Field of the invention
[0001] The present invention relates to bleaching compositions, in particular to hypochlorite
bleaching compositions, suitable for use in laundry applications such as hand and
machine laundry methods.
Background of the invention
[0002] Bleaching compositions are well-known in the art. Amongst the different bleaching
compositions available, those relying on bleaching by hypohalite bleaches such as
hypochlorite are often preferred, mainly for performance reasons, especially at lower
temperature.
[0003] However, a problem encountered with the use of hypochlorite based-compositions is
the resulting damage and/or yellowing of the fabrics being bleached.
[0004] It is therefore an object of the invention to provide a hypohalite-containing composition,
suitable for use in laundry applications, which provides improved fabric whiteness
to fabrics treated therewith.
[0005] It is another object of the invention to provide a hypohalite-containing composition,
suitable for use in laundry applications, which provides improved fabric safety to
fabrics treated therewith.
[0006] The Applicant has thus now surprisingly found that this problem is solved by the
use, in a hypohalite bleaching composition, or polymers comprising monomeric units
selected from the group consisting of unsaturated carboxylic acids, polycarboxylic
acids, sulphonic acids, phosphonic acids, and mixtures thereof.
[0007] Another advantage of the compositions of the invention is that they are chemically
stable. By "chemically stable", it is meant that the hypohalite bleaching compositions
of the present invention should not undergo more than 15% loss of available chlorine
after 5 days of storage at 50°C ± 0.5°C. The % loss of available chlorine may be measured
using the method described, for instance, in "Analyses des Eaux et Extraits de Javel"
by "La chambre syndicale nationale de L'eau de Javel et des produits connexes", pages
9-10 (1984). Said method consists in measuring the available chlorine in the fresh
compositions, i.e. just after they are made, and in the same compositions after 5
days at 50°C.
[0008] A further advantage of the compositions of the invention is that they are suitable
for the bleaching of different types 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 as 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 hypochlorite bleaches, on synthetic fibers, as evidenced by warning on
labels of commercially available hypochlorite bleaches and clothes.
Summary of the invention
[0009] The present invention is a liquid bleaching composition comprising :
- a hypohalite bleach, and
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof, with the proviso that when said polymer is a polyacrylate, the polymer is
present in an amount of less than 0.5% by weight.
[0010] In another aspect of the invention, a solid bleaching composition is provided comprising
:
- a hypohalite bleach, and
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof.
[0011] The present invention also encompasses the use, in a hypohalite bleaching composition
of a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof, for providing improved fabric whiteness and/or safety to the fabrics treated
therewith.
[0012] The present invention also encompasses a process of bleaching fabrics with a composition
comprising
- a hypohalite bleach,
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids,
sulphonic acids, phosphonic acids, and mixtures thereof,
where said fabrics are immersed in a bleaching solution formed by dissolving said
composition in water.
Detailed description of the invention
Hypohalite bleach
[0013] An essential component of the invention is a hypohalite bleach. Hypohalite bleaches
may be provided by a variety of sources, including bleaches that are oxidative bleaches
and subsequently lead to the formation of positive halide ions as well as bleaches
that are organic based sources of halides such as chloroisocyanurates.
[0014] Suitable hypohalite bleaches for use herein include the alkali metal and alkaline
earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate
dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates,
N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
[0015] For liquid compositions, the preferred hypohalite bleaches among the above described
are the alkali metal and/or alkaline earth metal hypochlorites selected from the group
consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and
mixtures thereof, more preferably the alkali metal sodium hypochlorite.
[0016] For solid compositions, the preferred hypohalite bleaches among the above described
are the alkali metal and/or alkaline earth metal hypochlorites selected from the group
consisting of lithium hypochlorites, calcium hypochlorites, chlorinated trisodium
phosphate dodecahydrates, potassium dichloroisocyanurates, sodium dichloroisocyanurates,
potassium trichlorocyanurates, sodium trichlorocyanurates, and mixtures thereof, more
preferably sodium dichloroisocyanurates and/or calcium hypochlorite.
[0017] Preferably, the liquid compositions according to the present invention comprise said
hypohalite bleach such that the content of active halide in the composition is of
from 0.1% to 20% by weight, more preferably from 2% to 8% by weight, most preferably
from 3% to 6% by weight of the composition.
[0018] Preferably, the solid compositions according to the present invention comprise said
hypohalite bleach such that the content of active halide in the composition is of
from 20% to 95% by weight, more preferably from 25% to 60% by weight of the composition.
Polymers
[0019] The other essential component of the invention is a polymer. That polymer, has surprisingly
been found to provide a reduction of the yellowing of the fabrics treated therewith,
i.e. improved whiteness, as well as providing improved fabric safety. Naturally, for
the purpose of the invention, the polymer has to be stable to the hypohalite bleach.
[0020] Suitable polymers for use are polymers comprising monomeric units selected from the
group consisting of unsaturated carboxylic acids, polycarboxylic acids, sulphonic
acids, phosphonic acids and mixtures thereof. Co-polymerisation of the above monomeric
units among them or with other co-monomers such as styrenesulfonic acid is also suitable.
[0021] Preferred examples of such polymers are the polymers and co-polymers of monomeric
units selected from the group consisting of acrylic acid, maleic 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 and/or phosphonic units. More preferred polymers are selected from
the group consisting of polyacrylate polymers, co-polymers of acrylic and maleic acid,
co-polymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably
modified with aminophosphonic and/or phosphonic groups.
[0022] The molecular weight for these polymers and co-polymers is preferably below 100,000,
most preferably between 500 and 50,000. 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.
[0023] Commercially available such polymers, suitable for use herein, are the polyacrylate
polymers sold under the tradename Good-Rite® from BF Goodrich, Acrysol® from Rohm
& Haas, Sokalan® from BASF, Norasol® from Norso Haas. Also suitable for use herein
are the co-polymers of styrene sulphonic acid and maleic acid, commercially available
under the tradename Versaflex® from National Starch such as Versaflex 157, as well
as Acumer® terpolymers from Rohm and Haas, in particular Acumer® 3100. Preferred commercially
available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate
polymers and more preferred are the polyacrylate polymer Norasol® 410N (MW 10,000)
and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000)
and its corresponding acid form Norasol® QR 784 (MW 4000).
[0024] A preferred polymer for use herein is a polyacrylate polymer modified with phosphonic
groups commercially available under the tradename Norasol® 440N (MW 4000) and its
corresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.
[0025] Mixtures of polymers as herein described may also be used in the present invention.
[0026] Polymers herein are preferably present in low amounts, i.e. in amounts of up to 0.5%
by weight, more preferably from 0.001% to 0.3% by weight, most preferably from 0.005%
to 0.2% by weight of the liquid composition.
[0027] The compositions may also be assessed for their whitening effect and/or safety on
the treated fabrics.
[0028] The whitening effect, i.e. 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 the same composition without the polymer.
[0029] The degree of yellowing can be determined by both visual and instumental grading.
Visually, the difference in yellowing between items treated with different compositions
can be determined by a team of expert panellists. Instrumentally, the assessment can
be determined with the help of Colorimeters such as Ganz Griesser® instruments (e.g.,
Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) or a ZEISS ELREPHO® or others
which are available for instance from Hunterlab® or Gardner®.
[0030] 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 della viscosità intrinseca in soluzione di
cuprietilendiammina (CED).
[0031] Solid compositions of the invention will preferably comprise an amount of said polymer
of from 0.01 % to 3% by weight, preferably from 0.05% to 2% by weight of the composition.
[0032] The compositions according to the present invention are either in liquid or solid
form. Solid forms include forms such as powders, tablets and granules. Preferably,
the compositions of the invention are in liquid aqueous form. More preferably, they
comprise water in an amount of from 60% to 98% by weight, more preferably of from
80% to 97% and most preferably of from 85% to 97% by weight of the total aqueous liquid
bleaching composition.
pH
[0033] The pH of the liquid compositions according to the present invention, as is, is typically
from 12 to 14 measured at 25°C. Solid compositions or liquid compositions of the invention
have a pH of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to
11.5, when diluted into 1 to 500 times its weight of water. It is in this alkaline
range that the optimum stability and performance of the hypohalite as well as fabric
whiteness and/or safety are obtained. The pH range can suitably be provided by the
pH buffering component mentioned hereinafter and the hypohalite bleach mentioned hereinbefore,
which are alkalis. However, in addition to these components, a strong source of alkalinity
may also optionally be used.
[0034] Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide,
potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such
as sodium and/or potassium oxide. A preferred strong source of alkalinity is a caustic
alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels
of such caustic alkalis, when present, are of from 0.1% to 1.5% by weight, preferably
from 0.5% to 1.5% by weight of the composition.
pH buffering component
[0035] A pH buffering component is an optional but preferred component for the compositions
of the invention. The pH buffering component ensures that the pH of the composition
is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably
from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight
of water.
[0036] Suitable pH buffering components for use herein are selected from the group consisting
of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates,
polysilicates, borates, metaborates, phosphates, stannates, alluminates and mixtures
thereof, and preferably are selected from the group consisting of sodium carbonate,
sodium silicate, sodium borate, and mixtures thereof.
[0037] The raw materials involved in the preparation of hypohalite bleaches usually contain
by-products, e.g calcium carbonate resulting in an amount of up to 0.4% by weight
of by-product within the hypohalite composition. However, at such amount, the by-product
will not have the buffering action defined above.
[0038] Liquid bleaching compositions herein will preferably contain an amount of pH buffering
component of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and
more preferably in an amount of from 0.6% to 3% by weight of the composition.
[0039] Solid bleaching compositions herein will preferably contain an amount of pH buffering
component of from 3% to 30% by weight, more preferably from 5% to 25% by weight, and
most preferably in an amount of from 10% to 20% by weight of the composition.
[0040] The composition according to the invention may also comprise further optional components
such as perfumes, bleach-stable surfactants, organic or inorganic alkalis, pigments,
dyes, optical brighteners, solvents, chelating agents, radical scavengers and mixtures
thereof.
[0041] Preferably, the compositions of the invention are used in diluted form in laundry
applications. The expression "used in diluted form" herein includes dilution by the
user, which occurs for instance in hand laundry applications, as well as dilution
by other means, such as in a washing machine. Preferably, the composition is diluted
into 5 to 500 times its weight of water for hand laundry application and 10 to 500
times its weight of water in a washing machine.
[0042] In another aspect of the invention, there is provided the use, in a hypohalite bleaching
composition, of the polymers described herein before for providing improved whiteness
and/or safety to the fabrics treated therewith. Accordingly, the present invention
also encompasses the use, in a hypohalite bleaching composition, of a polymer as described
herein before, for providing improved whiteness and/or safety to the fabrics treated
therewith. By "improved whiteness and/or safety", it is meant that hypohalite bleaching
compositions, comprising such a polymer, provide better whiteness, i.e. less yellowing,
and/or fabric safety compared to hypohalite bleaching compositions which do not comprise
said polymer.
[0043] In this embodiment the compositions, preferably but not compulsorily, comprise a
pH buffering component.
[0044] The invention is illustrated in the following non-limiting example, in which all
percentages are on a weight basis unless otherwise stated.
Example 1
[0045] The following compositions, according to the invention, were prepared:
| Composition (weight %) |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
| Sodium hypochlorite |
5.0 |
5.0 |
5.0 |
2.5 |
2.5 |
2.5 |
5.0 |
5.0 |
| Sodium hydroxide |
0.9 |
0.7 |
0.7 |
0.9 |
0.7 |
0.7 |
0.5 |
- |
| Sodium carbonate |
1.2 |
1.2 |
1.2 |
1.2 |
1.2 |
1.2 |
- |
1.5 |
| Sodium silicate |
- |
0.5 |
- |
- |
0.5 |
- |
- |
- |
| Sodium metaborate |
- |
- |
1.0 |
- |
- |
1.0 |
1.0 |
- |
| Norasol QR 784 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
| Water and minors to balance to 100 |
Example 2
[0046] The following compositions are in accordance with the present invention
| Composition (weight %) |
9 |
10 |
11 |
12 |
13 |
14 |
| Sodium hypochlorite |
5.0 |
5.0 |
5.0 |
2.5 |
2.5 |
2.5 |
| Sodium hydroxide |
0.7 |
0.7 |
0.7 |
0.9 |
0.7 |
0.7 |
| Sodium carbonate |
1.2 |
1.2 |
1.2 |
1.2 |
1.2 |
1.2 |
| Sodium silicate |
0.5 |
0.5 |
0.5 |
- |
0.5 |
0.5 |
| Norasol 410N |
0.1 |
- |
- |
0.1 |
- |
- |
| Versaflex 157 |
- |
0.1 |
- |
- |
- |
0.1 |
| PVSA* |
- |
- |
0.1 |
- |
0.1 |
- |
| Water and minors to balance to 100 |
| *Poly(vinylsulfonic acid, sodium salt) available from Aldrich (CAS 25053-27-4) |
| Composition (weight %) |
3 |
4 |
5 |
6 |
7 |
| Sodium hypochlorite |
5.0 |
5.0 |
3.5 |
3.5 |
5 |
| Sodium hydroxide |
1 |
1.5 |
1 |
1.5 |
0.8 |
| Sodium carbonate |
- |
- |
- |
- |
- |
| Sodium silicate |
- |
- |
- |
- |
- |
| Sodium metaborate |
- |
- |
- |
- |
- |
| Norasol QR 784 |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
| Water and minors to balance to 100 |
Example 3
[0047]
| Composition (weight %) |
1 |
2 |
3 |
4 |
5 |
| Sodium hypochlorite |
5.0 |
5.0 |
3.5 |
3.5 |
5 |
| Sodium hydroxide |
1 |
1.5 |
1 |
1.5 |
0.8 |
| Sodium carbonate |
- |
- |
- |
- |
- |
| Sodium silicate |
- |
- |
- |
- |
- |
| Sodium metaborate |
- |
- |
- |
- |
- |
| Versaflex 157 |
0.3 |
- |
0.1 |
- |
- |
| Norasol 440N |
- |
0.1 |
- |
0.2 |
- |
| Norasol 410N |
- |
0.1 |
0.1 |
- |
0.1 |
| Water and minors to balance to 100 |
1. A liquid bleaching composition comprising:
- a hypohalite bleach, and
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof,with the proviso that where said ingredient is a polyacrylate polymer, the
polymer is present in an amount of less than 0.5% by weight.
2. A solid bleaching composition comprising:
- a hypohalite bleach, and
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof.
3. The use, in a hypohalite bleaching composition of a polymer comprising monomeric units
selected from the group consisting of unsaturated carboxylic acids, polycarboxylic
acids, sulphonic acids, phosphonic acids, and mixtures thereof, for providing improved
whiteness and/or safety to the fabrics treated therewith.
4. A process of bleaching fabrics with a composition comprising
- a hypohalite bleach,
- a polymer comprising monomeric units selected from the group consisting of unsaturated
carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids, and mixtures
thereof,
where said fabrics are immersed in a bleaching solution formed by dissolving said
composition in water.
5. A bleaching composition according to claims 1 or 2, use according to claim 3 or process
according to claim 4, wherein said polymer is present in an amount of from 0.001%
to 0.5% by weight, preferably from 0.001% to 0.3%.
6. A bleaching composition, use or process according to claims 1-5, wherein said polymer
is selected from the group consisting of polyacrylate polymers, co-polymers of acrylic
and maleic acid, co-polymers of styrene sulphonic acid and maleic acid, and mixtures
thereof.
7. A bleaching composition, use or process according to either one of claims 1-6, wherein
said polymer has a molecular weight below 100.000.
8. A bleaching composition, use or process according to any one of claims 1-7, wherein
said composition comprises a pH buffering component which is selected from the group
consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates,
silicates, polysilicates, borates, metaborates, phosphates, stannates, alluminates,
and mixtures thereof.
9. A bleaching composition, use or process according to claim 8, wherein said pH buffering
component is selected from the group consisting of sodium carbonate, sodium silicates,
sodium borate, and mixtures thereof.
10. A bleaching composition, use or process according to any one of claims 1-9, wherein
said pH buffering component is in an amount of from 0.5% to 9% by weight, preferably
0.5% to 5% by weight of the liquid composition or in an amount of from 3% to 30% by
weight, preferably from 5% to 25% by weight of the solid composition.
11. A bleaching composition, use or process according to any one of claims 1-10, wherein
said hypohalite bleach is, for liquid bleaching compositions, an alkali metal sodium
hypochlorite or, for solid compositions, sodium dichloroisocyanurate and/or calcium
hypochlorite.
12. A bleaching composition, use or process according to any one of claims 1-11, wherein
said hypohalite, based on active halide, is present in an amount of from 0.1% to 20%
by weight, preferably from 2% to 8% by weight of the liquid composition or in an amount
of from 20% to 95% by weight, preferably from 25% to 60% by weight of the solid composition.
13. A bleaching composition, use or process according to any one of claims 1-12, wherein
said composition further comprises a strong source of alkalinity.