DE102008036267A1 - Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, useful e.g. as floor covering, comprises wetting surface of molding bodies with a composition of nanoparticle and release agent - Google Patents

Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, useful e.g. as floor covering, comprises wetting surface of molding bodies with a composition of nanoparticle and release agent

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Publication number
DE102008036267A1
DE102008036267A1 DE200810036267 DE102008036267A DE102008036267A1 DE 102008036267 A1 DE102008036267 A1 DE 102008036267A1 DE 200810036267 DE200810036267 DE 200810036267 DE 102008036267 A DE102008036267 A DE 102008036267A DE 102008036267 A1 DE102008036267 A1 DE 102008036267A1
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DE
Germany
Prior art keywords
characterized
preferably
nanoparticles
preceding
method according
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.)
Ceased
Application number
DE200810036267
Other languages
German (de)
Inventor
Friedbert Hitscherich
Matthias Prof. Dr. Scherge
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority to DE200810036267 priority Critical patent/DE102008036267A1/en
Publication of DE102008036267A1 publication Critical patent/DE102008036267A1/en
Application status is Ceased legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/047Coating with only one layer of a composition containing a polymer binder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, comprises wetting the surface of the molding bodies at least area-wise with a composition containing at least a nanoparticle and at least a release agent, and pressurizing the wetted molding body, where the nanoparticle diffuses in to the molding body. An independent claim is included for a nanoparticle-containing molding body.

Description

  • The The present invention particularly relates to a process for oleophobization of shaped bodies, in particular of plates, in which nanoparticles under pressure and Temperature exposure in the near-surface region of the plate be incorporated. The properties inherent in the nanoparticles thus go to the surface the plate over.
  • When Material for heavily loaded floor coverings Rubber is used very often. This material meets his Borders once oily or fatty substances penetrate the surface and contaminate them. Permanent foot contact leads to a change of the material (sticky surface) and hardly removable soiling.
  • at the conventional one After the rubber has been laid, production must undergo extensive basic cleaning and incorporation of care products. In case of improper care are often costly service measures necessary.
  • at environmentally friendly Rubber coverings could the problem so far only about aggregates altered Mixtures solved which increased the price of the product by more than double only occasionally used. Alternatively, rubber coverings become a elaborate and subjected to expensive coating with polyurethane paint. This coating seals the surface, but is problematic in terms of scratch resistance. About that Beyond is the natural material Rubber coated with a synthetic product, so that all ecological and aesthetic Advantages are lost.
  • outgoing It is therefore the task of the disadvantages of the prior art the present invention to provide a method with which simple way a reliable one and permanent oleophobization of polymer-containing moldings is feasible. It is also an object of the present invention to provide a corresponding oleophobized moldings provide. Furthermore, the present invention provides the Task, as uses of such oleophobized moldings too call.
  • These Task is relative the process for oleophobization with the features of the claim 1, re of the oleophobized molding with the features of claim 12 and with respect to Uses with the features of claim 16 solved. The respective dependent Claims represent advantageous developments.
  • Thus, according to the invention a process for the oleophobization of thermoplastic and / or viscoelastic Polymers and / or copolymers containing moldings, in which the surface of the molding at least in some areas with at least one kind of nanoparticles and wetting at least one release agent-containing composition and the at least partially wetted moldings in connection with pressure is applied, wherein the nanoparticles diffuse into the molding.
  • By result in the process according to the invention clear advantages. In addition to creating a lasting effect oleophobic effect - what the main one Advantage is - gives there are technological advantages, such as B. improved slip resistance. As far as a protective effect was a PU coating, allowed the method described here the immediate use of the pad without further steps. The rubber gets its natural surface. When another advantage The savings of basic cleaning are called as well as that subsequent complex and costly services.
  • The used according to the invention Nanoparticles preferably comprise polymers, copolymers and / or functionalized polymers and / or copolymers. The used Polymers and / or copolymers are not subject to any general restriction The polymers and / or copolymers can from a nearly be selected from any variety of polymers and / or copolymers, such as Polyalkylenes (e.g., polyethylene, polypropylene), polyacrylates (Poly (meth) acrylate), polyesters, polyamides. Under functionalized Polymers and / or copolymers according to the invention polymers understood that have branches branching from the main chain, wherein the side chain carries at least one functional group. there can For example, the functional groups may be selected from alcohol functionalities, carboxylic acid functionalities, carboxylic acid ester functionalities, carboxylic acid amide functionalities, in part fluorinated alkyl chains, perflourated alkyl chains, silanol functionalities, siloxane functionalities, primary, secondary and / or tertiary amine functionalities and / or Ammonium functionalities.
  • The average size of the nanoparticles used is likewise not subject to any particular restriction; preference is given to using nanoparticles having a mean diameter d 50 between 10 nm and 10 μm.
  • The method gives especially good results when the composition used, based on their total weight, between 50 and 99 Wt .-%, preferably between 75 and 95 wt .-%, particularly preferably between 80 and 90 wt .-% nanoparticles.
  • The Release agent according to the invention in the Composition is preferably a liquid substance, in which the nanoparticles can be dispersed and at volatilized the process conditions. Preferred release agents are thus selected from the group of organic solvents, especially acetic acid and / or methyl acetate.
  • Regarding the composition used (100 wt .-%), the release agent is preferably between 1 and 50 wt .-%, preferably between 5 and 25 wt .-%, particularly preferably between 10 and 20 wt .-% included.
  • On the applied amount of the composition used, the Oleophobisierungsgrad of the molding is controllable after performing the method. Depending on the desired oleophobization, therefore, from 1 to 500 g, more preferably from 50 to 200 g, of the composition are to be applied per m 2 of the surface to be wetted of the shaped body. The application of the composition can be carried out arbitrarily, for example, a brushing, applying by means of a sponge, spraying, spin coating or similar methods conceivable.
  • preferred Pressure ranges for the pressurization are between 5 and 500 bar, preferably between 100 and 300 bar, more preferably between 190 and 230 bar.
  • Farther It is beneficial while pressurizing the temperature to 100 to 400 ° C, continue preferably at 150 to 190 ° C adjust. For thermoplastic or viscoelastic materials takes place softening of the material used, so that the nanoparticles can diffuse more easily into the shaped body.
  • The Pressurization is in an advantageous embodiment of a Period between 10 seconds and 10 hours, preferably between 1 minute and 1 hr., More preferably carried out between 5 min and 20 min.
  • Prefers are the thermoplastic and / or viscoelastic polymers and / or Copolymers of the molding selected from the group consisting of natural or synthetic rubber materials, linoleum and / or PVC.
  • According to the invention, it does not matter whether natural or synthetic rubber materials are used, suitable rubber materials are listed below, for example:
    Natural rubber or gutta-percha or synthetic rubbers, such as. Styrene-butadiene rubber (SBR), polybutadiene rubber (BR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene rubber (EPDM), styrene-butadiene latex (SBL) silicone rubber (SI), linoleum and / or PVC.
  • According to the invention as well a nanoparticle-containing shaped body provided according to the in the Oleophobized described above inventive method has been.
  • In an advantageous embodiment is the penetration depth 99% of the nanoparticles in the molding between 0.1 and 200 μm, preferably between 0.5 and 100 μm, more preferably between 1 and 20 microns.
  • Quality Oleophobisierungsgrade of the molding show, if, based on the described in the foregoing Process treated surface of the molding, between 0.5 and 500 g nanoparticles, preferably between 25 and 200 g Nanoparticles are included diffused.
  • The high oleophobicity of the molding shows by the contact angle to Triölsäureglycerid, which is preferred at least 45 °, more preferably at least 55 °, particularly preferably at least 60 °, in particular at least 75 °. Of the Contact angle is determined according to a Standard method by wetting the surface of the molding with a drop of tri-acid glyceride as well following an optical measurement of the tangent of the surface of the Measure droplets with respect to the wetted surface. The higher the contact angle is the higher Oleophobia shows the body on it.
  • Of the moldings lies in particular in the form of a plate, for example one floorboard before, however, is the molding not on this embodiment limited.
  • uses of the shaped body according to the invention For example, floor coverings, facade cladding and / or floor mats.
  • Of the The present invention is based on the following exemplary embodiments as well as the attached Figures in more detail, without limiting the invention to the specific parameters shown.
  • there shows
  • 1 a schematic representation of the manufacturing process, as well
  • 2 an explanation of contact angles.
  • To achieve extensive oleophobization, the process of vulcanization is exploited. As a first process step, therefore, the modification of the release agent is carried out with a liquid containing functionalized nanoparticles. Thereafter, the rubber plates are coated and fed to the pressing process. Oleophobia is achieved by making the surface partially polar. This task is performed by the nanoparticles, which are distributed evenly in the release agent. During the vulcanization process, the nanoparticles are introduced into the near-surface volume (several tens of microns) by temperature and pressure (see 1 ).
  • The surface effect comes through the presence of nanoparticles on the surface, the Depot function results from the exposure of new particles by Abrasion.
  • To achieve extensive oleophobization, the process of pressurization (eg vulcanization) is exploited. As a first process step, therefore, the modification of the release agent is carried out with a liquid containing functionalized nanoparticles. Thereafter, the rubber plates are coated and fed to the pressing process. Oleophobia is achieved by making the surface partially polar. This task is performed by the nanoparticles, which are distributed evenly in the release agent. During the vulcanization process, the nanoparticles are introduced into the near-surface volume (several tens of microns) by temperature and pressure (see 1 ).
  • The surface effect comes about through the presence of nanoparticles on the surface, the depot function results from the exposure of new particles by abrasion.
  • In preliminary experiments it could be shown that the nanoparticles can be diluted with water as well as survive the vulcanization time of 10 minutes at 170 ° C without limiting their effect. 2 shows the effect on oil (food and machine oils) and alcohol (detergent). While the standard coating for oil achieved a small wetting angle, ie low resistance to soiling, the conditioning with nanoparticles shows a significant increase in the contact angle. Compared to alcohol, both coverings show small contact angles, compared to water a large angle with values above 80.
  • Of the achieved great by the process Wetting angle of the release agent (TM) according to the invention means low susceptibility towards oils and Fats. The smaller wetting angle to alcohol indicates improved cleanability with alcoholic detergents.
  • By introducing the nanoparticles into the near-surface volume of the rubber In the case of abrasion, a depot effect is present. Measurements of rubber flooring laid decades ago (eg Frankfurt Airport) showed lowest abrasion with wear rates of a few nanometers per Hour. This means that the rubber by the mechanical Contact with the shoe mainly close to the surface which is what causes the uptake of new nanoparticles the volume to the surfaces leads. By this process receives the oleophobic effect.
  • Evidence that the area has been oleophobized is made by contact angle measurements, see 1 , Here, a drop of a measuring liquid (oil, alcohol and water) is applied to the surface and the angle which the surface encloses with the droplet is measured. Table 1: Numerical values of wetting angles fluid TM default water 80 ° 70 ° oil 80 ° 20 °

Claims (16)

  1. Process for the oleophobization of thermoplastic and / or viscoelastic polymers and / or copolymers Moldings, at the surface of the molding at least in some areas with at least one kind of nanoparticles and wetting at least one release agent-containing composition and the at least partially wetted moldings in connection with pressure is applied, wherein the nanoparticles diffuse into the molding.
  2. Method according to claim 1, characterized in that that the nanoparticles polymers, copolymers and / or functionalized Polymers and / or copolymers include.
  3. Method according to one of the preceding claims, characterized in that the nanoparticles have a mean diameter d 50 between 10 nm and 10 microns.
  4. Method according to one of the preceding claims, characterized in that the nanoparticles based on 100 wt .-% of the composition between 50 and 99 wt .-%, preferably zwi 75 and 95 wt .-%, more preferably between 80 and 90 wt .-% are contained.
  5. Method according to one of the preceding claims, characterized characterized in that the release agent is selected from the group consisting from organic solvents, especially acetic acid and / or methyl acetate.
  6. Method according to one of the preceding claims, characterized characterized in that the release agent based on 100 wt .-% of Composition between 1 and 50 wt .-%, preferably between 5 and 25 wt .-%, more preferably between 10 and 20 wt .-% is.
  7. Method according to one of the preceding claims, characterized in that each 1 m 2 of the surface to be wetted of the shaped body with 1 to 500 g, preferably wetted with 50 to 200 g of the composition.
  8. Method according to one of the preceding claims, characterized characterized in that the pressurization with a pressure between 5 and 500 bar, preferably between 100 and 300 bar, more preferably between 190 and 230 bar is performed.
  9. Method according to one of the preceding claims, characterized characterized in that the pressurization at temperatures between 100 and 400 ° C, preferably between 150 and 190 ° C is performed.
  10. Method according to one of the preceding claims, characterized characterized in that the pressurization over a period between 10 sec and 10 hours, preferably between 1 minute and 1 hour, especially is preferably carried out between 5 min and 20 min.
  11. Method according to one of the preceding claims, characterized characterized in that the thermoplastic and / or viscoelastic Polymers and / or copolymers are selected from the group consisting from natural or synthetic rubber materials, linoleum and / or PVC.
  12. Nanoparticles containing moldings, produced according to a of the preceding claims.
  13. moldings according to the preceding claim, characterized in that the penetration depth of 99 of the nanoparticles in the molding between 0.1 and 200 microns, preferably between 0.5 and 100 μm, more preferably between 1 and 20 microns.
  14. Shaped body according to one of claims 12 to 13, characterized in that between 0.5 and 500 g nanoparticles, preferably between 25 and 200 g nanoparticles are diffused per m 2 surface of the shaped body.
  15. moldings according to one of the claims 12 to 14, characterized by a contact angle to Triölsäureglycerid of> 45 °, preferably> 55 °, particularly preferably> 60 °, in particular> 75 °.
  16. Use of a shaped article according to one of claims 13 to 15 as a floor covering, as facade cladding and / or as a doormat.
DE200810036267 2008-08-04 2008-08-04 Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, useful e.g. as floor covering, comprises wetting surface of molding bodies with a composition of nanoparticle and release agent Ceased DE102008036267A1 (en)

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DE200810036267 DE102008036267A1 (en) 2008-08-04 2008-08-04 Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, useful e.g. as floor covering, comprises wetting surface of molding bodies with a composition of nanoparticle and release agent

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DE200810036267 DE102008036267A1 (en) 2008-08-04 2008-08-04 Oleophobizing of molding bodies containing thermoplastic and/or viscoelastic polymers and/or copolymers, useful e.g. as floor covering, comprises wetting surface of molding bodies with a composition of nanoparticle and release agent

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014208249A1 (en) * 2014-04-30 2015-11-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of polymer films or plate-like elements made of polymer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10051182A1 (en) * 2000-10-16 2002-05-02 Nano X Gmbh Nanoparticle useful for coating substrate surfaces to impart hydrophobicity and oleophobicity, has specific substituents consisting of perfluorinated carbon chains and/or hydrocarbon chains
DE10205782A1 (en) * 2002-02-13 2003-08-21 Degussa Shaped body with a self-cleaning surface and a surface structure with hills formed by structure forming particles useful for drinking vessels, storage vessels, storage barrels, spraying protection devices, and textiles
DE10210667A1 (en) * 2002-03-12 2003-09-25 Creavis Tech & Innovation Gmbh Production of web products having self-cleaning surfaces by means of a calendering process, strip products themselves and use of these
DE10210674A1 (en) * 2002-03-12 2003-10-02 Creavis Tech & Innovation Gmbh Flächenextrudate with self-cleaning properties, and methods of making such extrudates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10051182A1 (en) * 2000-10-16 2002-05-02 Nano X Gmbh Nanoparticle useful for coating substrate surfaces to impart hydrophobicity and oleophobicity, has specific substituents consisting of perfluorinated carbon chains and/or hydrocarbon chains
DE10205782A1 (en) * 2002-02-13 2003-08-21 Degussa Shaped body with a self-cleaning surface and a surface structure with hills formed by structure forming particles useful for drinking vessels, storage vessels, storage barrels, spraying protection devices, and textiles
DE10210667A1 (en) * 2002-03-12 2003-09-25 Creavis Tech & Innovation Gmbh Production of web products having self-cleaning surfaces by means of a calendering process, strip products themselves and use of these
DE10210674A1 (en) * 2002-03-12 2003-10-02 Creavis Tech & Innovation Gmbh Flächenextrudate with self-cleaning properties, and methods of making such extrudates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014208249A1 (en) * 2014-04-30 2015-11-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of polymer films or plate-like elements made of polymer

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Effective date: 20120301