The invention relates to a process for coating a material surface, comprising the steps of:

The present invention is directed to a process for the manufacture of branched and optionally crosslinked coatings on bulk polymeric materials with high wettability by aqueous biological media and minimal irreversible adsorption of proteins, and their use for biomedical applications, especially contact lenses including extended-wear contact lenses. The need for highly wettable, minimally protein-fouling coatings is well recognized particularly in the contact lens field. Bulk polymeric materials that possess high oxygen permeability are of great interest for application as extended wear contact lenses. Unfortunately polymers that provide high oxygen transmission possess a relatively hydrophobic surface even if their water content is in the range of 20 to 30%. This leads to excessive discomfort and unacceptably rapid dewetting of the lens by the tear film when such lenses are worn by humans. Hence such contact lens bulk materials must be equipped with a coating that allows good wetting by the human tear fluid. Application of thin polymeric coatings, for instance from gas plasmas (glow discharges) struck in methane/air mixtures ameliorates this problem and enables comfortable wear of such composite lenses. However, the irreversible deposition of biological molecules (biofouling), particularly proteins, onto such coated lenses can lead to the onset of symptoms of discomfort in some wearers and therefore still presents a drawback that needs to be overcome to obtain an ultimately comfortable lens for even the most sensitive wearers.
It is the object of the present invention to provide hydrophilic polymer coatings that have the desirable property of providing superior resistance to fouling of contact lenses by tear film proteins while also allowing high wettability by the tear film. Surprisingly, this can be achieved by the use of branched and optionally crosslinked hydrophilic polymer-containing chains. The coatings of the present invention have been found to result in no observable protein adsorption even when complex multi-protein solutions were used, such as human tear fluid. Exposure to multicomponent protein media presents a far more demanding challenge for coatings intended to be protein-resistant than exposure to single protein solutions, and hence the protein-resisting abilities of the coatings of the present invention are clearly demonstrated.
The present invention therefore in one aspect relates to a process for coating a material surface, comprising the steps of: Coating Process
(a) covalently binding a compound comprising an ethylenically unsaturated double bond to the material surface;
(b) polymerizing a monomer comprising a reactive or crosslinkable group on the surface and thereby providing a primary polymer coating comprising reactive or crosslinkable groups,
(c) in case of a monomer comprising a reactive group in step (b) reacting the reactive groups of the primary coating with a further compound comprising an ethylenically unsaturated double bond and graft-polymerizing a hydrophilic monomer and optionally a co-monomer having a crosslinkable group onto the primary coating obtained according to step (b) and
(d) in case of crosslinkable groups being present in step (b) or (c) initiating crosslinking of said groups.
Examples of materials that may be coated according to the process of the invention are quartz, ceramics, glasses, silicate minerals, silica gels, metals, metal oxides, carbon materials such as graphite or glassy carbon, natural or synthetic organic polymers, or laminates, composites or blends of said materials, in particular natural or synthetic organic polymers which are known in large number. Some examples of polymers are polyaddition and polycondensation polymers (polyurethanes, epoxy resins, polyethers, polyesters, polyamides and polyimides); vinyl polymers (polyacrylates, polymethacrylates, polystyrene, polyethylene and halogenated derivatives thereof, polyvinyl acetate and polyacrylonitrile); elastomers (silicones, polybutadiene and polyisoprene); or modified or unmodified biopolymers (collagen, cellulose, chitosan and the like).
A preferred group of materials to be coated are those being conventionally used for the manufacture of biomedical devices, e.g. contact lenses, in particular contact lenses for extended wear, which are not hydrophilic per se. Such materials are known to the skilled artisan and may comprise for example polysiloxanes, perfluoropolyethers, fluorinated poly(meth)acrylates or equivalent fluorinated polymers derived e.g. from other polymerizable carboxylic acids, polyalkyl (meth)acrylates or equivalent alkylester polymers derived from other polymerizable carboxylic acids, or fluorinated polyolefines, such as fluorinated ethylene propylene, or tetrafluoroethylene, preferably in combination with specific dioxols, such as perfluoro-2,2-dimethyl-1,3-dioxol. Examples of suitable bulk materials are e.g. Lotrafilcon A, Neofocon, Pasifocon, Telefocon, Silafocon, Fluorsilfocon, Paflufocon, Silafocon, Elastofilcon, Fluorofocon or Teflon AF materials, such as Teflon AF 1600 or Teflon AF 2400 which are copolymers of about 63 to 73 mol % of perfluoro-2,2-dimethyl-1,3-dioxol and about 37 to 27 mol % of tetrafluoroethylene, or of about 80 to 90 mol % of perfluoro-2,2-dimethyl-1,3-dioxol and about 20 to 10 mol % of tetrafluoroethylene.
Another preferred group of materials to be coated are those being conventionally used for the manufacture of biomedical devices, e.g. contact lenses, which are hydrophilic per se, since reactive groups, e.g. carboxy, carbamoyl, sulfate, sulfonate, phosphate, amine, ammonium or hydroxy groups, are inherently present in the material and therefore also at the surface of a biomedical device manufactured therefrom. Such materials are known to the skilled artisan and comprise for example polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate (HEMA), polyvinyl pyrrolidone (PVP), polyacrylic acid, polymethacrylic acid, polyacrylamide, polydimethylacrylamide (DMA), polyvinyl alcohol or copolymers for example from two or more monomers from the group hydroxyethyl acrylate, hydroxyethyl methacrylate, N-vinyl pyrrolidone, acrylic acid, methacrylic acid, acrylamide, dimethyl acrylamide, vinyl alcohol and the like. Typical examples are e.g. Polymacon, Tefilcon, Methafilcon, Deltafilcon, Bufilcon, Phemfilcon, Ocufilcon, Focofilcon, Etafilcon, Hefilcon, Vifilcon, Tetrafilcon, Perfilcon, Droxifilcon, Dimefilcon, Isofilcon, Mafilcon, Nelfilcon or Atlafilcon.
Still another group of preferred materials to be coated are amphiphilic segmented copolymers comprising at least one hydrophobic segment and at least one hydrophilic segment which are linked through a bond or a bridge member. Examples are silicone hydrogels, for example those disclosed in PCT applications WO 96/31792 and WO 97/49740 which are herewith incorporated by reference.
The material to be coated may also be any blood-contacting material conventionally used for the manufacture of renal dialysis membranes, blood storage bags, pacemaker leads or vascular grafts. For example, the material to be modified on its surface may be a polyurethane, polydimethylsiloxane, polytetrafluoroethylene, polyvinylchloride, Dacron(trademark) or a composite made therefrom.
Moreover, the material to be coated may also be an inorganic or metallic base material with or without suitable reactive groups, e.g. ceramic, quartz, or metals, such as silicon or gold, or other polymeric or non-polymeric substrates. E.g. for implantable biomedical applications, ceramics or carbohydrate containing materials such as polysaccharides are very useful. In addition, e.g. for biosensor purposes, dextran coated base materials are expected to reduce nonspecific binding effects if the structure of the coating is well controlled. Biosensors may require polysaccharides on gold, quartz, or other non-polymeric substrates. The form of the material to be coated may vary within wide limits. Examples are particles, granules, capsules, fibres, tubes, films or membranes, preferably moldings of all kinds such as ophthalmic moldings, in particular contact lenses.
According to step (a) the compound comprising an ethylenically unsaturated group is suitably covalently bound to the surface of the material to be modified on its surface via reaction of a functional group of the material surface with a co-reactive group of the ethylenically unsaturated compound. Suitable functional groups may be inherently (a priori) present at the surface of the material to be modified on its surface. If substrates contain too few or no reactive groups, the material surface can be modified by methods known per se, for example plasma chemical methods (see, for example, WO 94/06485), or conventional functionalization with groups such as xe2x80x94OH, xe2x80x94NH2 or xe2x80x94CO2H. Suitable functional groups may be selected from a wide variety of groups well known to the skilled artisan. Typical examples are e.g. hydroxy groups, amino groups, carboxy groups, carbonyl groups, aldehyde groups, sulfonic acid groups, sulfonyl chloride groups, isocyanato groups, carboxy anhydride groups, lactone groups, azlactone groups, epoxy groups and groups being replaceable by amino or hydroxy groups, such as halo groups, or mixtures thereof. Amino groups and hydroxy groups are preferred.
The compound comprising an ethylenically unsaturated group according to step (a) may be for example, a vinyl monomer having from 2 to 18 C-atoms and preferably from 2 to 10 C-atoms, which is substituted by a reactive group wherein the above-mentioned meanings and preferences apply.
Suitable reactive groups of the vinyl monomer according to step (a) may be a hydroxy, amino, carboxy, carboxylic acid ester, carboxylic acid anhydride, epoxy, lactone, azlactone or isocyanato group. One group of preferred reactive groups comprises carboxy, carboxylic acid anhydride, azlactone or isocyanato, in particular isocyanato. Another group of preferred reactive groups comprises amino or in particular hydroxy.
Suitable vinyl monomers having a reactive group may be compounds of formula
wherein R1 is hydrogen, unsubstituted or hydroxy-substituted C1-C6-alkyl or phenyl,
R2 and R3 are each independently of the other hydrogen, C1-C4-alkyl, phenyl, carboxy or halogen,
R4 is hydrogen, C1-C4-alkyl or halogen,
R5 and R5xe2x80x2 are each an ethylenically unsaturated radical having from 2 to 6 C-atoms, or R5 and R5xe2x80x2 together form a bivalent radical xe2x80x94C(R2)xe2x95x90C(R4)xe2x80x94, and
(Alk*) is C1-C6-alkylene, and (Alk**) is C2-C12-alkylene.
The following preferences apply to the variables contained in formulae (1a)-(1e):
R1 is preferably hydrogen or hydroxy-C1-C4-alkyl, in particular hydrogen or xcex2-hydroxyethyl.
One of the variables R2 and R3 is preferably hydrogen and the other one is hydrogen, methyl or carboxy. Most preferably R2 and R3 are each hydrogen.
R4 is preferably hydrogen or methyl.
R5 and R5xe2x80x2 are preferably each vinyl or 1-methylvinyl, or R5 and R5xe2x80x2 together form a radical-C(R2)xe2x95x90C(R4)xe2x80x94 wherein R2 and R4 are each independently hydrogen or methyl. (Alk*) is preferably methylene, ethylene or 1,1-dimethyl-methylene, in particular a radical xe2x80x94CH2xe2x80x94 or xe2x80x94C(CH3)2xe2x80x94.
(Alk**) is preferably C2-C4-alkylene and in particular 1,2-ethylene.
Particularly preferred vinyl monomers having a reactive group are 2-isocyanatoethylmeth-acrylate (IEM), 2-vinyl-azlactone, 2-vinyl-4,4-dimethyl-azlactone, acrylic acid, methacrylic acid, acrylic acid anhydride, maleinic acid anhydride, 2-hydroxyethylacrylate (HEA), 2-hydroxymethacrylate (HEMA), glycidylacrylate or glycidylmethacrylate.
Throughout the application terms such as carboxy, carboxylic acid, xe2x80x94COOH, sulfo, xe2x80x94SO3H, amino, xe2x80x94NH2 and the like always include the free acid or amine as well as a suitable salt thereof, for example a biomedically or in particular occularly acceptable salt thereof such as, for example, a sodium, potassium, ammonium salt or the like (of an acid), or a hydrohalide such a hydrochloride (of an amine).
In a preferred embodiment of the invention, the covalent bonding between the inorganic or preferably material surface and the compound comprising an ethylenically unsaturated group occurs via reaction of a hydroxy, amino, alkylamino, thiol or carboxy group, particularly of a hydroxy or amino group, of the substrate surface with an isocyanato, azlactone, epoxy, carboxy anhydride, carboxy or hydroxy group, particularly with an isocyanato group, of the ethylenically unsaturated compound, for example using an ethylenically unsaturated compound of formula (1a)-(1e). Suitable methods for this are known from textbooks of organic chemistry. The reaction may be carried out, for example, at elevated temperature, for example from 0xc2x0 to 100xc2x0 C. and preferably at room temperature, and optionally in the presence of a catalyst. After the reaction, excess compounds can be removed, for example, with solvents.
According to a preferred embodiment of the invention the material to be coated is an organic polymer containing H-active groups, in particular xe2x80x94OH, xe2x80x94NH2 and/or xe2x80x94NHxe2x80x94, on the surface that are co-reactive with isocyanato groups, some or all of whose H atoms have been substituted by radicals of the formulaxe2x80x94C(O)N(H)-(Alk**)-OC(O)-C(R4)xe2x95x90CR2(R3), wherein (Alk**), R2, R3 and R4 have the meaning given above, particularly 2-isocyanatoethylmethacrylate (IEM).
In step (b) the vinyl monomer having a reactive or crosslinking group may be grafted as such or in admixture with a suitable vinyl co-monomer, preferably a hydrophilic vinyl co-monomer, onto the material surface.
A preferred embodiment of step (b) of the invention concerns co-polymerizing a vinyl monomer comprising a reactive group with a hydrophilic vinyl co-monomer.
Another preferred embodiment of step (b) is the co-polymerization of a vinyl monomer comprising a crosslinkable group, with a hydrophilic vinyl co-monomer.
A suitable vinyl monomer having a reactive group in step (b) independently may be one of the compounds comprising an ethylenically unsaturated group mentioned in step (a) where the above given meanings and preferences apply. A particularly preferred monomer having a reactive group in step (b) is acrylic acid.
Suitable monomers having a crosslinkable group include, without the following being an exhaustive list, difunctionalized active esters, such as ethylene glycolbis[sulfosuccinimidyl-succinate] and bis[sulfosuccinimdyl]suberate, sulfosuccinimidyl[4-azidosalicylamido]hexano-ate, difunctional isocyanates, diacrylates such as 1,4-butanedioldiacrylate or xcex1,xcfx89-PEG-diacrylate and diepoxides such as ethyleneglycoldiglycidylether.
Preferably, the crosslinkable monomer is a monofunctonal vinyl monomer, for example a vinyl monomer comprising an isocyanato, epoxy, hydroxy, amino or carboxy functionality. The crosslinking according to step (d) then may be accomplished through these groups, either by reaction with each other or with other functional groups being present in the polymer. For example, when using a monomer having a hydroxyalkyl group such as N-hydroxymethyl acrylamide, the hydroxyalkyl groups of the resulting polymer may be crosslinked afterwards in an acidic medium. Alternatively, functional groups in the resulting polymer such as those mentioned above may be crosslinked afterwards by adding a co-reactive difunctional compound, for example a diamine such as ethylenediamine, a diol, a polyol or a diisocyanate.
The expression xe2x80x9chydrophilic vinyl co-monomerxe2x80x9d is understood to mean a monomer that typically produces as homopolymer a polymer that is water-soluble or capable of absorbing at least 10% by weight water.
The proportion of vinyl monomers having a reactive group, if used, is preferably from 0.001 to 1 units per unit of hydrophilic vinyl co-monomer, especially from 0.01 to 0.5 units, more preferably from 0.02 to 0.2 units and in particular from 0.02 to 0.1 units. The number of crosslinking monomers, if used, is preferably from 0.001 to 0.1 units per unit of hydrophilic vinyl co-monomer, especially from 0.01 to 0.05 units and most preferably from 0.01 to 0.02 units.
Suitable hydrophilic vinyl co-monomers include, without the following being an exhaustive list, hydroxy-substituted C1-C2-alkyl acrylates and methacrylates, acrylamide, methacryl-amide, N-mono- or N,N-di-C1-C2-alkylacrylamide and -methacrylamide, ethoxylated acrylates and methacrylates, hydroxy-substituted C1-C2-alkyl vinyl ethers, sodium ethylenesulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinylsuccinimide, five- to seven-membered N-vinyl lactams, 2- or 4-vinylpyridine, amino- (the term xe2x80x9caminoxe2x80x9d also including quatemary ammonium), mono-C1-C2-alkylamino- or di-C1-C2-alkylamino-C1-C2-alkyl acrylates and methacrylates, allyl alcohol and the like. Preferred are acrylamide, N,N-di-C1-C2-alkyl(meth)acrylamides such as N,N-dimethyl acrylamide or five- to seven-membered N-vinyl lactams such as N-vinylpyrrolidone, in particular acrylamide.
The vinyl monomer having a reactive or crosslinking group, optionally in admixture with a hydrophilic vinyl co-monomer, may be applied to the modified material surface and polymerized there according to processes known per se. For example, the material is immersed in a solution of the vinyl monomer(s), or a layer of vinyl monomer(s) is first of all deposited on the modified material surface, for example, by dipping, spraying, spreading, knife coating, pouring, rolling, spin coating or vacuum vapor deposition. Suitable solvents, if used in the polymerization process, are water and, for example, dipolar aprotic solvents such as, for example, acetonitrile. The polymerization of the vinyl monomer(s) on the material surface then may be initiated, for example, thermally by the action of heat or by irradiation, particularly by UV radiation. Suitable light sources for the irradiation are known to the artisan and comprise for example mercury lamps, high pressure mercury lamps, xenon lamps, carbon arc lamps or sunlight. The time period of irradiation may depend, for example, on the desired properties of the resulting composite material but is usually in the range of up to 30 minutes, preferably from 10 seconds to 10 minutes, and particularly preferably from 0.5 to 5 minutes. It is advantageous to carry out the irradiation in an atmosphere of inert gas. After the polymerization, any non-covalently bonded monomers, oligomers or polymers formed can be removed, for example by treatment with suitable solvents.
In case of a thermally initiated polymerization of the vinyl monomer(s) on the material surface said polymerization may be carried out, for example, at elevated temperature, for example at a temperature of from 35 to 100xc2x0 C. and preferably 40 to 80xc2x0 C., for a time period of, for example, from 10 minutes to 48 hours and preferably 30 minutes to 36 hours in the absence or presence of one of the above-mentioned solvents. It is advantageous to carry out the thermally initiated polymerization in an atmosphere of inert gas.
Polymerization initiators are typically those that are initiating a radical polymerization of ethylenically unsaturated compounds. Suitable thermal polymerization initiators are known to the skilled artisan and comprise for example peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates or mixtures thereof. Examples are benzoylperoxide, tert.-butyl peroxide, di-tert.-butyl-diperoxyphthalate, tert.-butyl hydroperoxide, azo-bis(isobutyronitrile), 1,1xe2x80x2-azo-bis (1-cyclohexanecarbonitrile), 2,2xe2x80x2-azo-bis(2,4-dimethylvaleronitrile), 4,4xe2x80x2-azo-bis(4-cyanovaleric acid and the like.
Initiators for the radiation-induced polymerization may belong to different types, for example to the thioxanthone type and to the benzoin type, particularly benzoinmethylether, 1-hydroxycyclohexylphenyl ketone, Darocure 1173 and Irgacure types.
By means of the polymerization step (b), the vinyl monomer(s) may be grafted to the bulk material surface with formation of a primary coating comprising a plurality of polymer chains bonded to the surface. Each polymer chain contains reactive groups or crosslinking groups at regular intervals (if the vinyl monomer comprising the reactive or crosslinking group is used without a vinyl co-monomer) or statistically distributed (if the vinyl monomer comprising the reactive or crosslinking group is used in combination with a vinyl co-monomer). The reactive groups that are present in the polymer chains are those mentioned before in the description of the vinyl monomers comprising a reactive group.
A suitable further compound comprising an ethylenically unsaturated double bond in step (c) independently may be one of the compounds comprising an ethylenically unsaturated group mentioned in step (a) where the above given meanings and preferences apply. A particularly preferred compound having an ethylenically unsaturated double bond in step (c) is IEM.
A suitable hydrophilic monomer used in step (c) may be one of the hydrophilic vinyl co-monomers mentioned in step (b), wherein the above given meanings and preferences apply.
A suitable crosslinking monomer used in step (c) may be one of the monomers having a crosslinkable group as mentioned in step (b) wherein the above given meanings and preferences apply.
A preferred embodiment of step (c) comprises first of all reacting a compound comprising an ethylenically unsaturated double bond, in particular IEM, with the primary coating obtained according to step (b) and then graft polymerizing a hydrophilic monomer, in particular acrylamide, onto the primary coating.
A further preferred embodiment of step (c) comprises first of all reacting a compound comprising an ethylenically unsaturated double bond, in particular IEM, with the primary coating obtained according to step (b) and then graft polymerizing a mixture of a hydrophilic monomer, in particular acrylamide, and a crosslinking monomer onto the primary coating.
The graft polymerization in step (c) may be accomplished as described in step (b).
One embodiment of the optional step (d) comprises the crosslinking of crosslinkable groups being present on the modified material surface after step (b) or (c) with a difunctional compound selected from the group consisting of diisocyanates, diamines, dioles, 1,4-butanedioldiacrylates and xcex1,xcfx89PEG-diacrylates. A further embodiment of the optional step (d) comprises the crosslinking of crosslinkable groups being present on the modified material surface after step (b) or (c) by means of an addition or condensation reaction.
The coated material obtained according to the invention may be purified afterwards in a manner known per se, for example by washing or extraction with a suitable solvent such as water.
The coating thickness of the coated material surfaces obtained according to the process of the invention depends principally on the desired properties. It can be, for example, from 0.001 to 1000 xcexcm, preferably from 0.01 to 500 xcexcm, more preferably from 0.01 to 100 xcexcm, even more preferably from 0.05 to 50 xcexcm, especially preferably from 0.1 to 5 xcexcm and particularly preferably from 0.1 to 1 xcexcm.
A further embodiment of the invention relates to a material that is coated by the process of the invention.
The material that is coated by the process of the invention is, for example, an organic bulk material, preferably a biomedical device, e.g. an ophthalmic device, preferably a contact lens including both hard and particularly soft contact lenses, an intraocular lens or artificial comea. Further examples are materials useful for example as wound healing dressings, eye bandages, materials for the sustained release of an active compound such as a drug delivery patch, moldings that can be used in surgery, such as heart valves, vascular grafts, catheters, artificial organs, encapsulated biologic implants, e.g. pancreatic islets, materials for prostheses such as bone substitutes, or moldings for diagnostics, membranes or biomedical instruments or apparatus.
The biomedical devices, e.g. ophthalmic devices obtained according to the invention have a variety of unexpected advantages over those of the prior art which make those devices very suitable for practical purposes,e.g. as contact lens for extended wear or intraocular lens.
For example, they do have a high surface wettability which can be demonstrated by their contact angles, their water retention and their water-film break up time or tear film break up time (TBUT).
The TBUT plays an particularly important role in the field of ophthalmic devices such as contact lenses. Thus the facile movement of an eyelid over a contact lens has proven important for the comfort of the wearer; this sliding motion is facilitated by the presence of a continuous layer of tear fluid on the contact lens, a layer which lubricates the tissue/lens interface. However, clinical tests have shown that currently available contact lenses partially dry out between blinks, thus increasing friction between eyelid and the lens. The increased friction results in soreness of the eyes and reduced movement of the contact lenses. Now it has become feasible to considerably increase the TBUT of commercial contact lenses such as, for example, Focus Dailies (trademark), Focus New Vuess or Lotrafilcon A lenses, by applying a surface coating according to the invention. On the base curve of a contact lens, the pronounced lubricity of the coating facilitates the on-eye lens movement which is essential for extended wear of contact lenses. Moreover, the materials obtained by the process of the invention provide additional effects being essential for lenses for extended wear, such as an increased thickness of the pre-lens tear film which contributes substantially to low microbial adhesion and resistance to deposit formation. Due to the extremely soft and lubricious character of the novel surface coatings, biomedical articles such as in particular contact lenses coated by the process of the invention show a superior wearing comfort including improvements with respect to late day dryness and long term (overnight) wear. The novel surface coatings moreover interact in a reversible manner with occular mucus which contributes to the improved wearing comfort.
In addition, biomedical devices, e.g. ophthalmic devices such as contact lenses, coated by the process of the invention, have a very pronounced biocompatibility combined with good mechanical properties. For example, the devices are blood compatible and have a good tissue integration. In addition, there are generally no adverse eye effects observed, while the adsorption of proteins or lipids is low, also the salt deposit formation is lower than with conventional contact lenses. Generally, there is low fouling, low microbial adhesion and low bioerosion while good mechanical properties can be for example found in a low friction coefficient and low abrasion properties. Moreover, the dimensional stability of the materials obtained according to the invention is excellent. In addition, the attachment of a hydrophilic surface coating at a given bulk material according to the invention does not affect its visual transparency.
In summary, the ophthalmic devices obtained by the process of the invention, such as contact lenses and artificial cornea, provide a combination of low spoilation with respect to cell debris, cosmetics, dust or dirt, solvent vapors or chemicals, with a high comfort for the patient wearing such ophthalmic devices in view of the soft hydrogel surface which for example provides a very good on-eye movement of the ohthalmic device. Biomedical devices such as adhesion barriers in tissue surgery, renal dialysis membranes, blood storage bags, pacemaker leads or cardiovascular devices such as heart valves and artificial blood vessels (vascular grafts) coated by the process of the invention resist fouling by proteins, thus reducing the rate and extent of thrombosis. Blood-contacting devices fabricated according to the present invention are therefore haemocompatible and biocompatible. Diagnostics and biosensing applications suffer from reduced signal-to-noise ratios when non-specific protein adsorption occurs; hence, the present coatings offer scope for devices with greater range of sensitivity.
In the examples, if not indicated otherwise, amounts are amounts by weight, temperatures are given in degrees Celsius. Tear break-up time values in general relate to the pre-lens tear film non-invasive break-up time (PLTF-NIBUT) that is determined following the procedure published by M. Guillon et al., Ophthal. Physiol. Opt. 9, 355-359 (1989) or M. Guillon et al., Optometry and Vision Science 74, 273-279 (1997). Average advancing and receding water contact angles of coated and non-coated lenses are determined with the dynamic Wilhelmy method using a Krxc3xcss K-12 instrument (Kruss GmbH, Hamburg, Germany). Welling force on the solid is measured as the solid is immersed in or withdrawn from a liquid of known surface tension.

Abstract: (d) in case of crosslinkable groups being present in step (b) or (c) initiating crosslinking of said groups. The coated articles that are obtainable by the process of the invention have desirable characteristics regarding adherence to the substrate, durability, hydrophilicity, wettability, biocompatibility and permeability and are thus useful for the manufacture of biomedical articles such as ophthalmic devices.


A digital communication system with digital short message system text capability including a miniaturized transceiver and cooperating intelligent docking station which provides memory to store the received texts and for indication and selective display of the short message service texts plus additional external communication links to other networks.

Personal use radio frequency (RF) transceivers such as cellular phones continue to decrease in size approaching cigarette-pack size for convenient carrying in shirt pockets. Small transceivers are severely limited in their capability to include physically large components such as occasional-use digital memory banks. At the same time transceivers are being designed to include short message service (SMS) message capability. SMS messages are transmitted text which can be transmitted digitally to portable digital wireless transceivers such as cellular telephones where the messages may be displayed on a liquid crystal display. A typical message may, for example, include instructions to call a particular customer telephone number or to call the office. This service enables the cellular phone to finction as similar to a combination beeper and answering machine to record and later display brief messages transmitted in the absence of the user or while the user is otherwise occupied. While SMS has not yet become commercially available in the United States it is part of the European Global System for Mobile Communications (GSM) and is the subject of interim industry standards IS-136 and IS-137 in the United States.
However, the diminishing size of portable transceivers, whether RF or infrared, presents a challenge regarding the inclusion of adequate memory capability to receive, record and playback on demand a number of recorded texts.
In addition to the problem of adding memory capability to transceivers being shrunk in size, it is also desirable to be able to add external communications means to facilitate communications to other networks through other communications links further compounding the size problem.

Intelligent docking station for use with a portable wireless receiver to provide expanded short message services


A filter device, particularly for filtering melt-type fluids, such as polymer melts, includes at least one filter disk having two filter disk halves connected to each other by their edges and provided with filter material on their exterior surfaces. The filter disk halves are held apart by a supporting device delimiting a substantially free hollow area between them, through which a fluid can flow freely. Inwardly, they delimit an outflow opening for the melt-type filtered fluid. The supporting device has individual supporting cams of substantially equal outer dimensions and arranged in several groups. Separated from each other, the supporting cams extend radially outwardly form the outflow opening, are rigidly connected to at least one of the two halves, and traverse the hollow area in such a way as to rest against the other filter disk half. This results in a filter device which is economical to produce and which has enhanced filter performance when in operation. It is suited particularly to filtering melt-type liquids, such as polymer melts, under high pressure.

The present invention relates to a filter device, especially for filtering melt-like fluids, such as polymer melts, having at least one filter disk made up of two filter disk halves. The filter disk halves are connected with one another along one edge and are fitted with a fabric or cloth fabric filter material aligned on the exterior. The disk halves are held at some distance from one another by a support arrangement to define a hollow space between them having an essentially open flow-through passage. In the interior, an outlet opening is provided for the melt-like fluid.
U.S. Pat. No. 4,902,420 discloses a filter arrangement with a multi-layer construction. Between the fabric or cloth fabric filter materials lying facing one another a drainage plate is inserted as support device Longitudinal slots extend from the exterior to the interior to define a hollow space of small volume between the fabric or cloth fabric filter materials. The medium to be filtered, for example a polymer melt, in this system is subjected to increased flow resistance, so that the filter capacity is correspondingly decreased. Because of the complicated construction and the multiplicity of parts, the manufacturing costs are higher. Furthermore, the separation of the fluid streams in the filter disk occurring by the separation into various longitudinal slots causes the so-called memory effect. If, for instance, there is subsequent formation of blowholes or such phenomena out of the polymer melts, this leads to undesired formations of strips or lamina.
DE-AS 1,096,331 discloses a filter device having at least one filter disk formed of two filter disk halves connected with one another. Between them, the filter disk halves limit an essentially open passage, allowing flow-through in the hollow space. A fabric or cloth fabric filter material is aligned on the disk halves exterior. The filter disk half has a metal disk with discharge openings or is constructed of spoke-like fillets. Coiled ribs or fins or fillets are used as a support arrangement, and extend radially inward and at some distance from one another over the entire hollow space, which tapers conically outward to the exterior periphery. Insufficient support is provided for the filter disk halves with their fabric or cloth filter material, so that this filter arrangement can be used only in a limited manner. Especially when high pressures are present, it cannot be used without danger of breakdown. Additionally, the ribs or fins used in this filter arrangement separate the hollow space which is preferably open to flow-through into individual chambers. Here too, the flow resistance is increased, so that this filter arrangement does not suffice for the filtering of melt-like fluids.
Objects of the present invention are to provide improved filter arrangements which can be manufactured at low cost and which allow an increased filtering capacity during operation. Especially for the filtering of melt-like fluids, such as polymer melts, it can be designed for use under high pressures.
The support arrangement includes individual supporting cams with essentially identical exterior dimensions. The cams extend outwardly from the discharge opening, are arranged in a plurality of groups, are separated from one another radially, are securely connected with at least one of the two filter disk halves and pass through the hollow space. In this manner, each filter disk half is in contact with the other filter disk half, and the entire hollow space is available as an essentially open flow-through passage. The above-described drainage plates can then be deleted to save cost. Consequently, the flow volume of the melt-like fluid to be filtered, such as polymer melts, and consequently also the filtering capacity, are increased.
As a result of having the plurality of supporting cams arranged in groups, extending between the two filter disk halves of a filter disk and supporting this disk assembly, a high resistance to pressure stresses on the filter disk halves as well as on their fabric or cloth fabric filter materials is attained. Overall, a highly pressure-stable filter disk is realized for use in the filter device. Simultaneously, the offset arrangement of the supporting cams causes mixing of the melt flow, which thus counters the memory-effect.
With one preferred embodiment of the filter device according to the present invention, the individual group arrangements of supporting cams are arranged at different radial distances from the outlet opening and are aligned along concentric circles around this outlet opening. Such an arrangement allows a high degree of support for the filter disk halves. Accordingly, such arrangement has only a slightly negative influence on the dimensions of the opening of the, hollow space for flow-through between the filter disk halves in the sense of causing only a slight increase of flow resistance. Also, a favorable means of manufacturing the filter disk, and consequently the entire filter device, can be attained in this manner.
In another preferred embodiment of the filter device according to the present invention, the two filter disk halves of a filter disk are provided with supporting cams of identical dimensions on the adjacent and facing sides. Such sides either engage along a longitudinal separation line of the filter disk halves where they abut one another, and/or, wit contact with the relevant other filter disk half, they engage in the free spaces between the supporting cams of each relevant facing filter disk half. With such described arrangements, to save on outlay, the filter disk can be composed of identically constructed filter disk halves.
The outlay for the manufacture can be further decreased, insofar as the supporting cams are connected tightly with the relevant filter disk halves, by means of weld points produced by a projection-weld method.
With another preferred embodiment of the filter device according to the present invention, the two filter disk halves extend parallel to one another and define a disk-shaped hollow space of identical dimensions. A favorable flow-through of the melt-like fluid is attained in this manner, without increasing the wall shearing or thrust stresses when it comes to the flow resistance with the flow of the melt though the filter disk.
With one especially preferred embodiment of the filter device according to the present invention, the supporting cams form fillet-like solid box profiles. Such cams, in turn, can be mounted on the filter disk halves in such a manner that they free the discharge openings in the filter disk halves. As a result of the use of the solid box section profiles, the fabric or cloth fabric filter materials on the outside of the two filter disk halves of a filter disk can be securely supported and are not drawn into the box section profile of the supporting cams. For example, the filter materials could be drawn into the box section profile, if the supporting cams would be shaped out of the filter disk halves by a deepdrawing method or the like. Since the box section profiles are embodied as fillet-like, they can be used beneficially in the intermediate spaces between the openings of a filter disk half. They then do not have the capacity to negatively influence the open flow-through through these discharge openings. The arrangement can especially avoid the generation of flow shadows, since the discharge openings are grouped without any side spacing directly around the supporting cams and are left free.
With another especially preferred embodiment of the filter device according to the present invention, the discharge openings are formed in the filter disk halves by means of circular cutouts. In groups of different magnitudes, the circular cutouts extend along concentric circles around the outlet opening. By a certain selection of the grouping with discharge openings in the form of rows of holes, the flow ratios within the filter disk can improve for the melt-like fluid, and thus, the filter capacity can be increased. Preferably the filter disk halves and the supporting cams are formed of top-grade steel, so that these are not inclined to corrode, and consequently, cannot pollute the melt-like fluid. Insofar as spacing cams are arranged on the top and bottom of the filter disk, especially in the peripheral side border areas where the filter disk halves are connected with one another by a border welding joint, then in a cost-saving manner the traditional so-called spacer can be deleted. The known filter device would then serve to hold the filter disks inside the assembly at some spacing from one another Such a spacing is now realized by means of the spacing cams arranged directly on the filter disks.
Other objects, advantages and salient features of the present invention will become apparent from the following detailed description, which, taken in conjunction with the annexed drawings, discloses preferred embodiments of the present invention.


Cosmetic composition for the skin or skin appendages comprising a dispersion of solid organic particles in a binder and characterized in that at least a part of said organic particles is introduced in said composition in the form of particles having their surface coated with at least one cationic polymer. The cationic polymer comprises, for example, units containing primary, secondary, tertiary and/or quaternary amine groupings. The particles coated in this way are readily dispersible, even in fatty binders. The cosmetic compositions obtained show good adhesion to the skin and, in the case of compacted compositions, good cohesion properties.

The subject of the present invention is cosmetic compositions, containing a dispersion of solid particles, into which are introduced solid organic particles whose surface is coated with a cationic polymer.
It is known that various make-up products such as loose or compacted powders, foundations, blushers, eye shadows, as well as lipsticks, are provided in the form of compositions comprising a dispersion of solid organic particles in a fatty binder. They may be anhydrous compositions or else oil-in-water or water-in-oil emulsions.
Depending on the types of compositions, the solid organic particles are especially pigments (white and/or coloured), intended to confer on the skin of the face or lips a certain colouring, or even to colour the compositions themselves, or alternatively particles which act as fillers (in particular in compositions in the form of powders).
In lipsticks, the solid particles dispersed in an appropriate fatty binder are especially coloured pigments, optionally in combination with white pigments (for example fine particles of titanium dioxide) which make it possible to impart a shade to the colours provided by the coloured pigments.
Such coloured pigments are also used in nail varnish compositions which essentially consist of a dispersion of these pigments in a solution of a film-forming polymer and of a plasticizer in an appropriate organic solvent.
The preparation and use of the cosmetic compositions containing dispersions of solid particles pose several types of problem. One problem common to the preparation of all the compositions which have just been discussed lies in the difficulty of obtaining stable dispersions, so as to apply, for example to the skin, a regular make-up whose application is uniform and which retains a good homogeneity. For this, specialists have been led to perform surface treatments on the powders used, especially in order to modify the interfacial properties involved in the wetting and dispersion phenomena. The aim of these treatments is often to render the powder hydrophobic in order to enhance its incorporation into the formulation binders and oils, and to increase the stability of the dispersion by reducing the phenomena of flocculation and aggregation; see for example European Patent 279,319 which describes the coating of pigments with siliconized polymers.
These treatments therefore make it possible to solve the problems of stability of the dispersion by limiting the flocculation phenomena. However, they do not solve another important problem, namely the weak properties of adhesion of the solid particles to the skin. Indeed, it is known that the solid particles used especially in the compositions in the form of powders have only weak properties of adhesion to the skin. The surface treatments intended to improve the stablity of the dispersions in the fatty binders do not provide a substantial improvement as far as the adhesion properties are concerned.
It is known furthermore that the make-up products for the face and for the eyes are often provided in the form of compacted powders. The compacted powders are prepared by mixing the constituents of the powder with a binding agent and then converted to the desired form by compression in appropriate containers.
The compacted powders should exhibit special characteristics of hardness. The hardness is a function of the applied compacting pressure. If the compacted product is too soft, it will be highly brittle and too large a quantity of product will be removed at the time of application. In contrast, if it is too hard, the disintegration will be difficult. Furthermore, a compact product should exhibit a perfectly flat surface. Finally, it should respond favourably to the drop test, that is to say exhibit a reduced loss of weight after a drop performed under standardized conditions.
It has now been discovered that it is possible to obtain cosmetic compositions, comprising a dispersion of solid organic pigments in a binder, having good properties of stability and adhesion to the skin or to superficial body growths, by introducing into the said compositions solid organic particles whose surface has been coated with a cationic polymer. It was observed, surprisingly, that the coating of the solid organic particles with cationic polymers, which nevertheless constitute a hydrophilic coating, does not prevent a good dispersibility of the particles in the fatty binders from being obtained. In addition, the compacted compositions obtained with cationic polymer-coated solid organic particles surprisingly exhibit good cohesion properties which result especially in a very satisfactory behaviour in the drop test. Furthermore, the compositions thus obtained have good properties of adhesion to the skin or to superficial body growths (fingernails or nails), after application.
The subject of the present invention is therefore a cosmetic composition for the skin or superficial body growths (fingernails or nails), comprising a dispersion of solid organic particles in a binder, characterized in that at least a portion of the said organic particles are introduced into the said composition in the form of particles whose surface is coated with at least one cationic polymer.
In the compositions of the invention, solid organic particles are coated with the cationic polymer at the surface. This means that, after coating, there is neither a change in morphology nor notable modification in the sizes of the particles, as verifiable by electron microscopy.
In the present application, the expression xe2x80x9ccationic polymerxe2x80x9d denotes a polymer containing cationic groups or groups which can be ionized to cationic groups.
The preferred cationic polymers are chosen from those containing units comprising primary, secondary, tertiary and/or quaternary amine groups which may either form part of the polymer chain or be carried by a side substituent.
The cationic polymers used preferably have a molecular mass of between 103 and 3xc3x97106, approximately.
Preferably, the coated organic particles used in the compositions of the invention are coated solely with one (or more) cationic polymer(s).
The cationic polymers used are in particular those having a quaternization value, expressed as cationic equivalents per gram of polymer, of at least 0.05 cationic meq/g. Use is especially made of cationic polymers which contain for example at least 10% by weight of units comprising amine or quaternary ammonium groups.
When the cationic polymer contains amine or quaternary ammonium groups carried by a side substituent, the polymer chain is for example an acrylic, vinyl, siliconized, fluorinated or saccharide chain.
Among the cationic polymers, there may be mentioned more particularly quaternized proteins (or protein hydrolysates), quaternized polysiloxanes and polymers of quaternary polyammonium, polyaminoamide and polyamine type. These are known products.
Use is preferably made of cationic polymers which do not contain silicon, that is to say other than siliconized polymers.
It is more particularly preferable to use, as cationic polymer, a polymer containing ionized tertiary, secondary or primary amine group(s) or containing quaternary ammonium group(s), the latter being preferred.
The quaternary ammonium group may especially be obtained by quaternization of amino groups with conventional quaternization agents such as alkyl or aralkyl halides (for example methyl iodide, ethyl bromide or benzyl chloride), alkyl sulphates (for example dimethyl sulphate), and the like.
The ionized amine groups are obtained by salification of the amino groups with organic or inorganic acids such as hydrochloric, hydrobromic, lactic, acetic and glycolic acids and the like.
The quantities of polymer deposited on the particles vary with the procedure used for the coating. Generally, the proportion by weight of cationic polymer, relative to the total weight of the coated particles, is at least equal to 0.1%; the upper limit of the quantity of cationic polymer is sufficiently low for the particles to retain their individuality and their shape. In other words, the cationic polymer forms, at most, one thin (optionally lacunar) layer on the coated particles. Most often, the proportion by weight of cationic polymer in the coated particles is less than 10%, and in particular less than 8%, relative to the total weight of the coated particles.
The quaternized protein hydrolysates or proteins are in particular chemically modified polypeptides carrying at the chain end, or grafted thereto, quaternary ammonium groups. Their molecular mass can vary for example from 1500 to 10,000 and in particular from 2000 to 5000, approximately. Among these compounds, there may be mentioned especially:
hydrolysates of collagen carrying triethylammonium groups such as the products sold under the name xe2x80x9cQuat-Pro Exe2x80x9d by the Company Maybrook and termed in the CTFA dictionary xe2x80x9cTriethonium Hydrolyzed Collagen Ethosulfatexe2x80x9d;
hydrolysates of collagen carrying trimethylammonium or trimethylstearylammonium chloride groups, sold under the name xe2x80x9cQuat-Pro Sxe2x80x9d by the Company Maybrook and termed in the CTFA dictionary xe2x80x9cSteartrimonium Hydrolyzed Collagenxe2x80x9d;
hydrolysates of animal proteins carrying trimethylbenzylammonium groups such as the products sold under the name xe2x80x9cCrotein BTAxe2x80x9d by the Company Croda and termed in the CTFA dictionary xe2x80x9cBenzyltrimonium hydrolyzed animal proteinxe2x80x9d;
hydrolysates of proteins carrying on the polypeptide chain quaternary ammonium groups comprising at least one alkyl radical having 1 to 18 carbon atoms.
Among these protein hydrolysates, there may be mentioned inter alia:
xe2x80x9cCroquat Lxe2x80x9d whose quaternary ammonium groups comprise a C12 alkyl group;
xe2x80x9cCroquat Mxe2x80x9d whose quaternary ammonium groups comprise C10-C18 alkyl groups;
xe2x80x9cCroquat Sxe2x80x9d whose quaternary ammonium groups comprise a C18 alkyl group;
xe2x80x9cCrotein Qxe2x80x9d whose quaternary ammonium groups comprise at least one alkyl group having 1 to 18 carbon atoms.
These different products are sold by the Company Croda.
Other quaternized hydrolysates or proteins are for example those corresponding to the formula:
in which Xxe2x88x92 is an anion of an organic or inorganic acid, A denotes a protein residue derived from hydrolysates of collagen protein, R5 denotes a lipophilic group comprising up to 30 carbon atoms and R6 represents an alkylene group having 1 to 6 carbon atoms. There may be mentioned for example the products sold by the Company Inolex, under the name xe2x80x9cLexein QX 3000xe2x80x9d, termed in the CTFA dictionary xe2x80x9cCocotrimonium Collagen Hydrolysatexe2x80x9d.
There may also be mentioned quaternized plant proteins, such as wheat, maize or soya bean proteins: as quaternized wheat proteins, there may be mentioned those marketed by the Company Croda under the names xe2x80x9cHydrotriticum WQ or QMxe2x80x9d, termed in the CTFA dictionary xe2x80x9cCocodimonium Hydrolysed wheat proteinxe2x80x9d, xe2x80x9cHydrotriticum QLxe2x80x9d, termed in the CTFA dictionary xe2x80x9cLaurdimonium hydrolysed wheat proteinxe2x80x9d, or alternatively xe2x80x9cHydrotriticum QSxe2x80x9d, termed in the CTFA dictionary xe2x80x9cSteardimonium hydrolysed wheat proteinxe2x80x9d.
Another family of cationic polymers is that of the siliconized cationic polymers. Among these polymers, there may be mentioned:
(a) the quaternized polysiloxanes termed in the CTFA dictionary xe2x80x9cAmodimethiconexe2x80x9d and corresponding to the formula:
xe2x80x83in which xxe2x80x2 and yxe2x80x2 are integers depending on the molecular weight, generally such that said molecular weight is between 5000 and 10,000, approximately;
(b) the siliconized cationic polymers corresponding to the formula:
Rxe2x80x2aG3xe2x88x92axe2x80x94Si(OSiG2)nxe2x80x94(OSiGbRxe2x80x22xe2x88x92b)mxe2x80x94Oxe2x80x94SiG3xe2x88x92axe2x80x94Rxe2x80x2axe2x80x83xe2x80x83(III)
xe2x80x83in which:
G is a hydrogen atom or a phenyl, OH or C1-C8 alkyl, for example methyl, group,
a denotes the number 0 or an integer from 1 to 3, in particular 0,
b denotes 0 or 1 and in particular 1,
m and n are numbers such that the sum (n+m) can vary especially from 1 to 2000 and in particular from 50 to 150, it being possible for n to denote a number from 0 to 1999 and especially from 49 to 149 and it being possible for m to denote a number from 1 to 2000 and especially from 1 to 10;
Rxe2x80x2 is a monovalent radical of formula xe2x80x94CqH2qL in which q is a number from 2 to 8 and L is an optionally quaternized amino group chosen for example from the groups:
xe2x80x94NRxe2x80x3xe2x80x94CH2xe2x80x94CH2xe2x80x94Nxe2x80x2(Rxe2x80x3)2
xe2x80x94N(Rxe2x80x3)2
xe2x80x94N⊕(Rxe2x80x3)3Axe2x8ax96
xe2x80x94N⊕(Rxe2x80x3)H2Axe2x8ax96
xe2x80x94N(Rxe2x80x3)xe2x80x94CH2xe2x80x94CH2xe2x80x94N⊕Rxe2x80x3H2Axe2x8ax96,
xe2x80x83in which Rxe2x80x3 may denote hydrogen, phenyl, benzyl or a monovalent saturated hydrocarbon radical, for example an alkyl radical having from 1 to 20 carbon atoms and Axe2x8ax96 represents a halide ion such as for example fluoride, chloride, bromide or iodide.
A product corresponding to this definition is the polymer termed xe2x80x9ctrimethylsilylamodimethiconexe2x80x9d corresponding to the formula:
in which n and m have the meanings given above (cf. formula III).
Such polymers are described for example in Patent Application EP-A-95238.
(c) the siliconized cationic polymers corresponding to the formula:
xe2x80x83in which
R7 represents a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and in particular a C1-C18 alkyl or C2-C18 alkenyl, for example methyl, radical;
R8 denotes a divalent hydrocarbon radical, especially a C1-C8 alkylene radical or a C1-C18, for example C1-C8 divalent alkylenoxy radical;
Qxe2x88x92 is a halide, especially chloride, ion;
r represents a mean statistical value from 2 to 20 and in particular from 2 to 8;
s represents a mean statistical value from 20 to 200 and in particular from 20 to 50.
Such polymers are described more particularly in U.S. Pat. No. 4,185,087.
A polymer entering into this class is the polymer sold by the Company Union Carbide under the name xe2x80x9cUcar Silicone ALE 56xe2x80x9d.
When these siliconized polymers are used, a particularly advantageous embodiment is their simultaneous use with cationic and/or non-ionic surface-active agents. There may be used for example the product sold under the name xe2x80x9cEmulsion Cationique DC 929xe2x80x9d by the Company Dow Corning which comprises, in addition to amodimethicone, a cationic surface-active agent comprising a mixture of products corresponding to the formula:
in which R9 denotes alkenyl and/or alkyl radicals having from 14 to 22 carbon atoms, derived from tallow fatty acids, in combination with a non-ionic surface-active agent of formula:
C9H19xe2x80x94C6H4xe2x80x94(OC2H4)10xe2x80x94OH
known under the name xe2x80x9cNonoxynol 10xe2x80x9d.
Another commercial product which can be used according to the invention is the product sold under the name xe2x80x9cDow Corning Q2 7224xe2x80x9d by the Company Dow Corning comprising in combination the trimethylsilylamodimethicone of formula (IV), a non-ionic surface-active agent of formula:
C8H17xe2x80x94C6H4xe2x80x94(OCH2CH2)nxe2x80x94OH where n=40
also termed octoxynol-40,
another non-ionic surface-active agent of formula:
C12H25xe2x80x94(OCH2xe2x80x94CH2)nxe2x80x94OH where n=6
xe2x80x83also termed isolaureth-6,
and glycol.
The polymers of quaternary polyammonium, polyaminoamide and polyamine type which can be used in conformity with the present invention may be those mentioned especially in French Patents Nos. 2,505,348 or 2,542,997. Among these polymers, there may be mentioned:
(1) the quaternized or non-quaternized dialkylaminoalkyl acrylate- or methacrylate-vinylpyrrolidone copolymers such as the products sold under the name xe2x80x9cGafquatxe2x80x9d by the Company GAF Corporation such as for example Gafquat 734, 755 or HS100 or alternatively the product termed xe2x80x9cCopolymer 937xe2x80x9d. These polymers are described in detail in French Patents 2,077,143 and 2,393,573.
(2) The cellulose ether derivatives comprising quaternary ammonium groups described in French Patent 1,492,597 and in particular the polymers marketed under the names xe2x80x9cJRxe2x80x9d (JR 400, JR 125, JR 30M) or xe2x80x9cLRxe2x80x9d (LR 400, LR 30M) by the Company Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium salts of hydroxyethyl cellulose having reacted with an epoxide substituted by a trimethylammonium group.
(3) The cationic cellulose derivatives such as the cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and which are described especially in U.S. Pat. No. 4,131,576, such as hydroxyalkyl celluloses, like hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted especially with a salt of methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium.
The commercial products corresponding to this definition are more particularly the products solds under the name xe2x80x9cCelquat L 200xe2x80x9d and xe2x80x9cCelquat H 100xe2x80x9d by the Company National Starch.
(4) The cationic polysaccharides described more particularly in U.S. Pat. Nos. 3,589,578 and 4,031,307 and more particularly the product marketed under the name xe2x80x9cJaguar C. 13 Sxe2x80x9d sold by the Company Meyhall.
(5) The polymers consisting of piperazinyl units and straight- or branched-chain divalent alkylene or hydroxyalkylene radicals, optionally interrupted by one or more oxygen, sulphur or nitrogen atoms and/or by aromatic or heterocyclic rings as well as the oxidation and/or quaternization products of these polymers. Such polymers are described especially in French Patents 2,162,025 and 2,280,361.
(6) The water-soluble polyaminopolyamides prepared in particular by polycondensation of an acidic compound with a polyamine. These polyaminopolyamides may be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated anhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or alternatively by an oligomer resulting from the reaction of a bifunctional compound reactive towards a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used especially in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminopolyamide.
These polyaminopolyamides may be alkylated or, if they comprise one or more tertiary amine functional groups, quaternized.
Such polymers are described in particular in French Patents 2,252,840 and 2,368,508.
(7) The polyaminopolyamide derivatives resulting from the condensation of polyalkylenepolyamines with polycarboxylic acids followed by an alkylation using bifunctional agents. There may be mentioned for example the adipic acid-dialkylaminohydroxyalkyl-dialkylenetriamine polymers in which the alkyl radical comprises 1 to 4 carbon atoms and especially denotes methyl, ethyl or propyl. Such polymers are described in French Patent 1,583,363.
Among these derivatives, there may be mentioned more particularly adipic acid-dimethylaminohydroxypropyl-diethylenetriamine polymers sold under the names xe2x80x9cCartaretine F, F4 or F8xe2x80x9d by the Company Sandoz.
(8) The polymers obtained by reaction of a polyalkylenepolyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen for example from diglycolic acid, and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms, the molar ratio of the polyalkylenepolyamine to the dicarboxylic acid being for example between 0.8:1 and 1.4:1, and the resulting polyaminopolyamide then being reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine groups of the polyaminopolyamide of between 0.5:1 and 1.8:1. Such polymers are described in particular in U.S. Pat. Nos. 3,227,615 and 2,961,347.
Polymers of this type are in particular marketed under the name xe2x80x9cHercosett 57xe2x80x9d by the Company Hercules Incorporated or alternatively under the name xe2x80x9cPD 170xe2x80x9d or xe2x80x9cDelsette 101xe2x80x9d by the Company Hercules.
(9) The cyclopolymers such as homopolymers comprising as principal constituents of the chain units corresponding to the formulae (VI) or (VIxe2x80x2)
in which k and t are equal to 0 or 1, and the sum k+t=1, R12 denotes hydrogen or methyl, R10 and R11 independently denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group especially has 1 to 5 carbon atoms, a lower amidoalkyl group in which the alkyl has especially 1 to 6C, and where R10 and R11 may denote together with the nitrogen atom to which they are attached heterocyclic groups such as piperidyl or morpholinyl, as well as the copolymers comprising both units of formulae (VI) or (VIxe2x80x2) and units derived from acrylamide or diacetone acrylamide, Yxe2x8ax96 is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, sulphate, phosphate and the like. Among the polymers defined above, there may be mentioned more particularly the dimethyldiallylammonium chloride homopolymer sold under the name Merquat 100 and the dimethyldiallylammonium chloride and acrylamide copolymer sold under the name Merquat 550 by the Company Merck.
These polymers are described more particularly in French Patent 2,080,759 and its certificate of addition No. 2,190,406.
(10) The quaternary polyammonium polymer containing repeat units corresponding to the formula:
in which R13 R14, R15 and R16, being identical or different, represent aliphatic, alicyclic or arylaliphatic hydrocarbon radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively the R13 and R14 and/or R15 and R16 pairs constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen or alternatively R13, R14, R15 and R16 represent a linear or branched C2-C16 alkyl radical substituted by a nitrile, ester, acyl or amide group or by a group
xe2x80x83where R17 is an alkylene and D a quaternary ammonium group,
A2 and B2 represent alkylene, especially polymethylene, groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated and which may contain, bonded to or intercalated into the principal chain, one or more aromatic rings, or one or more oxygen or sulphur atoms, or one or more SO, SO2, disulphide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups and X1xe2x8ax96 denotes an anion derived from an inorganic or organic acid,
it being possible for A2, R13 and R15 additionally to form, together with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, when A2 denotes a saturated or unsaturated, linear or branched alkylene or hydroxyalkylene radical, B2 may also denote a group:
xe2x80x94(CH2)nxe2x80x94COxe2x80x94Dxe2x80x94OCxe2x80x94(CH2)nxe2x80x94
xe2x80x83which D denotes:
a) a glycol residue of formula: xe2x80x94Oxe2x80x94Zxe2x80x94Oxe2x80x94 where Z denotes a linear or branched hydrocarbon radical or a group corresponding to the formula:
[CH2xe2x80x94CH2xe2x80x94O]xxe2x80x94CH2xe2x80x94CH2xe2x80x94
xe2x80x83where x and y denote a number from 1 to 4 representing a mean or defined degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine residue:
c) a bis-primary diamine residue of formula:
xe2x80x94NHxe2x80x94Yxe2x80x94NYxe2x80x94
xe2x80x83where Y denotes a linear or branched bivalent hydrocarbon radical or alternatively the radical
xe2x80x94CH2xe2x80x94CH2xe2x80x94Sxe2x80x94Sxe2x80x94CH2xe2x80x94CH2xe2x80x94
d) a ureylene group of formula:
xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94
xe2x80x83Xxe2x8ax96 is an anion such as chloride or bromide.
Polymers of this type are described in particular in French Patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and U.S. Pat. Nos. 2,273,780, 3,206,462, 2,375,853, 2,388,614, 2,454,547, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.
(11) The quaternary polyammonium polymers consisting of units of formula:
in which
R18, R19, R20 and R21, which are identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, xcex2-hydroxyethyl, xcex2-hydroxypropyl or xe2x80x94CH2CH2(OCH2CH2)pOH radical where p is the number 0 or an integer between 1 and 6, provided that R18, R19, R20 and R21 do not simultaneously represent a hydrogen atom, x and y, which are identical or different, are integers between 1 and 6;
m is the number 0 or an integer between 1 and 34,
X denotes a halogen atom,
A denotes the residue of a divalent hydrocarbon radical optionally comprising heteroatoms, and in particular the radical:
xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94
Such compounds are described especially in European Patent Application 122,324.
(12) The homopolymers or copolymers derived from acrylic or methacrylic acids and comprising units:
in which
the R24 groups independently denote H or CH3, the A1 groups independently denote a linear or branched alkyl group of 1 to 6 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms, the R25, R26 and R27 groups, which are identical or different, independently denoting an alkyl group having from 1 to 18 carbon atoms or a benzyl radical,
R22 and R23 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms,
X2xe2x88x92 denotes an anion, for example methosulphate or halide such as chloride or bromide.
The comonomer(s) which can be used in the preparation of the corresponding copolymers belongs (belong) to the family of the acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides which are nitrogen-substituted by lower alkyls, alkyl esters of acrylic or methacrylic acids, vinylpyrrolidone or vinyl esters.
(13) The quaternary vinylpyrrolidone and vinyl imidazole polymers such as for example the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the Company B.A.S.F.
Other cationic polymers which can be used in conformity with the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.
Among the cationic polymers which can be used in the compositions of the invention, there may be mentioned especially the following polymers:
the polymer comprising units of formula:
xe2x80x83sold under the name xe2x80x9cMirapol AD 1xe2x80x9d. by the Company Miranol,
the polymer comprising units of formula:
xe2x80x83sold under the name xe2x80x9cMirapol AZ1xe2x80x9d by the Company Miranol,
poly(methacrylamidopropyltrimethylammonium chloride) sold under the name xe2x80x9cPolymaptacxe2x80x9d by the Company Texaco Chemicals;
the quaternized polymers of ionene type described in French Patent No. 2,270,846 and more particularly those comprising the units:
the quaternary ammonium polymers of the type described in U.S. Pat. No. 4,157,388 and more particularly that sold under the name xe2x80x9cMirapol A 15xe2x80x9d by the Company Miranol;
poly(dimethylbutenylammonium chloride)-xcex1,xcfx89-bis(triethanolammonium chloride) sold under the name xe2x80x9cOnamer Mxe2x80x9d by the Company Onyx Internationale.
The organic particles intended to be coated in conformity with the invention may optionally be particles having undergone beforehand one or more known surface treatments of chemical, electronic and/or mechanical nature. They may additionally be inorganic or organic particles coated with an organic substance, such as the composite particles which are described below.
The organic particles intended to be coated with a cationic polymer according to the invention comprise, for example:
cochineal carmine,
carbon black,
organic lakes or insoluble sodium, potassium, calcium, barium, aluminium, zirconium or strontium salts of acid dyes such as haloacid dyes, azo dyes, anthraquinone dyes, and the like. There may in particular be mentioned, among these lakes, those known under the following names:
melanin pigments derived from natural or synthetic sources and which can be obtained: (A) by oxidation of at least one indole compound, or (B) by oxidative or enzymatic polymerization of melanin precursors, or (C) by extraction of melanin from substances containing it, or (D) by culturing microorganisms.
(A) Melanin pigments can, in the first place, be obtained by oxidation of at least one indole compound chosen especially from those corresponding to the formula:
in which:
R1 and R3 represent, independently of one another, a hydrogen atom or a C1-C4 alkyl group;
R2 represents a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or a (C1-C4)alkoxycarbonyl group;
the R4 to R7 substituents represent a hydrogen atom, a C1-C4 alkyl group or an xe2x80x94NHRo or xe2x80x94OZ group, Ro denoting a hydrogen atom or a C2-C4 acyl or C2-C4 hydroxyalkyl group, and the Z radical denoting a hydrogen atom, a C2-C14 acyl group, a C1-C4 alkyl group or a trimethylsilyl group,
being understood that R5 can additionally represent a halogen atom, and being understood that:
at least one of the R4 to R7 radicals represents an OZ or NHRo group, one at most of the R4 to R7 radicals representing NHRo and two at most of the R4 to R7 radicals representing OZ and, in the case where Z represents a hydrogen atom, the two OH groups are in the 5- and 6-positions; and at least one of the R4 to R7 radicals represents a hydrogen atom, and in the case where only one of these radicals represents a hydrogen atom, only one radical from the R4 to R7 radicals then represents NHRo or OZ, the other radicals representing a C1-C4 alkyl group or alternatively, if appropriate, for R5, a halogen atom;
and their alkali metal, alkaline-earth metal, ammonium or amine salts, as well as the hydrochlorides, hydrobromides, sulphates and methanesulphonates.
The indole compounds of formula (IX) above are preferably chosen from 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxy-5-methoxyindole, 4-hydroxy-5-ethoxyindole, 2-carboxy-5-hydroxyindole, 5-hydroxy-6-methoxyindole, 6-hydroxy-7-methoxyindole, 5-methoxy-6-hydroxyindole, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole, 2-carboxy-5,6-dihydroxyindole, 4-hydroxy-5-methylindole, 2-carboxy-6-hydroxyindole, 6-hydroxy-N-methylindole, 2-ethoxycarbonyl-5,6-dihydroxyindole, 4-hydroxy-7-methoxy-2,3-dimethylindole, 4-hydroxy-5-ethoxy-N-methylindole, 6-hydroxy-5-methoxy-2-methylindole, 6-hydroxy-5-methoxy-2,3-dimethylindole, 6-hydroxy-2-(ethoxycarbonyl)indole, 7-(xcex2-hydroxy)-3-methylindole, 5-hydroxy-6-methoxy-2,3-dimethylindole, 5-hydroxy-3-methylindole, 5-acetoxy-6-hydroxyindole, 5-hydroxy-2-(ethoxycarbonyl)indole, 6-hydroxy-2-carboxy-5-methylindole, 6-hydroxy-2-ethoxycarbonyl-5-methoxyindole, 6-(N-xcex2-hydroxyethylamino)indole, 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, N-methyl-6-(hydroxyethylamino)indole, 6-amino-2,3-dimethylindole, 6-amino-2,3,4,5-tetramethylindole, 6-amino-2,3,4-trimethylindole, 6-amino-2,3,5-trimethylindole, 6-amino-2,3,6-trimethylindole, 5,6-diacetoxyindole, 5-methoxy-6-acetoxyindole, 5,6-dimethoxyindole, 5,6-methylenedioxyindole, 5,6-trimethylsilyloxyindole, the phosphoric ester of 5,6-dihydroxyindole, 5,6-dibenzyloxyindole and the addition salts of these compounds.
5,6-Dihydroxyindole is one of the preferred compounds.
Oxidation of the indole compound of formula (IX) can be carried out in aqueous or water/solvent(s) medium, exposed to the air, in the presence or absence of an alkaline agent and/or of a metal oxidation catalyst such as, for example, the cupric ion.
The reaction medium preferably consists of water and can, if appropriate, consist of a mixture of water and at least one solvent chosen so that it quickly dissolves the indole compound of formula (IX). Mention may be made among these solvents, by way of examples, of lower C1-C4 alcohols, such as ethyl alcohol, propyl or isopropyl alcohol or tert-butyl alcohol, alkylene glycols, such as ethylene glycol or propylene glycol, alkyl ethers of alkylene glycols, such as the monomethyl, monoethyl and monobutyl ethers of ethylene glycol or the monomethyl ethers of propylene glycol and of dipropylene glycol, and methyl lactate.
Oxidation can be also carried out by using hydrogen peroxide in the presence of an alkaline agent, such as preferably aqueous ammonia, or in the presence of an iodide ion, the iodide preferably being the iodide of an alkali metal or alkaline-earth metal or ammonium iodide.
It is also possible to carry out the oxidation by using periodic acid and its water-soluble salts and derivatives, permanganates and dichromates, for example of sodium or of potassium, sodium hypochlorite, potassium ferricyanide, ammonium persulphate, silver oxide, lead oxide, ferric chloride, sodium nitrite, the salts of rare-earth metals, including especially cerium, and organic oxidizing agents chosen from ortho- and para-benzoquinones, mono- or diimines of ortho- and para-benzoquinones, 1,2- and 1,4-naphthoquinones or mono- or dimines of 1,2- and 1,4-naphthoquinones, such as defined in Application EP-A-0,376,776. The preferred salt of periodic acid is sodium periodate.
It is possible to activate the oxidizing agents with a pH modifier.
It is also possible to carry out an enzymatic oxidation.
The insoluble product is isolated by filtration, centrifuging, lyophilization or atomization; it is then ground or micronized in order to achieve the desired particle size.
(B) Melanin pigments can also arise from the oxidative or enzymatic polymerization of melanin precursors, such as L-tyrosine, L-dopa, catechol and their derivatives.
(C) Melanin pigments can finally arise on the extraction of melanin from natural substances such as human hair or cephalopod ink (cuttlefish, octopuses), alternatively known under the name of sepiomelanin, in which case the pigment is ground and purified before it is used.
(D) Melanin pigments can be obtained by culturing microorganisms. These microorganisms produce melanin either naturally or by genetic modification or by mutagenesis. Methods of preparation of these melanins are described, for example, in Patent Application WO-90 04029.
The melanin pigment can be present at the surface or incorporated in a coloured or uncoloured, lamellar or non-lamellar, inorganic or organic, particulate filler. Composite melanin pigments are thus obtained.
In this case, the melanin pigment can result from the oxidation of at least one indole compound of formula (IX), as defined above, as a mixture with the particulate filler, in a medium which is essentially non-solvent for the said filler, at a temperature which can range from room temperature to approximately 100xc2x0 C., or alternatively can result from the oxidative polymerization of melanin precursor on the filler.
The non-lamellar inorganic particles used in this process are in particular inert inorganic particles having a particle size of less than 20 micrometers. Such particles are especially calcium carbonate, silica or titanium oxide particles.
Such composite melanin pigments, deposited on inorganic fillers, are described, as well as their preparation, in Patent Application FR-2,618,069.
By an analogous process, it is possible to prepare composite melanin pigments with coloured inorganic particles.
The appellation xe2x80x9ccoloured inorganic particles xe2x80x9d is given to non-white particles consisting of metal salts, which are insoluble in the cosmetic medium, which can be used in cosmetics, such as those referenced in the Color Index under the chapter xe2x80x9cInorganic Colouring Mattersxe2x80x9d and carrying the numbers 77000 to 77947, with the exception of white pigments and particles which are provided in the lamellar form, such as lamellar iron oxide. These coloured inorganic particles can consist of a single pigment or of a mixture of pigments and can thus be provided in the form of nacreous or interferential pigments.
The coloured inorganic particles are in particular non-white particles, preferably chosen from iron oxides, with the exception of lamellar iron oxide, ultramarine blue (which is a complex sulphosilicate), chromium oxides, manganese violet (which is an ammonium manganese pyrophosphate) and Prussian blue (which is an iron ferricyanide).
Such composite melanin pigments, deposited on a coloured inorganic filler, are described in French Patent Application 92 0415, filed Jan. 16, 1992.
Lamellar particles are inorganic or organic particles which are provided in the form of optionally laminated layers. These layers are characterized by a thickness which is lower than the greater dimension of the particle. The ratio of the greater dimension to the thickness is preferably between 2 and 100. The greatest dimension is generally less than 50 micrometers. Such composite melanin pigments deposited on a lamellar filler are described, as well as their preparation, in European Patent Application No. 467,767.
The non-lamellar organic particles are particles of inert polymers chosen from crystalline or amorphous, organic or inorganic, natural or synthetic polymers with a crosslinked network having, for example, a molecular weight of between 5,000 and 5,000,000. Composite-melanin pigments on a polymeric filler, as well as their preparation, are described in European Patent Application No. 379,409;
the particles obtained by oxidative polymerization have at least one indoline compound of formula:
xe2x80x83in which formula:
R10 and R8 represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical;
R9 represents a hydrogen atom, a C1-C4 alkyl radical or a carboxyl or (C1-C4)alkoxycarbonyl group;
R12 denotes a hydrogen atom, a C1-C4 alkyl, hydroxyl, alkoxy (C1-C4), amino or C1-C10 alkylamino radical or halogen;
R11 denotes a hydrogen atom or a hydroxyl, C1-C4 alkoxy or amino group; with the condition that at least one of the R11 or R12 radicals denotes a hydroxyl, alkoxy or amino group; and with the condition that, when R11 denotes an amino group, R12 cannot denote an alkylamino radical;
it also being possible for R11 and R12 to form a C1-C2 alkylenedioxy group, when they are in the 5- and 6-positions;
and their salts.
The compounds corresponding to the formula (X) are chosen especially from the group consisting of 5,6-dihydroxyindoline, 6-hydroxyindoline, 5,6-methylenedioxyindoline, 7-methoxy-6-hydroxyindoline, 6,7-dihydroxyindoline, 5-hydroxy-4-methoxyindoline, 4,5-dihydroxyindoline, 5-methoxy-6-hydroxyindoline, 4-hydroxy-5-methoxyindoline, 5-hydroxy-6-methoxyindoline, 4,7-dihydroxyindoline, 6-aminoindoline, N-ethyl-4-hydroxyindoline, 1-ethyl-6-aminoindoline, 5,6-diaminoindoline, 1-methyl-6-aminoindoline, 2-methyl-6-aminoindoline, 3-methyl-6-aminoindoline, 2-methyl-5,6-diaminoindoline, 5-chloro-7-aminoindoline, 3-methyl-5,7-diaminoindoline, 5,7-diaminoindoline, 2-methyl-5,7-diaminoindoline, 7-aminoindoline, 2-methyl-7-aminoindoline, 4-aminoindoline, 4-amino-6-chloroindoline, 4-amino-6-iodoindoline, 4-amino-5-bromoindoline, 4-amino-5-hydroxyindoline, 4-amino-7-hydroxyindoline, 4-amino-5-methoxyindoline, 4-amino-7-methoxyindoline, 5-aminoindoline, 2,3-dimethyl-5-aminoindoline, 1-methyl-5-aminoindoline, 2-methyl-5-aminoindoline, 5-[N-(1-methylhexyl)amino]indoline, 5,6-dimethoxyindoline and 5,6-dihydroxy-2-carboxyindoline.
In the compounds of formula (X), the C1-C4 alkyl radicals preferably denote methyl, ethyl, propyl, isopropyl, butyl or isobutyl; the C1-C10 radicals preferably denote methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylhexyl, 1-methylheptyl or 1-methyloctyl; the alkoxy radicals preferably denote methoxy, ethoxy, propoxy and butoxy; halogen preferably denotes bromine, chlorine or iodine.
The salts of the compounds of formula (X) are, in particular, hydrochlorides, hydrobromides, sulphates or methanesulphonates or salts of alkali metals or alkaline-earth metals, of ammonium or of amines.
The particles obtained by co-oxidation of at least one indoline compound of formula (X) and of at least one indole derivative. The latter can be chosen from mono- and dihydroxyindoles or amino indoles, as described more particularly in Patent EP-A-2,398,826 and Patent Applications EP-A-425,345 and GB-A-2,224,754.
These indoles correspond more particularly to the formula (IX). During the co-oxidation, it is possible to use up to 50%, in moles, of indole derivatives with respect to the total number of moles of derivatives to be oxidized. The oxidation conditions are identical to those of the melanin pigments described above.
Just like the melanin pigments, the products resulting from the oxidative polymerization of at least one indoline compound of formula (X) may be present at the surface of a particulate filler or incorporated in the said coloured or uncoloured, lamellar or non-lamellar, inorganic or organic, particulate filler. These are then composite pigments.
The inorganic particulate fillers are those mentioned above for the composite melanin pigments.
The non-lamellar organic fillers are chosen from the particles of:
a) optionally modified polymers derived from keratin;
b) silk fibroins;
c) optionally deacetylated polymers derived from chitin;
d) cellulose polymers;
e) synthetic polymers chosen from:
(i) optionally crosslinked poly(methyl methacrylate), polystyrene, polypropylene or polyethylene;
(ii) crosslinked poly-xcex2-alanine;
(iii) crosslinked polymers of styrene-divinylbenzene, methyl methacrylate-ethylene glycol dimethacrylate or vinyl stearate-divinylbenzene;
(iv) hollow microspheres of copolymers of vinylidene chloride and acrylonitrile;
(v) porous microspheres of polyamide 12, polyamide 6 or copolyamide 6/12;
(vi) silicone powders consisting especially of organosiloxane elastomers, resins or gums.
Such non-lamellar organic fillers are mentioned especially in European Patent Application No. 379,409.
The lamellar fillers are chosen from L-lauroyllysine, ceramic microparticles optionally covered with zirconium powder, lamellar titanium dioxide, lamellar talc, boron nitride, lamellar mica, bismuth oxychloride or transparent red iron oxide.
Such lamellar fillers are mentioned especially in European Patent Application No. 467,767.
Such composite pigments, as well as their preparation, are described especially in French Patent Application No. 92-00417, filed on Jan. 16, 1992.
In the compositions of the invention, the proportions of coated organic particles dispersed in the binder depend on the type of composition; the proportions are customary for the type of composition considered.
In order to coat the particles, a known method, for example one of the following methods, may be used:
1) A solution of the polymer is prepared in one of its good solvents. The powder to be coated is dispersed in this solution with vigorous stirring and a poor solvent for the polymer is added without proceeding up to the precipitation of the polymer in the solution, but only up to the first cloudiness. The suspension is then left vigorously stirring, for example for 4 hours. The suspension is allowed to settle, is rinsed with a non-solvent of the polymer and dried, for example at 80xc2x0 C., under reduced pressure.
2) A solution of the polymer is prepared in which the powder to be coated is dispersed. The system is left vigorously stirring and a precipitant of the polymer is slowly added so as to gently precipitate the polymer at the surface of the powder. The mixture is allowed to settle, it is rinsed with a non-solvent of the polymer and the powder is dried.
3) A solution is prepared with a good solvent of the polymer and the powder to be coated is dispersed therein. A poor solvent of the polymer is chosen whose boiling point is greater than that of the good solvent and a slow evaporation of the system is carried out. This results in the formation of a coacervate which gradually coats the powder, and then the powder is dried.
4) The so-called fluidized air bed technique is used: a dilute solution of the polymer is sprayed hot in a cyclone in which the powder is kept buoyant.
5) A solution of the polymer is prepared in which the powder to be coated is dispersed. The system is left vigorously stirring and the solvent is evaporated slowly so as to gently precipitate the polymer at the surface of the powder. It is allowed to settle, rinsed with a non-solvent of the polymer and the powder is dried.
6) The technique of coating by atomization is used. A suspension of particles in water is prepared; once the suspension is homogenized, an aqueous solution of the polymer is introduced therein. The mixture is left stirring for 2 hours and the suspension is atomized in an atomizing device.
During the atomization, the mixture preferably remains under magnetic stirring.
7) The technique of coating by freeze-drying is used. The polymer is dissolved in water and then an aqueous suspension of particles is incorporated therein, with stirring. The mixture is left stirring for 6 to 8 hours and is then placed on the freeze dryer for at least 18 hours. A pulverulent product is recovered which is sieved.
The compositions of the invention may be anhydrous compositions. The anhydrous compositions are provided especially in the form of a compacted powder, a cast powder, a lipstick or a nail varnish.
The compositions of the invention may also be provided in the form of water-in-oil or oil-in-water type emulsions and may be used as foundation or mascara for example.
These compositions are prepared according to the customary methods.
In the make-up compositions, the binder is a customary fatty binder consisting of an oil, a mixture of oils or a mixture of oil and wax(es).
In the lipsticks, the binder is also a fatty binder generally consisting of a mixture of (natural or synthetic) waxes of high melting point, (synthetic, mineral or vegetable) oils and (natural or synthetic) waxes of low melting point.
In the nail varnishes, the binder consists of the solution of the film-forming polymer and the plasticizer in the chosen organic solvent.
In the emulsions, the binder is a customary fatty binder consisting of an oil or a mixture of oils.
When the composition comprises a micronized pigment of metal oxides chosen especially from titanium, zinc, cerium or zirconium oxides or mixtures thereof, it may constitute a composition for protecting the skin or hair against ultraviolet rays.
The invention also relates to the use, in the preparation of a cosmetic composition containing a dispersion of solid particles in a binder, of organic particles whose surface is coated with at least one cationic polymer. In this use, the composition, and especially the organic particles, the cationic polymer, as well as the binder, are in particular as defined above.

Cosmetic composition containing solid organic particles coated with a cationic polymer