bleaching
compositions
according to the present invention in amounts up to 30%, preferably of from
0.1 % to 20% and more preferably of from 0.1 % to 10% by weight of the total
composition.
Surtactants for use herein include other anionic surfactants, nonionic
surfactants, cationic surfactants, amphoteric surfactants, zwitterionic
surfactants,
and mixtures thereof. Naturally, for the purpose of the invention, the
additional
surfactants have to be stable to the used bleach.
Optional polymers
An optional component of the bleaching cornpositions herein is a polymer.
Naturally, for the purpose of the invention, the polymer has to be stable in
the
presence of the used bleach.
Suitable polymers for use are polymers comprising monomeric units selected
from the group consisting of unsaturated carbexyfic acids, poiycarboxylic
acids,
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sulphonic acids, phosphonic acids and mixtures thereof. Co-polymerisation of
the above monomeric units among them or with other co-monomers such as
styrenesuifonic acid is also suitable
Preferred examples of such polymers are the polymers and co-polymers of
monomeric units selected from the group consisting of acrylic acid, malefic
acid,
vinylsulphonic acid and mixtures thereof. Also suitable for use herein are the
above mentioned polymers and co-polymers which are modified in order to
contain other functional groups such as aminophosphonic andlor phosphonic
units. More preferred polymers are selected from the group consisting of
pofyacrylate polymers, co-polymers of acrylic and malefic acid, co-polymers of
styrene suiphonic acid and malefic acid, and mixtures thereof, preferably
modified with aminophosphonic andlor phosphonic groups.
The molecular weight for these polymers and co-polymers is preferably below
100,000, most preferably between 500 and 50,000. In an embodiment of the
present invention where the bleaching compositions herein comprise a
hypochlorite bleach, the most suitable polymers and co-polymers for use herein
will be soluble in an amount up to 0.1% by weight, in an aqueous composition
comprising 5% by weight of sodium hypochlorite with its pH adjusted to 13 with
sodium hydroxide.
Commercially available polymers, suitable for use herein, are the polyacrylate
polymers sold under the tradename Good-Rite~ from BF Goodrich, Acrysoi~
from Rohm 8~ Haas, Sokalan~ from BASF, Norasoi~ from Norso Haas. Also
suitable for use herein are the co-polymers of styrene sulphonic acid and
malefic
acid, commercially available under the tradename Versaflex~ from National
Starch such as Versafiex 157, as well as Acumer~ terpoiymers from Rohm and
Haas, in particular Acumer~ 37 00. Preferred commercially available polymers
are the polyacrylate polymers, especially the Norasol~ polyacrylate polymers
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37
and more preferred are the polyacryiate poiymerr Norasol~ 410N (MW 10,000)
and the polyacryfate polymer modified with phoaphonic groups Norasoi~ 440N
(MW 4000} and its corresponding acid form Norasol~ QR 784 (MW 4000).
A preferred polymer for use herein is a poly<acrylate polymer modified with
phosphonic groups commercially available under the tradename Norasol~ 440N
(MW 4000) and its corresponding acid form Nonasol~ QR 784 {MW 4000) from
Norso-Haas.
Mixtures of the polymers described herein may also be used in the present
invention.
Polymers herein are preferably present in low announts, i.e., in amounts of up
to
10% by weight, preferably up to 1 %, more prefE~rably from 0.001 % to 0.5% by
weight, most preferably from 0.005% to 0.2% by weight of the liquid
composition.
Optional briQhteners _
The bleaching compositions according to the: present invention may also
comprise a brightener or a mixture thereof as an optional ingredient.
Naturally,
for the purpose of the invention, the brightener has to be stable in the
presence
of the bleach used. The brighteners may be deaired herein to further enhance
the whiteness performance of the bleaching compositions herein:
Brighteners are compounds which have the ability to fluoresce by absorbing
ultraviolet wave-lengths of light and re-emitting visible light. Brighteners,
also
referred to as fluorescent whitening agent (f=WA), have been extensively
described in the art, see for instance EP-A-0 26°.i 041, EP-A-0 322
564, EP-A-0
317 979 or "Fluorescent whitening agents" by A.K. Sarkar, published by
MERROW, especially page 71-72.
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32
Commercial optical brighteners which may be useful in the present invention
can
be classified into subgroups, which include, but are not necessarily limited
to,
derivatives of stilbene, pyrazoiine, coumarin, carboxylic acid,
methinecyanines,
dibenzothiophene-5,5-dioxide, azoies, 5- and 6-membered-ring heterocycles,
and other miscellaneous agents. Examples of such brighteners are disclosed in
"The Production and Application of Fluorescent Brightening Agents", M.
Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical
brighteners which may also be used in the present invention include
naphthlimide, benzoxazoie, benzofuran, benzimidazoie and any mixtures
thereof.
Examples of optical brighteners which are useful in the present bleaching
compositions are those identified in U.S. Patent 4,790,856: These brighteners
include the PHORWHITE~ series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal-UNPACK, Tinopai CBS~ and Tinopal
SBMO available from Ciba-Geigy; Artic White CC~ and Artic White CWD~; the
2-(4-styryl-phenyl)-2H-naptho[1,2-dJtriazoles; 4,4'-bis(1,2,3-triazol-2-yi)-
stiibenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
Specific examples of brighteners useful herein include 4-methyl-7-diethyl-
amino
coumarin; 1,2-bis{-benzimidazol-2-yl)ethyiene; 1,3-diphenyl-pyrazolines; 2,5-
bis(benzoxazol-2-yl}thiophene; 2-styryi-naptho-(1,2-d]oxazole; 2-(stilbene-4-
yl)-
2H-naphtho[1,2-d]triazoie, 3-phenyl-7-(isoindoiinyl) coumarin; 3-methyl-7-
{isoindolinyl) coumarin; 3-chloro-7-(isoindolinyl) coumarin; 4-(isoindoiinyl}-
4'-
methylstilbene; 4-(isoindolinyl)-4'-methoxystilbene; sodium 4-(isoindolinyl)-
4'-
stilbenesulfonate; 4-(isoindolinyl}-4'-phenylstilbene; 4-(isoindolinyl)-3-
methoxy-
4'-methylstilbene; 4-(2-chloroisoindoiinyl}-4'-{2-methylisoindoiinyi)-2,2'-
stilbenedisosulfonic acid; disodium 4,4'-diisoindolinyl-2,2'-stiibene
disulfonate;
4;4'-diisoindolinyl-2,2'-stilbenedisulfonamide; disodium 4,4'-(7,8-dichloro-1-
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33
isoindolinyl)2,2-stilbenedisuifonate; disodium 4,4'-(7-chloro-1-
isoindolinyl)2,2-
stilbenedisulfonate; disodium 4,4'-(6-Isopropoxy-1-isoindolinyl)2,2-
stilbenedisuffonate; disodium 4,4'-(7,8-diisopropyl-1-isoindolinyl)2,2-
stilbenedisulfonate; disodium 4,4'=(7-butoxy-1-isoindolinyl)2,2-
stilbenedisuffonate; disodium 4,4'-(6-trifluoromethyl-1-isoindolinyl}2,2-
stilbenedisulfonate; disodium 4,4'-[6-(1,4,7-trioxanonyl}-1-isoindolinyl)j2,2-
stilbenedisulfonate; disodium 4,4'-(7-methoxymethyl-1-isoindolinyl)2,2-
stilbenedisuffonate; disodium 4,4'-(6-phenyl-1-isoindolinyl)2,2-
stilbenedisulfonate; disodium 4.,4'-(6-naphthyl-1-isoindolinyl)2,2-
stilbenedisuifonate; disodium 4,4'-(6-:methylsulfonyl-1-isoindolinyl)2,2-
stilbenedisuifonate; disodium 4,4'-(7-cyano-1-isoindolinyl)2,2-
stilbenedisuifonate;
and disodium 4,4'-[7-(1,2,3-trihydroxypropyl)-1-isoindolinyl))2,2-
stilbenedisuifonate; disodium 4-isoindolinyl-4'-ethoxy-2,2'-
stilbenedisulfonate;
disodium 4-isoindolinyl-4'-methoxy-2,2'-stilbenedisuifonate; disodium 4-
isoindofinyi-4'-ethoxy-2,2'-stilbenedisulfonamide;; disodium 4-isoindoiinyi-4'-
methyi-2,2'-stilbenedisulfonamide; 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-
2,2'-
stiibenedisulfonic acid and mixture thereof. Se:e also U.S. Patent 3,646,015,
U.S. Patent 3,346,502 and U.S. Patent 3,3513,153 for further examples of
brighteners useful herein.
Indeed one of the functionally equivalent derivative salts of 4,4'-bis(4-
phenyl-2H-
1,2,3-triazol-2-yl)-2,2'-stilbenedisulfonic acid, namely its sodium salt is
available
from Mobay Chemical Corporation, a subsidiary of Bayer AG under the name
Phorvvite~ CAN. The amine salt is available from Molay under the name
Phorwite~ CL solution. The potassium salt is available under the name
Phorwite~ BHC 766.
Other specific examples of optical brighteners u;>eful in the present
invention are
those having the structural formula:
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WO 00/15744 PCT/US99I21588
34
R3 R
H H
C C O N ~O
R2 S03M S~3M R~
wherein R~ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-
methylamino, morphilino, chloro and amino; and M is a salt-forming cation such
as sodium or potassium.
When in the above formula, R~ is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-aniiino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt. This particular brightener species is commercially marketed under the
tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the detergent
compositions
herein. -
When in the above formula, R~ is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-{N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy
Corporation.
When in the above formula, R' is anilino, R2 is morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphifino-s-triazine-
2-
yl)amino]2,2'-stiibenedisulfonic acid, sodium salt. This particular brightener
CA 02341188 2001-02-19
WO 00/15744 PCT/US99/21588
species is commercially marketed under the tradename Tinopal AMS-GX by
Ciba Geigy Corporation.
Other substituted stilbene 2,2'-disulfonic acid derivatives also include 4-4'-
bis (2-
2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under
the
trade name Brightener 49~ or other hydrophilic brighteners Like for example
Brightener 3~ or Brightener 470, also commerci,aily available from Ciba-Geigy.
Further specific examples of brighteners useful in the present invention
include
the polycyciic oxazole derivatives such as benzo-oxazoie derivatives, or
mixtures thereof and particularly preferred herein the benzo-oxazole
derivatives.
An example of such a brightener is benzoxazole;2,2'-(thiophenaldyl)bis having
the following formula C18H10N2O2S, commercially available from Ciba-Geigy
under the trade name Tinopal SOP~. This brightener is almost insoluble in
water, i.e. it has a solubility being lower than 1 gram per liter. Another
example
of such a brightener is bis(sulfobenzofuranyl)biiphenyl, commercially
available
from Ciba-Geigy under the trade name Tinopal PLC~.
Typically the bleaching compositions according to the present invention may
comprise up to 1.0% by weight of the total composition of a brightener or a
mixture thereof, preferably from 0.005% to 0.5°/<>, more preferably
from 0.005%
to 0.3% and most preferably from 0.008% to 0.1 °,io.
Process of bleaching fabrics:
In the present invention, the bleaching composition of the present invention
is
used by applying the composition to the fabric to be treated. The compositions
according to the present invention are preferably used in liquid form.
By "in liquid fom'3" it is meant that liquid compositions can be used per se
in neat
or in diluted form, and solid compositions, for example granules, tablets or
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36
powders, are dissolved in an appropriate solvent, typically water, before use,
i.e., before being contacted to said fabrics.
By "in diluted form", it is meant herein that the compositions for the
bleaching of
fabrics according to the present invention may be diluted with a solvent by
the
user, the preferred solvent is water. Such dilution may occur for instance in
hand
laundry applications as well as by other means such as in a washing machine.
Said compositions can be used at a dilution level of up to 500:1
(soivent:composition), preferably from 5:1 to 200:1 and more preferably from
10:1 to 80:1 {solvent:composition).
Fabrics to be treated herein include, but are not limited to, clothes,
curtains,
drapes, bed linens, bath linens, table cloths, sleeping bags, tents,
upholstered
furniture and the like, andlor carpets.
By "treating a fabric", it is meant herein bleaching andlor disinfecting said
fabric
as the compositions of the present invention comprise a bleach.
In the process of treating (e.g., bleaching) a fabric, a bleaching composition
according to the present invention is contacted with the fabrics to be
treated.
This can be done either in a so-called "pretreatment mode", where a liquid
bleaching composition, as defined herein, is applied neat onto said fabrics
before the fabrics are rinsed, or washed then rinsed, or in a "soaking mode"
where a bleaching composition, as defined herein, is first diluted in an
aqueous
bath and the fabrics are immersed and soaked in the bath, before they are
rinsed, or in a "through the wash mode", where a bleaching composition, as
defined herein, is added on top of a wash liquor formed by dissolution or
dispersion of a typical laundry detergent. !t is also essential in both cases,
that
i 1...
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WO OO/I5744 PCT/IJS99/21588
37
the fabrics be rinsed after they have been contacted with said composition,
before said composition has completely dried off.
The compositions according to the present invention are preferably used on
fabrics in a liquid form. More specifcaily, the process of bleaching fabrics
according to the present invention comprises t;he steps of first contacting
said
fabrics with a bleaching composition according to the present invention, in
its
diluted form, then allowing said fabrics to remain in contact with said
composition, for a period of time suffcient to bleach said fabrics, typically
1 to 60
minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If
said
fabrics are to be washed, i.e., with a conventions! composition comprising at
least one surface active agent, said washing nnay be conducted by contacting
said fabrics at the same time with a bleaching composition according to the
present invention and said detergent composition, or said washing may be
conducted before or after said fabrics have bE~en bleached. Accordingly, said
process allows the bleaching of fabrics and optionally the washing of fabrics
with
a detergent composition comprising at least one; surface active agent before
the
step of contacting said fabrics with said bleaching composition and/or in the
step
where said fabrics are contacted with said bleaching composition and/or after
the step where said fabrics are contacted with the bleaching composition and
before the rinsing step and/or after the rinsing step.
In another embodiment of the present invention the process of bleaching
fabrics
comprises the step of contacting fabrics with a liquid bleaching composition
according to the present invention; in its neat form, of allowing said fabrics
to
remain in contact with said bleaching composition for a period of time
sufficient
to bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute
to
70 minutes and then rinsing said fabrics with water. If said fabrics are to be
washed, i.e., with a conventional composition comprising at least one surface
active agent, said washing may be conducted before or after that said fabrics
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38
have been bleached. In an embodiment of the present invention wherein the
liquid bleaching composition of the present invention, is contacted to the
fabrics
in its neat form, it is preferred that the level of hypohaiite bleach, is from
0.01
to 5%, preferably from 0.1 % to 3.5%, more preferably from 0.2% to 2% and most
preferably from 0.2% to 1 %. Advantageously, the present invention provides
liquid hypohalite bleach-containing compositions that may be applied neat onto
a fabric to bleach, despite a standing prejudice against using hypochlorite-
containing compositions neat on fabrics.
It is preferred to perform the bleaching process herein before said fabrics
are
washed. indeed, it has been observed that bleaching said fabrics with the
compositions according to the present invention (diluted andlor neat bleaching
processes) prior to washing them with a detergent composition provides
superi~ar
whiteness and stain removal with less energy and detergent than if said
fabrics
are washed first, then bleached.
Alternatively instead of following the neat bleaching process as described
above
(pretreatment application) with a rinsing step and/or a conventional washing
step
with a liquid or powder conventional detergent, the bleaching pre-treatment
operation may also be followed by the diluted bleaching process as described
above either in bucket (hand operation) or in a washing machine.
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39
Examples
The following bleaching compositions which further illustrate the present
invention were made by mixing the listed ingredients in the listed
proportions:
Compositions I II III I'~V V VI VII
(weight %)
Sodium hypochlorite5.0 5.0 5.0 :?.5 2.5 5.0 5.0
Sodium hydroxide 1.3 1.3 1.3 ().7 1.4 0.7 1:4
Sodium carbonate 1.2 1.2 1.2 'I.0 1.2 1.2 1.2
Sodium silicate -- -- -- -- -- 0.2
Sodium metaborate1.0 -- 0.75 'I.0 0.750.5 --
Sodium tetraborate-- -- 1.0 -- -- -- --
Sodium borate -- 1.0 -- -- -- -- 1.0
C12E3S 1.0 3.0 5.0 -- 10.02.0 --
C10E2S _- -- - 5.0 __ -_ 2.0
Minors and water 100%-----------------------------
---------------balance
up to
Compositions Vlll IX X ~;I XII XIII XIV
(weight %)
Sodium hypochlorite5.0 5.0 5.0 2.5 2.5 5.0 5.0
Sodium hydroxide 1.3 1.3 1.3 0.7 1:4 0.7 1.4
Sodium carbonate 1.2 1.2 1.2 1.0 1.2 1.2 1.2
Sodium silicate -- -- -- --~ -- 0.2 --
Sodium metaborate1.0 -- 0.75 1.0 0.75 0.5 --
Sodium tetraborate-- -- 1.0 -- -- -- --
Sodium borate -- 1.0 -- - - -- 1.0
Plurafac LF231 1.0 -- 2.0 1,0 -- 5.0 --
~
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WO 00/15744 PCT/US99121588
C 12114E7C -- 1.0 -- -- 0.5 -- 0.5
Minors and water -------------------balance up to 100%------------------
C12E3S is an alkyl C12 (ethoxy)3 sulphate commercially available from Albright
& Wilson or Rhone Poulenc.
C10E2S is an alkyl C10 (ethoxy)2 sulphate commercially available from Albright
Wilson.
Plurafac LF231~ is a capped alkoxylated non-ionic surfactant commercially
available from BASF.
C12114E7C is an alkyl ethoxy carboxyiate commercially available from Clariant.
All the above bleaching compositions provide excellent fabric safety andlor
excellent fabric yellowing-prevention to fabrics when used to treat fabrics.
