Technical field
[0001] The present invention relates to a bleaching composition which can be used to bleach
various surfaces including but not limited to, hard-surfaces as well as fabrics, clothes,
carpets and the like.
Background of the invention
[0002] Commonly encountered liquid aqueous bleaching compositions suitable for the bleaching
of stains on fabrics and hard-surfaces are based on halogen bleaches, especially hypochlorite
bleaches. Halogen bleaches are extremely effective bleaching agents, however they
also present a number of drawbacks which can sometimes dissuade a consumer from choosing
the halogen-containing product. For example halogen bleaches, especially chlorine
bleaches, emit a pungent odour during and after use (e.g., on consumer hands and/or
surfaces treated therewith) which some consumer find disagreeable.
[0003] Furthermore, it is known in the art halogen bleach-containing compositions (typically
hypochlorite) are relatively aggressive to fabrics and may cause damage when used
in relatively high concentration and/or repeated usage. In particular the consumer
may perceive damage to the fabric itself (e.g. loss of tensile strength) or damage
to the colour intensity of the fabric. While colour and fabric damage may be minimised
by employing milder oxygen bleaches such as hydrogen peroxide, the bleach performance
characteristics of such peroxygen bleaches are much less desirable than those of the
halogen bleaching agents. Therefore, liquid aqueous activated peroxygen bleach-containing
compositions have been developed containing activators, i.e., compounds which enhance
peroxygen bleaching performance. However these bleaches do not perform as well as
hypohalogen bleaches in stain removal.
[0004] It is thus an object of the present invention to provide a bleaching composition
which not only delivers effective bleaching performance, when used in laundry applications
and/or in any household application (e.g. bleaching/disinfecting of hard-surfaces),
but is also safe to the surfaces treated, e.g. to fabrics per se and/or colours.
[0005] Also another problem encountered when formulating bleaching compositions, is their
tendency to chemical and physical instability upon prolonged periods of storage. Thus
it is thus a further object of the present invention to provide bleaching composition
delivering effective bleaching performance which are chemically and physically stable
upon prolonged periods of storage.
[0006] GB-A-2,279,660, published on 11
th January 1995, and GB-A-2,281,744, published on 15
th March 1995, both disclose aqueous liquid laundry detergent compositions comprising
solid, substantially water-insoluble organic peroxyacid bleach, agar or xanthan polysaccharide,
and a pH jump system.
[0007] EP-A-0 347 988, published on 27
th December 1989, describes a bleaching composition comprising a peroxyacid, a natural
gum and a polymer selected from polyvinyl alcohol, cellulose derivatives and mixtures
thereof.
[0008] EP-A-0 412 599, published on 13
th February 1991, discloses a bleaching composition comprising a solid, substantially
water-insoluble organic peroxy acid stably suspended in an aqueous medium characterized
in that the aqueous medium also comprises an effective amount of triethylene glycol
and/or polyethylene glycol
[0009] It has now been found that a bleaching composition according to the present invention
comprising a peroxycarboxylic acid and a polymeric system meets all of the objectives
as described above.
[0010] It is by combining these ingredients that a bleaching composition is provided which
exhibits a great flexibility in the surfaces and soils it may bleach. Indeed, the
compositions according to the present invention are particularly suitable in any laundry
application, e.g., as a laundry detergent or a laundry additive, and when used as
a laundry pre-treater.
[0011] An advantage of the compositions of the present invention is that these bleaching
compositions are suitable for the bleaching of different types of fabrics including
natural fabrics, (e.g., fabrics made of cotton, and linen), synthetic fabrics such
as those made of polymeric fibres of synthetic origin (e.g., polyamide-elasthane)
as well as those made of both natural and synthetic fibres. For example, the bleaching
compositions of the present invention herein may be used on synthetic fabrics despite
a standing prejudice against using bleaches on synthetic fabrics, as evidenced by
wamings on labels of clothes and commercially available bleaching compositions like
hypochlorite-containing compositions.
[0012] Another advantage of the bleaching compositions according to the present invention
is that they can be used in a variety of conditions, i.e., in hard and soft water
as well as when used neat or diluted. More particularly, it has been found that the
liquid aqueous compositions of the present invention find a preferred application
when used in their diluted form in any application and especially in any conventional
laundry application. Indeed, upon dilution (typically at a dilution level of 20ml/L
or more (composition:water)) the compositions of the present invention become less
acidic, e.g., from a pH of about 1.5 to about 6.5 or more. The compositions according
to the present invention although delivering effective bleaching performance in their
neat form surprisingly exhibit further enhanced bleaching performance in their diluted
form. Actually, this "pH jump" effect allows to formulate acidic liquid aqueous compositions
(i.e. pH below 7, preferably below 3 and more preferably below 2) which are physically
and chemically stable upon prolonged periods of storage and which deliver outstanding
bleaching performance under diluted usage conditions.
[0013] Yet another advantage of the compositions of the present invention is that they exhibit
also effective stain removal performance on various stains including enzymatic stains
and/or greasy stains.
Summary of the Invention
[0014] The present invention relates to a bleaching composition having a pH below pH7, the
composition comprising a solid, substantially water insoluble peroxycarboxylic acid
having the general formula:
where R is C1-20 alkyl group and where A, B, C and D are independently either hydrogen
or substituent groups individually selected from the group consisting of alkyl, hydroxyl,
nitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehyde,
or mixtures thereof;
and a polymeric system which comprises a combination of:
at least one gum-type polymer selected from the group consisting of polysaccharide
hydrocolloids, xanthan gum, guar gum, succinoglucan gum, cellulose, and mixtures thereof;
and at least one polycarboxylic polymer,
wherein the ratio of the gum-type polymer to polycarboxylic polymer is from 100:1
to 1:100, and wherein the polycarboxylic polymer is a cross-linked polycarboxylic
polymer having a molecular weight of at least 100,000.
Detailed description of the invention
The bleaching composition
[0015] The compositions according to the present invention are preferably liquid compositions
as opposed to a solid or a gas. As used herein "liquid" includes "pasty" compositions.
The liquid compositions herein are preferably aqueous compositions, comprising water
at a level of preferably 10 to 99%, more preferably from 50% to 98% by weight of the
bleaching composition.. The liquid compositions according to the present invention
have a pH below 7. Preferably, the pH of the compositions according to the present
invention is from 0.1 to 6.5, more preferably from 0.5 to 5, even more preferably
from 2 to 4. Formulating the compositions according to the present invention in the
acidic pH range is critical to the chemical stability of the compositions according
to the present invention. The pH of the composition is preferably below the pKa of
the peracid used. It is believed that the acidic pH controls/limits the formation
of highly reactive species which are instable in acidic medium upon storage, and thus
contributes to the stability of the compositions for prolonged periods of storage.
[0016] The pH of the compositions may be adjusted by any acid or alkaline species known
to those skilled in the art. Examples of acidic species suitable for use herein are
organic acids, such as citric acid and inorganic acids, such as sulphuric acid, sulphonic
acid and/or metanesulphonic acid. Examples of alkaline species are sodium hydroxide,
potassium hydroxide and/or sodium carbonate.
[0017] The bleaching performance of the present composition may be evaluated by the following
test methods on various type of bleachable stains.
[0018] A suitable test method for evaluating the bleaching performance on a soiled fabric
under diluted conditions is the following: A composition according to the present
invention is diluted with water typically at a dilution level of 1 to 100 ml/L, preferably
20 ml/L (composition :water), then the soiled fabrics are soaked in it for 20 minutes
to 6 hours and then rinsed. Alternatively the bleaching composition can be used in
a washing machine at a dilution level of typically at a dilution level of 1 to 100
ml/L (composition :water). In the washing machine the soiled fabrics are washed at
a temperature of from 30° to 70°C for 10 to 100 minutes and then rinsed. The reference
composition in this comparative test undergoes the same treatment. Soiled fabrics/swatches
with for example tea, coffee and the like may be commercially available from E.M.C.
Co. Inc..
[0019] The bleaching performance is then evaluated by comparing side by side the soiled
fabrics treated with a composition of the present invention with those treated with
the reference, e.g., the same composition but comprising no bleach or a different
bleach. A visual grading may be used to assign difference in panel units (psu) in
a range from 0 to 4.
[0020] An advantage of the compositions of the present invention is that they are physically
and chemically stable upon prolonged periods of storage.
[0021] Chemical stability of the compositions herein may be evaluated by measuring the concentration
of available oxygen at given storage time after having manufactured the compositions.
By "chemically stable", it is meant herein that the compositions of the present invention
comprising a peracid do not undergo more than 15% AvO loss, in one month at 25°C and
preferably not more than 10%.
[0022] The loss of available oxygen (AvO) of a peracid-containing composition over time
can be measured by titration with potassium permanganate after reduction with a solution
containing ammonium ferrous sulphate. This stability test method is well known in
the art and is reported, for example, on the technical information sheet of Curox
R commercially available from Interox. Alternatively peracid concentration can also
be measured using a chromatography method described in the literature for peracids
(F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids,
Analyst, Vol 113, May 1988, p 793-795).
[0023] By "physically stable", it is meant herein that no phase separation occurs in the
compositions according to the present invention for a period of 7 days at 50°C.
Peroxy Carboxylic acid
[0024] The bleaching composition of the present invention comprises a solid, substantially
water insoluble pre-formed peroxy carboxylic acid (hereafter referred to as peracid).
The peracid has the general formula
where R is C1-20 alkyl group and where A, B, C and D are independently either hydrogen
or substituent groups individually selected from the group consisting of alkyl, hydroxyl,
nitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehydes
or mixtures thereof.
[0025] In a preferred aspect of the present invention R is an alkyl group having from 3
to 12 carbon atoms, more preferably from 5 to 9 carbon atoms. Preferred substituent
groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon
atoms, but more preferably hydrogen.
[0026] Preferred peracids are selected from the group consisting of phthaloyl amido peroxy
hexanoic acid (also known as phthaloyl amido peroxy caproic acid) phthaloyl amido
peroxy heptanoic acid, phthaloyl amido peroxy octanoic acid, phthaloyl amido peroxy
nonanoic acid, phthaloyl amido peroxy decanoic acid and mixtures thereof.
[0027] Even more preferred peracids are any of having general formula:
wherein R is selected from C1-4 alkyl and n is an integer of from 1 to 5.
[0028] In a particularly preferred aspect of the present invention the peracid has the formula
such that R is CH
2 and n is 5 i.e. phthaloyl amido-peroxy caproic acid or PAP.
[0029] The peracid is preferably used as a substantially water-insoluble solid or wetcake
and is available from Ausimont under the trade name Euroco.
[0030] The peracid may be present at a level in the composition of from 0.1% to 10% more
preferably 0.5% to 8% and most preferably 1% to 6%. Alternatively the peracid may
be present at a much higher level of for example 10% to 40%, more preferably from
15% to 30%, most preferably from 20% to 25%.
Polymeric system
[0031] The composition of the present invention comprises a polymeric system comprising
at least two polymers. The first polymer is a gum-type polymer and the second is a
cross-linked polycarboxylate polymer. The composition may additionally comprise further
polymers.
[0032] The gum-type polymer may be selected from the group consisting of polysaccharide
hydrocolloids, xanthan gum, guar gum, succinoglucan gum, Cellulose, derivatives of
any of the above and mixtures thereof. In a preferred aspect of the present invention
the gum-type polymer is a xanthan gum or derivative thereof.
[0033] The gum-type polymer is preferably present at a level of from 0.01% to 10%, more
preferably from 0.1% to 3%.
[0034] The polycarboxylate polymer can be a homo or copolymer of monomer units selected
from acrylic acid, methacrylic acid, maleic acid, malic acid, maleic anhydride. Preferred
polycarboxylate polymers are Carbopol from BF Goodrich. Suitable polymers have molecular
weight in the range of from 10 000 to 10 000 000, more preferably 100 000 to 10 000000.
[0035] The cross-linked polycarboxylate polymer is preferably present at a level of from
0.01% to 2%, more preferably from 0.01% to 1%, most preferably from 0.1% to 0.8%.
[0036] The ratio of gum-type polymer to cross-linked polycarboxylate polymer is from 100:1
to 1:100, more preferably from 10:1 to 1:10.
Optional ingredients
[0037] The compositions herein may further comprise a variety of other optional ingredients
such as surfactants, chelating agents, radical scavengers, antioxidants, stabilisers,
builders, soil suspending polymer, polymeric soil release agents, pH control agents,
dye transfer inhibitor, solvents, suds controlling agents, suds booster, brighteners,
perfumes, pigments, dyes and the like.
Surfactants
[0038] The compositions of the present invention may comprise a surfactant or a mixture
thereof including nonionic surfactants, anionic surfactants, cationic surfactants,
zwitterionic surfactants and/or amphoteric surfactants.
[0039] Typically, the compositions according to the present invention may comprise from
0.01% to 50% by weight of the total composition of a surfactant or a mixture thereof,
preferably from 0.1 % to 30 % and more preferably from 0.2% to 10%.
[0040] Suitable anionic surfactants for use in the compositions herein include water-soluble
salts or acids of the formula ROSO
3M wherein R preferably is a C
10-C
24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C
10-C
20 alkyl component, more preferably a C
12-C
18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.,
sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C
12-
16 are preferred for lower wash temperatures (e.g., below about 50°C) and C
16-
18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C).
[0041] Other suitable anionic surfactants for use herein are water-soluble salts or acids
of the formula RO(A)
mSO
3M wherein R is an unsubstituted C
10-C
24 alkyl or hydroxyalkyl group having a C
10-C
24 alkyl component, preferably a C
12-C
20 alkyl or hydroxyalkyl, more preferably C
12-C
18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and about 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
ethoxylated sulfates as well as alkyl propoxylated 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 alkanolamines such as ethylamine, diethylamine, triethylamine,
mixtures thereof, and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate, C
12-C
18E(1.0)M), C
12-C
18 alkyl polyethoxylate (2.25) sulfate, C
12-C
18E(2.25)M), C
12-C
18 alkyl polyethoxylate (3.0) sulfate C
12-C
18E(3.0), and C
12-C
18 alkyl polyethoxylate (4.0) sulfate C
12-C
18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
[0042] Other particularly suitable anionic surfactants for use herein are alkyl sulphonates
including water-soluble salts or acids of the formula RSO
3M wherein R is a C
6-C
22 linear or branched, saturated or unsaturated alkyl group, preferably a C
12-C
18 alkyl group and more preferably a C
14-C
16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-,
and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium
and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
[0043] Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids
of the formula RSO
3M wherein R is an aryl, preferably a benzyl, substituted by a C
6-C
22 linear or branched saturated or unsaturated alkyl group, preferably a C
12-C
18 alkyl group and more preferably a C
14-C
16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g.,
methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations,
such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium
cations derived from alkylamines such as ethylamine, diethylamine, triethylamine,
and mixtures thereof, and the like).
[0044] The alkylsulfonates and alkyl aryl sutphonates for use herein include primary and
secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates. By "secondary
C6-C22 alkyl or C6-C22 alkyl aryl sulphonates", it is meant herein that in the formula
as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl
chain being placed between two other carbons of the said alkyl chain (secondary carbon
atom).
[0045] For example C14-C16 alkyl sulphonate salt is commercially available under the name
Hostapur ® SAS from Hoechst and C8-alkylsulphonate sodium salt is commercially available
under the name Witconate NAS 8® from Witco SA. An example of commercially available
alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma. Particularly preferred
alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under
trade name Nansa® available from Albright&Wilson.
[0046] Other anionic surfactants useful for detersive purposes can also be used herein.
These can include salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap,
C
8-C
24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g., as described in British
patent specification No. 1,082,179, C
8-C
24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl
ester sulfonates such as C
14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,
isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated
C
12-C
18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C
6-C
14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described below), branched primary alkyl
sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH
2CH
2O)
kCH
2COO-M
+ wherein R is a C
8-C
22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin
acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin, and resin acids and hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al.
at Column 23, line 58 through Column 29, line 23,
[0047] Other particularly suitable anionic surfactants for use herein are alkyl carboxylates
and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain,
preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy
and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20,
preferably from 5 to 15. Preferred alkylalkoxycarboxylate for use herein is sodium
laureth 11 carboxylate (i.e., RO(C
2H
4O)
10-CH
2COONa, with R= C12-C14) commercially available under the name Akyposoft® 100NV from
Kao Chemical Gbmh.
[0048] Suitable amphoteric surfactants for use herein include amine oxides having the following
formula R
1R
2R
3NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted,
linear or branched hydrocarbon chain 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 R
1R
2R
3NO 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 C8-C10 amine oxides as well as C12-C16 amine oxides commercially
available from Hoechst.
[0049] Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic
group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same
molecule at a relatively wide range of pH's. The typical anionic hydrophilic groups
are carboxylates and sulfonates, although other groups like sulfates, phosphonates,
and the like can be used. A generic formula for the zwitterionic surfactants to be
used herein is :
R
1-N
+(R
2)(R
3)R
4X
-
wherein R
1 is a hydrophobic group; R
2 is hydrogen, C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group; R
3 is C
1-C
6 alkyl, hydroxy alkyl or other substituted C
1-C
6 alkyl group which can also be joined to R
2 to form ring structures with the N, or a C
1-C
6 carboxylic acid group or a C
1-C
6 sulfonate group; R
4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically
an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon
atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group.
[0050] Preferred hydrophobic groups R
1 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 R
1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18,
and more preferably from 10 to 16. These simple alkyl groups are preferred for cost
and stability reasons. However, the hydrophobic group R
1 can also be an amido radical of the formula R
a-C(O)-NH-(C(R
b)
2)
m, wherein R
a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms,
preferably up to 18, more preferably up to 16, R
b 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(R
b)
2) moiety.
[0051] Preferred R
2 is hydrogen, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
3 is a C
1-C
4 carboxylic acid group or C1-C4 sulfonate group, or a C
1-C
3 alkyl and more preferably methyl. Preferred R
4 is (CH2)
n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is
from 1 to 3.
[0052] Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275,
2,702,279 and 2,255,082.
[0053] 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, myristyl 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 Amonyl 265®.
Lauryl betaine is commercially available from Albright & Wilson under the trade name
Empigen BB/L®.
[0054] Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine
or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine. For example C10-C14
fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from
Sherex Company under the trade name "Varion CAS® sulfobetaine".
[0055] A further example of betaine is Lauryl-immino-dipropionate commercially available
from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
[0056] Suitable cationic surfactants for use herein include derivatives of quaternary ammonium,
phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants for
use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon
groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to
30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to
20 carbon atoms, and wherein the other hydrocarbon groups (i.e. three when one hydrocarbon
group is a long chain hydrocarbon group as mentioned hereinbefore or two when two
hydrocarbon groups are long chain hydrocarbon groups as mentioned hereinbefore) linked
to the nitrogen are independently substituted or unsubstituted, linear or branched,
alkyl chain of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and
more preferably are methyl groups. Preferred quaternary ammonium compounds suitable
for use herein are non-chloride/non halogen quaternary ammonium compounds. The counterion
used in said quaternary ammonium compounds are compatible with any persulfate salt
and are selected from the group of methyl sulfate, or methylsulfonate, and the like.
[0057] Particularly preferred for use in the compositions of the present invention are trimethyl
quaternary ammonium compounds like myristyl trimethylsulfate, cetyl trimethylsulfate
and/or tallow trimethylsulfate. Such trimethyl quaternary ammonium compounds are commercially
available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN CM®.
[0058] Amongst the nonionic surfactants, alkoxylated nonionic surfactants and especially
ethoxylated nonionic surfactants are suitable for use herein. Particularly preferred
nonionic surfactants for use herein are the capped alkoxylated nonionic surfactants.
[0059] Suitable capped alkoxylated nonionic surfactants for use herein are according to
the formula:
R
1(O-CH
2-CH
2)
n-(OR
2)
m-O-R
3
wherein R
1 is a C
8-C
24 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably
R
1 is a C
8-C
18 alkyl or alkenyl group, more preferably a C
10-C
15 alkyl or alkenyl group, even more preferably a C
10-C
15 alkyl group;
wherein R
2 is a C
1-C
10 linear or branched alkyl group, preferably a C
2-C
10 linear or branched alkyl group ;
wherein R
3 is a C
1-C
10 alkyl or alkenyl group, preferably a C
1-C
5 alkyl group, more preferably methyl;
and wherein n and m are integers independently ranging in the range of from 1 to 20,
preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
[0060] These surfactants are commercially available from BASF under the trade name Plurafac®,
from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
Preferred capped nonionic alkoxylated surfactants of the above formula are those commercially
available under the tradename Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
Chelating agents
[0061] The compositions of the present invention may comprise a chelating agent as a preferred
optional ingredient. Suitable chelating agents may be any of those known to those
skilled in the art such as the ones selected from the group comprising phosphonate
chelating agents, amino carboxylate chelating agents, other carboxylate chelating
agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'-
disuccinic acids, or mixtures thereof.
[0062] The presence of chelating agents contribute to further enhance the chemical stability
of the compositions. A chelating agent may be also desired in the compositions of
the present invention as it allows to increase the ionic strength of the compositions
herein and thus their stain removal and bleaching performance on various surfaces.
[0063] Suitable phosphonate chelating agents for use 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 phosphonates,
and diethylene triamine penta methylene phosphonates (DTPMP). The phosphonate compounds
may be present either in their acid form or as salts of different cations on some
or all of their acid functionalities. Preferred phosphonate chelating agents to be
used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane
1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially
available from Monsanto under the trade name DEQUEST®.
[0064] Polyfunctionally-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.
[0065] 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.
[0066] Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates,
diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine
triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates,
ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic
acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted
ammonium salt forms. Particularly suitable amino carboxylates to be used herein are
diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which
is, for instance, commercially available from BASF under the trade name Trilon FS®
and methyl glycine di-acetic acid (MGDA).
[0067] Further carboxylate chelating agents to be used herein include salicylic acid, aspartic
acid, glutamic acid, glycine, malonic acid or mixtures thereof.
[0068] Another chelating agent for use herein is of the formula:
wherein R
1, R
2, R
3, and R
4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl,
aryloxy, -Cl, -Br, -NO
2, -C(O)R', and -SO
2R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl,
and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and
aryloxy; and R
5, R
6, R
7, and R
8 are independently selected from the group consisting of -H and alkyl.
[0069] Particularly preferred chelating agents to be used herein are amino aminotri(methylene
phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta
methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic
acid, and mixtures thereof.
[0070] Typically, the compositions according to the present invention comprise up to 5%
by weight of the total composition of a chelating agent, or mixtures thereof, preferably
from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.
Radical scavengers
[0071] The compositions of the present invention may comprise a radical scavenger or a mixture
thereof.
[0072] Suitable radical scavengers for use herein include the well-known substituted mono
and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures
thereof. Preferred such radical scavengers for use herein include di-tert-butyl hydroxy
toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone,
tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechoi, t-butyl catechol,
benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate
or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene. Such radical
scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories
under the trade name Nipanox S1 ®.
[0073] Radical scavengers when used, are typically present herein in amounts up to 10% by
weight of the total composition and preferably from 0.001 % to 0.5% by weight.
[0074] The presence of radical scavengers may contribute to the chemical stability of the
bleaching compositions of the present invention as well as to the safety profile of
the compositions of the present invention.
Suds controlling agents
[0075] The compositions according to the present invention may further comprise a suds controlling
agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
Particularly suitable to be used in the present invention are the 2-alkyl alkanols
having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12
and a terminal hydroxy group, said alkyl chain being substituted in the α position
by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and
more preferably 3 to 6. Such suitable compounds are commercially available, for instance,
in the Isofol® series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl
decanol).
[0076] Other suds controlling agents may include alkali metal (e.g., sodium or potassium)
fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from
about 10 to about 20 carbon atoms.
[0077] The fatty acids including those used in making the soaps can be obtained from natural
sources such as, for instance, plant or animal-derived glycerides (e.g., palm oil,
coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow,
grease, lard and mixtures thereof). The fatty acids can also be synthetically prepared
(e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process).
[0078] Alkali metal soaps can be made by direct saponification of fats and oils or by the
neutralization of the free fatty acids which are prepared in a separate manufacturing
process. Particularly useful are the sodium and potassium salts of the mixtures of
fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow
and coconut soaps.
[0079] The term "tallow" is used herein in connection with fatty acid mixtures which typically
have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18,
2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are
saturated). Other mixtures with similar distribution, such as the fatty acids derived
from various animal tallows and lard, are also included within the term tallow. The
tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated
fatty acid moieties to saturated fatty acid moieties.
[0080] When the term "coconut" is used herein it refers to fatty acid mixtures which typically
have an approximate carbon chain length distribution of about 8% C8, 7% C10, 48% C12,
17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed
being saturated). Other sources having similar carbon chain length distribution such
as palm kernel oil and babassu oil are included with the term coconut oil.
[0081] Other suitable suds controlling agents are exemplified by silicones, and silica-silicone
mixtures. Silicones can be generally represented by alkylated polysiloxane materials
while silica is normally used in finely divided forms exemplified by silica aerogels
and xerogels and hydrophobic silicas of various types. These materials can be incorporated
as particulates in which the suds controlling agent is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds controlling agent can be dissolved or
dispersed in a liquid carrier and applied by spraying on to one or more of the other
components.
[0082] A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S.
Patent 3 933 672. Other particularly useful suds controlling agents are the self-emulsifying
silicone suds controlling agents, described in German Patent Application DTOS 2 646
126 published April 28, 1977. An example of such a compound is DC-544, commercially
available from Dow Corning, which is a siloxane-glycol copolymer.
[0083] Especially preferred silicone suds controlling agents are described in Copending
European Patent application EP-A-0646167. Said compositions can comprise a silicone/silica
mixture in combination with fumed nonporous silica such as AerosilR.
[0084] Especially preferred suds controlling agent are the suds controlling agent system
comprising a mixture of silicone oils and the 2-alkyl-alcanols.
[0085] Typically, the compositions herein may comprise up to 4% by weight of the total composition
of a suds controlling agent, or mixtures thereof, preferably from 0.1% to 1.5% and
most preferably from 0.1% to 0.8%.
Stabilisers
[0086] The compositions of the present invention may further comprise up to 10%, preferably
from 2% to 4% by weight of the total composition of an alcohol according to the formula
HO - CR'R" - OH, wherein R' and R" are independently H or a C2-C10 hydrocarbon chain
and/or cycle. Preferred alcohol according to that formula is propanediol. Indeed,
we have observed that these alcohols in general and propanediol in particular also
improve the chemical stability of the compositions.
[0087] Other stabilizers like inorganic stabilizers may be used herein. Examples of inorganic
stabilizers include sodium stannate and various alkali metal phosphates such as the
well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.
Soil suspending polymer
[0088] The compositions according to the present invention may further comprise a soil suspending
polyamine polymer or mixtures thereof, as optional ingredient. Any soil suspending
polyamine polymer known to those skilled in the art may be used herein. Particularly
suitable polyamine polymers for use herein are polyalkoxylated polyamines. Such materials
can conveniently be represented as molecules of the empirical structures with repeating
units :
and
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R
1 may be a C
1-C
20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30,
most preferably from 10-20; n is an integer of at least 2, preferably from 2-20, most
preferably 3-5; and X- is an anion such as halide or methylsulfate, resulting from
the quatemization reaction.
[0089] The most highly preferred polyamines for use herein are the so-called ethoxylated
polyethylene amines, i.e., the polymerized reaction product of ethylene oxide with
ethyleneimine, having the general formula :
when y = 2-30. Particularly preferred for use herein is an ethoxylated polyethylene
amine, in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated
hexamethylene diamine.
[0090] Soil suspending polyamine polymers contribute to the benefits of the present invention,
i.e., that when added on top of said diacyl peroxide, further improve the stain removal
performance of a composition comprising them, especially under laundry pretreatment
conditions, as described herein. Indeed, they allow to improve the stain removal performance
on a variety of stains including greasy stains, enzymatic stains, clay/mud stains
as well as on bleachable stains.
[0091] Typically, the compositions comprise up to 10% by weight of the total composition
of such a soil suspending polyamine polymer or mixtures thereof, preferably from 0.1
% to 5% and more preferably from 0.3% to 2%.
[0092] The compositions herein may also comprise other polymeric soil release agents known
to those skilled in the art. Such polymeric soil release agents are characterised
by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres,
such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic
fibres and remain adhered thereto through completion of washing and rinsing cycles
and, thus, serve as an anchor for the hydrophilic segments. This can enable stains
occurring subsequent to treatment with the soil release agent to be more easily cleaned
in later washing procedures.
[0093] The polymeric soil release agents useful herein especially include those soil release
agents having: (a) one or more nonionic hydrophile components consisting essentially
of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene
unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii)
a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene
units wherein said mixture contains a sufficient amount of oxyethylene units such
that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity
of conventional polyester synthetic fiber surfaces upon deposit of the soil release
agent on such surface, said hydrophile segments preferably comprising at least about
25% oxyethylene units and more preferably, especially for such components having about
20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more
hydrophobe components comprising (i) C
3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C
3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C
4-C
6 alkylene or oxy C
4-C
6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are
present in the form of C
1-C
4 alkyl ether or C
4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose
derivatives are amphiphilic, whereby they have a sufficient level of C
1-C
4 alkyl ether and/or C
4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces
and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic
fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and
(b).
[0094] Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization
of from about 1 to about 200, although higher levels can be used, preferably from
3 to about 150, more preferably from 6 to about 100. Suitable oxy C
4-C
6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO
3S(CH
2)
nOCH
2CH
2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
[0095] Polymeric soil release agents useful in the present invention also include cellulosic
derivatives such as hydroxyether cellulosic polymers, co-polymeric blocks of ethylene
terephthalate or propylene terephthalate with polyethylene oxide or polypropylene
oxide terephthalate, and the like. Such agents are commercially available and include
hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents
for use herein also include those selected from the group consisting of C
1-C
4 alkyl and C
4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol,
et al.
[0096] Soil release agents characterised by poly(vinyl ester) hydrophobe segments include
graft co-polymers of poly(vinyl ester), e.g., C
1-C
6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application 0 219 048, published
April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind
include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West
Germany).
[0097] One type of preferred soil release agent is a co-polymer having random blocks of
ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight
of this polymeric soil release agent is in the range of from about 25,000 to about
55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929
to Basadur issued July 8, 1975.
[0098] Another preferred polymeric soil release agent is a polyester with repeat units of
ethylene terephthalate units which contains 10-15% by weight of ethylene terephthalate
units together with 90-80% by weight of polyoxyethylene terephthalate units, derived
from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this
polymer include the commercially available material ZELCON 5126 (from Dupont) and
MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0099] Another preferred polymeric soil release agent is a sulfonated product of a substantially
linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
These soil release agents are fully described in U.S. Patent 4,968,451, issued November
6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
[0100] Preferred polymeric soil release agents also include the soil release agents of U.S.
Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic,
especially sulfoaroyl, end-capped terephthalate esters.
[0101] Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl
units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The
repeat units form the backbone of the oligomer and are preferably terminated with
modified isethionate end-caps. A particularly preferred soil release agent of this
type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy
and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two
end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent
also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing
stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene
sulfonate, toluene sulfonate, and mixtures thereof. See U.S. Pat. No. 5,415,807, issued
May 16, 1995, to Gosselink et al.
[0102] If utilised, soil release agents will generally comprise from 0.01% to 10.0%, by
weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably
from 0.2% to 3.0%.
Dye transfer inhibitor
[0103] The compositions of the present invention may also include one or more materials
effective for inhibiting the transfer of dyes from one dyed surface to another during
the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, co-polymers of N-vinylpyrrolidone
and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used, these agents typically comprise from 0.01% to 10% by weight of the composition,
preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
[0104] More specifically, the polyamine N-oxide polymers preferred for use herein contain
units having the following structural formula: R-A
x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the
N-O group can form part of the polymerizable unit or the N-O group can be attached
to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=;
x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or
alicyclic groups or any combination thereof to which the nitrogen of the N-O group
can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole,
pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented
by the following general structures:
wherein R
1, R
2, R
3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof;
x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part
of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides
has a pKa <10, preferably pKa <7, more preferred pKa <6.
[0105] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof. These polymers include random or block co-polymers where one
monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine
N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
However, the number of amine oxide groups present in the polyamine oxide polymer can
be varied by appropriate co-polymerization or by an appropriate degree of N-oxidation.
The polyamine oxides can be obtained in almost any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more preferred
1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials
can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent
compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular
weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
[0106] Co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
determined by light scattering as described in Barth, et al.,
Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which
are incorporated herein by reference.) The PVPVI co-polymers typically have a molar
ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably
from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These co-polymers can be
either linear or branched.
[0107] The present invention compositions may also employ a polyvinylpyrrolidone ("PVP")
having an average molecular weight of from 5,000 to 400,000, preferably from 5,000
to 200,000, and more preferably from 5,000 to 50,000.
[0108] PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897
and EP-A-256,696, incorporated herein by reference. Compositions containing PVP can
also contain polyethylene glycol ("PEG") having an average molecular weight from 500
to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on
a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from
3:1 to 10:1.
Suds booster
[0109] If high sudsing is desired, suds boosters such as C
10-C
16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
The C
10-C
14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants such as the amine
oxides, betaines and sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCl
2, MgSO
4, and the like, can be added at levels of, for example, 0.1%-2%, to provide additional
suds and to enhance grease removal performance.
Brightener
[0110] Any optical brighteners, fluorescent whitening agents or other brightening or whitening
agents known in the art can be incorporated in the instant compositions when they
are designed for fabric treatment or laundering, at levels typically from about 0.05%
to about 1.2%, by weight, of the detergent compositions herein. 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, pyrazoline,
coumarin, carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,
5- and 6- membered-ring heterocyclic brighteners, this list being illustrative and
nonlimiting. 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).
[0111] Specific examples of optical brighteners which are useful in the present compositions
are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available
from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis,
located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners
include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 2,5-bis(benzoxazol-2-yl)thiophene;
2-styryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole.
See also U.S. Patent 3,646,015, issued February 29, 1972, to Hamilton. Anionic brighteners
are typically preferred herein.
pH control agent
[0112] A variety of suitable means can be used for adjusting the pH of the compositions,
including organic or inorganic acids, alkanolamines and the like. It may be advantageous
to use alkanolamines, in particular monoethanolamine, inasmuch as they have an additional
effect of regulating the viscosity of the emulsion, without compromising on its physical
stability.
Minor Ingredients
[0113] The composition described herein may also comprise minor ingredients such as pigment
or dyes and perfumes.
Processes of treating surfaces
[0114] In the present invention, the liquid aqueous composition of the present invention
needs to be contacted with the surface to treat.
[0115] By "surfaces", it is meant herein any inanimate surface. These inanimate surfaces
include, but are not limited to, hard-surfaces typically found in houses like kitchens,
bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth
vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary
fittings such as sinks, showers, shower curtains, wash basins, WCs and the like, as
well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table
cloths, sleeping bags, tents, upholstered fumiture and the like, and carpets. Inanimate
surfaces also include household appliances including, but not limited to, refrigerators,
freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers
and so on.
[0116] By "treating a surface", it is meant herein bleaching and/or disinfecting said surfaces
as the compositions of the present invention comprise a bleaching system based of
peracid compound or a mixture thereof and optionally cleaning as said compositions
may comprise a surfactant or any other conventional cleaning agents.
[0117] Thus, the present invention also encompasses a process of treating, especially bleaching
a fabric, as the inanimate surface. In such a process a composition according to the
present invention is contacted with the fabrics to be treated.
[0118] 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 liquid 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 liquid bleaching composition, as defined herein, is added on top
of a wash liquor formed by dissolution or dispersion of a typical laundry detergent.
It is also essential in both cases, that the fabrics be rinsed after they have been
contacted with said composition, before said composition has completely dried off.
[0119] The processes of bleaching surfaces according to the present invention, especially
fabrics, delivers effective whiteness performance as well as effective stain removal
performance.
[0120] The compositions according to the present invention are preferably contacted to fabrics
in a liquid form. Indeed, by "in a liquid form", it is meant herein the liquid compositions
according to the present invention per se in neat or in their diluted form.
[0121] The compositions according to the present invention are typically used in diluted
form in a laundry operation. By "in diluted form", it is meant herein that the compositions
for the bleaching of fabrics according to the present invention may be diluted by
the user, preferably with 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 diluted up to 500 times, preferably from 5 to 200 times and more preferably
from 10 to 80 times.
[0122] More specifically, the process of bleaching fabrics according to the present invention
comprises the 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 sufficient 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 conventional
composition comprising at least one surface active agent, said washing may be conducted
together with the bleaching of said fabrics 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 that said fabrics have
been bleached. Accordingly, said process according to the present invention allows
to bleach fabrics and optionally to wash 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 said bleaching composition and before the rinsing step and/or after the rinsing
step.
[0123] 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 10 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 have been bleached. Advantageously, the present
invention provides liquid bleaching compositions that may be applied neat onto a fabric
to bleach, despite a standing prejudice against using bleach-containing compositions
neat on fabrics while being safe to colors and fabrics perse.
[0124] Alternatively instead of following the neat bleaching method as described herein
above (pretreater application) by a rinsing step with water and/or a conventional
washing step with a liquid or powder conventional detergent, the bleaching pretreatment
operation may also be followed by the diluted bleaching process as described herein
before either in bucket (hand operation) or in a washing machine.
[0125] It is preferred to perform the bleaching processes herein after said fabrics have
been washed with a conventional laundry detergent composition. Indeed, it has been
observed that bleaching said fabrics with the compositions according to the present
invention (typically diluted bleaching methods) after to washing them with a detergent
composition provides superior whiteness and stain removal with less energy and detergent
than if said fabrics are bleached first then washed.
[0126] In another embodiment the present invention also encompasses a process of treating
a hard-surface, as the inanimate surface. In such a process a composition, as defined
herein, is contacted with the hard-surfaces to be treated. Thus, the present invention
also encompasses a process of treating a hard-surface with a composition, as defined
herein, wherein said process comprises the step of applying said composition to said
hard-surface, preferably only soiled portions thereof, and optionally rinsing said
hard-surface.
[0127] In the process of treating hard-surfaces according to the present invention the composition,
as defined herein, may be applied to the surface to be treated in its neat form or
in its diluted form typically up to 200 times their weight of water, preferably into
80 to 2 times their weight of water, and more preferably 60 to 2 times.
[0128] When used as hard surfaces bleaching/disinfecting compositions the compositions of
the present invention are easy to rinse and provide good shine characteristics on
the treated surfaces.
[0129] By "hard-surfaces", it is understood any hard-surfaces as mentioned herein before
as well as dishes.
Packaging form of the liquid compositions:
[0130] Depending on the end-use envisioned, the compositions herein can be packaged in a
variety of containers including conventional bottles, bottles equipped with roll-on,
sponge, brusher or sprayers.
[0131] In one embodiment of the present invention the composition is packaged in a two compartment
container, wherein the bleaching composition as described herein is packaged in one
compartment and a second composition is packaged in the second compartment. In a particularly
preferred aspect, the second composition is a conventional heady duty liquid detergent
composition, preferably comprising ingredients, particularly bleach-sensitive ingredients
such as surfactants, enzymes and perfumes.
[0132] The invention is further illustrated by the following examples.
Examples
[0133] Following compositions were made by mixing the listed ingredients in the listed proportions
(weight % unless otherwise specified).
Compositions |
I |
II |
III |
IV |
V |
(% weight) |
|
|
|
|
|
Alkylsulfonate |
1 |
1.5 |
0.5 |
2 |
- |
Sodium alkyl-3-ethoxy sulfate |
1 |
0.5 |
1.5 |
- |
2 |
PAP |
3 |
2 |
4 |
1 |
5 |
Hydroxyethanediphosphonate |
0.1 |
0.05 |
0.16 |
0.1 |
- |
di-tert butyl hydroxy toluene |
0.05 |
- |
- |
- |
0.1 |
Propyl gallate |
- |
0.1 |
- |
0.05 |
- |
Perfume |
- |
0.2 |
0.2 |
0.3 |
0.1 |
brightener |
- |
0.01 |
0.05 |
0.03 |
- |
NaOH |
- |
- |
0.1 |
0.05 |
- |
xanthan gum |
0.2 |
- |
0.3 |
0.5 |
- |
carbopol ETD 2691 |
|
0.1 |
- |
- |
0.2 |
carbopol ETD 2623 |
0.3 |
- |
0.8 |
1 |
- |
carboxylmethoxycellulose |
- |
1 |
- |
- |
0.8 |
Alkanizing / acidizing agent up to pH |
3.9 |
2.5 |
3.5 |
4 |
3 |
[0134] Witkonate NAS 8® is an alkylsulphonate available from Witco AS Sodium alkyl-3-ethoxy
sulfate is commercially available from Albright & Wilson BHT is di-tert butyl hydroxy
toluene.
HEDP is ethane 1-hydroxy diphosphonate commercially available from Monsanto under
the serie Dequest®.
PAP is phthalimidoperoxyhexanoic acid available from Ausimont under the tradename
Euroco®
Carbopol®ETD 2623 and 2991 are polymers available from BFGoodrich