Patent Grant
7071156
The present invention relates to a composition for fabric care, in particular for cotton-based fabrics, comprising nanoparticles or a nanolatex of a polymer which is insoluble under the direct and/or indirect working conditions of the said composition in an aqueous or wet medium.
The expression “fabric care” means the protection of fabrics against physical or chemical degradation phenomena and/or the provision of benefits thereto, for instance softening and/or crease-resistance properties.
The machine washing of fabrics leads to a physical and chemical degradation of the fibres and most particularly of cotton fibres. The alkalinity delivered by detergents and also by certain specific compounds such as oxidizing substances (perborate or percarbonate) or certain enzymes may be the cause of the chemical degradation of cotton fibres. However, it is generally the combination of the chemical and mechanical actions which leads to degradation of the fibres. The mechanical action is produced during the washing, rinsing, spin-drying or tumble-drying, when the latter takes place in a tumble dryer. This degradation of the fibres leads to the formation of fibrils at the surface of the textile which end up causing colored textiles to lose their radiance. This degradation also induces a decrease in the strength of the textile which, at the extreme, may lead to tearing of the fabrics. This degradation of textiles may be evaluated quantitatively either by a loss of the colors of colored textiles or by a reduction in the tear strength of the textile. It is generally necessary to carry out 10 to 20 cumulative machine washes in order to perceive this type of degradation.
Cleaning in a washing machine, which systematically includes a spin-drying operation, also leads to creased fabrics, which is accentuated during the tumble-drying stage, in particular by the formation of inter-fibre hydrogen bonds. It is thus necessary to iron the fabrics in order to make them look presentable.
In order to reduce the degradation of the fibres during washing or rinsing, the suppliers of chemical products or detergents have made use of changes in detergent formulations or have used certain specific additives.
Mention may be made in particular of detergents comprising no oxidizing system, but which have reduced cleaning capacities.
Silicone-based compounds have also been used, and in particular aminosilicones (US-A-4 585 563; WO 92/07927; WO 98/39401).
The Applicant has found that the use, in compositions for treating fabrics, in particular cotton-based fabrics, of nanoparticles or of a nanolatex of insoluble polymers makes it possible to prevent the degradation of the fabrics and/or to give them crease-resistance and/or softening properties.
Such compositions may especially be compositions for washing and/or rinsing and/or softening fabrics, for destaining fabrics before washing (“prespotting”), for tumble-drying wet fabrics in a tumble dryer or for ironing fabrics.
According to the invention, the expression “polymer nanoparticles” means particles with a diameter from about 10 to 500 nm, preferably from 20 to 300 nm, most particularly from 20 to 100 nm and even more particularly from 20 to 50 nm.
The expression “polymer nanolatex” means a stable aqueous dispersion of solid polymer nanoparticles with a mean size from about 10 to 500 nm, preferably from 20 to 300 nm, most particularly from 20 to 100 nm and even more particularly from 20 to 50 nm. Such a dispersion generally has a solids content from about 10% to 50% by weight and preferably from about 20% to 40% by weight.
A first subject of the invention consists of a composition for fabric care, characterized in that it comprises nanoparticles or at least one nanolatex of at least one polymer (P) which is insoluble under the working conditions of the said composition in an aqueous or wet medium.
A second subject of the invention consists of a process for fabric care by treating these fabrics with a composition, in an aqueous or wet medium, comprising nanoparticles or at least one nanolatex of at least one polymer (P) which is insoluble in the said medium.
A third subject of the invention consists of the use, in a composition for treating fabrics in an aqueous or wet medium, of nanoparticles or of at least one nanolatex of at least one polymer (P) which is insoluble in the said medium, as an agent for fabric care.
The composition and the working (or treatment) conditions may be in numerous forms.
The said composition may be
Thus, the composition of the invention may be:
The composition of the invention is particularly suitable for fabric care, especially for cotton-based fabrics, in particular fabrics containing at least 35% cotton.
The said polymer (P) preferably has a glass transition temperature Tg from about −40° C. to 150° C., preferably from about 0 to 100° C. and most particularly from about 10 to 80° C.
The term “polymer” means either a homopolymer or a copolymer derived from two or more monomers.
For good implementation of the invention, the said polymer (P) comprises:
The said monomer units (N) and (F) are preferably derived from α-β monoethylenically unsaturated monomers.
The said monomer units (R) are preferably derived from diethylenically unsaturated monomers.
The average molar mass of the said polymer (measured by gel permeation chromatography (GPC) THF and expressed as polystyrene equivalents) may preferably be at least 20 000.
As examples of monomers from which the hydrophobic units (N) are derived, mention may be made of:
As examples of monomers from which the cationic or cationizable hydrophilic units (F1) are derived, mention may be made of:
As examples of monomers from which the amphoteric hydrophilic units (F2) are derived, mention may be made of:
As examples of monomers from which the anionic or anionizable hydrophilic units (F3) are derived, mention may be made of:
As examples of monomers from which the uncharged or non-ionizable hydrophilic units (F4) are derived, mention may be made of:
As examples of monomers from which the crosslinking units (R) are derived, mention may be made is of:
The said polymers (P) may be obtained in a known manner by free-radical polymerization in aqueous medium of ethylenically unsaturated monomers. The said nanolatices may be obtained in particular by free-radical emulsion polymerization in water.
Processes for obtaining nanoparticulate latices of small diameter are described in Colloid Polym. Sci. 266:462-469 (1988) and in Journal of Colloid and Interface Science. Vol. 89, No. 1, September 1982, pages 185 et seq. One method for preparing latices of particles with a mean size of less than 100 nm, in particular with a mean size ranging from 1 to 60 nm and most particularly from 5 to 40 nm, is described in EP-A-644 205.
The choice and relative amounts of the monomer(s) from which the unit(s) (N), (F) and (R) of the polymer (P) are derived are such that the said polymer (P) has a glass transition temperature Tg from about −40° C. to 150° C., preferably from about 0 to 100° C. and most particularly from about 10 to 80° C., and remains insoluble under the working conditions of the composition of the invention.
According to the invention, the said polymer (P) is considered as insoluble when less than 15% and preferably less than 10% of its weight is soluble in the aqueous or wet working medium of the composition of the invention, that is to say in particular under the temperature and pH conditions of the said medium.
The working pH for the composition of the invention may range from about 2 to about 12, depending on the desired use.
When it is
For good implementation of the invention, at least 70% of the total mass of the said polymer (P) is formed from hydrophobic unit(s) (N).
When hydrophilic units (F) are present, they preferably represent not more than 30% of the total mass of the polymer (P).
When crosslinking units (R) are present, they generally represent not more than 20%, preferably not more than 10% and most particularly not more than 5% of the total mass of the polymer (P).
A first embodiment of the invention consists of a composition (C1) comprising nanoparticles or at least one nanolatex of at least one uncharged or non-ionizable polymer (P1) comprising
Preferably, according to this first embodiment, the said uncharged or non-ionizable polymer (P1) comprises:
The said uncharged or non-ionizable polymer (P1) may be used in any type of fabric care composition mentioned above, the working pH of which may range from 2 to 12, namely detergent formulations, rinsing and/or softening formulations, tumble dryer additives, aqueous ironing formulations or prespotters.
A second embodiment of the invention consists of a composition (C2) comprising nanoparticles or at least one nanolatex of at least one polymer (P2) containing anionic or anionizable units and being free of cationic or cationizable units, comprising
The said polymer (P2) can be used in fabric care compositions of non-cationic nature, namely detergent formulations, tumble dryer additives, aqueous ironing formulations or prespotters.
A third embodiment of the invention consists of a composition (C3) comprising nanoparticles or at least one nanolatex of at least one polymer (P3) containing amphoteric units, comprising
The said polymer (P3) with a molar ratio of the cationic charges to the anionic charges ranging from 1/99 to 80/20 may be used in tumble dryer additives and aqueous ironing formulations.
The said polymer (P3) with a molar ratio of the cationic charges to the anionic charges ranging from 1/99 to 60/40 and preferably from 5/95 to 50/50 may also be used in detergent formulations and prespotters.
A fourth embodiment of the invention consists of a composition (C4) comprising nanoparticles or at least one nanolatex of at least one polymer (P4) containing both cationic or cationizable units and anionic or anionizable units, comprising
The said polymer (P4) with a molar ratio of the cationic charges to the anionic charges ranging from 1/99 to 80/20 may be used in tumble dryer additives and aqueous ironing formulations.
The said polymer (P4) with a molar ratio of the cationic charges to the anionic charges ranging from 1/99 to 60/40 and preferably from 5/95 to 50/50 may also be used in detergent formulations and prespotters.
A fifth embodiment of the invention consists of a composition (C5) comprising nanoparticles or at least one nanolatex of at least one polymer (P5) containing cationic or cationizable units and being free of anionic or anionizable units, comprising
The said polymer (P5) may be used in any type of fabric care composition mentioned above, the working pH of which may range from 2 to 12, namely detergent formulations, rinsing and/or softening formulations, tumble dryer additives, aqueous ironing formulations or prespotters.
In a most preferred manner, when the composition (C5) is a detergent composition, the said monomer units (F1) are cationizable units derived from at least one cationizable monomer with a pKa of less than 11 and preferably of less than 10.5.
As examples of nanoparticles or a nanolatex of polymer (P), mention may be made in particular of nanoparticles or a nanolatex of copolymers containing units derived from
The amount of nanoparticles or of nanolatex of polymer (P) present in the care composition according to the invention may range from 0.05% to 10% as dry weight relative to the dry weight of the said composition, depending on the desired application.
Thus, the said polymer (P) may be used as follows:
Other constituents may be present, along with the nanoparticles or the nanolatex of polymer (P), in the care composition according to the invention. The nature of these constituents depends on the desired use of the said composition.
Thus, when it is a detergent formulation, for washing fabrics, it generally comprises:
The detergent formulation may comprise surfactants in an amount corresponding to about 3% to 40% by weight relative to the detergent formulation, these surfactants being such as
Anionic Sulfactants
The detergent adjuvants (“builders”) for improving the surfactant properties may be used in amounts corresponding to about 5–50% and preferably to about 5–30% by weight for the liquid detergent formulations or to about 10–80% and preferably 15–50% by weight for the powder detergent formulations, these detergent adjuvants being such as:
Mineral Detergent Adjuvants
The detergent formulation may also comprise at least one oxygen-releasing bleaching agent comprising a percompound, preferably a persalt.
The said bleaching agent may be present in an amount corresponding to about 1% to 30% and preferably from 4% to 20% by weight relative to the detergent formulation.
As examples of percompounds which may be used as bleaching agents, mention should be made in particular of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and sodium persulphate.
The preferred bleaching agents are sodium perborate monohydrate or tetrahydrate and/or sodium carbonate peroxyhydrate.
The said agents are generally combined with a bleaching activator which generates, in situ in the washing medium, a peroxycarboxylic acid in an amount corresponding to about 0.1% to 12% and preferably from 0.5% to 8% by weight relative to the detergent formulation. Among these activators, mention may be made of tetraacetylethylenediamine, tetraacetyl-methylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzenesulphonate, pentaacetylglucose and octaacetyllactose.
Mention may also be made of non-oxygenated bleaching agents, which act by photo-activation in the presence of oxygen, these being agents such as sulphonated aluminium and/or zinc phthalocyanins.
The detergent formulation may also comprise soil-release agents, anti-redeposition agents, chelating agents, dispersants, fluorescers, foam suppressants, softeners, enzymes and various other additives.
Soil-Release Agents
These may be used in amounts of about 0.01–10%, preferably about 0.1–5% and more preferably about 0.2–3% by weight.
Mention may be made more particularly of agents such as:
These may be used in amounts generally of about 0.01–10% by weight for a powder detergent formulation or about 0.01–5% by weight for a liquid detergent formulation.
Mention may be made in particular of agents such as:
Agents for chelating iron and magnesium may be present in amounts of about 0.1–10% and preferably of about 0.1–3% by weight.
Mention may be made, inter alia, of:
These may be present in an amount of about 0.1–7% by weight, to control the calcium and magnesium hardness, these being agents such as:
Fluorescers (Brighteners)
These may be present in an amount of about 0.05–1.2% by weight, these being agents such as:
stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azole, methinecyanin, thiophene, etc. derivatives (“The production and application of fluorescent brightening agents” -M. Zahradnik, published by John Wiley & Sons, New York, 1982).
Foam Suppressants
These may be present in amounts which may be up to 5% by weight, these being agents such as:
These may be present in amounts of about 0.5–10% by weight, these being agents such as clays.
Enzymes
These may be present in an amount which may be up to 5 mg by weight and preferably of about 0.05–3 mg of active enzyme/g of detergent formulation, these being enzymes such as:
Mention may be made, inter alia, of:
The detergent formulation may be used, in particular in a washing machine, in a proportion of from 0.5 g/l to 20 g/l and preferably from 2 g/l to 10 g/l to carry out washing operations at a temperature from about 25 to 90° C.
A second embodiment of the care composition of the invention consists of an aqueous liquid formulation for rinsing and/or softening fabrics.
It may be used in a proportion of from 0.2 to 10 g/l and preferably from 2 to 10 g/l.
Along with the nanoparticles or the nanolatex of polymer (P), there may be present other constituents of the type such as:
A third embodiment of the care composition of the invention consists of an additive for drying fabrics in a suitable tumble dryer.
The said additive comprises a flexible solid support consisting, for example, of a strip of woven or nonwoven textile or a sheet of cellulose, comprising nanoparticles or impregnated with the nanolatex of polymer (P); the said additive is introduced at the time of tumble-drying into the wet fabrics to be dried at a temperature from about 50 to 80° C. for 10 to 60 minutes.
The said additive may also comprise cationic softeners (up to 99%) and color-fast agents (up to 80%), such as those mentioned above.
A fourth embodiment of the care composition of the invention consists of an ironing formulation which may be sprayed directly onto the dry fabrics before ironing.
The said formulation may also contain silicone-based polymers (from 0.2% to 5%), nonionic surfactants (from 0.5% to 5%) or anionic surfactants (from 0.5% to 5%), fragrances (0.1% to 3%) or cellulose derivatives (0.1% to 3%), for instance starch; spraying the said formulation onto the fabrics makes it easier to iron them and limits the creasing of the fabrics when they are worn.
A fifth embodiment of the care composition of the invention consists of a prespotter which is in the form of an aqueous dispersion or a solid (stick).
Along with the nanoparticles or the nanolatex of polymer (P), there may be present other constituents of the type such as:
A second subject of the invention consists of a process for caring for fabric's by treating them with a composition, in an aqueous or wet medium, comprising at least nanoparticles or a nanolatex of at least one polymer (P) that is insoluble in the said medium.
The type of composition, and also the amounts of polymer (P) and other additives which may be used, have already been mentioned above.
A third subject of the invention consists of the use, in a composition for treating fabrics in an aqueous or wet medium, of nanoparticles or of at least one nanolatex of at least one polymer (P) that is insoluble in the said medium, as a fabric care agent.
The type of composition, and also the amounts of polymer (P) and other additives which may be used, have already been mentioned above.
The said nanoparticles or the said nanolatex protect the fabrics in particular against physical or chemical degradation and/or give them benefits such as softening and/or crease-resistance properties.
The diameters of the nanoparticles or nanolatices of polymer according to the invention may be determined in a well-known manner by light scattering or by transmission electron microscopy.
The examples which follow are given for illustrative purposes.
The polymer (P) latices used to prepare the formulations in the examples of the invention are the latices (I) and (II) below:
Latex (I) of
washing operation is carried out in a Tergotometer laboratory machine which is well known in the profession to detergent composition formulators. The machine simulates the mechanical and thermal effects of pulsating-type American washing machines, but, by virtue of the presence of 6 washing drums, it makes it possible to carry out simultaneous series of tests with an appreciable saving in time.
25×25 cm test pieces are cut from unfinished cotton. The cotton test pieces are first ironed so that they all have the same level of creasing before washing.
They are then washed using the above detergent formulation containing latex (I) and rinsed once, under the following conditions:
The test pieces are then creased under a 3 kg press for 20 seconds, after which they are dried vertically overnight.
The same operation is carried out using the same detergent formulation, but free of latex (I).
A digital color photograph is then taken of the dry test pieces, which is then converted into 256 grey scale levels (grey scale from 0 to 255).
The number of pixels corresponding to each grey scale level are counted.
For each histogram obtained, the standard deviation σ of the distribution of the grey scale level is measured. σ1 corresponds to the standard deviation obtained with the detergent formulation containing no latex. σ2 corresponds to the standard deviation obtained with the detergent formulation containing latex (I).
The performance value is given by the equation −Δσ=σ2−σ1
The performance values obtained are as follows:
These positive values of −Δσ are representative of a crease-resistance property provided by the detergent formulation comprising the latex according to the invention.
Rinsing/Softening Formulation
| Number | Date | Country | Kind |
|---|---|---|---|
| 00 10945 | Aug 2000 | FR | national |
| 01 07590 | Jun 2001 | FR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3340217 | Woodruff | Sep 1967 | A |
| 3544501 | Feamley et al. | Dec 1970 | A |
| 4746455 | Matsuda et al. | May 1988 | A |
| Number | Date | Country |
|---|---|---|
| WO 9800449 | Jan 1998 | EP |
| 1 416 813 | Jan 1966 | FR |
| WO 9800449 | Jan 1998 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20020065208 A1 | May 2002 | US |
