EP1587607A2 - Feuille de polymere souple respirante et son procede de production - Google Patents

Feuille de polymere souple respirante et son procede de production

Info

Publication number
EP1587607A2
EP1587607A2 EP04702279A EP04702279A EP1587607A2 EP 1587607 A2 EP1587607 A2 EP 1587607A2 EP 04702279 A EP04702279 A EP 04702279A EP 04702279 A EP04702279 A EP 04702279A EP 1587607 A2 EP1587607 A2 EP 1587607A2
Authority
EP
European Patent Office
Prior art keywords
polymer film
film
nanoparticles
flexible
funnel
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Withdrawn
Application number
EP04702279A
Other languages
German (de)
English (en)
Inventor
Dietmar Fink
Udo Küppers
Jose Rojas-Chapana
Helmut Tributsch
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.)
Hahn Meitner Institut Berlin GmbH
Original Assignee
Hahn Meitner Institut Berlin GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hahn Meitner Institut Berlin GmbH filed Critical Hahn Meitner Institut Berlin GmbH
Publication of EP1587607A2 publication Critical patent/EP1587607A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0032—Organic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • 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

Definitions

  • the invention relates to a flexible, breathable polymer film with a spatially ordered structure from the gas exchange through the
  • Polymer film enable capillary pores and a method for producing such polymer films.
  • Such a polymer film is a functional, porous membrane.
  • Nature has developed a large number of such functional membranes for all life to come.
  • This also includes the organic / inorganic composite systems of egg shells. Its structure is designed in such a way that it guarantees the vital gas exchange processes (C ⁇ 2 / ⁇ 2 exchange) and danger prevention for future life (microorganisms) through the entire structural structure of the eggshell.
  • This efficient biological property is used as a model for the technical development of a functional membrane, as will be described below.
  • An ostrich egg is characterized by high stability due to optimized composite layers with the participation of microparticles of the CaCO 3 type and spatially ordered structures. It shows the ability to skillfully control gas exchange processes as a breathing membrane and has an effect as antibacterial protection against the penetration of microorganisms (antifouling properties). In addition, the ostrich egg has high reflection properties.
  • breathable bionic membranes Packs in the medical and pharmaceutical sector, biocompatible, antibacterial and breathable implants, breathable films for "cladding" in construction and design, flexible covers, sensor-integrated films for controlling gas transport, active membranes with self-diagnosis system, intelligent encapsulations on a molecular or nanoscale size as a depot for active substances, flexible elements or covers for applications in vehicle and traffic technology, active covers (cell covers) as functional parts of new robot generations, active covers (membranes) in the field of environmental technology, active covers in filter technology, Hazard protection, mouth filters and textile and clothing technology.
  • the catalyst can be reused and that the UV radiation required for the chemical reaction can be taken from both artificial light and sunlight otocatalytically active material (doped or micro-heterogeneous material) towards a long-wave sensitivity, blue light can be used for irradiation.
  • blue light can be used for irradiation.
  • short-wave light irradiation in a wavelength range from 300 nm to 600 nm is suitable for producing the described photocatalytic effect.
  • US 6,187,696 B1 is a layered composite known with a fibrous substrate on which a film is laminated, which is vapor-permeable but liquid-blocking. However, the layer composite is preferably free of micropores.
  • a flexible structure coated with a photocatalytic material is known for the moisture-regulating packaging of foods, in which a resin layer is arranged between the substrate and the photocatalytic layer in order to improve adhesion and to protect the substrate and catalytic activity of the photocatalytic material.
  • titanium dioxide as an n-conducting semiconductor material is a good photocatalytic material with disinfectant and antimicrobial properties, which can activate various chemical reactions under UV radiation, in particular can decompose ethylene gas as a fermentation gas from food. It is also known that a high catalytic activity is achieved if the titanium oxide is involved in powder form or as a suspension in a solution. The activity can be increased further if the substrate has a porous structure on its surface in order to increase the contact areas of the substrate with the reactant. A penetration of the flexible substrate with a photocatalytically active material to increase the catalytic activity is not apparent from the US patent.
  • Such ceramic membranes are highly fragile and therefore not suitable as packaging material.
  • the titanium dioxide is filled into the pores using the sol-gel process and then fired at high temperatures and converted into ceramic.
  • small solid rods made of hard ceramic ("fibrilles"; typically a few 10 ⁇ m long, approx. 1 ⁇ m diameter) are formed after firing.
  • the AI 2 ⁇ 3 membrane is dissolved and glued to the ceramic rods on an epoxy resin.
  • the known arrangement thus has the only function of that of photocatalytic activity.
  • the difference to the massive titanium dioxide can be seen in the much larger surface of the many ceramic rods, which causes an increase in the reaction rate. A controlled gas exchange in a film-like structure cannot be guaranteed with this known arrangement.
  • the task for the present invention is therefore, based on the last-mentioned publication as the closest prior art and the model of ostrich ice cream from nature, to be seen in a porous material that optimally implements photocatalysis and a method based on the sol-gel method Specify production in which the control and neutralization of microorganisms while maintaining gas exchange is guaranteed.
  • the polymer film should be watertight and a wide range of uses should be achieved while at the same time being inexpensive to produce with regard to the materials and process steps used.
  • the solution according to the invention for this task provides the following structure: flexible, breathable polymer film with a spatially ordered structure from capillary pores that can be selected from the gas exchange through the polymer film, with funnel-shaped extensions in at least one surface of the polymer film and with at least in the area of the funnel-shaped extensions the capillary pores applied composite layer structure of at least one transparent, the polymer film protective binder film made of chemically inert, inorganic nanoparticles and at least one lining film adhering to the binder film made of short-wave light irradiation, photocatalytically active, hydrophilic, non-toxic metal oxide nanoparticles, which are antibacterial and self-cleaning, the effectiveness of which is based on the choice of the opening angle of the funnel-shaped extensions the capillary pores is adjustable.
  • the present invention based on the bioanalogous evaluation of the ultrastructure of the ostrich eggshell and its suitability for the selection of surface-active agents, it is possible to provide a flexible polymer film in the function of a functional ceramic porous membrane with modification by a nanoscale particle system.
  • a technically applicable packaging film is produced with the physicochemical properties, which allows breathability and protects the potential, breathing packaged goods against bacterial attack and thus against premature aging and early spoilage.
  • Packaged "living" food, such as As fruit can be kept fresh longer by the bionic membrane packaging according to the invention and protected from drying out or loss of aroma.
  • the modified polymer film itself can be easily recycled or disposed of.
  • porous polymer films whose funnel-shaped enlarged pores with a diameter of only a few micrometers beforehand, for example by high-energy heavy ion irradiation of large film rolls and subsequent etching (one-sided etching to achieve funnel-shaped extensions in only one surface - single cone -, two-sided etching to achieve this) from funnel-shaped extensions in both surfaces - double cone -) were subjected to a nanotechnologically functional design of the specially funnel-shaped pores in the form of a special lining.
  • the lining is not in a large, hard form, but in the form of tiny particles in the nanometer range (5 nm-100 nm) both inside and outside the pore volume in a largely homogeneous distribution that does not impair the flexibility of the polymer film.
  • a composite layer structure in which a lining layer with the required properties has been applied to a binder layer to improve adhesion and protect the substrate film has proven to be particularly favorable. Adequate homogeneity of the pores and chemical resistance of the end product are two of several quality properties.
  • bionic packaging can be made available as an environmentally friendly and inexpensive packaging alternative.
  • the polymer film according to the invention represents an artificial eggshell membrane with a functional nanoparticle lining in a bio-analogous structure and shows the structural appearance of a photocatalytic, breathable, smooth and evenly shiny packaging prototype in almost any form of application.
  • One criterion for the realization of the required quality properties is the interactions at the interfaces between the substrate, binder and lining film or nanoparticles.
  • Knowledge of the interface phenomena and the internal structure of the ostrich egg shell allows a targeted selection of the components with the aim of optimizing the bionic prototype to be developed (pore membrane in foil form) depending on the particle size and the specific surface properties of the porous membrane.
  • well-defined pores with an antibacterial and self-cleaning lining which is also referred to below as “functional lining”, thus ensure effective gas exchange in the polymer film according to the invention through the porous film as a breathing function with simultaneous antibacterial effect of the inorganic surface.
  • the life of foods packaged with the film according to the invention without additives can be significantly extended.
  • the polymer film according to the invention with membrane function is flexible and thus robust and versatile.
  • the functional lining is produced with a photocatalytically active material, this is a short-wave light irradiation, usually UV light irradiation, photocatalytically active, hydrophilic, non-toxic metal oxide in the form of nanoparticles.
  • these criteria meet ceramic materials, for example zinc oxide or trivalent iron oxide.
  • the best known is titanium dioxide, which is approved as non-toxic in the food industry. Photoactivity is believed to be the cause of the required hydrophilic properties.
  • the photoactivity is a semiconductor effect that occurs in relation to titanium dioxide on anatase crystallites, but also rutile and other crystallite forms as well as mixed forms thereof show photoactivity.
  • Titanium dioxide is extremely resistant to chemicals and only soluble in very strong acids. In contrast, it is stable in bases. Catalysts and carrier materials made of titanium dioxide do not release any interfering ions in their special applications.
  • packaging chemistry does the following: the ripening products, such as fruits, vegetables and flowers, release ethylene gas, a gaseous plant product, which in turn stimulates further ripening.
  • the ripening products such as fruits, vegetables and flowers
  • ethylene gas a gaseous plant product
  • the photocatalytically active contained in the polymer film according to the invention Particle material breaks down the ethylene gas so that the food can be transported and stored longer without the addition of inhibitors.
  • further modifications of the polymer film also serve to further develop it into an active packaging material for objects and spaces.
  • the modifications include, for example, sensors integrated in the polymer film for measuring gases which are relevant to the ripening process, for example button-shaped oxygen sensors.
  • the measured values determined can then be displayed qualitatively, for example, via integrated indicators. These can be fields with possible color changes.
  • Microencapsulated oxygen storage depots can also be integrated into the polymer film. For example, these can be nanoparticles that release oxygen.
  • the storage depots serve as a fresh-keeping reservoir in the event of the membrane structure of the polymer film not functioning, so that a significant increase in the fresh-keeping time can be achieved.
  • actuators can be integrated into the polymer film, which interact with existing sensors and storage depots in control loops.
  • the actuators are usually valves, for example in the form of swellable nanoparticles, which close the pores when necessary.
  • they can also be expandable and shrinkable tubes that are embedded in the polymer film and receive chemical control commands.
  • the described surface modification of a flexible, well-defined porous polymer film according to the invention which can be carried out on one or both sides, has found a way to a functional membrane for a variety of possible uses.
  • a surface modification on both sides a polymer film which can be used on both sides is produced, and when used it does not relate to a specific film orientation with respect to modified surface must be observed.
  • a production can be carried out for one or both surfaces of the polymer film used in accordance with the procedure mentioned in the process claim.
  • Chemically inert nanoparticles are applied in a composite layer or mixed structure with controlled coating rates using a one-sided or double-sided sol-gel process.
  • the particles condense gel
  • the particle concentration rises sharply when the water evaporates.
  • transparent films are formed with a largely homogeneous particle distribution, the flexibility of which increases with decreasing thickness.
  • colloidal particle solutions can also be applied to the polymer film, using stabilizing, highly concentrated particle dispersions for homogeneous coating of the films. Further details on the claimed production method according to the invention and on preferred embodiments thereof can be found in the special description part.
  • core traces can be made visible if the plastics are etched, since the etching rates in the area of the core trace are generally orders of magnitude higher than for the unirradiated material (approx. 103 for Krlones).
  • the irradiated areas are therefore detached from the film.
  • Capillary pores (traces) are formed, the diameter (a few hundred nm to 2 ⁇ m) of which is given by the duration of the etching process and the number of which is given by the number of projectile ions during the irradiation.
  • funnel-shaped traces with different opening angles can be produced.
  • the etching can be done on one side (one-sided funnel) or on both sides to create pores with funnels at each pore end (double cone).
  • the particles then accumulate in the highest concentration in the funnel area, since in the case of curved surfaces, the potential energy is reduced by the surface difference that occurs. In this way, where the photocatalytic effect of the nanoparticles is essential, namely at the entrance to the pores, the best possible photocatalytic effect can be achieved through the highly concentrated addition.
  • the funnel shape also proves to be from This is an advantage because it enables extensive access of the short-wave light into the interior of the capillary, thus ensuring the sterilizing and self-cleaning effect of the lining layer.
  • the short-wave light also passes through the film and thus falls into both funnel areas, so that a great catalytic activity of the lining film is achieved.
  • a reflective silver layer is evaporated onto one side of the polymer film, only funnels on that side are also irradiated. The light is reflected and does not pass through the film.
  • a polymer film modified on one side can be used, but its orientation in use must then be observed, which is not necessary in the case of a film modified on both sides.
  • FIG. 1 shows an SEM overview image of the surface of an irradiated and subsequently etched polyethylene terephthalate film with a representation of funnel-shaped micropores.
  • the polymer film has approximately 30 million pores per cm 2 .
  • the pore diameter is 500 nm.
  • Fission products from reactors or ions from heavy ion accelerators can be used to irradiate the film, whereby the radiation at the accelerator offers some decisive advantages: the activation of the film inherent in a reactor by gap fragments is avoided, the higher intensity of the accelerator jets enables high pore densities to be achieved, Due to the defined incidence, the same size and energy of the ions, defined pore sizes can be achieved and, due to the higher ion energies, thicker films can also be used.
  • both a 300 MeV 36 Ar 14+ beam at 3x10 7 cm “2 and a 250 MeV 78 Kr 12+ beam at 1x10 6 cm “ 2 were applied to the heavy ion accelerator at ISL-HMI Berlin through a metallic mask on three different polymer films (compare below), consisting of polyethylene terephthalate PET, Polyimide Pl and cereal starch shot. The polymer films were then etched. As Etchants were taken from those that have long been proven for etching ion traces, namely 5 Moi / I NaOH at 450 ° C for PET and corn starch, and NaOCI solution at 50 ° C for pH concentrated 8 with Pl -10.
  • Etching the polymer film with NaOH or NaOCI is absolutely necessary in order to create the pores, whereby the surface bonds are broken. It is known that the OH attack breaks up the (-O -) groups connecting the monomers and replaces them with (OH) end groups.
  • the SEM examinations were carried out in the HMI. SEM investigations allow the qualitative and, under defined conditions, quantitative detection of the surface of porous films of fixed species.
  • a computer-controlled scanning electron microscope (Oxford 440) is available in a conventional three-lens version with acceleration voltages up to 40 kV with a maximum sample size of 250 mm diameter, a maximum theoretical resolution of 200,000 times and a maximum practical resolution depending on the sample up to 50,000 times.
  • the SEM investigation of the surface changes in the interaction of the solid active phase (porous polymer film) with the inorganic binder components (nanoparticles) provides information about the binding and the morphology of the coatings on the surface of the films.
  • the foil samples to be examined are scanned in a grid-like manner by a strongly bundled electron beam with a diameter of a few nm.
  • the number of secondary electrons released in the surface area and that of the reflected beam electrons are influenced by the surface geometry and result in the topography contrast.
  • the average atomic number of the existing elements gives the material contrast.
  • the gray scale value of each pixel correlates with the number of electrons generated at the corresponding scanning point. With vertical radiation, inclined surfaces appear brighter than horizontal ones. Surface levels appear bright. Pores and gaps appear dark. Sample locations with predominantly light elements appear darker than those with heavier elements.
  • polymer systems are suitable as a carrier film for the invention.
  • these include inorganic polymer films, for example made of silicon rubber or polysilicon, and organic polymer films, for example made of polyethylene terephthalate PET, polyethylene PE, polyimide PI, polycarbonate PC or polyamide PA.
  • Composite composite materials made from mixtures or with block or copolymers can also be used.
  • films made from renewable raw materials such as cereal or potato starch can also be realized, which are of ecological importance as biodegradable packaging.
  • a material is said to be biodegradable if all organic components are subject to degradation caused by biological activity.
  • Biodegradable films in which a renewable raw material is only added as a filler to a conventional plastic (PE or PP) cannot be described as biodegradable in the aforementioned sense.
  • Biodegradable films for the packaging sector are mainly made from natural starch due to the then relatively low price (e.g. corn starch, potato starch).
  • Other biodegradable films contain cellulose, sugar or lactic acid.
  • biodegradable films are currently about four to five times more expensive than PE films and are therefore not of great interest for an inexpensive packaging film.
  • PET Polyethylene terephthalate PET, which is derived from petroleum, has long been known among plastics because the base material was developed in 1941 as a polyester in the USA and has been used as a high-quality synthetic fiber in the textile industry ever since.
  • Today's PET is a refined polyester with further improved material properties.
  • PET is suitable for packaging, containers, foils, Fibers and much more.
  • PET packaging is characterized by a low raw material requirement. The high strength of PET makes it possible to produce very thin-walled containers and foils. Constant further developments mean that PET packaging is becoming ever lighter. Since products made of PET meet the strictest hygienic requirements and their use is very widespread in the cosmetics and food sector and especially in medicine, PET films are particularly suitable as polymer films for the present invention.
  • Polyimide Pl is a normally non-meltable, colored (often amber-colored) high-performance polymer with above all aromatic molecules with high heat resistance.
  • Pl have excellent high-temperature properties and excellent resistance to radiation. They are inherently flame retardant and produce little smoke when burned. Creep occurs only to a small extent, wear resistance is very good.
  • Pl are however very expensive. Their water absorption capacity is moderate, they tend to hydrolise and are attacked by alkalis and concentrated acids. Because of these excellent properties, Pl can be used as an alternative polymer film for the invention for high quality goods. The same applies to polyamide PA as a polymer film.
  • the polymer film according to the invention was tested on various prototypes.
  • the composite layer system built up consisted of an alternating layer structure of titanium dioxide and silicon dioxide with a total thickness of less than 500 nm.
  • the layer thickness distribution was determined by SEM investigations.
  • Silicon dioxide acts as a binder. It serves to bind the photocatalytically active substances to the pore surface, but at the same time also protects the unmodified polymer film from a harmful influence of the active substance.
  • Selected nanoscale species Selected nanoscale species
  • Ti0 2 powder (P25, Degussa) was used for the photocatalytically active, hydrophilic, non-toxic metal oxide nanoparticles.
  • the titanium dioxide is in the crystal forms anatase and rutile or P25 (mixture of anatase and rutile, Degussa-Hüls AG).
  • a SiO 2 dispersion (Levasil, Bayer) was chosen to provide the chemically inert, inorganic nanoparticles.
  • Si0 2 -Levasil products are aqueous colloidally dispersed solutions of amorphous silicon dioxide particles with excellent stability against sedimentation.
  • the silicon dioxide is in the form of spherical individual particles which are not cross-linked with one another.
  • Levasil types A significant product feature of the Levasil types is the irreversible transition of the colloidally dissolved silicon dioxide into solid water-insoluble silicon dioxide.
  • the following Levasil types are suitable for film treatment: Levasil 100/45%, particle size 30 nm, pH 10, concentration 45%; Levasil 200/30%, particle size 15 nm, pH 9.0, concentration 30%.
  • a composite layer system can easily be expanded with layer cycles or additional layers.
  • embedded precious metals such as gold or silver
  • metals from the iron group for example iron, cobalt or nickel, which have other functional properties, are also suitable.
  • Nickel for example, has an algicidal effect and is also active in the dark without light. Mixtures of the elements are also possible.
  • a sol-gel addition of natural dyes can lead to highly wash-resistant stains.
  • entire layers or only partial island areas can be built up. The additionally stored substances only appear in relatively low concentrations. Due to its properties, silver can also be used as a binder layer.
  • metallic silver As a precursor to the lining, metallic silver has therefore been tested as an alternative to SiO 2.
  • Chemical precipitation ensures nanoscale silver particles, which shield the film substrate untreated by the etching against photocatalytic TiO 2 activity.
  • Chemical precipitation using AgN0 3 , NaOH, glucose or NH 4 OH while reducing the size of the particles ensures continuous nanoscale layers of silver particles. If such layers are used, however, the modified polymer film loses its transparency and assumes a metallic sheen. Regardless of whether a transparent layer formation with Ti0 2 / Si0 2 occurs or whether an Ag layer is deposited as a precursor, the porous property of the films, which is essential to the invention, is retained.
  • the photocatalytically active, hydrophilic, non-toxic metal oxide nanoparticles themselves can also be modified before they are processed.
  • they can be coated with a low concentration of a swelling layer of an additional substance, for example calcium hydroxyapatite or just calcium apatite.
  • the additional substance is used in particular to dock living substances and to destroy them.
  • silver only kills as an additional substance, but does not destroy it.
  • the substances for the alternating layer structure applied to the polymer films which was produced by the sol-gel process, were at atmospheric pressure by hydrolysis and condensation of compounds soluble in the reaction medium of at least one element from the group Si, Al, Ti and Zr , optionally in combination with a biocompatible binder aminosilane (N-2-aminoethyl) -3-aminopropyltrimethoxysilane) and subsequent heat treatment (60 ° C., 1 hour).
  • a biocompatible binder aminosilane N-2-aminoethyl) -3-aminopropyltrimethoxysilane
  • subsequent heat treatment 60 ° C., 1 hour.
  • the combination Ti / Si is always used in the following, since these components are known in detail in their effects.
  • other compounds such as zinc oxide (known from medicine for anti-inflammatory dressings) or cerium oxide can also be used.
  • SiO 2 a primary substance takes part in the reaction, namely SiO 2 .
  • the Ti0 2 Sedimentation mainly takes place after the Si0 2 is already on the substrate surface (foil). This process can therefore provide excellent film protection against the photocatalytic activity of Ti0 2 .
  • Silicon dioxide is known to react with alkalis to form silicates, so SiO 2 levasil dispersions were selected which are alkaline stabilized.
  • the polymer film sample already treated with SiO 2 was brought into the second reaction zone (Dip-Coating II).
  • This reaction is completely analogous to Si0 2 (dip Coating II) carried out.
  • Si0 2 -containing Levasil solution type 200S / 30%, pH 3.8; Ti0 2 20g / 100 ml Levasil
  • the additional and decisive sol-gel process depends in particular on the furnace temperature and the controlled temperature gradient. Significant gelation is already observed at 30 ° C. This is due to the extreme water and temperature sensitivity of the Ti0 2 / Si0 2 system . If the oven temperature is lower, the dispersion will not condense. On the other hand, if the temperature is too high, the temperature-sensitive polymer films will be destroyed. In this respect, the sol-gel transition was carried out under air and normal pressure at moderate oven and substrate temperatures. From a temperature of 60 ° C they show Films have stable properties after treatment, while films that have been treated above 100 ° C suffer from poor stability (tears). A sol-gel process of approx. 1 hour at 60 ° C thus already represents a suitable process for film coating. After the thermal treatment, it is necessary to rinse all of the samples repeatedly with distilled water until the condensed deposits have completely dissolved. The process steps mentioned can also be repeated cyclically to expand the composite layer system.
  • Levasil silica is very prone to appear in a colloidal state and to form gels with heat treatment.
  • the thin SiO 2 layers that are to be used as protective layers practically behave as a closed, monodisperse layer. No aggregates can be seen in the Si0 coating.
  • This picture of the chemical behavior of silicon dioxide shows in connection with the secondary Ti0 2 coating that the use of SiO 2 as a binder and protective agent is a suitable process for film coating.
  • FIG. 2 shows an SEM overview picture to show an Ar-irradiated polyimide (PI) film which is coated with Ti0 2 / Si0 2 nanoparticle Levasil (200/30%; pH: 9.0; particle size: 10 nm - 20 nm) coated is: there are approximately 30 million pores per cm 2 with a pore diameter of 3 ⁇ m.
  • the white rings correspond to heavily coated zones.
  • FIG. 3 shows a SEM photograph of an Ar-irradiated polyimide (PI) film which has been precoated with a primary SiO nanoparticle Levasil solution (200/30%; pH: 9.0; particle size: 10 nm).
  • PI Ar-irradiated polyimide
  • FIG. 4 shows an SEM photograph of a Kr-irradiated polyethylene terephthalate (PET) film which was coated with a primary SiO 2 nanoparticle Levasil solution (200/30%; pH: 9.0; particle size: 10 nm -20 nm ; Reaction time: 60 min) and coated with TiO 2 powder, which was dissolved in Levasil (200S / 30% Si0 2 colloidal dispersion, pH: 3.8; particle size 10 nm-20 nm; reaction time 60 min).
  • layer thicknesses of approximately 200 nm were observed. With the help of electron microscopic examinations, typical layer formation, particle formation and division and layer thickness are examined. A narrowing of the pores could be determined by the capillary, homogeneous particle arrangement, which is connected to the entire surface layer thickness of the film. In such investigations, layer thicknesses of approximately 200 nm-300 nm were observed. The direct measurement of the layer thickness can only be carried out on specifically produced cross sections. This measurement requires consideration of various side influences and their applicability depends heavily on the mechanical properties of the film.
  • FIG. 5 shows a high-resolution SEM image of an Ar-irradiated polyimide (Pl) film (coated with a primary SiO 2 nanoparticle-Levasil solution (200/30%; pH: 9.0; particle size: 10 nm -20 nm ) and after-coated with Ti0 powder, dissolved in Levasil 200S / 30% Si0 2 colloidal dispersion, pH: 3.8; particle size 10 nm -20 nm).
  • the film is provided with approx. 20 million pores per cm 2 with a pore diameter of 2.0 ⁇ m).
  • the porous PI film was completely covered with nanoparticles (TiO 2 / SiO 2 ) by the sol-gel process.
  • FIG. 6 shows a high-resolution SEM image of an Ar-irradiated polyimide (PI) film, which was coated with a primary SiO 2 nanoparticle-Levasil solution (200/30%; pH: 9.0, particle size: 10 nm - 20 nm) precoated and post-coated with Ti0 2 powder, dissolved in Levasil (200S / 30% -SiO 2 colloidal dispersion, pH: 3.8; particle size 10 nm -20 nm).
  • the film is provided with approx. 20 million pores per cm 2 with an inner pore diameter of 2.0 ⁇ m.
  • the image shows 3 pores with a diameter of approx.
  • the Ti0 2 and Si0 2 particles are clearly recognizable both inside and outside the pore volume.
  • the built-in building blocks indicate that a capillary reaction takes place between the inner wall of the pores and the nanoparticles.
  • a connection between the NaOH-etched edges of the pore openings and the number of fixed particles is clearly recognizable. Because of their reduced potential as cylindrical surfaces, these regions in particular offer better adhesion than the smooth surfaces for the Ti0 2 particles.
  • the Si0 2 layer underneath is also clearly recognizable due to its particle size. With a longer duration of the dip coating process, the foils show a complete, closed TiO 2 layer on the zones immediately near the pore openings.
  • FIG. 7 shows a SEM image of a pore opening (approx. 2 ⁇ m diameter) in the case of a Kr-irradiated polyethylene terephthalate (PET) film (coated with a primary SiO 2 nanoparticle-Levasil solution (200/30%; pH: 9 , 0; particle size: 10 nm -20 nm; reaction time: 60 min) and coated with Ti0 2 powder, dissolved in Levasil 200S / 30% Si0 2 colloidal dispersion, pH: 3.8; particle size 10 nm-20 nm) The picture shows the opening of a coated capillary tube that shows a strong affinity for nanoparticles.
  • PET polyethylene terephthalate
  • the region around the capillary opening shows a rather modest one Ti0 2 - enrichment.
  • By maximizing the depth of field it was possible to look inside the capillary at depths of 21.6 ⁇ m.
  • the total film thickness is 30 ⁇ m.
  • the figure thus shows the strong affinity of the nanoparticles to the pores (particle incorporation). Different layer formation mechanisms work together under the conditions mentioned above.
  • FIG. 8 shows an enlarged SEM image of a Kr-irradiated polyethylene terephthalate (PET) film (precoated with a primary SiO 2 nanoparticle-Levasil solution (200/30%; pH: 9.0; particle size: 10 nm-20 nm and coated with Ti0 2 powder, dissolved in Levasil 200S / 30% Si0 2 colloidal dispersion, pH: 3.8; particle size 10 nm-20 nm.
  • PET Kr-irradiated polyethylene terephthalate
  • Silver deposition as the precursor of the Ti0 2 / Si0 coating is advisable for technical and functional reasons.
  • the reason for a silver coating of foils is that the etched ion traces (pores) are protected against the photocatalytic activity of Ti0 2 and the light is better guided into the capillary interior. This is achieved by applying a very highly reflective silver mirror to the surface of the porous film, which is obtained after chemical precipitation.
  • Silver nitrate, NaOH, glucose, and NH 4 OH are used. In fact, silver nitrate creates a very homogeneous and stable coating on both PET and PI films. According to SEM measurements, the Ag coating has a thickness of approx. 50 nm-100 nm.
  • FIG. 9 shows one. SEM image of a porous polyimide film irradiated with Ar and coated with a 100 nm thick Ag film. The picture shows a closed, homogeneous Ag layer on the PI surface of the film. The pores of the film structure have remained after the coating (1.0 ⁇ m diameter). Ag-coated films promote the fixation of anionically charged particles.
  • FIG. 10 shows an SEM image of a Kr-irradiated polyethylene terephthalate (PET) film, which is provided with a primary Ag layer as a precursor layer and with TiO 2 powder, dissolved in Levasil solution 200S / 30% SiO 2 colloidal dispersion, pH: 3.8; Particle size 10 nm -20 nm is coated.
  • PET polyethylene terephthalate
  • the use of a well-adhering silver mirror on the PET surface promotes the interaction of the ceramic components (Ti0 / Si0 2 ) in the sense of Stabilization of the monodisperse particles (50 nm -100 nm) against aggregating particle formation while maintaining the porosity of the film.
  • funnel-shaped traces with different opening angles can be produced as capillary pores in the preparation of polymer films.
  • sol-gel process a gelatinous network (gel) of inorganic or inorganic / organic substances can be assembled from a liquid mixture (sol).
  • the quality of the porous polymer films is decisively determined by the properties and the thickness of the TiO 2 / SiO 2 layers.
  • the film coatings that can be achieved remain transparent if the addition of particles is of the order of nanometers.
  • the thickness and quality of the Ti0 2 / Si0 layers is strongly influenced by the material of the film substrates, by the slightest surface contamination, by aging of the surface due to the temperature and humidity of the air and by the interface chemistry of various film substrates (transport processes ).
  • Silicon dioxide or silicon dioxide-containing Ti0 2 layers were used in the present invention both as an insulation layer to keep the photocatalytic activity of the Ti0 2 away from the polymer substrate of the films and as a template (binder) of the TiO 2 coating to the Ti0 Apply 2 sol evenly on the foils.
  • the present invention can provide an inexpensive method for producing the functional polymer films, since the costs for the polymer films, the layer material, the agents and the costs for the necessary heat treatment are comparatively low ,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Wrappers (AREA)

Abstract

Dans la nature, on trouve des membranes fonctionnelles présentant des fonctions différentes qui, grâce à l'ensemble de leur constitution structurale et matérielle, permettent le déroulement de processus d'échanges gazeux et de purification. Des membranes et des feuilles techniques connues manquent toutefois soit de fonctionnalité soit de souplesse. L'invention concerne une feuille de polymère bon marché, souple, respirante qui, dans la zone de ses pores d'élargissant en forme d'entonnoir dans la partie superficielle, est modifiée avec un système de particules nanométriques et convient en particulier pour l'emballage. La modification mentionnée est obtenue à l'aide d'une structure stratifiée composite constituée d'un film de liant composé de nanoparticules inorganiques chimiquement inertes, et d'un film de revêtement composé de nanoparticules d'oxyde métallique hydrophiles, non toxiques, activées photocatalytiquement par exposition de courte durée à un rayonnement lumineux, ces dernières nanoparticules ayant un effet antibactérien et autopurifiant. L'efficacité de ces nanoparticules peut être maîtrisée par sélection de l'angle d'ouverture des zones élargies en entonnoir des pores. Il est possible d'utiliser différents adjuvants de couche pour élargir la fonctionnalité. La feuille de polymère qui est pourvue de pores capillaires en forme d'entonnoir, par exemple, par irradiation ionique de haute énergie et par une attaque monofaciale ou bifaciale, peut être obtenue grâce à un traitement de surface bon marché pouvant être réalisé dans les conditions ambiantes et se faisant dans un système sol-gel comportant des dispersions colloïdales contenant des nanoparticules, en particulier à base de céramique.
EP04702279A 2003-01-15 2004-01-15 Feuille de polymere souple respirante et son procede de production Withdrawn EP1587607A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10301984 2003-01-15
DE10301984A DE10301984B4 (de) 2003-01-15 2003-01-15 Flexible, atmungsaktive Polymerfolie
PCT/DE2004/000091 WO2004064478A2 (fr) 2003-01-15 2004-01-15 Feuille de polymere souple respirante et son procede de production

Publications (1)

Publication Number Publication Date
EP1587607A2 true EP1587607A2 (fr) 2005-10-26

Family

ID=32602772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04702279A Withdrawn EP1587607A2 (fr) 2003-01-15 2004-01-15 Feuille de polymere souple respirante et son procede de production

Country Status (5)

Country Link
US (1) US20060194037A1 (fr)
EP (1) EP1587607A2 (fr)
JP (1) JP2006518287A (fr)
DE (1) DE10301984B4 (fr)
WO (1) WO2004064478A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10272639B2 (en) 2015-03-23 2019-04-30 Emd Millipore Corporation Abrasion resistant film for biocontainers

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060078653A1 (en) * 2004-10-07 2006-04-13 Ching-Fuh Lin Preservation structure and preservation repository using the same
DE102005015276B4 (de) * 2005-03-26 2006-12-07 Hahn-Meitner-Institut Berlin Gmbh Vorrichtung zur Reinigung von Flüssigkeiten
JP4794981B2 (ja) * 2005-10-27 2011-10-19 新日鐵化学株式会社 低誘電性ポリイミドフィルム及びその製造方法並びに配線基板用積層体
DE102006005614A1 (de) * 2006-02-06 2007-08-09 Thor Gmbh Formgegenstand mit selbstreinigender Oberflächenstruktur
DE102006023375A1 (de) * 2006-05-17 2007-11-22 Nano-X Gmbh Beschichtungsmaterial
AU2006347731B2 (en) * 2006-08-31 2012-09-13 Kimberly-Clark Worldwide, Inc. Highly breathable biodegradable films
US20080166493A1 (en) * 2007-01-09 2008-07-10 Inframat Corporation Coating compositions for marine applications and methods of making and using the same
US8852689B2 (en) * 2007-05-29 2014-10-07 Innova Dynamics, Inc. Surfaces having particles and related methods
FR2919308B1 (fr) * 2007-07-23 2009-12-11 Commissariat Energie Atomique Procede de preparation d'un materiau nanocomposite par depot chimique en phase vapeur.
WO2009025955A1 (fr) * 2007-08-23 2009-02-26 University Of Virginia Patent Foundation Nanoparticules métalliques immobilisées en tant que matériaux uniques pour des applications thérapeutiques et de biodétection
WO2009051817A1 (fr) * 2007-10-19 2009-04-23 One Green World, Inc. Nanocristaux de dioxyde de titane photocatalytique
AU2009230868A1 (en) * 2008-03-31 2009-10-08 Commonwealth Scientific And Industrial Research Organisation Membrane and process for steam separation, purification and recovery
EP2352584B1 (fr) * 2008-04-04 2017-02-15 Carrier Corporation Dispositif photocatalytique présentant une structure mélangée de photocatalyseur et silice
WO2010114550A1 (fr) 2009-04-02 2010-10-07 Carrier Corporation Dispositif photocatalytique présentant une structure mélangée de photocatalyseur/silice
FR2929757B1 (fr) * 2008-04-08 2010-09-03 Commissariat Energie Atomique Procede d'elaboration d'une membrane comportant des micropassages en materiau poreux par polissage mecano-chimique
FR2929863B1 (fr) * 2008-04-10 2013-09-27 Centre Nat Rech Scient Recouvrement d'un substrat par un film de polymere stable en milieu liquide
CA2734864A1 (fr) 2008-08-21 2010-02-25 Innova Dynamics, Inc. Surfaces et revetements ameliores, et procedes associes
KR101010037B1 (ko) 2008-10-15 2011-01-21 삼화페인트공업주식회사 내지문성 수지 조성물 및 이를 포함하는 내지문성 강판
DE102011016553A1 (de) 2010-07-16 2012-01-19 Johnson Controls Gmbh Flexibles Material für einen Bezug oder Überzug eines Sitzes
KR101820327B1 (ko) 2010-08-07 2018-01-19 티피케이 홀딩 컴퍼니 리미티드 표면 매립 첨가제를 가진 디바이스 콤포넌트 및 이와 관련된 제조 방법
US10155361B2 (en) 2011-11-09 2018-12-18 Corning Incorporated Method of binding nanoparticles to glass
CN103947002B (zh) 2011-06-28 2017-10-13 苏州诺菲纳米科技有限公司 并入了添加剂的透明导体以及相关的制造方法
EP3739598B1 (fr) 2011-08-24 2023-12-06 Tpk Holding Co., Ltd Conducteurs transparents texturés et procédés de fabrication associés
WO2013026428A1 (fr) 2011-08-25 2013-02-28 Johnson Controls Gmbh Matière flexible pour housse ou revêtement de siège
TWI521016B (zh) 2012-07-18 2016-02-11 財團法人工業技術研究院 蝕刻含聚亞醯胺之膜層的方法
CN102785437B (zh) * 2012-07-19 2016-08-03 中国航空工业集团公司北京航空材料研究院 一种复合导电薄层及其制备方法和应用
KR101368487B1 (ko) * 2013-04-30 2014-02-28 김태훈 자동차 도막 보호용 통기성 필름
EP3129129B1 (fr) 2014-04-11 2022-06-01 3M Innovative Properties Company Articles microporeux dotés d'un réseau poreux tridimensionnel de nanoparticules de silice interconnectées frittées à l'acide et procédés de fabrication de ceux-ci
WO2017196656A1 (fr) 2016-05-13 2017-11-16 3M Innovative Properties Company Articles multicouches comprenant des revêtements sur des substrats de membrane de microfiltration, et leurs procédés de fabrication
WO2018169737A1 (fr) 2017-03-15 2018-09-20 3M Innovative Properties Company Articles multicouches comprenant des revêtements contenant un métal sur des substrats de membrane de microfiltration
CN107715698A (zh) * 2017-11-09 2018-02-23 济南大学 一种用于景观水的净化膜材料的制备方法及所得产品和应用
US11002063B2 (en) * 2018-10-26 2021-05-11 Graffiti Shield, Inc. Anti-graffiti laminate with visual indicia
CN115605809A (zh) * 2020-05-15 2023-01-13 新加坡国立大学（Sg） X射线检测膜、其制造方法及用途
CN113797927A (zh) * 2020-06-12 2021-12-17 赵石永 一种杀菌薄膜及其制备方法和其在照明装置中的应用
CN113289500B (zh) * 2021-05-24 2022-04-22 湖南澳维新材料技术有限公司 一种高通量反渗透膜的制备方法及所得高通量反渗透膜
US20250040579A1 (en) 2021-11-25 2025-02-06 Neggst Foods Gmbh Vegan-based egg white substitute product
DE102021130977A1 (de) 2021-11-25 2023-05-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verwendung eines thermoplastischen, biobasierten und bioabbaubaren Materials mit spröder Bruchmechanik als Schale für ein Ei oder Eiersatzprodukt sowie ein mit einer solchen Schale umhülltes veganes Eiersatzprodukt
CN115569519A (zh) * 2022-09-14 2023-01-06 暨南大学 一种导电聚醚砜超滤膜及其制备方法
CN117552157A (zh) * 2023-11-13 2024-02-13 常州雅美特窗饰股份有限公司 一种自调节式幻彩发光卷帘面料及其制造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391609A (en) * 1993-06-09 1995-02-21 Mobil Oil Corp. Transparent films providing a barrier to the transmission of ultra-violet light
US5849311A (en) * 1996-10-28 1998-12-15 Biopolymerix, Inc. Contact-killing non-leaching antimicrobial materials
WO1997000134A1 (fr) * 1995-06-19 1997-01-03 Nippon Soda Co., Ltd. Structure porteuse de photocatalyseur et materiau de revetement photocatalytique
DE19536033C2 (de) * 1995-09-28 1997-08-28 Oxyphen Gmbh Dresden Hydrophobe Kapillarporenmembran und Verfahren zur Herstellung
JPH09278928A (ja) * 1996-04-09 1997-10-28 Nitto Denko Corp 機能性多孔質樹脂フィルム及びその製造法
FR2803237A1 (fr) * 1999-12-29 2001-07-06 Iniversite Catholique De Louva Procede de creation de pores dans un materiau polymere en feuilles ou une couche polymere telle qu'un film mince d'epaisseur egale a une centaine de nanometres, prealablement deposee sur un support metallique
JP3752120B2 (ja) * 2000-02-10 2006-03-08 ジャパンゴアテックス株式会社 光触媒膜及びその製造方法
DE10015660A1 (de) * 2000-03-29 2001-10-04 Wolff Walsrode Ag Transparente, tiefziehfähige und frühsiegelnde Folie mit UV-Sperreigenschaften sowie deren Verwendung als Verpackungsmaterial für Lebensmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10272639B2 (en) 2015-03-23 2019-04-30 Emd Millipore Corporation Abrasion resistant film for biocontainers
US10675836B2 (en) 2015-03-23 2020-06-09 Emd Millipore Corporation Abrasion resistant film for biocontainers
US11110684B2 (en) 2015-03-23 2021-09-07 Emd Millipore Corporation Abrasion resistant film for biocontainers

Also Published As

Publication number Publication date
WO2004064478A3 (fr) 2004-09-30
DE10301984A1 (de) 2004-07-29
DE10301984B4 (de) 2008-07-03
WO2004064478A2 (fr) 2004-08-05
JP2006518287A (ja) 2006-08-10
US20060194037A1 (en) 2006-08-31

Similar Documents

Publication Publication Date Title
DE10301984B4 (de) Flexible, atmungsaktive Polymerfolie
DE69307208T2 (de) Verfahren zur Herstellung von Überzugfilmen aus Titanoxyd
Liu et al. Bio-inspired titanium dioxide materials with special wettability and their applications
JP5777337B2 (ja) 抗菌性材料
DE69711526T2 (de) Kristalline Titanoxid-Nanoröhrchen und Verfahren zu ihrer Herstellung
Ubonchonlakate et al. Photocatalytic disinfection of P. aeruginosa bacterial Ag-doped TiO2 film
US9491947B1 (en) Method of synthesizing nanoparticles and a nanoparticle-polymer composite using a plant extract
DE10392572T5 (de) Verfahren zur Herstellung von mesoporösen TiO2-Dünnfilmen mit hohen fotokatalytischen und antibakteriellen Wirksamkeiten
EP1923117A2 (fr) Materiau filtrant et procede de fabrication, filtre et procede de filtrage
US20190300727A1 (en) Compositions comprising diatom frustules and applications thereof
US12251667B2 (en) Nanofunctionalised polymeric support with photocatalytic nanoparticles based on titanium dioxide and its use as photocatalysts
DE60314650T2 (de) Verfahren zur herstellung von lösungen zur verwendung als beschichtung in photokatalytischen und transparenten filmen
Bechelany Review on Natural
Yapa et al. Synergistic antimicrobial nanofiber membranes based on metal incorporated silica nanoparticles as advanced antimicrobial layers
Renuka et al. Synthesis, characterization and applications of titanium dioxide nanoparticles
JP3246916U (ja) 金属ナノ粒子等の吸着による抗菌及び抗ウイルス性処理が施された成形品
DE102006020993A1 (de) Photokatalysator, Herstellungsverfahren dafür und Gegenstände, die den Photokatalysator verwenden
Prawira et al. TiO2-M self-cleaning coating with antimicrobial and superhydrophilic properties
DE60118183T2 (de) Selbstreinigende durchsichtige schallbarriere und verfahren zu ihrer herstellung
DE10146375B4 (de) Biokompositmaterial, Verfahren zu dessen Herstellung und Verwendung
Oopath et al. Antibacterial surface based on hierarchical polyurethane acrylate/zinc oxide structures
Arcidiacono Comparative synthesis and characterization of zinc oxide nanopowders via chemical and biological methods: integration into polymer matrices for surfaces.
Abu Bakar et al. Eco-friendly natural rubber–silver (NR–Ag) composites for photo-assisted degradation of methyl orange dye
DE102007026866A1 (de) Photokatalytisch aktive Schicht sowie Zusammensetzung und Verfahren zu ihrer Herstellung
DE102022113852B4 (de) Nanokomposit-Polymermaterial und Verfahren zum Herstellen eines Nanokomposit-Polymermaterials

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050811

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TRIBUTSCH, HELMUT

Inventor name: ROJAS-CHAPANA, JOSE

Inventor name: KUEPPERS, UDO

Inventor name: FINK, DIETMAR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070320