EP1858966A1 - Composition comprising a thermoplastic polymer and a hydrophilizing agent - Google Patents
Composition comprising a thermoplastic polymer and a hydrophilizing agentInfo
- Publication number
- EP1858966A1 EP1858966A1 EP06726017A EP06726017A EP1858966A1 EP 1858966 A1 EP1858966 A1 EP 1858966A1 EP 06726017 A EP06726017 A EP 06726017A EP 06726017 A EP06726017 A EP 06726017A EP 1858966 A1 EP1858966 A1 EP 1858966A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermoplastic polymer
- composition according
- hydrophilizing agent
- composition
- polypropylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3976—Including strand which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous composition, water solubility, heat shrinkability, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/693—Including a paper layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/696—Including strand or fiber material which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous compositions, water solubility, heat shrinkability, etc.]
Definitions
- the invention relates to a process for the preparation of thermoplastic polymers which makes it possible to obtain a hydrophilic behavior of the surface of objects manufactured with these thermoplastic polymers.
- thermoplastic polymers and additives are shaped by any conventional means (extrusion, injection, printing films ...) to obtain the desired objects.
- the invention finally relates to the applications of these objects in thermoplastic polymers with hydrophilized surfaces.
- Plastics such as polyesters, polyamides, polyolefins, and more particularly polypropylene normally have very hydrophobic surfaces, which is a drawback for many applications of objects made from these thermoplastics.
- sails or films, porous or discontinuous, made from polypropylene or polyester yarns or fibers, obtained by the so-called nonwoven technique, which we will call under the generic term "non-woven textile surface” have an essentially hydrophobic surface behavior. This behavior requires that they be superficially coated, in post-treatment, with soluble surfactant compositions, to be used in applications such as hygiene, wiping, diapers ....
- This surface treatment has the disadvantage of not being durable and also of allowing the surfactant used in the treatment layer to dissolve in the water in contact with it. This point is particularly to be avoided in hygiene applications like diapers.
- hydrophilization of the surface of objects is sought in other applications for example those for mass objects such as parts for the automotive industry. It is desired to be able to paint these parts, and plastics such as polypropylene are not suitable for painting.
- the surface treatment with a coating of a hydrophilic or amphiphilic species is not a viable solution because the hydrophilizing treatment is neither durable nor adherent.
- hydrophilicity is sought because it would clean the water in question.
- food containers polyolefin (PE, PP) pose a cleaning problem when you want to wash in an automatic dishwasher.
- hydrophilicity of polypropylene packaging or films is also sought to prevent slugging, dust deposition, fogging, during the storage of products wrapped polypropylene films in the departments of sales.
- hydrophilicity contributes to the non-adhesion of dust or greasy soils, but also to the flow of static electricity charges responsible for certain types of ensalatorium.
- thermoplastic polymer that has a more hydrophilic surface.
- One of the aims of the present invention is therefore to find a means of preparing a thermoplastic polymer which has a more hydrophilic surface.
- thermoplastic polymer and hydrophilizing agent selected from anionic surfactants in the form of salts or in acid form.
- thermoplastic polymer in which the hydrophilizing agent has been incorporated.
- thermoplastic polymer polyesters, polyamides, polyolefins such as polyethylene and polypropylene.
- anionic surfactants in the form of salts or in acid form, mention may be made of:
- alkylsulphonic acids arylsulphonic acids, optionally substituted with one or more hydrocarbon groups, and whose acidic function is partially or totally salified, such as C 8 -C 50 , especially C 8 -C 30 , alkylsulphonic acids, preferably C 22 -C ⁇ , benzenesulfonic acid, naphthalenesulfonic acids substituted by one to three alkyl groups C 1 -C 30, preferably C 4 -C 16 alkyl and / or alkenyl C 2 -C 30, preferably C 4 -C 1B -
- the mono- or diesters of alkylsulfosuccinic acids of which the linear or branched alkyl part, optionally substituted with one or more hydroxylated and / or alkoxylated, linear or branched C 2 -C 4 (preferably ethoxylated, propoxylated, ethopropoxylated) groups; ).
- the phosphate esters chosen more particularly from those comprising at least one saturated, unsaturated or aromatic hydrocarbon group, linear or branched, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted by at least one alkoxylated (ethoxylated) group, propoxylated, ethopropoxylated).
- phosphate ester groups mono- or diesterified so that one or two free acid groups or partially or totally salified.
- the preferred phosphate esters are of the mono- and diester type of phosphoric acid and of alkoxylated (ethoxylated and / or propoxylated) mono-, di- or tristyrylphenol, or of alkoxylated (ethoxylated) mono-, di- or trialkylphenol and / or propoxylated), optionally substituted with one to four alkyl groups; phosphoric acid and a C 8 -C 30 alcohol, preferably C 10 -C 22 alkoxylated (ethoxylated or ethopropoxylated); phosphoric acid and a C 8 -C 22 alcohol, preferably C 10 -C 22 , non-alkoxylated.
- sulphate esters obtained from saturated or aromatic alcohols, optionally substituted with one or more alkoxylated groups (ethoxylated, propoxylated, ethopropoxylated), and for which the sulphate functional groups are in the free acid form, or partially or completely neutralized .
- sulfate esters obtained more particularly from saturated or unsaturated C 8 -C 20 alcohols which may comprise 1 to 8 alkoxylated units (ethoxylated, propoxylated, ethopropoxylated); sulphate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C 2 -C 30 hydroxycarbon groups, and in which the number of alkoxylated units is between 2 and 40; sulphate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol in which the number of alkoxylated units ranges from 2 to 40.
- the anionic surfactants may be in acid form (they are potentially anionic), or in a form partially or totally salified, with a counter-ion.
- the counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of formula N (R) 4 + in which R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted with an oxygen atom.
- R which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted with an oxygen atom.
- the anionic surfactants are preferably used in the form of sodium salts. Even more preferably, the anionic surfactant is sodium alkysulphonate, the alkyl group of which is linear or branched, comprising on average from 6 to 30 carbon atoms.
- the anionic surfactant has, for example, the following formula: CH 3 - (CH 2
- a product that can be used is an anionic product sold by Rhodia under the name Catafor FL or Catafor AFL, in solid form.
- the amount of hydrophilizing agent introduced into the polymer is such that the weight ratio between the hydrophilizing agent and the thermoplastic polymer is between 1/99 and 10/90.
- the hydrophilizing agent is mixed and co-melted with the thermoplastic polymer.
- the thermoplastic polymer is generally in the form of solid granules.
- the hydrophilizing agent can be mixed at room temperature with the polymer granules and then introduced into a mixing tool heated.
- the hydrophilizing agent may also be introduced into the mixing tool in which the polymer in the molten state is already present.
- the temperature mixing tool may be a vessel provided with rotors and heated by a fluid circulation. This is called an internal mixer. It is a "batch" process.
- a Brabender mixer may be mentioned. After cooling, a blank of solid material is recovered which can be shaped in a mold by compression.
- the temperature mixing tool may also be an extruder in which the material is transported, heated and kneaded by rotating screw members. It is a "continuous" process.
- a Werner ZSK30 extruder may be mentioned. A rush of molten material is recovered which is cooled and then cut to obtain granules. These granules can then be injected in the form of test pieces or finished materials.
- the hydrophilizing agent When the hydrophilizing agent is in solid form, that is to say in the form of a powder, flake or granules, the incorporation is then easily as indicated above.
- the hydrophilizing agent When the hydrophilizing agent is in liquid form, 100% hydrophilizing agent, or the hydrophilizing agent in solution in a solvent, there are several possibilities of incorporation.
- the present invention therefore also relates to a process for preparing a composition comprising the thermoplastic polymer and the hydrophilizing agent, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer in molten form.
- the present invention therefore also relates to a process for preparing a composition comprising the thermoplastic polymer and the hydrophilizing agent, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer optionally with other ingredients, for example fillers or stabilizers, by mixing with the thermoplastic polymer before melting, by direct introduction into the molten thermoplastic polymer, and / or by masterbatch.
- the melt blends of thermoplastic polymer and hydrophilizing agent can be shaped by any conventional means (extrusion, injection, pulling films ...) to obtain the desired objects.
- the melt blends of thermoplastic polymer and hydrophilizing agent can thus be formed into molding powder, in the form of an extruded and / or blown and / or injected object, in the form of a film, or in the form of fibers. yarns or filaments, optionally assembled in woven or nonwoven textile surface.
- the invention also relates to the applications of these objects in thermoplastic polymers with hydrophilized surfaces.
- thermoplastic polymer with a hydrophilized surface examples of objects made of thermoplastic polymer with a hydrophilized surface, mention may in particular be made of a nonwoven textile surface comprising fibers based on a composition according to the invention.
- thermoplastic polymer with a hydrophilized surface examples include mass objects such as parts for the automotive industry.
- objects made of thermoplastic polymer with a hydrophilized surface include food containers made of polyolefin (polyethylene or polypropylene).
- thermoplastic polymer with a hydrophilized surface examples include packaging or polypropylene films.
- the invention finally relates to a use of anionic surfactants in the form of salts or in acid form as defined above as hydrophilizing agent of a composition comprising a thermoplastic polymer.
- Surface hydrophilicity is evaluated by measuring the contact angle between a drop of purified, distilled water and said surface.
- a drop of distilled water of calibrated size is deposited under standardized and repetitive conditions on the surface to be to study. It spreads or retracts more or less depending on the hydrophilicity of the surface, and with suitable equipment, it is possible to measure the angle formed by the deposited drop and the surface.
- the apparatus used may be, for example, a goniometer for measuring the wetting angle, for example of the Tantec mark. It is also possible to use an automatic measuring device, such as the IT Concept company's droplet monitor with optical bench. This is the case of the measurements that have been made in the examples presented below.
- the manipulation consists in depositing on the clean and smooth surface of the sample a drop of water of calibrated volume equal to two microliters using a syringe.
- the drop is illuminated by a uniform light source, type integrating sphere, the image of his profile is projected by a telecentric telephoto lens on a CCD camera. It is digitized and then processed by software to determine several times per second the right and left contact angles defined as the angles between the plane formed by the support and tangent planes on either side of the base of the drop.
- pure polypropylene has a contact angle with pure water of 105 °.
- the hydrophilizing agents when they are mixed with the thermoplastic polypropylene polymer make it possible to lower this value very substantially, at levels between 70 and 85 °.
- the constituents (94.9% of isotactic polypropylene homopolymer polypropylene polymer sold by ATOFINA under the name PPH4060, 5% of hydrophilizing additive and 0.1% of Irganox B225 thermal stabilizer) are introduced into the tank of a mixer. internal brand "Brabender" brought to a temperature of 15O 0 C.
- the tank is equipped with two counter-rotating rotors of thermoplastic type W50, rotating at a speed of rotation of 125 RPM. Given the internal shear, the final temperature of the mixture is between 18O 0 C and 190 0 C.
- a charged polymer blank is extracted from the tank, and is pressed into a mold 800 microns thick, between two compression plates heated to 200 0 C under 200 bar pressure for 2 minutes. The mold is then cooled between two trays cooled to 18 0 C under a pressure of 200 bar for 4 minutes. After cooling and consolidation, these specimens are subjected to various physico-chemical tests to check the hydrophilicity of their surface and the resulting properties.
- the measurements were made in the examples presented below using a drop tensiometer with optical bench called the SDT 200 from the company IT Concept.
- the manipulation consists in depositing on the clean and smooth surface of the sample a drop of water of calibrated volume equal to two microliters using a syringe.
- the drop is illuminated by a uniform light source, type integrating sphere, the image of his profile is projected by a telecentric telephoto lens on a CCD camera. It is digitized and then processed by software to determine several times per second the right and left contact angles defined as the angles between the plane formed by the support and tangent planes on either side of the base of the drop.
- Table I corresponds to the average of 10 to 15 measurements.
- PP means polypropylene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention concerns a method for preparing thermoplastics to obtain a hydrophilic behaviour of the surface of objects made from said thermoplastics. The invention also concerns the additives used to obtain said surface hydrophily, said additives being mixed and jointly melted with the thermoplastics (mass-additivation process). The melted mixtures of thermoplastics and additives are shaped by any conventional means (extrusion, injection, film stretching) to obtain the desired objects. The invention further concerns the uses of said thermoplastic objects with hydrophilized surfaces.
Description
COMPOSITION COMPRENANT UN POLYMERE THERMOPLASTIQUE ET UN AGENT D'HYDROPHILISATION COMPOSITION COMPRISING A THERMOPLASTIC POLYMER AND A HYDROPHILIZATION AGENT
L'invention concerne un procédé de préparation de polymères thermoplastiques permettant d'obtenir un comportement hydrophile de la surface des objets fabriqués avec ces polymères thermoplastiques.The invention relates to a process for the preparation of thermoplastic polymers which makes it possible to obtain a hydrophilic behavior of the surface of objects manufactured with these thermoplastic polymers.
Elle concerne également les additifs utilisés pour obtenir cette hydrophilie de surface, lesdits additifs étant mélangés et co-fondus avec les thermoplastiques (additivation dans la masse).It also relates to the additives used to obtain this surface hydrophilicity, said additives being mixed and co-melted with the thermoplastics (additive in the mass).
Les mélanges fondus des polymères thermoplastiques et des additifs sont mis en forme par tous moyens conventionnels (extrusion, injection, tirage de films...) pour obtenir les objets désirés. L'invention concerne enfin les applications de ces objets en polymères thermoplastiques à surfaces hydrophilisées.The melt blends of the thermoplastic polymers and additives are shaped by any conventional means (extrusion, injection, printing films ...) to obtain the desired objects. The invention finally relates to the applications of these objects in thermoplastic polymers with hydrophilized surfaces.
Les plastiques tels les polyesters, les polyamides, les polyoléfines, et plus particulièrement le polypropylène présentent normalement des surfaces très hydrophobes, ce qui constituent un inconvénient pour de nombreuses applications des objets fabriqués à partir de ces thermoplastiques. Par exemple, les voiles ou les films, poreux ou discontinus, fabriqués à partir de fils ou de fibres de polypropylène ou de polyester, obtenus par la technique dite des non tissés, que nous appellerons sous le terme générique de «surface textile non tissée » ont un comportement de surface essentiellement hydrophobe. Ce comportement nécessite qu'ils soient enduits superficiellement, en post-traitement, avec des compositions de surfactants solubles, pour être utilisables dans les applications comme l'hygiène, l'essuyage, les couches culottes....Plastics such as polyesters, polyamides, polyolefins, and more particularly polypropylene normally have very hydrophobic surfaces, which is a drawback for many applications of objects made from these thermoplastics. For example, sails or films, porous or discontinuous, made from polypropylene or polyester yarns or fibers, obtained by the so-called nonwoven technique, which we will call under the generic term "non-woven textile surface" have an essentially hydrophobic surface behavior. This behavior requires that they be superficially coated, in post-treatment, with soluble surfactant compositions, to be used in applications such as hygiene, wiping, diapers ....
Ce traitement de surface a le désavantage de ne pas être durable et aussi de laisser dissoudre dans l'eau au contact le surfactant utilisé dans la couche de traitement. Ce point est particulièrement à éviter dans les applications hygiène comme les couches culottes.This surface treatment has the disadvantage of not being durable and also of allowing the surfactant used in the treatment layer to dissolve in the water in contact with it. This point is particularly to be avoided in hygiene applications like diapers.
Egalement l'hydrophilisation de la surface d'objets est recherchée dans d'autres applications par exemple celles concernant des objets massiques telles des pièces pour l'industrie automobile. On désire pouvoir peindre ces pièces, et les plastiques tels le polypropylène ne sont pas aptes à être peints. Dans ce cas, le traitement de surface par une enduction d'une espèce hydrophile ou amphiphile n'est pas une solution viable car le traitement hydrophilisant n'est ni durable ni adhérent.
Dans une autre sorte d'application, l'hydrophilie est recherchée car elle permettrait de nettoyer à l'eau la surface en question. En particulier les récipients à usage alimentaire en polyoléfine (PE, PP) posent un problème de nettoyage lorsqu'on veut les laver dans un lave-vaisselle automatique. Alors que tous les ustensiles en verre ou en céramiques ressortent propres et secs du lave-vaisselle, les ustensiles en polyoléfines ressortent encore mouillés, avec des gouttes d'eau non étalées, à cause de la grande hydrophobie des ustensiles et récipients concernés.Also the hydrophilization of the surface of objects is sought in other applications for example those for mass objects such as parts for the automotive industry. It is desired to be able to paint these parts, and plastics such as polypropylene are not suitable for painting. In this case, the surface treatment with a coating of a hydrophilic or amphiphilic species is not a viable solution because the hydrophilizing treatment is neither durable nor adherent. In another type of application, hydrophilicity is sought because it would clean the water in question. In particular food containers polyolefin (PE, PP) pose a cleaning problem when you want to wash in an automatic dishwasher. While all the glass or ceramic utensils are clean and dry from the dishwasher, the polyolefin utensils are still wet, with non-spreading drops of water, because of the great hydrophobicity of the utensils and containers concerned.
Enfin l'hydrophilie des emballages ou des films en polypropylène est aussi recherchée pour éviter l'ensalissement, le dépôt de poussière, la buée, lors du stockage des produits emballés sous films polypropylène dans les rayons des surfaces de vente. A ce niveau, l'hydrophilie contribue à la non adhésion de poussières ou de salissures grasses, mais aussi à l'écoulement des charges d'électricité statique responsable de certains types d'ensalissement.Finally the hydrophilicity of polypropylene packaging or films is also sought to prevent slugging, dust deposition, fogging, during the storage of products wrapped polypropylene films in the departments of sales. At this level, hydrophilicity contributes to the non-adhesion of dust or greasy soils, but also to the flow of static electricity charges responsible for certain types of ensalissement.
Le besoin existait de trouver un moyen de préparer un polymère thermoplastique qui présente une surface plus hydrophile.The need existed to find a way to prepare a thermoplastic polymer that has a more hydrophilic surface.
Un des buts de la présente invention est donc de trouver un moyen de préparer un polymère thermoplastique qui présente une surface plus hydrophile.One of the aims of the present invention is therefore to find a means of preparing a thermoplastic polymer which has a more hydrophilic surface.
Ce but, et d'autres, est atteint par la présente invention qui a donc pour objet une composition comprenant un polymère thermoplastique et en agent d'hydrophilisation choisi parmi les tensioactifs anioniques sous forme de sels ou sous forme acide.This object, and others, is achieved by the present invention which therefore relates to a composition comprising a thermoplastic polymer and hydrophilizing agent selected from anionic surfactants in the form of salts or in acid form.
Elle concerne également un procédé de préparation du polymère thermoplastique dans lequel l'agent d'hydrophilisation a été incorporé.It also relates to a process for preparing the thermoplastic polymer in which the hydrophilizing agent has been incorporated.
L'invention concerne enfin les applications de ce polymère thermoplastique à surface hydrophilisée. Par polymère thermoplastique on entend les polyesters, les polyamides, les polyoléfines tels que le polyéthylène et le polypropylène.The invention finally relates to the applications of this thermoplastic polymer with hydrophilized surface. By thermoplastic polymer is meant polyesters, polyamides, polyolefins such as polyethylene and polypropylene.
Par tensioactifs anioniques sous forme de sels ou sous forme acide, on peut citer :By anionic surfactants in the form of salts or in acid form, mention may be made of:
- les acides alkylsulfoniques, les acides arylsulfoniques, éventuellement substitués par un ou plusieurs groupements hydrocarbonés, et dont la fonction acide est partiellement ou totalement salifiée, comme les acides alkylsulfoniques en C8-C50, plus particulièrement en C8-C30, de préférence en Ciθ-C22, les acides benzènesulfoniques, les acides naphtalènesulfoniques, substitués par un à trois groupements alkyles en C1-C30, de préférence en C4-C16, et/ou alcényles en C2-C30, de préférence en C4-C1B-alkylsulphonic acids, arylsulphonic acids, optionally substituted with one or more hydrocarbon groups, and whose acidic function is partially or totally salified, such as C 8 -C 50 , especially C 8 -C 30 , alkylsulphonic acids, preferably C 22 -C θ, benzenesulfonic acid, naphthalenesulfonic acids substituted by one to three alkyl groups C 1 -C 30, preferably C 4 -C 16 alkyl and / or alkenyl C 2 -C 30, preferably C 4 -C 1B -
- les mono- ou diesters d'acides alkylsulfosucciniques, dont la partie alkyle, linéaire ou ramifiée, éventuellement substituée par un ou plusieurs groupements hydroxylés et/ou alcoxylés, linéaires ou ramifiés en C2-C4 (de préférence éthoxylés, propoxylés, éthopropoxylés).
- les esters phosphates choisis plus particulièrement parmi ceux comprenant au moins un groupement hydrocarboné saturé, insaturé ou aromatique, linéaire ou ramifié, comprenant 8 à 40 atomes de carbone, de préférence 10 à 30, éventuellement substitués par au moins un groupement alcoxylé (éthoxylé, propoxylé, éthopropoxylé). En outre, ils comprennent au moins un groupe ester phosphate, mono- ou diestérifié de telle sorte que l'on puisse avoir un ou deux groupes acides libres ou partiellement ou totalement salifiés. Les esters phosphates préférés sont du type des mono- et diesters de l'acide phosphorique et de mono-, di- ou tristyrylphénol alcoxylé (éthoxylé et/ou propoxylé), ou de mono-, di- ou trialkylphénol alcoxylé (éthoxylé et/ou propoxylé), éventuellement substitué par un à quatre groupements alkyles ; de l'acide phosphorique et d'un alcool en C8-C30, de préférence en C10-C22 alcoxylé (éthoxylé ou éthopropoxylé); de l'acide phosphorique et d'un alcool en C8-C22, de préférence en Ci0-C22, non alcoxylé.the mono- or diesters of alkylsulfosuccinic acids, of which the linear or branched alkyl part, optionally substituted with one or more hydroxylated and / or alkoxylated, linear or branched C 2 -C 4 (preferably ethoxylated, propoxylated, ethopropoxylated) groups; ). the phosphate esters chosen more particularly from those comprising at least one saturated, unsaturated or aromatic hydrocarbon group, linear or branched, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted by at least one alkoxylated (ethoxylated) group, propoxylated, ethopropoxylated). In addition, they comprise at least one phosphate ester group, mono- or diesterified so that one or two free acid groups or partially or totally salified. The preferred phosphate esters are of the mono- and diester type of phosphoric acid and of alkoxylated (ethoxylated and / or propoxylated) mono-, di- or tristyrylphenol, or of alkoxylated (ethoxylated) mono-, di- or trialkylphenol and / or propoxylated), optionally substituted with one to four alkyl groups; phosphoric acid and a C 8 -C 30 alcohol, preferably C 10 -C 22 alkoxylated (ethoxylated or ethopropoxylated); phosphoric acid and a C 8 -C 22 alcohol, preferably C 10 -C 22 , non-alkoxylated.
- les esters sulfates obtenus à partir d'alcools saturés, ou aromatiques, éventuellement substitués par un ou plusieurs groupements alcoxylés (éthoxylés, propoxylés, éthopropoxylés), et pour lesquels les fonctions sulfates se présentent sous la forme acide libre, ou partiellement ou totalement neutralisées. A titre d'exemple, on peut citer les esters sulfates obtenus plus particulièrement à partir d'alcools en C8-C20, saturés ou insaturés, pouvant comprendre 1 à 8 motifs alcoxylés (éthoxylés, propoxylés, éthopropoxylés) ; les esters sulfates obtenus à partir de phénol polyalcoxylé, substitués par 1 à 3 groupements hydroxycarbonés en C2-C30, saturés ou insaturés, et dans lesquels le nombre de motifs alcoxylés est compris entre 2 et 40 ; les esters sulfates obtenus à partir de mono-, di- ou tristyrylphénol polyalcoxylés dans lesquels le nombre de motifs alcoxylés varie de 2 à 40. Les tensioactifs anioniques peuvent être sous forme acide (il sont potentiellement anioniques), ou sous une forme partiellement ou totalement salifiée, avec un contre-ion. Le contre-ion peut être un métal alcalin, tel que le sodium ou le potassium, un alcalino- terreux, tel que le calcium, ou encore un ion ammonium de formule N(R)4 + dans laquelle R, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle en C1-C4 éventuellement substitué par un atome d'oxygène. Les tensioactifs anioniques sont utilisés de préférence sous forme de sels de sodium. De manière encore plus préférée, le tensioactif anionique est un alkysulphonate de sodium, dont le groupe alkyle est linéaire ou branché, comprenant en moyenne de 6 à 30 atomes de carbones. Le tensioactif anionique présente par exemple la formule suivante : CH3-(CH2)π-CH2-SO3Na dans laquelle n est un nombre moyen compris entre 8 et 16.sulphate esters obtained from saturated or aromatic alcohols, optionally substituted with one or more alkoxylated groups (ethoxylated, propoxylated, ethopropoxylated), and for which the sulphate functional groups are in the free acid form, or partially or completely neutralized . By way of example, mention may be made of sulfate esters obtained more particularly from saturated or unsaturated C 8 -C 20 alcohols, which may comprise 1 to 8 alkoxylated units (ethoxylated, propoxylated, ethopropoxylated); sulphate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C 2 -C 30 hydroxycarbon groups, and in which the number of alkoxylated units is between 2 and 40; sulphate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol in which the number of alkoxylated units ranges from 2 to 40. The anionic surfactants may be in acid form (they are potentially anionic), or in a form partially or totally salified, with a counter-ion. The counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of formula N (R) 4 + in which R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted with an oxygen atom. The anionic surfactants are preferably used in the form of sodium salts. Even more preferably, the anionic surfactant is sodium alkysulphonate, the alkyl group of which is linear or branched, comprising on average from 6 to 30 carbon atoms. The anionic surfactant has, for example, the following formula: CH 3 - (CH 2 ) π -CH 2 -SO 3 Na wherein n is an average number of between 8 and 16.
Un produit pouvant être utilisé est un produit anionique vendu par Rhodia sous le nom de Catafor FL ou Catafor AFL, sous forme solide.
La quantité d'agent d'hydrophilisation introduite dans le polymère est telle que le rapport en poids entre l'agent d'hydrophilisation et le polymère thermoplastique est compris entre 1/99 et 10/90.A product that can be used is an anionic product sold by Rhodia under the name Catafor FL or Catafor AFL, in solid form. The amount of hydrophilizing agent introduced into the polymer is such that the weight ratio between the hydrophilizing agent and the thermoplastic polymer is between 1/99 and 10/90.
L'agent d'hydrophilisation est mélangé et co-fondu avec le polymère thermoplastique. Le polymère thermoplastique se présente en général sous forme de granulés solide.The hydrophilizing agent is mixed and co-melted with the thermoplastic polymer. The thermoplastic polymer is generally in the form of solid granules.
L'agent d'hydrophilisation peut être mélangé à température ambiante avec les granulés de polymères puis introduit dans un outil de mélange porté en température.The hydrophilizing agent can be mixed at room temperature with the polymer granules and then introduced into a mixing tool heated.
L'agent d'hydrophilisation peut également être introduit dans l'outil de mélange dans lequel est déjà présent le polymère à l'état fondu. L'outil de mélange en température peut être une cuve munie de rotors et chauffée par une circulation de fluide. On parle alors de mélangeur interne. C'est un procédé "batch".The hydrophilizing agent may also be introduced into the mixing tool in which the polymer in the molten state is already present. The temperature mixing tool may be a vessel provided with rotors and heated by a fluid circulation. This is called an internal mixer. It is a "batch" process.
On peut citer par exemple un mélangeur Brabender. On récupère après refroidissement une ébauche de matière solide qui peut être mise en forme dans un moule par compression. L'outil de mélange en température peut également être une extrudeuse dans laquelle la matière est transportée, chauffée et malaxée par des éléments de vis en rotation. C'est un procédé en "continu". On peut citer par exemple une extrudeuse Werner ZSK30. On récupère un jonc de matière fondue qui est refroidit puis coupé pour obtenir des granulés. Ces granulés peuvent ensuite être injectés sous forme de pièces d'essais ou de matériaux finis.For example, a Brabender mixer may be mentioned. After cooling, a blank of solid material is recovered which can be shaped in a mold by compression. The temperature mixing tool may also be an extruder in which the material is transported, heated and kneaded by rotating screw members. It is a "continuous" process. For example, a Werner ZSK30 extruder may be mentioned. A rush of molten material is recovered which is cooled and then cut to obtain granules. These granules can then be injected in the form of test pieces or finished materials.
Lorsque l'agent d'hydrophilisation est sous forme solide, c'est-à-dire sous forme d'une poudre, de paillettes ou de granulés, l'incorporation se fait alors aisément comme indiqué ci-dessus. Lorsque l'agent d'hydrophilisation est sous forme liquide, 100% d'agent hydrophilisant, ou l'agent hydrophilisant en solution dans un solvant, il existe plusieurs possibilités d'incorporation.When the hydrophilizing agent is in solid form, that is to say in the form of a powder, flake or granules, the incorporation is then easily as indicated above. When the hydrophilizing agent is in liquid form, 100% hydrophilizing agent, or the hydrophilizing agent in solution in a solvent, there are several possibilities of incorporation.
Il est possible de réaliser une incorporation directe de liquide, avec ou sans évaporation du solvant suivant si la température d'ébullition du liquide (agent hydrophilisant ou solvant) est en dessous ou au dessus de la température de transformation (autour deIt is possible to carry out a direct incorporation of liquid, with or without evaporation of the following solvent if the boiling temperature of the liquid (hydrophilizing agent or solvent) is below or above the transformation temperature (around
18O0C).18O 0 C).
Il est possible également d'imprégner ce liquide sur un support poreux, comme par exemple une silice de précipitation pour obtenir une poudre. Cette poudre peut alors être mise en forme pour faciliter son utilisation. On peut citer par exemple le document FR 2 843 122 incorporé par référence qui décrit des moyens pour incorporer des liquides dans des polymères thermoplastiques.It is also possible to impregnate this liquid on a porous support, such as for example a precipitated silica to obtain a powder. This powder can then be shaped to facilitate its use. For example, reference may be made to FR 2,843,122, which discloses means for incorporating liquids into thermoplastic polymers.
La présente invention a donc également pour objet un procédé de préparation d'une composition comprenant le polymère thermoplastique et l'agent hydrophilisant,
caractérisé en ce qu'on mélange l'agent d'hydrophilisation et le polymère thermoplastique sous forme fondue.The present invention therefore also relates to a process for preparing a composition comprising the thermoplastic polymer and the hydrophilizing agent, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer in molten form.
La présente invention a donc également pour objet un procédé de préparation d'une composition comprenant le polymère thermoplastique et l'agent hydrophilisant, caractérisé en ce que l'agent d'hydrophilisation est mélangé au polymère thermoplastique éventuellement avec d'autres ingrédients, par exemple des charges ou des stabilisants, par mélange au polymère thermoplastique avant fusion, par introduction directe dans le polymère thermoplastique fondu, et/ou par mélange maître. Les mélanges fondus de polymère thermoplastique et d'agent hydrophilisant peuvent être mis en forme par tous moyens conventionnels (extrusion, injection, tirage de films...) pour obtenir les objets désirés.The present invention therefore also relates to a process for preparing a composition comprising the thermoplastic polymer and the hydrophilizing agent, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer optionally with other ingredients, for example fillers or stabilizers, by mixing with the thermoplastic polymer before melting, by direct introduction into the molten thermoplastic polymer, and / or by masterbatch. The melt blends of thermoplastic polymer and hydrophilizing agent can be shaped by any conventional means (extrusion, injection, pulling films ...) to obtain the desired objects.
Les mélanges fondus de polymère thermoplastique et d'agent hydrophilisant peuvent ainsi être mis sous forme de poudre à mouler, sous forme d'un objet extrudé et/ou soufflé et/ou injecté, sous forme d'un film, ou sous forme de fibres fils ou filaments, éventuellement assemblés en surface textile tissée ou non tissée.The melt blends of thermoplastic polymer and hydrophilizing agent can thus be formed into molding powder, in the form of an extruded and / or blown and / or injected object, in the form of a film, or in the form of fibers. yarns or filaments, optionally assembled in woven or nonwoven textile surface.
L'invention concerne également les applications de ces objets en polymères thermoplastiques à surfaces hydrophilisées.The invention also relates to the applications of these objects in thermoplastic polymers with hydrophilized surfaces.
A titre d'exemples d'objets en polymère thermoplastique à surface hydrophilisée on peut citer notamment une surface textile non tissée comprenant des fibres à base d'une composition selon l'invention.As examples of objects made of thermoplastic polymer with a hydrophilized surface, mention may in particular be made of a nonwoven textile surface comprising fibers based on a composition according to the invention.
On peut citer en particulier une surface textile non tissée comprenant des fibres à base d'une composition selon l'invention dans laquelle le polymère thermoplastique est à base de polypropylène. Cette surface textile peut être utilisée dans la fabrication de couche-culotte pour bébé, de produit d'hygiène féminine ou de produit pour le soin de l'incontinence des adultes. A titre d'exemples d'objets en polymère thermoplastique à surface hydrophilisée on peut citer également des objets massiques telles des pièces pour l'industrie automobile. A titre d'exemples d'objets en polymère thermoplastique à surface hydrophilisée on peut citer également les récipients à usage alimentaire en polyoléfine (polyéthylène ou polypropylène.In particular, a nonwoven textile surface comprising fibers based on a composition according to the invention in which the thermoplastic polymer is based on polypropylene may be mentioned. This textile surface can be used in the manufacture of baby diaper, feminine hygiene product or adult incontinence care product. Examples of objects made of thermoplastic polymer with a hydrophilized surface include mass objects such as parts for the automotive industry. Examples of objects made of thermoplastic polymer with a hydrophilized surface include food containers made of polyolefin (polyethylene or polypropylene).
A titre d'exemples d'objets en polymère thermoplastique à surface hydrophilisée on peut citer également les emballages ou des films en polypropylène.Examples of objects made of thermoplastic polymer with a hydrophilized surface include packaging or polypropylene films.
L'invention concerne enfin une utilisation de tensioactifs anioniques sous forme de sels ou sous forme acide tel que défini précédemment à titre d'agent d'hydrophilisation d'une composition comprenant un polymère thermoplastique.The invention finally relates to a use of anionic surfactants in the form of salts or in acid form as defined above as hydrophilizing agent of a composition comprising a thermoplastic polymer.
L'hydrophilie de surface est évaluée par la mesure de l'angle de contact entre une goutte d'eau purifiée, distillée et ladite surface. Une goutte d'eau distillée de taille calibrée est déposée dans des conditions standardisées et répétitives sur la surface à
étudier. Elle s'étale ou se rétracte plus ou moins selon l'hydrophilie de la surface, et avec un appareillage adapté, il est possible de mesurer l'angle formé par la goutte déposée et la surface.Surface hydrophilicity is evaluated by measuring the contact angle between a drop of purified, distilled water and said surface. A drop of distilled water of calibrated size is deposited under standardized and repetitive conditions on the surface to be to study. It spreads or retracts more or less depending on the hydrophilicity of the surface, and with suitable equipment, it is possible to measure the angle formed by the deposited drop and the surface.
L'appareillage utilisé peut être par exemple un goniomètre de mesure de l'angle de mouillage, par exemple de marque Tantec. Il est possible également d'utiliser un appareil de mesure automatique, tel que le tensiomètre à goutte avec banc optique de la société IT Concept. C'est le cas des mesures qui ont été effectuées dans les exemples présentés ci-dessous. La manipulation consiste à déposer sur la surface propre et lisse de l'échantillon une goutte d'eau de volume calibré égale à deux microlitres à l'aide d'une seringue. La goutte est éclairée par une source lumineuse uniforme, de type sphère intégrante, l'image de son profil est projetée par un téléobjectif télécentrique sur une caméra CCD. Elle est numérisée et ensuite traitée par un logiciel pour déterminer plusieurs fois par seconde les angles de contact droit et gauche définis comme les angles entre le plan formé par le support et les plans tangents de part et d'autre de la base de la goutte.The apparatus used may be, for example, a goniometer for measuring the wetting angle, for example of the Tantec mark. It is also possible to use an automatic measuring device, such as the IT Concept company's droplet monitor with optical bench. This is the case of the measurements that have been made in the examples presented below. The manipulation consists in depositing on the clean and smooth surface of the sample a drop of water of calibrated volume equal to two microliters using a syringe. The drop is illuminated by a uniform light source, type integrating sphere, the image of his profile is projected by a telecentric telephoto lens on a CCD camera. It is digitized and then processed by software to determine several times per second the right and left contact angles defined as the angles between the plane formed by the support and tangent planes on either side of the base of the drop.
Typiquement, le polypropylène pur a un angle de contact avec l'eau pure de 105°. Les agents hydrophilisants lorsqu'ils sont mélangés au polymère thermoplastique polypropylène permettent d'abaisser très sensiblement cette valeur, à des niveaux compris entre 70 et 85°. D'autres aspects et avantages des produits objets de l'invention apparaîtront à la lumière des exemples qui sont présentés ci-dessous à titre illustratif et nullement limitatif.Typically, pure polypropylene has a contact angle with pure water of 105 °. The hydrophilizing agents when they are mixed with the thermoplastic polypropylene polymer make it possible to lower this value very substantially, at levels between 70 and 85 °. Other aspects and advantages of the products which are the subject of the invention will emerge in the light of the examples which are presented below by way of illustration and in no way limitative.
Sans indication contraire, tous les pourcentages indiqués dans la présente demande sont des pourcentages en poids.Unless otherwise indicated, all percentages given in this application are percentages by weight.
Exemple 1 -Mise en œuvre de ces produitsExample 1 -Implementation of these products
Les constituants (94,9% de polymère polypropylène homopolymère isotactique en granulés commercialisé par la société ATOFINA sous le nom PPH4060, 5% d'additif hydrophilisant et 0,1% de stabilisant thermique Irganox B225) sont introduits dans la cuve d'un mélangeur interne de marque "Brabender" portée à une température de 15O0C.The constituents (94.9% of isotactic polypropylene homopolymer polypropylene polymer sold by ATOFINA under the name PPH4060, 5% of hydrophilizing additive and 0.1% of Irganox B225 thermal stabilizer) are introduced into the tank of a mixer. internal brand "Brabender" brought to a temperature of 15O 0 C.
La cuve est munie de deux rotors contra-rotatifs de type thermoplastique W50, tournant à une vitesse de rotation de 125 RPM. Compte tenu du cisaillement interne, la température finale du mélange est comprise entre 18O0C et 1900C. Après une temps de mélangeage de 5 minutes, une ébauche de polymère chargée est extraite de la cuve, et est pressée dans un moule de 800 μm d'épaisseur, entre deux plateaux de compression chauffés à 2000C sous 200 bars de pression pendant 2 minutes. Le moule est ensuite refroidi entre deux plateaux refroidis à 180C sous une pression de 200 bars pendant 4 minutes.
Après refroidissement et consolidation, ces éprouvettes font l'objet de divers tests physico-chimiques destinés à vérifier l'hydrophilie de leur surface et les propriétés qui en découlent.The tank is equipped with two counter-rotating rotors of thermoplastic type W50, rotating at a speed of rotation of 125 RPM. Given the internal shear, the final temperature of the mixture is between 18O 0 C and 190 0 C. After a mixing time of 5 minutes, a charged polymer blank is extracted from the tank, and is pressed into a mold 800 microns thick, between two compression plates heated to 200 0 C under 200 bar pressure for 2 minutes. The mold is then cooled between two trays cooled to 18 0 C under a pressure of 200 bar for 4 minutes. After cooling and consolidation, these specimens are subjected to various physico-chemical tests to check the hydrophilicity of their surface and the resulting properties.
Remarques sur la mise en œuvre et effet des additifs sur les mélanges fondus :Remarks on the implementation and effect of additives on the melted mixtures:
On note différents effets physiques pendant le mélangeage dans le malaxeur Brabender, qui peuvent apporter des avantages importants au niveau de cette phase préparatoire. Pour le Catafor FL (ou « AFL »), on note un effet lubrifiant. Le produit fini (éprouvette) à un toucher modifié, qualifié de "doux" (soft) ou de soyeux.There are different physical effects during mixing in the Brabender kneader, which can provide significant benefits in this preparatory phase. For the Catafor FL (or "AFL"), there is a lubricating effect. The finished product (test specimen) has a modified feel, described as "soft" or soft.
Exemple 2 - Effets hydrophilisantsExample 2 - Hydrophilizing Effects
Ils sont donnés (par l'intermédiaire de la mesure de l'angle de contact avec de l'eau distillée) dans le tableau I suivant, et en fonction du vieillissement des éprouvettes à l'air libre.They are given (via the measurement of the contact angle with distilled water) in the following Table I, and according to the aging of the specimens in the open air.
Les mesures ont été effectuées dans les exemples présentés ci-dessous en utilisant un tensiomètre à goutte avec banc optique dénommé le SDT 200 de la société IT Concept. La manipulation consiste à déposer sur la surface propre et lisse de l'échantillon une goutte d'eau de volume calibré égale à deux microlitres à l'aide d'une seringue. La goutte est éclairée par une source lumineuse uniforme, de type sphère intégrante, l'image de son profil est projetée par un téléobjectif télécentrique sur une caméra CCD. Elle est numérisée et ensuite traitée par un logiciel pour déterminer plusieurs fois par seconde les angles de contact droit et gauche définis comme les angles entre le plan formé par le support et les plans tangents de part et d'autre de la base de la goutte. Le résultat indiqué dans le tableau I correspond à la moyenne de 10 à 15 mesures.The measurements were made in the examples presented below using a drop tensiometer with optical bench called the SDT 200 from the company IT Concept. The manipulation consists in depositing on the clean and smooth surface of the sample a drop of water of calibrated volume equal to two microliters using a syringe. The drop is illuminated by a uniform light source, type integrating sphere, the image of his profile is projected by a telecentric telephoto lens on a CCD camera. It is digitized and then processed by software to determine several times per second the right and left contact angles defined as the angles between the plane formed by the support and tangent planes on either side of the base of the drop. The result shown in Table I corresponds to the average of 10 to 15 measurements.
Tableau ITable I
PP signifie polypropylène La surface des éprouvettes est nettoyée à l'éthanol préalablement au dépôt de la goutte pour la mesure de l'angle de contact. On constate que l'hydrophilie de la surface est bien obtenue durablement.
PP means polypropylene The surface of the test pieces is cleaned with ethanol prior to depositing the drop for the measurement of the contact angle. It is found that the hydrophilicity of the surface is well obtained durably.
Claims
1. Composition comprenant un polymère thermoplastique et en agent d'hydrophilisation choisi parmi les tensioactifs anioniques sous forme de sels ou sous forme acide; de préférence sous forme de sels de sodium.A composition comprising a thermoplastic polymer and a hydrophilizing agent selected from anionic surfactants in the form of salts or in acid form; preferably in the form of sodium salts.
2. Composition selon la revendication 1 , caractérisée en ce que le tensioactif anionique est un alkysulphonate de sodium, dont le groupe alkyle est linéaire ou branché, comprenant en moyenne de 6 à 30 atomes de carbones.2. Composition according to claim 1, characterized in that the anionic surfactant is a sodium alkysulphonate, the alkyl group is linear or branched, comprising on average from 6 to 30 carbon atoms.
3. Composition selon l'une des revendications précédentes, caractérisée en ce que le tensioactif anionique présente la formule suivante:3. Composition according to one of the preceding claims, characterized in that the anionic surfactant has the following formula:
CH3-(CH2)H-CH2-SO3Na dans laquelle n est un nombre moyen compris entre 8 et 16.CH 3 - (CH 2 ) H -CH 2 -SO 3 Na wherein n is an average number of between 8 and 16.
4. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère thermoplastique est choisi parmi les polyesters, les polyamides, ou les polyoléfines tels que le polyéthylène et le polypropylène.4. Composition according to one of the preceding claims, characterized in that the thermoplastic polymer is selected from polyesters, polyamides, or polyolefins such as polyethylene and polypropylene.
5. Composition selon l'une des revendications précédentes, caractérisée en ce que le polymère thermoplastique est à base de polypropylène.5. Composition according to one of the preceding claims, characterized in that the thermoplastic polymer is based on polypropylene.
6. Composition selon l'une des revendications précédentes, caractérisée en ce qu'elle est sous poudre de poudre à mouler, sous forme d'un objet extrudé et/ou soufflé et/ou injecté, sous forme d'un film, ou sous forme de fibres fils ou filaments, éventuellement assemblés en surface textile tissée ou non tissée.6. Composition according to one of the preceding claims, characterized in that it is under powder of molding powder, in the form of an extruded object and / or blown and / or injected, in the form of a film, or under fiber form son or filaments, optionally assembled in woven or nonwoven fabric surface.
7. Composition selon l'une des revendications précédentes, caractérisée en ce que le rapport en poids entre l'agent d'hydrophilisation et le polymère thermoplastique est compris entre 1/99 et 10/90.7. Composition according to one of the preceding claims, characterized in that the weight ratio between the hydrophilizing agent and the thermoplastic polymer is between 1/99 and 10/90.
8. Procédé de préparation d'une composition selon l'une des revendications précédentes, caractérisé en ce qu'on mélange l'agent d'hydrophilisation et le polymère thermoplastique sous forme fondue.8. Process for preparing a composition according to one of the preceding claims, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer in molten form.
9. Procédé selon la revendication précédente, caractérisé en ce que l'agent d'hydrophilisation est mélangé au polymère thermoplastique éventuellement avec d'autres ingrédients, par exemple des charges ou des stabilisants, par mélange au polymère thermoplastique avant fusion, par introduction directe dans le polymère thermoplastique fondu, et/ou par mélange maître.9. Method according to the preceding claim, characterized in that the hydrophilizing agent is mixed with the thermoplastic polymer optionally with other ingredients, for example fillers or stabilizers, by mixing with the thermoplastic polymer before melting, by direct introduction into the molten thermoplastic polymer, and / or by masterbatch.
10. Surface textile non tissée comprenant des fibres à base de la composition selon l'une des revendications précédentes, dans laquelle le polymère thermoplastique est à base de polypropylène.10. A nonwoven textile surface comprising fibers based on the composition according to one of the preceding claims, wherein the thermoplastic polymer is based on polypropylene.
11. Surface textile selon la revendication précédente, comprise dans une couche-culotte pour bébé, un produit d'hygiène féminine ou un produit pour le soin de l'incontinence des adultes.11. Textile surface according to the preceding claim, included in a baby diaper, a feminine hygiene product or a product for the care of adult incontinence.
12. Utilisation de tensioactifs anioniques sous forme de sels ou sous forme acide selon l'une quelconque des revendications 1 à 3 à titre d'agent d'hydrophilisation d'une composition comprenant un polymère thermoplastique. 12. Use of anionic surfactants in the form of salts or in acid form according to any one of claims 1 to 3 as hydrophilizing agent of a composition comprising a thermoplastic polymer.
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US66115305P | 2005-03-14 | 2005-03-14 | |
PCT/FR2006/000479 WO2006097597A1 (en) | 2005-03-14 | 2006-03-03 | Composition comprising a thermoplastic polymer and a hydrophilizing agent |
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JP (2) | JP2008535955A (en) |
WO (1) | WO2006097597A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2922892B1 (en) * | 2007-10-24 | 2010-11-26 | Rhodia Operations | HYDROPHILIZATION AGENT OF ORGANIC PLASTIC MATERIAL. |
BRPI0910011A2 (en) * | 2008-06-12 | 2016-01-19 | 3M Innovative Properties Co | durable hydrophilic composition, article and processes for manufacturing a durable hydrophilic composition |
US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
WO2010042668A1 (en) | 2008-10-07 | 2010-04-15 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
CN102365100B (en) * | 2009-03-27 | 2015-04-01 | 3M创新有限公司 | Hydrophilic polypropylene melt additives |
EP2414574B1 (en) | 2009-03-31 | 2018-12-12 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
JP5702526B2 (en) * | 2009-04-30 | 2015-04-15 | Esファイバービジョンズ株式会社 | Fiber assembly carrying sulfated cellulose having antiviral properties |
US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
BR112012023312A2 (en) | 2010-03-15 | 2019-09-24 | Ross Tech Corporation | plunger and hydrophobic surface production methods |
JP2014512417A (en) | 2011-02-21 | 2014-05-22 | ロス テクノロジー コーポレーション. | Superhydrophobic and oleophobic coatings containing low VOC binder systems |
CN107419353A (en) * | 2011-04-27 | 2017-12-01 | 三井化学株式会社 | Fiber, non-woven cloth and application thereof |
DE102011085428A1 (en) | 2011-10-28 | 2013-05-02 | Schott Ag | shelf |
GB201119521D0 (en) | 2011-11-11 | 2011-12-21 | Axis Shield Asa | Assay cartridge |
EP2791255B1 (en) | 2011-12-15 | 2017-11-01 | Ross Technology Corporation | Composition and coating for superhydrophobic performance |
BR102012010783A2 (en) * | 2012-05-07 | 2014-03-25 | Braskem Sa | Polyolefin Granulation Process, Polyolefin Resin, Polyolefin Fiber, Polyolefin Fiber Use, and Cement Composites |
BR112014032676A2 (en) | 2012-06-25 | 2017-06-27 | Ross Tech Corporation | elastomeric coatings that have hydrophobic and / or oleophobic properties |
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JPS4421656Y1 (en) | 1967-06-27 | 1969-09-12 | ||
US3637900A (en) * | 1969-04-22 | 1972-01-25 | Kanegafuchi Spinning Co Ltd | Polyamide fibers with aliphatic sulfonic acid containing antistatic agents |
US4873277A (en) * | 1986-10-31 | 1989-10-10 | General Electric Company | Aromatic carbonate resin exhibiting improved impact properties |
JP3444674B2 (en) * | 1994-12-07 | 2003-09-08 | カネボウ株式会社 | Nonwoven fabric using polyolefin resin composition |
JPH1060764A (en) * | 1996-08-13 | 1998-03-03 | Teijin Ltd | Conjugated nonwoven fabric |
JPH10325060A (en) * | 1997-03-28 | 1998-12-08 | Teijin Ltd | Hydrophilic nonwoven fabric |
JPH11269281A (en) * | 1998-03-20 | 1999-10-05 | Teijin Ltd | Hydrophilic film |
-
2006
- 2006-03-03 EP EP06726017A patent/EP1858966A1/en not_active Withdrawn
- 2006-03-03 US US11/886,304 patent/US8287509B2/en not_active Expired - Fee Related
- 2006-03-03 WO PCT/FR2006/000479 patent/WO2006097597A1/en active Application Filing
- 2006-03-03 JP JP2008501351A patent/JP2008535955A/en active Pending
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2012
- 2012-02-02 JP JP2012020923A patent/JP2012107251A/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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WO2006097597A1 (en) | 2006-09-21 |
US20090105679A1 (en) | 2009-04-23 |
US8287509B2 (en) | 2012-10-16 |
JP2012107251A (en) | 2012-06-07 |
JP2008535955A (en) | 2008-09-04 |
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