EP1954869A1 - Production of superhydrophobic fibrous substrates - Google Patents

Production of superhydrophobic fibrous substrates

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Publication number
EP1954869A1
EP1954869A1 EP06841826A EP06841826A EP1954869A1 EP 1954869 A1 EP1954869 A1 EP 1954869A1 EP 06841826 A EP06841826 A EP 06841826A EP 06841826 A EP06841826 A EP 06841826A EP 1954869 A1 EP1954869 A1 EP 1954869A1
Authority
EP
European Patent Office
Prior art keywords
substrate
microparticles
fibrous substrate
fibrous
superhydrophobic
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.)
Granted
Application number
EP06841826A
Other languages
German (de)
French (fr)
Other versions
EP1954869B1 (en
Inventor
Henri Cramail
Pierre Chambon
Eric Cloutet
Serge Ravaine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
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Publication date
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Publication of EP1954869A1 publication Critical patent/EP1954869A1/en
Application granted granted Critical
Publication of EP1954869B1 publication Critical patent/EP1954869B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material

Definitions

  • the present invention relates to a process for the preparation of fibrous superhydrophobic substrates, superhydrophobic fibrous substrates and the use of such substrates.
  • a material is considered superhydrophobic when the contact angle of a drop of water deposited on its surface is greater than 140 degrees.
  • Such materials have interesting properties in a wide variety of fields, including clothing, stationery or paints.
  • the invention provides a process for preparing a fibrous superhydrophobic substrate, comprising the following successive steps: preparation of hydrophobic microparticles of heart-shell type, said microparticles having a polyurethane core and a polydimethylsiloxane bark or polybutadiene; depositing, on the fibrous substrate, a liquid suspension of said microparticles in an organic solvent.
  • fibrous substrate is meant any material consisting of synthetic or natural fibers.
  • Microparticle means particles of micrometric size.
  • hydrophobic core-shell microparticles having a polyurethane core and a bark formed of a polystyrene-poly (ethylene oxide) copolymer, a hydroxypolystyrene, or poly (butyl acrylate) have been synthesized by the inventors, as described in the following publications: B. Radhakrishnan et al., Colloid Polym Sci (2002), 280, 1122-1130, and B. Radhakrishnan et al., Colloid Polym Sci (2003), 281, 516-530. However, these particles, once deposited on fibrous substrates, did not give said substrates a superhydrophobic character.
  • the first step of the process according to the invention preferably involves a stepwise polymerization method in a medium dispersed in an organic solvent, a first monomer consisting of a diol, for example ethane-1,2-diol, and a second di-isocyanate monomer, for example tolylene di-isocyanate, in the presence of polydimethylsiloxane (PDMS) or polybutadiene which acts as a reactive stabilizer.
  • PDMS polydimethylsiloxane
  • the organic solvent used for the preparation of the microparticles may be cyclohexane or supercritical carbon dioxide.
  • the microparticles obtained have a diameter generally of between 0.5 and 5 microns.
  • the size of the particles is adjusted by varying various parameters: the mass percentage of the reactive stabilizer, the stirring speed, the rate and order of addition of the monomers, the molar mass of the reactive stabilizer and the functionality of the stabilizer. reagent.
  • the fibrous substrate that is to be made superhydrophobic hereinafter referred to as the substrate to be treated, is made of natural fibers selected from the group comprising cellulose, wool, cotton, silk, and can be filter paper.
  • the substrate to be treated consists of synthetic fibers selected from the group comprising polyamides and polyesters, and may have a porosity of between 1 and 10 microns.
  • the substrate is a polyamide fabric.
  • This deposition may be carried out for example by filtering the suspension of microparticles through the fibrous substrate, or by soaking the fibrous substrate in the microparticle suspension, then evaporation of the solvent, or by deposition of the suspension on the fibrous substrate and then evaporation of the solvent.
  • the subject of the invention is a superhydrophobic fibrous substrate in which the fibers are impregnated with core-shell microparticles, said microparticles having a polyurethane core and a polydimethylsiloxane or polybutadiene bark.
  • the microparticles have a diameter generally of between 0.5 and 5 microns.
  • the substrate is for example made of a polyamide fabric or filter paper. Depending on its nature, it can be used for the manufacture of textiles for clothing, or for the manufacture of coatings for printing.
  • Example 1 relates to the preparation of hydrophobic microparticles, and the following examples relate to the deposition of microparticles on different substrates.
  • Polyurethane particles having a core-shell structure are prepared by a process in dispersion in cyclohexane, in the presence of polydimethylsiloxane.
  • the reactive stabilizer PDMS-OH, molar mass 4670 g. mol "1 (0.5 g, ie 16.7% by weight), the monomer ethane-1,2-diol (0.6 g) and cyclohexane (20 g) are introduced into the reactor and then left at 60 ° C. with stirring for a few minutes
  • the tolylene diisocyanate comonomer (1.9 g) is then added and the reaction mixture is stirred for at least 6 hours.
  • the latex obtained is recovered, centrifuged, and then the particles are dispersed again in cyclohexane. This operation is repeated twice.
  • the particles obtained are characterized by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • Figure 1 shows a SEM image of these particles, whose diameter is equal to 2.2 microns.
  • the process was repeated to obtain particles having a diameter of 3.5 and 4.2 ⁇ m respectively, using a weight percentage of polydimethylsiloxane equal to 9% and 4%, respectively.
  • Example 2
  • the test was reproduced successively with polyamide webs having a porosity of 1 .mu.m, 5 .mu.m and 10 .mu.m respectively, and with microparticles having a diameter of 2.2 .mu.m, 3.5 .mu.m and 4.2 .mu.m.
  • FIGS. 2a and 2b show clichés obtained at two different scales, the side of the square formed by a plate representing respectively 147 microns and 37 microns, for the fabric having a porosity of 1 ⁇ m treated with a suspension of particles having a diameter of 2.2 ⁇ m.
  • Example 3 Embodiment of the process with a substrate consisting of filter paper
  • Example 4 A process analogous to that of Example 2 was carried out using a filter paper instead of a polyamide cloth. Tests were carried out with particles having a diameter of 2.2 ⁇ m, 3.5 ⁇ m and 4.2 ⁇ m. A homogeneous deposition which respects the surface topology of the filter paper is obtained, as illustrated in FIGS. 3a and 3b, which show scanning electron microscopy photographs obtained at different scales, the side of the square formed by a plate representing respectively 147 microns and 37 microns, for filter paper treated with a suspension of particles having a diameter of 3.5 microns.
  • FIGS. 3a and 3b show scanning electron microscopy photographs obtained at different scales, the side of the square formed by a plate representing respectively 147 microns and 37 microns, for filter paper treated with a suspension of particles having a diameter of 3.5 microns.
  • Example 4
  • FIGS. 4 to 8 are optical microscopy photographs showing a drop of water deposited respectively on the following substrates: FIG. 4: 5 ⁇ m porosity polyamide fabric and 2.2 ⁇ m diameter particles; FIG. 5: polyamide fabric having a porosity of 1 ⁇ m and particles with a diameter of 2.2 ⁇ m; FIG. 6: polyamide fabric having a porosity of 1 ⁇ m and particles with a diameter of 4.2 ⁇ m; FIG. 7: filter paper and particles with a diameter of 2.2 ⁇ m; FIG. 8: filter paper and particles with a diameter of 3.5 ⁇ m.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Process for the production of a superhydrophobic fibrous substrate. The process involves preparing hydrophobic core-shell microparticles, the microparticles having a core of polyurethane and a shell of polydimethylsiloxane or of polybutadiene, then depositing a liquid suspension of the microparticles on the fibrous substrate. Superhydrophobic fibrous substrates of this kind are useful for the manufacture of textiles intended for apparel, or of coatings for printing.

Description

Préparation de substrats fibreux superhydrophobes Preparation of superhydrophobic fibrous substrates
La présente invention concerne un procédé de préparation de substrats superhydrophobes fibreux, des substrats fibreux superhydrophobes ainsi que l'utilisation de tels substrats. Un matériau est considéré comme superhydrophobe lorsque l'angle de contact d'une goutte d'eau déposée sur sa surface est supérieur à 140 degrés.The present invention relates to a process for the preparation of fibrous superhydrophobic substrates, superhydrophobic fibrous substrates and the use of such substrates. A material is considered superhydrophobic when the contact angle of a drop of water deposited on its surface is greater than 140 degrees.
De tels matériaux présentent des propriétés intéressantes dans des domaines très variés, notamment l'habillement, la papeterie ou les peintures.Such materials have interesting properties in a wide variety of fields, including clothing, stationery or paints.
Dans le domaine de l'habillement ou de la papeterie, les matériaux que l'on souhaite rendre superhydrophobes présentent généralement un caractère fibreux.In the field of clothing or stationery, the materials that one wishes to make superhydrophobic generally have a fibrous character.
Pour fabriquer des matériaux fibreux superhydrophobes, on connaît, notamment de WO 04/058419, EP 0 985 740 et EP 0 985 741, des procédés utilisant des composés fluorés greffés. Toutefois, les matériaux obtenus par ces procédés présentent plusieurs inconvénients. Tout d'abord, le greffage chimique des agents organiques fluorés est peu robuste vis-à-vis d'actions mécaniques répétées (essuyages, lavages) inhérentes à l'utilisation des matériaux, en particulier lorsqu'il s'agit de textiles. En outre, la dégradation des matériaux dans le temps provoque la libération d'agents polluants pour l'environnement. On connaît également d'autres procédés de fabrication de matériaux superhydrophobes, notamment de WO 04/090065 et WO 04/033788, qui ne font pas intervenir le greffage chimique de composés fluorés. Toutefois, -la mise en œuvre de tous ces procédés est complexe. Les inventeurs ont trouvé que, de manière surprenante, il est possible d'obtenir des matériaux superhydrophobes par simple dépôt sur un substrat fibreux de particules hydrophobes ayant une structure et une nature chimique particulières . En outre, le caractère superhydrophobe des matériaux obtenus n'est pas sensible au vieillissement, pendant plusieurs mois, lorsque ceux-ci sont laissés au repos.In order to manufacture superhydrophobic fibrous materials, processes are known, in particular from WO 04/058419, EP 0 985 740 and EP 0 985 741, using processes that use grafted fluorinated compounds. However, the materials obtained by these methods have several disadvantages. Firstly, the chemical grafting of fluorinated organic agents is not robust with respect to repeated mechanical actions (wiping, washing) inherent in the use of materials, particularly when it comes to textiles. In addition, the degradation of materials over time causes the release of pollutants for the environment. Other processes for producing superhydrophobic materials, in particular WO 04/090065 and WO 04/033788, which do not involve the chemical grafting of fluorinated compounds, are also known. However, the implementation of all these methods is complex. The inventors have found that, surprisingly, it is possible to obtain superhydrophobic materials by simply depositing on a fibrous substrate hydrophobic particles having a particular structure and chemical nature. In addition, the superhydrophobic nature of the materials obtained is not sensitive to aging, for several months, when they are left to rest.
Ainsi, selon un premier aspect, l'invention propose un procédé de préparation d'un substrat superhydrophobe fibreux, comprenant les étapes successives suivantes : préparation de microparticules hydrophobes de type cœur-écorce, lesdites microparticules présentant un cœur en polyuréthane et une écorce en polydiméthylsiloxane ou en polybutadiène ; dépôt, sur le substrat fibreux, d'une suspension liquide desdites microparticules dans un solvant organique.Thus, according to a first aspect, the invention provides a process for preparing a fibrous superhydrophobic substrate, comprising the following successive steps: preparation of hydrophobic microparticles of heart-shell type, said microparticles having a polyurethane core and a polydimethylsiloxane bark or polybutadiene; depositing, on the fibrous substrate, a liquid suspension of said microparticles in an organic solvent.
Par substrat fibreux, on entend tout matériau constitué de fibres synthétiques ou naturelles. Par microparticule, on entend des particules de dimension micrométrique.By fibrous substrate is meant any material consisting of synthetic or natural fibers. Microparticle means particles of micrometric size.
D' autres microparticules hydrophobes de type cœur-écorce, présentant un cœur en polyuréthane et une écorce formée d'un copolymère polystyrène-poly (éthylène oxyde), d'un hydroxypolystyrène, ou de poly (butylacrylate) ont été synthétisées par les inventeurs, tel que décrit dans les publications suivantes : B. Radhakrishnan et al., Colloid Polym Sci (2002), 280, 1122-1130, et B. Radhakrishnan et al., Colloid Polym Sci (2003), 281, 516-530. Toutefois, ces particules, une fois déposées sur des substrats fibreux, n'ont pas conféré auxdits substrats un caractère superhydrophobe. Ainsi, le choix particulier des microparticules utilisées dans le procédé selon l'invention est à l'origine des propriétés superhydrophobes conférées aux substrats fibreux. La première étape du procédé selon l'invention fait de préférence intervenir une méthode de polymérisation par étapes en milieu dispersé dans un solvant organique, d'un premier monomère constitué d'un diol, par exemple d' éthane- 1,2-diol, et d'un deuxième monomère de type di-isocyanate, par exemple le tolylène di-isocyanate, en présence de polydiméthylsiloxane (PDMS) ou de polybutadiène qui joue un rôle de stabilisant réactif. Cette méthode est décrite de façon détaillée par P. Chambon et al., Polymer (2005), 46, 1057- 1066.Other hydrophobic core-shell microparticles having a polyurethane core and a bark formed of a polystyrene-poly (ethylene oxide) copolymer, a hydroxypolystyrene, or poly (butyl acrylate) have been synthesized by the inventors, as described in the following publications: B. Radhakrishnan et al., Colloid Polym Sci (2002), 280, 1122-1130, and B. Radhakrishnan et al., Colloid Polym Sci (2003), 281, 516-530. However, these particles, once deposited on fibrous substrates, did not give said substrates a superhydrophobic character. Thus, the particular choice of microparticles used in the process according to the invention is at the origin of the superhydrophobic properties imparted to the fibrous substrates. The first step of the process according to the invention preferably involves a stepwise polymerization method in a medium dispersed in an organic solvent, a first monomer consisting of a diol, for example ethane-1,2-diol, and a second di-isocyanate monomer, for example tolylene di-isocyanate, in the presence of polydimethylsiloxane (PDMS) or polybutadiene which acts as a reactive stabilizer. This method is described so detailed by P. Chambon et al., Polymer (2005), 46, 1057-1066.
Le solvant organique utilisé pour la préparation des microparticules peut être le cyclohexane ou le dioxyde de carbone supercritique.The organic solvent used for the preparation of the microparticles may be cyclohexane or supercritical carbon dioxide.
Les microparticules obtenues présentent un diamètre généralement compris entre 0,5 et 5 microns.The microparticles obtained have a diameter generally of between 0.5 and 5 microns.
La taille des particules est ajustée en faisant varier différents paramètres : le pourcentage massique du stabi- lisant réactif, la vitesse d'agitation, la vitesse et l'ordre d'addition des monomères, la masse molaire du stabilisant réactif et la fonctionnalité du stabilisant réactif.The size of the particles is adjusted by varying various parameters: the mass percentage of the reactive stabilizer, the stirring speed, the rate and order of addition of the monomers, the molar mass of the reactive stabilizer and the functionality of the stabilizer. reagent.
Selon un premier mode de réalisation, le substrat fibreux que l'on souhaite rendre superhydrophobe, dénommé ci-après substrat à traiter, est constitué de fibres naturelles choisies dans le groupe comprenant la cellulose, la laine, le coton, la soie, et peut être du papier filtre.According to a first embodiment, the fibrous substrate that is to be made superhydrophobic, hereinafter referred to as the substrate to be treated, is made of natural fibers selected from the group comprising cellulose, wool, cotton, silk, and can be filter paper.
Selon une autre réalisation, le substrat à traiter est constitué de fibres synthétiques choisies dans le groupe comprenant les polyamides et les polyesters, et il peut présenter une porosité comprise entre 1 et 10 microns. Selon une réalisation préférentielle, le substrat est une toile de polyamide.According to another embodiment, the substrate to be treated consists of synthetic fibers selected from the group comprising polyamides and polyesters, and may have a porosity of between 1 and 10 microns. According to a preferred embodiment, the substrate is a polyamide fabric.
De nombreux modes de dépôt des microparticules sur le substrat fibreux conduisent à l'obtention d'un substrat superhydrophobe. Ce dépôt peut être réalisé par exemple par filtration de la suspension de microparticules à travers le substrat fibreux, ou par trempage du substrat fibreux dans la suspension de microparticules, puis évaporation du solvant, ou par déposition de la suspension sur le substrat fibreux puis évaporation du solvant.Many modes of deposition of the microparticles on the fibrous substrate lead to the production of a superhydrophobic substrate. This deposition may be carried out for example by filtering the suspension of microparticles through the fibrous substrate, or by soaking the fibrous substrate in the microparticle suspension, then evaporation of the solvent, or by deposition of the suspension on the fibrous substrate and then evaporation of the solvent.
Selon un deuxième aspect, l'invention a pour objet un substrat fibreux superhydrophobe dans lequel les fibres sont imprégnées par des microparticules de type cœur-écorce, lesdites microparticules présentant un cœur en polyuréthane et une écorce en polydiméthylsiloxane ou en polybutadiène.According to a second aspect, the subject of the invention is a superhydrophobic fibrous substrate in which the fibers are impregnated with core-shell microparticles, said microparticles having a polyurethane core and a polydimethylsiloxane or polybutadiene bark.
Les microparticules présentent un diamètre généralement compris entre 0,5 et 5 microns. Le substrat est par exemple constitué d'une toile polyamide ou de papier filtre. Selon sa nature, il peut être utilisé pour la fabrication de textiles destinés à l'habillement, ou bien pour la fabrication de revêtements pour l'imprimerie.The microparticles have a diameter generally of between 0.5 and 5 microns. The substrate is for example made of a polyamide fabric or filter paper. Depending on its nature, it can be used for the manufacture of textiles for clothing, or for the manufacture of coatings for printing.
La présente invention est illustrée ci-après par des exemples concrets de réalisation, auxquels elle n'est cependant pas limitée. L'exemple 1 porte sur la préparation de microparticules hydrophobes, et les exemples suivants portent sur le dépôt de microparticules sur différents substrats .The present invention is illustrated hereinafter by concrete examples of embodiment, to which it is however not limited. Example 1 relates to the preparation of hydrophobic microparticles, and the following examples relate to the deposition of microparticles on different substrates.
Exemple 1Example 1
Des particules de polyuréthane à structure cœur-écorce sont préparées par un procédé en dispersion dans le cyclohexane, en présence de polydiméthylsiloxane. A cet effet, le stabilisant réactif PDMS-OH, de masse molaire 4670 g. mol"1 (0,5 g, soit 16,7% massique), le monomère éthane-1, 2-diol (0,6 g) et le cyclohexane (20 g) sont introduits dans le réacteur puis laissés à 600C sous agitation pendant quelques minutes. Le co-monomère tolylène di-isocyanate (1,9 g) est ensuite ajouté et le milieu réactionnel est laissé sous agitation pendant au moins 6 heures.Polyurethane particles having a core-shell structure are prepared by a process in dispersion in cyclohexane, in the presence of polydimethylsiloxane. For this purpose, the reactive stabilizer PDMS-OH, molar mass 4670 g. mol "1 (0.5 g, ie 16.7% by weight), the monomer ethane-1,2-diol (0.6 g) and cyclohexane (20 g) are introduced into the reactor and then left at 60 ° C. with stirring for a few minutes The tolylene diisocyanate comonomer (1.9 g) is then added and the reaction mixture is stirred for at least 6 hours.
En fin de réaction, le latex obtenu est récupéré, centrifugé, puis les particules sont dispersées à nouveau dans du cyclohexane. Cette opération est répétée deux fois.At the end of the reaction, the latex obtained is recovered, centrifuged, and then the particles are dispersed again in cyclohexane. This operation is repeated twice.
Les particules obtenues sont caractérisées par microscopie électronique à balayage (MEB) . La figure 1 présente un cliché MEB de ces particules, dont le diamètre est égal à 2,2 μm. Le procédé a été reproduit pour obtenir respectivement des particules ayant un diamètre de 3,5 et 4,2 μm, en utilisant un pourcentage massique de polydiméthylsiloxane respectivement égal à 9% et 4%. Exemple 2The particles obtained are characterized by scanning electron microscopy (SEM). Figure 1 shows a SEM image of these particles, whose diameter is equal to 2.2 microns. The process was repeated to obtain particles having a diameter of 3.5 and 4.2 μm respectively, using a weight percentage of polydimethylsiloxane equal to 9% and 4%, respectively. Example 2
Mise en œuyre du procédé avec un substrat constitué par une toile de polyamideEmbodiment of the process with a substrate consisting of a polyamide fabric
Une solution contenant 1% en masse de microparticules dans le cyclohexane, préparée selon le mode opératoire de l'exemple 1, est filtrée à l'aide d'une trompe à eau, sur une toile de polyamide de 10 cm2. L'essai a été reproduit successivement avec des toiles de polyamide ayant une porosité respective de 1 μm, 5 μm et 10 μm, et avec des microparticules ayant un diamètre de 2,2 μm, 3,5 μm et 4,2 μm.A solution containing 1% by weight of microparticles in cyclohexane, prepared according to the procedure of Example 1, is filtered using a water pump, on a polyamide cloth of 10 cm 2 . The test was reproduced successively with polyamide webs having a porosity of 1 .mu.m, 5 .mu.m and 10 .mu.m respectively, and with microparticles having a diameter of 2.2 .mu.m, 3.5 .mu.m and 4.2 .mu.m.
Dans chacun des essais, la surface de la toile est ensuite caractérisée par microscopie électronique à balayage. On constate qu'un dépôt homogène qui respecte la topologie de surface de la toile de polyamide est obtenu. Les figures 2a et 2b, présentent des clichés obtenus à deux échelles différentes, le côté du carré formé par un cliché représentant respectivement 147 microns et 37 microns, pour la toile ayant une porosité de 1 μm traitée par une suspension de particules ayant un diamètre de 2,2 μm.In each of the tests, the surface of the fabric is then characterized by scanning electron microscopy. It is found that a homogeneous deposit which respects the surface topology of the polyamide fabric is obtained. FIGS. 2a and 2b show clichés obtained at two different scales, the side of the square formed by a plate representing respectively 147 microns and 37 microns, for the fabric having a porosity of 1 μm treated with a suspension of particles having a diameter of 2.2 μm.
Exemple 3 Mise en œuyre du procédé avec un substrat constitué par du papier filtreExample 3 Embodiment of the process with a substrate consisting of filter paper
Un procédé analogue à celui de l'exemple 2 a été mis en œuvre en utilisant un papier filtre à la place d'une toile de polyamide. Des essais ont été effectués avec des particules ayant un diamètre de 2,2 μm, 3,5 μm et 4,2 μm. Un dépôt homogène qui respecte la topologie de surface du papier filtre est obtenu, comme cela est illustré sur les figures 3a et 3b, qui présentent des clichés de microscopie électronique à balayage obtenus à des échelles différentes, le côté du carré formé par un cliché représentant respectivement 147 microns et 37 microns, pour le papier filtre traité par une suspension de particules ayant un diamètre de 3,5 μm. Exemple 4A process analogous to that of Example 2 was carried out using a filter paper instead of a polyamide cloth. Tests were carried out with particles having a diameter of 2.2 μm, 3.5 μm and 4.2 μm. A homogeneous deposition which respects the surface topology of the filter paper is obtained, as illustrated in FIGS. 3a and 3b, which show scanning electron microscopy photographs obtained at different scales, the side of the square formed by a plate representing respectively 147 microns and 37 microns, for filter paper treated with a suspension of particles having a diameter of 3.5 microns. Example 4
L'angle de contact d'une goutte d'eau déposée à la surface des substrats traités obtenus dans les exemples 2 et 3 a été mesuré à l'aide d'un goniomètre. Les résultats sont rassemblés dans le tableau 1 ci-après.The contact angle of a drop of water deposited on the surface of the treated substrates obtained in Examples 2 and 3 was measured using a goniometer. The results are summarized in Table 1 below.
A titre comparatif, le dépôt de différents types de particules a également été réalisé sur une plaque de verre.For comparison, the deposition of different types of particles was also performed on a glass plate.
Tableau 1Table 1
Les figures 4 à 8 sont des clichés de microscopie optique montrant une goutte d'eau déposée respectivement sur les substrats suivants : figure 4 : toile de polyamide de porosité 5 μm et particules de diamètre 2,2 μm ; figure 5 : toile de polyamide de porosité 1 μm et particules de diamètre 2,2 μm ; figure 6 : toile de polyamide de porosité 1 μm et particules de diamètre 4,2 μm; figure 7 : papier filtre et particules de diamètre 2,2 μm ; figure 8 : papier filtre et particules de diamètre 3,5 μm.FIGS. 4 to 8 are optical microscopy photographs showing a drop of water deposited respectively on the following substrates: FIG. 4: 5 μm porosity polyamide fabric and 2.2 μm diameter particles; FIG. 5: polyamide fabric having a porosity of 1 μm and particles with a diameter of 2.2 μm; FIG. 6: polyamide fabric having a porosity of 1 μm and particles with a diameter of 4.2 μm; FIG. 7: filter paper and particles with a diameter of 2.2 μm; FIG. 8: filter paper and particles with a diameter of 3.5 μm.
Il apparaît d'après ces résultats que les substrats fibreux sur lesquels est mis en œuvre le procédé selon l'invention acquièrent des propriétés de superhydrophobieIt appears from these results that the fibrous substrates on which the process according to the invention is carried out acquire properties of superhydrophobia.
(angle de contact d'une goutte d'eau supérieur à 140°) , contrairement à un substrat non fibreux tel qu'une plaque de verre. (contact angle of a drop of water greater than 140 °), unlike a non-fibrous substrate such as a glass plate.

Claims

Revendications claims
1. Procédé de préparation d'un substrat superhydrophobe fibreux, caractérisé en ce qu'il comprend les étapes successives suivantes : préparation de microparticules hydrophobes de type cœur-écorce, lesdites microparticules présentant un cœur en polyuréthane et une écorce en polydiméthylsiloxane ou en polybutadiène ; dépôt d' une suspension liquide desdites microparticules sur le substrat fibreux. A process for the preparation of a fibrous superhydrophobic substrate, characterized in that it comprises the following successive steps: preparation of hydrophobic microparticles of core-shell type, said microparticles having a polyurethane core and a polydimethylsiloxane or polybutadiene bark; depositing a liquid suspension of said microparticles on the fibrous substrate.
2. Procédé selon la revendication 1, caractérisé en ce que la préparation des microparticules hydrophobes est réalisée par polymérisation par étapes en milieu dispersé dans un solvant organique, d'un premier monomère constitué d'un diol et d'un deuxième monomère de type di-isocyanate, en présence de polydiméthylsiloxane ou de polybutadiène.2. Method according to claim 1, characterized in that the preparation of the hydrophobic microparticles is carried out by stepwise polymerization in medium dispersed in an organic solvent, a first monomer consisting of a diol and a second monomer di type. isocyanate in the presence of polydimethylsiloxane or polybutadiene.
3. Procédé selon la revendication 2, caractérisé en ce que le premier monomère est l' éthane-1, 2-diol et le deuxième monomère est le tolylène di-isocyanate.3. Process according to claim 2, characterized in that the first monomer is ethane-1,2-diol and the second monomer is tolylene diisocyanate.
4. Procédé selon la revendication 2 ou 3, caractérisé en ce que le solvant organique est choisi parmi le cyclohexane et le dioxyde de carbone supercritique.4. Method according to claim 2 or 3, characterized in that the organic solvent is selected from cyclohexane and supercritical carbon dioxide.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les microparticules ont un diamètre compris entre 0,5 et 5 microns. 5. Method according to any one of claims 1 to 4, characterized in that the microparticles have a diameter of between 0.5 and 5 microns.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le substrat fibreux est constitué de fibres naturelles choisies dans le groupe comprenant la cellulose, la laine, le coton, la soie.6. Method according to any one of claims 1 to 5, characterized in that the fibrous substrate is made of natural fibers selected from the group consisting of cellulose, wool, cotton, silk.
7. Procédé selon la revendication 6, caractérisé en ce que le substrat fibreux est du papier filtre.7. Method according to claim 6, characterized in that the fibrous substrate is filter paper.
8. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le substrat fibreux est constitué de fibres synthétiques choisies dans le groupe comprenant les polyamides et les polyesters. 8. Method according to any one of claims 1 to 5, characterized in that the fibrous substrate is made of synthetic fibers selected from the group comprising polyamides and polyesters.
9. Procédé selon la revendication 8, caractérisé en ce que le substrat fibreux présente une porosité comprise entre 1 et 10 microns. 9. The method of claim 8, characterized in that the fibrous substrate has a porosity of between 1 and 10 microns.
10. Procédé selon la revendication 8 ou 9, caractérisé en ce que le substrat fibreux est une toile de polyamide.10. The method of claim 8 or 9, characterized in that the fibrous substrate is a polyamide fabric.
11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le dépôt est réalisé par filtration de la suspension de microparticules à travers le substrat fibreux.11. Method according to any one of claims 1 to 10, characterized in that the deposition is carried out by filtration of the microparticle suspension through the fibrous substrate.
12. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le dépôt est réalisé par trempage du substrat fibreux dans la suspension de microparticules, puis évaporation du solvant.12. Method according to any one of claims 1 to 10, characterized in that the deposition is carried out by dipping the fibrous substrate in the microparticle suspension, and then evaporating the solvent.
13. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le dépôt est réalisé par déposition de la suspension de microparticules sur le substrat fibreux puis évaporation du solvant. 13. Method according to any one of claims 1 to 10, characterized in that the deposition is carried out by deposition of the microparticle suspension on the fibrous substrate and then evaporation of the solvent.
14. Substrat fibreux superhydrophobe, caractérisé en ce que les fibres dudit substrat sont imprégnées par des microparticules de type cœur-écorce, lesdites microparticules présentant un cœur en polyuréthane et une écorce en polydiméthylsiloxane ou en polybutadiène. 14. A superhydrophobic fibrous substrate, characterized in that the fibers of said substrate are impregnated with microparticles of core-shell type, said microparticles having a polyurethane core and a bark of polydimethylsiloxane or polybutadiene.
15. Substrat selon la revendication 14, caractérisé en ce que les microparticules ont un diamètre compris entre 0,5 et 5 microns .15. Substrate according to claim 14, characterized in that the microparticles have a diameter of between 0.5 and 5 microns.
16. Substrat selon la revendication 14 ou 15, caractérisé en ce qu'il est constitué d'une toile de polyamide.16. Substrate according to claim 14 or 15, characterized in that it consists of a polyamide fabric.
17. Substrat selon la revendication 14 ou 15, caractérisé en ce qu'il est constitué de papier filtre.17. Substrate according to claim 14 or 15, characterized in that it consists of filter paper.
18. Utilisation d'un substrat selon la revendication 14, pour la fabrication de textiles destinés à 1' habillement .18. Use of a substrate according to claim 14 for the manufacture of textiles for clothing.
19. Utilisation d'un substrat selon la revendication 14, pour la fabrication de revêtements pour l'imprimerie. 19. Use of a substrate according to claim 14 for the manufacture of coatings for printing.
EP20060841826 2005-12-01 2006-11-29 Production of superhydrophobic fibrous substrates Not-in-force EP1954869B1 (en)

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PCT/FR2006/002615 WO2007063217A1 (en) 2005-12-01 2006-11-29 Production of superhydrophobic fibrous substrates

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CN102091583B (en) * 2010-12-17 2014-05-07 湖南大学 Preparation method for cauliflower-shaped super-hydrophobic active grains
US9237973B2 (en) 2012-01-31 2016-01-19 Kimberly-Clark Worldwide, Inc. Treated apertures
CN102702948B (en) * 2012-05-29 2014-08-20 绍兴金隆机械制造有限公司 Preparation method of superhydrophobic glove coating and method for producing glove
CN105814155A (en) 2013-12-09 2016-07-27 3M创新有限公司 Curable silsesquioxane polymers, compositions, articles, and methods
FR3015988B1 (en) * 2013-12-27 2022-11-11 Arjo Wiggins Fine Papers Ltd IMPREGNATING A PAPER USING A SUPERCRITICAL FLUID
US10370564B2 (en) 2014-06-20 2019-08-06 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
WO2015195355A1 (en) 2014-06-20 2015-12-23 3M Innovative Properties Company Adhesive compositions comprising a silsesquioxane polymer crosslinker, articles and methods
US9957416B2 (en) 2014-09-22 2018-05-01 3M Innovative Properties Company Curable end-capped silsesquioxane polymer comprising reactive groups
KR20170063735A (en) 2014-09-22 2017-06-08 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Curable polymers comprising silsesquioxane polymer core silsesquioxane polymer outer layer, and reactive groups
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