WO2000006633A1 - Revetement pour substrat en plastique - Google Patents

Revetement pour substrat en plastique Download PDF

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Publication number
WO2000006633A1
WO2000006633A1 PCT/GB1999/002414 GB9902414W WO0006633A1 WO 2000006633 A1 WO2000006633 A1 WO 2000006633A1 GB 9902414 W GB9902414 W GB 9902414W WO 0006633 A1 WO0006633 A1 WO 0006633A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
glazing
plastic
plastic substrate
inorganic
Prior art date
Application number
PCT/GB1999/002414
Other languages
English (en)
Inventor
Paul Arthur Holmes
Original Assignee
Pilkington Plc
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 Pilkington Plc filed Critical Pilkington Plc
Priority to AU50577/99A priority Critical patent/AU5057799A/en
Publication of WO2000006633A1 publication Critical patent/WO2000006633A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/778—Windows
    • B29L2031/7782—Glazing
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

  • This invention relates to a coating resistant to scratching and in particular to plastic glazings for automotive use which incorporate such a coating.
  • Glazings for automotive use conventionally comprise safety glass which may be laminated (widely used for windscreens) or toughened (widely used for sidelights and backlights).
  • the desire to improve vehicle fuel consumption makes it desirable to provide an automotive glazing lighter in weight than a conventional automotive glazing, whilst maintaining the structural rigidity and toughness required in automotive glazings.
  • Plastic glazings for vehicles have been tried with limited success.
  • Such glazings generally comprise a synthetic resin, such as polycarbonate or acrylic, which has a lower density than glass.
  • synthetic resins have poor resistance to scratching, that is abrasion resistance (resistance to marking by an abrasive pad) and/or scratch resistance (resistance to a permanent visible scratch from a point load), and their surface durability may be improved by application of a coating resistant to scratching.
  • Conventional thin (1 to 10 ⁇ m) hard coats such as siloxane have been applied to the surface of plastic glazings by dip coating, but their application is costly and time consuming.
  • GB 2305890 discloses an alternative method of providing a coating resistant to scratching on a plastic substrate.
  • a mixture of a resin and a glass filler form a hard coating on the substrate surface which is resistant to scratching.
  • this coating may cause problems. It is important that the refractive index of both the resin and the glass filler correspond because a mismatch between them leads to haze in the glazing. Matching the refractive indexes of these materials is difficult and even it matched, the temperature dependence of refractive index is unlikely to be the same for both materials, and so haze develops in the glazing as the temperature changes. This problem is particularly prevalent in outdoor glazings which are subject to climatic changes in temperature.
  • a coating resistant to scratching for a plastic substrate comprising a plurality of components including an inorganic polymer and an inorganic filler wherein at most only one of the components has a particle size towards the lower range of or above the wavelength of visible light.
  • the coating has a single effective refractive index and the aforementioned problems associated with matching the refractive indexes of the individual components are avoided.
  • Such a coating is particularly advantageous in applications where the coating is subject to temperature changes, for example on automotive glazings which are subject to climatic changes in temperature.
  • additives that may be incorporated into the coating include hydrophobic additives, hydrophilic additives, anti-static additives and/or photocatalytic additives.
  • the additive should have a particle size below or towards the lower range of the wavelength of visible light.
  • the inorganic polymer may be thermoplastic which enables the coating to be applied to a plastic substrate by a number of methods, such as laminating a preformed film of the coating to the substrate, co-extruding a film of the coating with the plastic substrate, or by a multiple injection moulding method.
  • the coating may have a thickness of at least 0.05mm and preferably has a thickness of at least 0.1mm.
  • inorganic polymer is preferably a silicone resin and the inorganic filler is preferably colloidal silica having a particle size less than about 500 nm.
  • the coating may be exposed to a plasma treatment process to decompose the inorganic polymer to its organic oxide.
  • the plasma treatment modifies the surface of the coating in such a way to enhance its resistance to scratching.
  • the silicone resin decomposes to silica which is well known to have excellent resistance to scratching.
  • the inorganic oxide of the plasma treated surface may have a thickness of at least 5 nm providing an extremely thin surface which is particularly resistant to scratching.
  • the coating may also include an ultra-violet absorbing or reflecting species.
  • a plastic glazing comprising a plastic substrate having a coating according to the first aspect of the invention applied to at least one of its surfaces.
  • An adhesive having a low modulus (one having a tensile modulus of less than about lOOMPa, preferably less than lOMPa) may be employed to improve the adhesion between the coating and the substrate.
  • the low modulus layer is also believed to enhance the energy absorption and impact resistance of the glazing by at least reducing or preventing cracks propagating from the coating through to the substrate by blunting the crack tip.
  • the coating may surround the plastic substrate so that each surface of the glazing is resistant to scratching.
  • the plastic substrate is preferably impact resistant and polycarbonate is a particularly suitable material.
  • Plastic glazings according to the invention may be at least 3mm thick and in certain applications it may be desirable for them to have a greater thickness. For example they may be installed into the openings of vehicles in which the width of the glazing channels is nominally 4mm or 5mm or more. Use ot the structure of the present invention permits the production of durable plastic glazings, including curved glazings, which are suitable for automotive use
  • the glazing may further include at least one ultra-violet (uv) absorbing or reflecting layer which when the glazing is fitted into a vehicle, may serve to protect the interior of the vehicle from degradation by sunlight.
  • uv absorbing or reflecting species may serve to protect an aromatic plastic substrate (one that includes aromatic units in the polymer chains), such as polycarbonate, which tends to degrade on exposure to uv radiation.
  • a method of forming a plastic glazing by multiple injection moulding comprising the steps of injecting a skin material into a mould, the skin material comprising a plurality of components including an inorganic polymer and an inorganic filler and at most only one of the components has a particle size towards the lower range of or above the wavelength of visible light, injecting a plastic substrate material into the mould which forces the skin material to the surfaces of the mould such that in the finished glazing the skin material forms a coating which surrounds the plastic substrate.
  • the glazing is injection moulded it may be manufactured in a variety of shapes with a surface finish dictated by the surface of the mould cavity without the need for a clean environment. In particular curved glazings suitable for automotive use may be manufactured.
  • a low modulus material may be injected into the mould after the injection of the skin material and before injection of the plastic substrate material so that in the finished glazing the low modulus material is located between the coating and the plastic substrate.
  • the low modulus layer may improve the adhesion between the skin and the substrate and may enhance the energy absorption and impact resistance of the glazing by at least reducing or preventing cracks propagating from the coating through to the substrate by blunting the crack tip.
  • the skin material may comprise a silicone resin and the inorganic filler may comprise colloidal silica having a particle size less than about 500nm.
  • the method preferably comprises the further step of exposing at least one surface of the glazing to a plasma treatment process which causes the inorganic polymer to decompose to its inorganic oxide.
  • the plasma treatment decomposes the silicone to silica which has a good finish and is well known to have excellent resistance to scratching.
  • Figure 1 and 2 are enlarged schematic cross sections of a coating according to the invention.
  • Figures 3 and 4 are schematic cross sections of a dual injection moulding system for moulding a glazing according to an embodiment of the invention.
  • Figure 5 is a schematic cross section of an injection moulded glazing according to an embodiment of the invention.
  • Figure 6 is a schematic cross section of a the glazing of Figure 5 which has been exposed to a plasma treatment process.
  • Figure 7 is a schematic cross section of an injection moulded glazing according to another embodiment of the invention which has been exposed to a plasma treatment process.
  • the coating 1 may have a thickness t of at least 0.05mm but preferably is at least 0.1mm thick.
  • the coating comprises a random mixture of an inorganic polymer 2 such as a silicone resin, for example polydimethylsiloxane, and an inorganic filler 3 such as colloidal silica.
  • the inorganic filler has a particle size towards the lower range of or below the wavelength of visible light (400 - 700nm) and typically colloidal silica has a particle size of less than about 500nm and commonly less than about lOOnm.
  • the polydimethylsiloxane may comprise between about 20% to 80 % by weight ot the coating with the remainder comprising colloidal silica. Preferably the proportion is about 50% of each.
  • Such a coating has a single effective refractive index and problems concerned with matching the refractive indexes of the individual components are avoided. This is particularly advantageous in situations where the coating is subject to temperature changes, for example on automotive glazings which are subject to climatic changes in temperature. If more than one of the components of the coating has a particle size above the lower range of visible light then the refractive indexes of those components would need to be matched or haze would develop in the glazing. Even if their refractive indexes were matched it is likely that haze would develop as the temperature changes because the temperature dependence of refractive index is unlikely to be the same for each component.
  • the coating may be incorporated into relatively small quantities of other components to provide the coating with additional properties.
  • pigments and/or dyes may be incorporated to provide a tint or solar control properties, especially uv protection, to the coating (and hence a glazing when applied thereto).
  • the uv absorbing or reflecting species may serve to protect the interior of the vehicle from degradation by sunlight.
  • the uv absorbing or reflecting species may serve to protect an aromatic plastic substrate (one that includes aromatic units in the polymer chains), such as polycarbonate, which tends to degrade on exposure to uv radiation.
  • Hydrophobic additives such as a fluorinated compound to impart anti- soiling and rain shedding properties
  • hydrophilic additives such as a surfactant for anti misting properties
  • anti-static additives such as titanium dioxide in anatase form for self cleaning properties
  • photocatalytic additives such as titanium dioxide in anatase form for self cleaning properties
  • the surface durability of the coating may be enhanced by exposing a surtace of the coating to a plasma treatment process to modify its surface, and a coating which has been so treated is shown in Figure 2.
  • a suitable plasma system known to those skilled in the art is used in which the outer surface of the inorganic polymer decomposes to its inorganic oxide.
  • the plasma gas is an oxidising gas such as air or oxygen.
  • the coating is exposed to the plasma treatment for a time sufficient to allow an oxide layer 5 having a thickness of at least 5nm to be formed at the surface, but it will be appreciated that thicker layers, for example up to lOOnm, may be desirable in certain applications to improve further the surface hardness and resistance to scratching.
  • the plasma treatment process causes the polydimethylsiloxane to decompose to silica which has a good finish and is well known to be particularly resistant to scratching, and the coating is suitable for use in automotive glazings which require this property.
  • the inorganic polymer component of the coating may be a thermoset material but is preferably a thermoplastic material which enables the coating to be applied to a suitable plastic substrate, such as polycarbonate or acrylic, by a number of methods.
  • the coating may be formed as a film by conventional methods such as extrusion or blow moulding, and the film may be adhered to the substrate by heating under pressure. Adhesion may be improved by bonding the coating to the substrate with a suitable low modulus adhesive layer, for example a preformed interlayer having a tensile modulus of less than about lOOMPa and preferably less than lOMPa.
  • Polyurethane or PVB are suitable adhesive layers, and a thickness of as little as 10 microns and ideally about 100 microns can be used for this purpose, although the ready availability of these materials in greater thickness, eg 0.38mm, may make it more convenient to use somewhat thicker layers than is necessary.
  • a low modulus adhesive layer improves the adhesion between the coating and the substrate and has the added advantage of enhancing the energy absorption and impact resistance of the glazing. It is believed mat the low modulus adhesive at least reduces or prevents cracks propagating from the coating through to the substrate by blunting the crack tip.
  • the coating and plastic substrate may be coextruded and then cut to shape to form a glazing.
  • a coated plastic glazing may also be formed by a multiple injection moulding method which is used to form multi layered products.
  • a mould 10 comprises mould sections 12 and 14 defining a mould cavity 16, and is mounted on a multiple injection moulding machine of known type. Such machines are available in commerce from Battenfeld Fischer of Lohmar, Germany.
  • a skin material 18 comprising a mixture of an inorganic polymer such as a silicone resin, for example polydimethylsiloxane, and an inorganic filler such as colloidal silica having a particle size of less than about 500 nm, is firstly injected into cavity 16 slightly ahead of a core material 20 such as polycarbonate.
  • Injection of the core material 20 forces the skin material to the periphery of the cavity to the extent that on completion of the injecting, the skin material 18 surrounds the core material 20 in the form of a coating 30.
  • the moulded composite 31 is cured prior to removal from the mould.
  • the amount of skin material is chosen such that in the finished glazing its thickness is as least 0.05mm and preferably at least 0.1 mm.
  • the polydimethylsiloxane may comprise between about 20% to 80 % by weight of the skin material with the remainder comprising colloidal silica. Preferably the proportion is about 50% of each.
  • pigments and or dyes may be incorporated to provide a tint or solar control properties, especially uv protection, to the coating (and hence the glazing).
  • Other components that may be incorporated include hydrophobic additives, hydrophilic additives, anti-static additives and/or photocatalytic additives. As previously described with reference to the coating as such, in each case the additive should have a particle size towards the lower range of or below the wavelength of visible light.
  • the surface durability of the glazing may be enhanced by exposing at least one of its major surfaces to a plasma treatment process as hereinbefore described to modify the surface of the coating.
  • Figure 6 shows such a glazing which has had all of its surfaces exposed to a plasma treatment and comprises an outer silica layer 32, a layer 30 comprising a mixture of polydimethylsiloxane and colloidal silica and a layer 20 of polycarbonate.
  • a coating is particularly suitable as an automotive glazing with the silica surface outermost thereby avoiding dangerous spall within the vehicle when impact of the glazing occurs.
  • the glazing may also include a low modulus adhesive layer 34 having a tensile modulus of less than about lOOMPa and preferably less than lOMPa between the core and the skin by injecting the low modulus material after injection of the skin material and before injection of the core material.
  • a low modulus adhesive layer 34 having a tensile modulus of less than about lOOMPa and preferably less than lOMPa between the core and the skin by injecting the low modulus material after injection of the skin material and before injection of the core material.
  • Polyurethane or PVB are examples of suitable low modulus materials and an amount of such material is selected so that in the finished glazing its thickness is as little as 10 microns, although ideally a thickness of 100 microns or more may be used.
  • the glazing is formed by moulding it may be manufactured in a variety of shapes with a surface finish dictated by the surface of the mould cavity without the need for a clean environment.
  • curved glazings suitable for automotive use may be manufactured.
  • Glazings in accordance with the present invention may be manufactured at thicknesses suitable to be fitted into openings, especially motor vehicle openings, designed to be glazed with conventional nominal 3mm glazings. However some automotive glazings are designed to be glazed with glazings nominally 4mm or 5mm or more and so the glazing may be up to 5mm or more.
  • solar control materials such as uv absorbing or reflecting species, may be loaded into a component of the glazing other than the coating to provide the glazing with desirable solar control properties.
  • the glazing may include a specific uv absorbing or reflecting layer but preferably the uv absorbing or reflecting species is loaded into at least one of the components of the glazing, in particular the low modulus layer.
  • An infra red absorbing or reflecting species may likewise be incorporated into a component of the glazing.

Abstract

L'invention concerne un revêtement (1, 30) résistant aux griffures destiné à un substrat en plastique. Le revêtement comprend un certain nombre de constituants dont un polymère inorganique (2) et une matière de charge inorganique (3). Au moins tous les constituants à l'exception d'un seul ont une dimension des particules proche ou au-dessous de la gamme inférieure de la longueur d'onde de la lumière visible. Ce revêtement (1, 30) présente un indice monoréfrigent effectif, ce qui évite les problèmes liés à la compatibilité des indices de réfraction des constituants pris séparément. Le revêtement (1, 30) offre des avantages particuliers dans des applications où il est soumis à des changement de température comme, par exemple, dans les vitrages d'automobiles exposés à des changements de température dus au climat. La durabilité de la surface du revêtement (1, 30) peut être améliorée par exposition d'au moins une partie de sa surface à un processus de traitement au plasma.
PCT/GB1999/002414 1998-07-27 1999-07-26 Revetement pour substrat en plastique WO2000006633A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50577/99A AU5057799A (en) 1998-07-27 1999-07-26 Coating for plastic substrate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9816269.6 1998-07-27
GBGB9816269.6A GB9816269D0 (en) 1998-07-27 1998-07-27 Plastic glazings

Publications (1)

Publication Number Publication Date
WO2000006633A1 true WO2000006633A1 (fr) 2000-02-10

Family

ID=10836198

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/002414 WO2000006633A1 (fr) 1998-07-27 1999-07-26 Revetement pour substrat en plastique

Country Status (3)

Country Link
AU (1) AU5057799A (fr)
GB (1) GB9816269D0 (fr)
WO (1) WO2000006633A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004018338A1 (de) * 2004-04-15 2005-11-10 Sto Ag Beschichtungsmaterial
WO2010138351A2 (fr) * 2009-05-28 2010-12-02 Dow Global Technologies Inc. Compositions de géopolymères modifiés, procédés et utilisations
WO2014097309A1 (fr) 2012-12-17 2014-06-26 Asian Paints Ltd. Revêtement autonettoyant répondant à des stimuli

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2010879A (en) * 1977-12-23 1979-07-04 Dow Corning Flexible Coating Resins From Siloxane Resins Having a Very Low Degree of Organic Substitution
US4374158A (en) * 1979-11-14 1983-02-15 Toray Industries, Inc. Process for producing transparent shaped article having enhanced anti-reflective effect
EP0101326A1 (fr) * 1982-08-18 1984-02-22 Foster Grant Corporation Procédé d'application d'un revêtement résistant à l'abrasion sur un substrat et articles revêtus au moyen de ce procédé
EP0266225A1 (fr) * 1986-10-31 1988-05-04 Hashimoto Forming Industry Co Ltd Procédé pour produire des articles moulés en matière plastique avec des surfaces revêtues de couches dures
US5385955A (en) * 1992-11-05 1995-01-31 Essilor Of America, Inc. Organosilane coating composition for ophthalmic lens
WO1996007525A1 (fr) * 1994-09-02 1996-03-14 Rover Group Limited Procede de preparation d'un revetement resistant a l'abrasion sur un substrat en plastique
US5654090A (en) * 1994-04-08 1997-08-05 Nippon Arc Co., Ltd. Coating composition capable of yielding a cured product having a high refractive index and coated articles obtained therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2010879A (en) * 1977-12-23 1979-07-04 Dow Corning Flexible Coating Resins From Siloxane Resins Having a Very Low Degree of Organic Substitution
US4374158A (en) * 1979-11-14 1983-02-15 Toray Industries, Inc. Process for producing transparent shaped article having enhanced anti-reflective effect
EP0101326A1 (fr) * 1982-08-18 1984-02-22 Foster Grant Corporation Procédé d'application d'un revêtement résistant à l'abrasion sur un substrat et articles revêtus au moyen de ce procédé
EP0266225A1 (fr) * 1986-10-31 1988-05-04 Hashimoto Forming Industry Co Ltd Procédé pour produire des articles moulés en matière plastique avec des surfaces revêtues de couches dures
US5385955A (en) * 1992-11-05 1995-01-31 Essilor Of America, Inc. Organosilane coating composition for ophthalmic lens
US5654090A (en) * 1994-04-08 1997-08-05 Nippon Arc Co., Ltd. Coating composition capable of yielding a cured product having a high refractive index and coated articles obtained therefrom
WO1996007525A1 (fr) * 1994-09-02 1996-03-14 Rover Group Limited Procede de preparation d'un revetement resistant a l'abrasion sur un substrat en plastique

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004018338A1 (de) * 2004-04-15 2005-11-10 Sto Ag Beschichtungsmaterial
US7955430B2 (en) 2004-04-15 2011-06-07 Sto Ag Coating material
WO2010138351A2 (fr) * 2009-05-28 2010-12-02 Dow Global Technologies Inc. Compositions de géopolymères modifiés, procédés et utilisations
WO2010138351A3 (fr) * 2009-05-28 2011-09-01 Dow Global Technologies Llc Compositions de géopolymères modifiés, procédés et utilisations
CN102741191A (zh) * 2009-05-28 2012-10-17 陶氏环球技术有限责任公司 改性地质聚合物组合物、方法及用途
US8815348B2 (en) 2009-05-28 2014-08-26 Dow Global Technologies Llc Modified geopolymer compositions, processes and uses
US8901230B2 (en) 2009-05-28 2014-12-02 Dow Global Technologies Llc Modified geopolymer compositions, processes and uses
WO2014097309A1 (fr) 2012-12-17 2014-06-26 Asian Paints Ltd. Revêtement autonettoyant répondant à des stimuli

Also Published As

Publication number Publication date
GB9816269D0 (en) 1998-09-23
AU5057799A (en) 2000-02-21

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