The present invention relates to a reinforced and preferably surface sealed building element and to a method and apparatus for the manufacture of these elements.
The invention was developed primarily for building sheet materials made predominantly from fibre cement and will be described hereinafter with reference to this application. However, it will be clear that the invention is not limited to this particular use and can readily be adapted to other building products and/or elements made from different materials.
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
Selection of building materials for a given use depends largely upon the nature of the intended application and in many cases each of the products available represent a compromise between strength characteristics, durability and ease of installation, the latter being largely determined by workability characteristics such as ease of cutting, fixing and handling.
For example, natural timber has good inherent bending strength characteristics making it easy to transport and suitable for use in a variety of load bearing applications. However, it is generally fairly costly and lacks durability, particularly in damp or wet applications.
By contrast, manufactured wood products and fibre cement products, for example, are generally less expensive and more versatile in their application to form different shapes and types of building elements. However, these products generally have relatively lower bending strength to weight ratio due to their inherent weakness under tensile loads. They are also generally porous and prone to some degree of moisture absorption. While in the case of fibre cement products, this does not lead to significant reductions in durability, with most materials there is usually a resultant decrease in the strength characteristics with prolonged and cyclic exposure to moisture. There is also usually a corresponding increase in mass, which may be relevant to the issue of transportation and installation.
The problem of low bending specific strength in building elements made of homogenous bonded materials such as fibre cement has been addressed to some degree by using various forms of added reinforcement. In some cases a reinforcing element is introduced into the main body of the building material during manufacture. However, this has generally required major modifications to the material manufacturing process which can be costly and may inhibit the flexibility of the manufacturing plant.
Other solutions have included the step of externally attaching some form of reinforcing element to the completed base product using fasteners or an adhesive. Examples of this concept as applied to fibre cement building substrates are described in WO 02/081842. However, in conventional production processes, this additional step is generally off line from the normal production line, requires a specific additional fastener/adhesive, is labour intensive and/or time consuming thereby adding substantially to the cost of the product.
It is an object of the invention to provide a reinforced building element, and a method and apparatus for the manufacture of such elements, which overcomes or substantially ameliorates one or more of the disadvantages of the prior art or at least provides a useful alternative.
According to a first aspect of the invention, there is provided a reinforced building element including:
a rigid substrate having a first face; and
a layer of reinforcing material;
wherein said reinforcing material is adhered to said first face of said rigid substrate using a radiation curable resin.
The term “rigid” is used herein to refer to any kind of generally rigid and at least partially self supporting substrate and includes substrates that may have some degree of inherent flexibility due to their material and/or structure.
The term “radiation” is used herein to refer to radiation from U/V (ultra violet) to higher wavelengths.
According to a second aspect of the invention there is provided a method of manufacturing a reinforced building element including the steps of:
(a) applying a radiation curable resin to a first face of a rigid substrate;
(b) applying a reinforcing material to the layer of a radiation curable resin; and
(c) curing the resin to thereby adhere said reinforcing material to the rigid substrate.
The radiation curable material may be undergo full curing in a single step in step c). Alternatively the radiation curable coating may be partially cured as an initial step prior to application of the reinforcing material. Preferably this initial partial curing achieves a “tackiness” suitable for initial holding and positioning on the reinforcing material.
In one embodiment, the radiation curable material is fully cured prior to application of the reinforcing material. In this embodiment, the curable material is formulated to develop on adhesive/gripping texture on curing and thereby adhere the reinforcing material.
The coating of radiation curable resin may be formed from one or more layers, preferably two layers, and the layer of reinforcing material is applied and embedded between these layers. In other words, in a particularly preferred embodiment, the radiation curable material is applied, optionally this layer undergoes a partial cure, the reinforcing material is applied over the first layer of radiation curable material, a second layer of such curable material applied, or indeed a different formulation, and the entire assembly subject to full curing.
The method may also include the further action of optionally applying several layers of radiation curable material with or without partial/full curing, prior to application of the reinforcing material.
In other variations, the partial/full curing of the radiation curable material may be applied in combination with mechanical keying by surface scuffing with equipment such as a fine sander or denibber. These intermediate steps can be repeated as desired to build up the layers of material prior to final curing step.
According to a third aspect, the present invention comprises a method of manufacturing a reinforced building element including the steps of:
(a) combining a reinforcing material with a radiation curable resin, the quantity of resin being sufficient to adhere the reinforcing material to a rigid substrate;
(b) applying the combined reinforcing material and resin to a first face of a rigid substrate; and
(c) curing the resin to thereby adhere said reinforcing material to the rigid substrate.
According to a fourth aspect of the invention, there is provided an apparatus for manufacturing a reinforced building elements, the apparatus including:
means for supporting a rigid substrate such that a first face thereof is exposed;
first coating means for applying a first layer of radiation curable resin to said first face;
application means for applying a reinforcing material to said first layer of radiation curable resin; and
first radiation application means for curing the applied resin.
In the preferred form, the apparatus comprises an automated system for producing a reinforced building element, the system including:
means to support a rigid substrate such that a first face thereof is exposed;
an applicator for applying a first layer of radiation curable resin to said first face of the substrate;
reinforcing feed means downstream of said applicator for feeding and applying a reinforcing material to said applied first layer of radiation curable resin; and
a radiation application device for applying radiation to the applied resin, reinforcing material and substrate assembly.
Desirably the system also includes means to automatically convey the substrate downstream through the applicators/devices etc. Optionally, the mechanism may also act to support the substrate in the required orientation.
In a particularly preferred form the system further includes;
a second radiation application device located immediately downstream of the first applicator device for applying a measured dose of radiation to achieve a predetermined “tackiness” in the resin prior to the reinforcing material being applied.
The system may also include a second resin applicator downstream of the reinforcing feed means to apply a second layer of radiation curable resin on top of the reinforcing material.
In other variations, additional resin applicator devices, with or without corresponding downstream radiation application devices, may be provided upstream of the reinforcing feed means, to build up the base resin coating prior to application of the reinforcing material.
Similarly, additional resin application devices, with or without corresponding downstream radiation application devices may be provided downstream of the reinforcing feed means for implying additional building up the top sealer coatings to the element prior to final curing of the applied resin, reinforcing and substrate assembly.
Preferably the rigid substrate is a manufactured matrix material. More preferably, the material is an hydraulically or cement bound material. Most preferably the material comprises fibre reinforced cement. In one preferred embodiment, the material is cellulose fibre reinforced cement.
In the preferred form, the building element is a building sheet or panel.
In one preferred form the building element is a sheet specifically configured for use as a structural element. The structural element can be structural flooring, such as a sub-floor panel. One advantage of the fibre cement structural flooring is that it does not require a tile backerboard to adhere tiles to the structural flooring. In typical construction where it is desired to lay tile on a floor, a wood-based sub floor is first installed and then a tile backerboard is installed on top of the sub floor. The disclosed embodiments alleviate the necessity of hauling, sizing, and installing two layers of flooring prior to installing tile. In another preferred form, the building element is a sheet specifically configured for use in wet areas, such as bathrooms, laundry rooms, or kitchen areas where contact with water is possible. In a particularly preferred form, embodiments of the fibre cement sheet composition include those disclosed in U.S. Pat. No. 6,572,697 entitled “Fibre Cement Building Materials with Low Density Additives”, the full contents of which are hereby expressly incorporated herein by way of cross-reference.
In addition, the preferred fibre cement sheets may be formulated according to embodiments disclosed in U.S. Pat. No. 6,346,146 entitled “Building Products” and also according to embodiments disclosed in Australian Patent No. 515151, entitled “Fibre Reinforced Cementitious Articles” the full contents of these documents being expressly incorporated herein by way of cross-reference.
Most preferably, the reinforced building element is a structural flooring sheet for use in wet areas and is configured to include connecting means in the form of grooves formed in opposite longitudinal edges of each sheet configured either to interact with corresponding tongues formed on edges of adjacent sheets or with a complimentary elongate joining member adapted for simultaneous engagement with the respective adjacent grooves of adjoining sheets. This configuration is generally used where the joint is required to span between support framing such as floor joists.
In one particular embodiment, the planks are narrow “decking” type planks, joinable by the aforementioned tongue and groove arrangement. This clearly has a significant advantage in being able to modify fibre reinforced cementitious planks for outdoor use in decking and the like.
The layer of reinforcing material can comprise any suitable continuous strand, ribbon, rod, mesh or sheet material having a higher tensile strength and similar or higher modulus of elasticity to that of the rigid substrate, where radiation curing can pass sufficiently through and/or around the material to cure the embedding sealer sufficiently to adhere the reinforcing material to the substrate. Preferably, the reinforcing material is selected such that once adhered to the substrate via the cured sealer it provides load transfer that results in an improved strength and toughness to the substrate material by greater than 5%.
Suitable reinforcing materials include fabrics made from continuous fibres such as glass fibre, alkali resistant glass fibre or carbon fibre.
The radiation curable resin can be any radiation curable material which provide efficient adherence between the fibre reinforce cement and the reinforcement materials.
The Applicant's have in fact found that radiation curable materials conventionally used as sealers for fibre reinforced cement are surprisingly useful for this purpose. Indeed they can be provided in quite low quantity, yet still act to secure the reinforcing material to the fibre reinforced cement. Further, if such a sealer is used the fibre reinforced rigid substrate is not only sealed but simultaneously, its mechanical properties are significantly improved by addition of the reinforced material.
In another embodiment, the radiation curable resin is a pressure sensitive adhesive. This embodiment is particularly useful since in some cases the reinforcing material will be applied to the rigid substrate by a roller. Applying a radiation curable pressure sensitive adhesive to the rigid substrate allows a roller to apply the fibre reinforced material with potentially less prospect of the rollers being fouled with uncured or partially cured resin.
The radiation curable resin material is preferably applied in layers from 1 to 1000 μm with 5 to 200 μm being more preferable and 10 to 120 μm being most preferred. The curable or polymerisable components used in forming the radiation curable materials and blends of the present invention include, but are not limited to, urethane, acrylic, epoxy and polyesters or compounds having multiple functional types such as polyester epoxies and urethane acrylics.
The curable or polymerisable components may be monomers, oligomers or polymers. The oligomers are prepared from a range of monomers with functionality including, but not limited to, isocyanate, hydroxyl, polyether, epoxy, carboxylic acid and ethylenic unsaturation. The monomers used in such a composite, include but are not limited to acrylate functionalised alcohols, diols and polyols, acrylate functional ethoxylated and/or propxylated alcohol, diols and polyols, and acrylate functional ethylene and propylene glycols and ethylene and propyelene polyglycols. Other monomers effective in preparing such composites include but are limited to derivatives of unsaturated carboxylic acids and diacids such as acrylate, methacryalte, maleate and fumarate esters, and vinylic functional materials such as vinyl ethers, and vinyl pyrolidones. Blends or mixtures of the polymerisable components as herein described may also be used.
It is particularly preferred to use polymerisable compounds based on including ethylenically unsaturated monomers.
It is preferable that the curable resin compositions used in the present invention have high solids content. Particularly, it is preferred if the curable resin has a solids curable polymerisable component content higher than 50%, more preferably higher than 70 and even more preferable if the resin forming compositions have a curable polymerisable content of around 80-100%. As will be clear to persons skilled in the art suitable curable resins may include pigmented systems where the pigment is a non-curable component or clear resin systems which have curable components in the greater 90% range.
It is preferable to use a combination of lower molecular weight monomers and higher molecular weight oligomers in order to achieve the most desirable viscosity for application, the best cure behaviour once exposed to radiation, and the most desirable physical and mechanical properties once cured. Lower molecular weight monomers may be present in amounts ranging from 10-50% by weight, with 10-30% being more preferable, and 15-25% being most preferred. Higher molecular weight oligomers may be present in amounts ranging from 10-50% by weight, with 15-40% being more preferable, and 20-35% being most preferred.
If filler is used, it may be present in amounts ranging from 5 to 80% by weight on the basis of the whole, whereas surface treatment additives are used in amounts ranging from 0.01 to 2% by weight, with respect to the filler, and from 0.01 to 0.5% by weight, with respect to the whole of the composition.
The above mentioned polymerisable compounds can be used as such or in mixture with additives such as catalysts, photo initiators, mineral or organic fillers, anti-wetting agents, dyes, plasticisers, pigments, stabilisers, shockproofing agents, insulating agents, flame retarding agents and the like, which are added in order to improve the physical-chemical properties of the finished product.
In some embodiments the building element has one or more additional functional surfaces to the first face, and these surfaces may also be sealed or processed in some other manner which may include lamination with other materials.
Preferred embodiments in the invention will now be described, by way of example only, with reference to the accompanying drawings in which:
Referring to
The building sheet 1 is manufactured by: first applying a coating of radiation curable resin to the first face 3; then applying a layer of reinforcing material 5 to the applied layer of radiation curable resin 4 such that the material is at least partially embedded therein; and then fully curing the applied sealer to adhere the material to the substrate.
As shown in
In one preferred variation to this method, the applied layer of radiation curable resin 4 is first partially cured to achieve a predetermined “tackiness” in the resin so as to hold and retain the applied reinforcing material 5 prior to full curing of the resin.
A preferred second embodiment building sheet 10 is shown in
Please note that in variations to both embodiments, multiple first layers of curable resin 4 can be applied, with or without partial curing, prior to application of the reinforcing material, to build up the base coating. Similarly, in the embodiment of
Of course other application methods and thicknesses can be used, such as by wetting the reinforcement material with resin prior to placing it in contact with the substrate. In this way, the reinforcing material sticks to the substrate without having a first base coat of resin applied to the substrate. Subsequently, a layer of resin can be applied to encapsulate the resin and increase the bonding between the substrate and reinforcing material.
It should be noted that where multiple layers of resin are applied, it is generally preferred to at least partially cure or mechanically key an underlying layer of resin prior to a further layer being applied, as this helps both the interlayer bonding and, the application process.
This technique of several layers is useful for increasing film build and overcoming coverage problems or minimising defects in the underlying coats.
Referring next to
The apparatus 20 includes a simple belt or roller conveyor 21 which serves to support the rigid substrate sheet 2 such that it's upper first face 3 is exposed and transfer the substrate in a downstream direction through the manufacturing apparatus. The conveyor 21 has a first end at a loading station 22 which is the location at which the prepared substrate sheets 2 are applied to the conveyor 21.
Immediately downstream of the loading station 22 is a first roller coating apparatus 23 for applying a first layer of radiation (preferably UV) curable resin e.g. sealer that has adjacent thereto a first radiation (preferably UV) application device 24 for optionally partially curing the sealer applied at 23.
After the radiation application device 24 a reinforcing material application device is provided as shown generally at 25. This device includes a feed attachment 26 for storing, tensioning and feeding a flexible layer of reinforcing material 5 and an application mechanism 27 which is adjustable to further control tension in the material and/or to apply pressure to push the reinforcing material onto the uncured or partially cured sealer coated substrate passing therebelow.
Downstream of the reinforcing material application device 25 is a second roller coating device or laminating device 28 for applying a second layer of radiation curable sealer on top of the applied reinforcing material 5. At the exit of this second roller coating device is one or more second radiation application devices for curing the applied radiation curable sealer.
In variations to this apparatus, the section marked X, comprising the first roller coating device 23 and first radiation application device 24, may be replicated at least once prior to the reinforcing material application device at 25. In this manner, it is possible, to build up the layer of sealer before the reinforcing material is applied. Similarly, the section Y comprising the second roller coating device and second radiation application device or devices can also be replicated to build up the sealer applied on top of the reinforcing material. Such additional units would preferably be located at position Z.
In the preferred form a clear UV curable sealer is used.
This method and some limited representative variations is summarised schematically in
Step 210:
In this step, a UV curable clear resin or sealer (such as that described in the example that follows) is applied onto the surface via a roller coater ensuring full coverage of the panel
Step 220: [Optional]
In this step, the panel is then passed through mercury lamps at a reduced UV dosage & intensity to partially cure the UV clear resin
Step 230: [Optional]
In this step, the UV clear resin is reapplied onto the panel with no UV curing
Step 240:
In this step, the glass fibre mesh is layed down onto the wet or partially/gel cured resin which can be patted down or left sitting on the surface
Step 250:
In this step, the panels with the glass fibre mesh passes under the roller coater where the mesh is pushed down to follow the contours of the surface & another layer of resin is applied to bind down & encapsulate the glass fibre mesh.
Step 260:
In this step, the panel passes under the UV light (at higher UV dosage & intensity) to fully cure the coating.
Further optional steps can be inserted between steps 250 and 260 to apply further coatings of UV resin which can optionally be gel cured prior to application of further coats before the final cure at step 260.
Tests were conducted on a range of samples of fibre reinforced cement flooring panels modified in accordance with the preferred form of the invention. In each case the sample was tested against the unreinforced base product.
The materials specifications and processing details for the samples made according to the invention are set out below:
Further details of the mesh are provided under the section heading Reinforcing Materials hereafter.
The flooring board panel is a medium density (approx 0.95 g/cc) cellulose fibre reinforced cement board, which for the purposes of these tests were unsealed. The control board is identified as “no mesh” in the results table. This control board has neither the radiation curable resin or mesh applied.
The board treated in accordance with the present invention is preferably sanded prior to application of the reinforcing material and radiation curable resin. Hence the apparent inconsistencies in the thickness between the control board and the treated board in the results table below.
The samples of the invention were tested against the control samples under the following three conditions:
The 3 point flexural test was used to determine the bending strength of the materials manufactured according to the methods disclosed herein. The diagram in
Samples are tested in different conditions to give the range of properties across fully saturated to fully dry. Samples taken from the examples given were tested in one or several of the conditions being saturated, equilibrium or oven dry.
Saturated Condition (SAT)
Specimens are fully immersed in water and vacuum saturated at −100 KPa for a minimum of 24 hrs in standard laboratory conditions.
Equilibrium Condition (EQ)
Specimens are conditioned in a controlled atmosphere to 23±2° C. and 50±10% humidity for 3 days minimum.
Oven Dry (OD)
Samples were conditioned in an oven set to 60±2° C. for 48 hrs minimum.
Samples are tested on a MTS Q-Test Universal Testing Machine. Specimen weight, thickness, length and width are measured before testing. The span used for testing the nominal 19 mm thick material was 360 mm. Load(N) and deflection(mm) were measured during the test until break occurred. The following calculations were used to determine the mechanical properties of the material.
The data from the test was then processed to derive various mechanical properties as described below and in
Break Load, Fu, is the maximum load sustained b the specimen.
Break Deflection, Du, is the deflection, corrected to zero, at which the final maximum load, Fu, was recorded (i.e. The deflection at which the break load is recorded)
Linearization Points are the points on the load deflection curve used to calculate zero deflection. Loads for the 1st and 2nd linearization are 40% and 60%, respectively, of the Break Load.
Zero Deflection (0) is defined by the Linearization Points from which an extrapolation is extended to zero load to determine the corresponding zero deflection.
Offset Base, D40, is the deflection corresponding to the base load of 40% the Break Load.
Offset is the displacement of a line drawn parallel to the line through the linearization points to calculate the proof load. The offset is given as a percentage of the offset base and is 10% of D40.
Proof Load, Fp, is equal to or above the intersection of the load deflection curve and a line drawn parallel to the linearization points but displaced by the offset deflection. The proof load may be very close to the break load in very brittle materials.
Proof Deflection, Dp, is the deflection corresponding to the proof load, Fp.
Span, S, is the distance between the centre of the supports.
Thickness, t, is the average thickness measured at 4 points spaced out evenly around the specimen.
Width, w, is the average width measured at each end of the specimen.
Mechanical Property Calculations
Modulus of Rupture (MOR) is the maximum flexural stress supported by the specimen, and can be determined according to the following formula:
Energy B is an estimate of the specific total energy absorbed by the specimen before breaking load. The specific total energy is proportional to the area of region B shown on the load/deflection curve. This value is obtained by integration of the area B divided by specimen volume within the test span. (kJ/m3)
Strain Ultimate is the strain at breaking load and can be calculated by the following formula:
The results are set out in the table below:
As can be seen, the sealed reinforced product has significantly improved performance in all measured properties. It can be seen in virtually all areas namely Break Load, Break, Deflection, Modulous of Rupture, Strain Ultimate and Energy B the board treated in accordance with a preferred embodiment of the present invention has significantly improved properties as compared with the control board.
Material Variations
Substrate
The rigid substrate material is preferably a moisture stable sheet material such as cellulose fibre reinforced cement of a density range from 0.80 g/cc to 1.5 g/cc. Typical materials are James Hardie™ Fibre cement internal linings, external claddings and sheet flooring. When the invention is used as a reinforced sheet structural flooring material, it is preferable to use ≧15 mm thick, nailable lower density fiber cement which is lighter weight, more workable and more nailable using conventional pneumatic and power nailing equipment than conventional compressed fibre cement products (approx. 1.6 g/cc dry density).
Preferably, the sheets must be strong enough to meet loading requirements for domestic construction flooring on supporting members spaced at 450 mm and 600 mm centres as specified, for example, in AS/NZS 1170.1:2002.
In line with the United States requirements, the supporting members need to be spaced out 16 inches, 19.2 inches and 24 inch centers in the US as specified in ASTM E330 and E661.
The preferred fibre cement sheets may be formulated according to embodiments disclosed in U.S. Pat. No. 6,346,146 entitled “Building Products” and also according to embodiments disclosed in Australian Patent No. 515151, entitled “Fibre Reinforced Cementitious Articles” the full contents of these documents expressly incorporated herein by way of cross-reference. Most preferably, when used for structural flooring, the sheet is configured to include connecting means such as in the form of grooves formed in opposite longitudinal edges of each sheet configured either to interact with corresponding tongues formed on edges of adjacent sheets or with a complimentary elongate joining member adapted for simultaneous engagement with the respective adjacent grooves of adjoining sheets.
In general terms it is preferable for the face of the substrate to which the sealer and reinforcing is to be applied to be relatively flat. However, where this is not possible, use of a sufficiently flexible reinforcing material, along with a deformable or contoured applicating device should assist in ensuring bonding to the contoured surface.
Reinforcing Material
The reinforcing material is any continuous strand, ribbon, rod or sheet material of significantly higher strength and similar or higher modulus of elasticity to that of the substrate material where radiation curing can pass sufficiently through and/or around the material to cure the embedding resin sufficiently to adhere the reinforcing material to the sheet flooring and preferably also provide load transfer that results in an improved strength and toughness material by greater than 5%. Examples of reinforcing material are continuous fibres such as glass fibre, alkali resistant glass fibre or carbon fibre.
The reinforcing material may be coated or uncoated. In some embodiments the reinforcing material may include a coating which is compatible with the radiation curable material to assist in adherence.
The supplier of the glass fibre used in the example described above is: —
A Jiangsu Jiuding New Material Co., Ltd., No. 219 East Yuejin Road, Rugao City Jiangsu Province China. The glass fibres used were from this supplier were uncoated and coated fiberglass mesh CAP60-20*10 or polymer coated fiberglass mesh CAP80-20*20. The technica properties of this glass are listed below.
The uncoated mesh was found to be more pliant and better able to follow irregularities in the base sheet.
Radiation Curable Material
The radiation curable material, resin or sealer is applied in layers which may be from 1 to 1000 μm thick, with 5 to 200 μm being more preferable and 10 to 120 μm being most preferred. The curable or polymerisable components used in forming the radiation curable materials and blends of the present invention include, but are not limited to, urethane, acrylic, epoxy and polyesters or compounds having multiple functional types such as polyester epoxies and urethane acrylics.
The curable or polymerisable components may be monomers, oligomers or polymers. The oligomers are prepared from a range of monomers with functionality including, but not limited to, isocyanate, hydroxyl, polyether, epoxy, carboxylic acid and ethylenic unsaturation. The monomers used in such a composite, include but are not limited to acrylate functionalized alcohols, diols and polyols, acrylate functional ethoxylated and/or propxylated alcohol, diols and polyols, and acrylate functional ethylene and propylene glycols and ethylene and propyelene polyglycols. Other monomers effective in preparing such composites include but are limited to derivatives of unsaturated carboxylic acids and diacids such as acrylate, methacryalte, maleate and fumarate esters, and vinylic functional materials such as vinyl ethers, and vinyl pyrolidones. Blends or mixtures of the polymerisable components as herein described may also be used.
It is particularly preferred to use polymerisable compounds based on including ethylenically unsaturated monomers.
It is preferable that the curable resin compositions used in the present invention have high solids content. Particularly, it is preferred that the curable resin has a solids content higher than 50%, more preferably higher than 70% and even more preferable if the resin forming compositions have a solids content of around 80-100%.
It is preferable to use a combination of lower molecular weight monomers and higher molecular weight oligomers in order to achieve the most desirable viscosity for application, the best cure behaviour once exposed to radiation, and the most desirable physical and mechanical properties once cured. Lower molecular weight monomers may be present in amounts ranging from 10-50% by weight, with 10-30%-being more preferable, and 15-25% being most preferred. Higher molecular weight oligomers may be present in amounts ranging from 10-50% by weight, with 15-40% being more preferable, and 20-35% being most preferred.
If inorganic filler is used, it may be present in amounts ranging from 5 to 80% by weight on the basis of the whole, whereas surface treatment additives are preferably used in amounts ranging from 0.01 to 2% by weight, with respect to the filler, and from 0.01 to 0.5% by weight, with respect to the whole of the composition.
The above mentioned polymerisable compounds can be used as such or in mixture with additives such as catalysts, photo initiators, mineral or organic fillers, anti-wetting agents, dyes, plasticizers, pigments, stabilizers, shockproofing agents, insulating agents, flame retarding agents and the like, which are added in order to improve the physical-chemical properties of the finished product.
Examples of radiation curable material/resin/sealer:
Different techniques can be used for the preparation of the composite sheets. For example, a radiation curable compound may be flood coated, roller or brush coated or spray coated onto fibre cement.
To cure a UV curable form of the resin at a film build of 40-50 gsm a UV-A dose of at least 0.15 J/cm2 is required for full cure and a UV-A intensity >1 W/cm2. At 60 m/minute this equates to 3 medium pressure mercury lamps running at a power input of 450 W/inch.
The preferred forms of resin/sealer are curable by V, infra-red, or near infra-red.
In one example of the invention formation process, a fibre cement board is coated with a radiation curable material and a glass fibre mesh is immediately placed on top, this can then be cured with a suitable radiation source such as UV.
In another example the fibre cement board is coated with a radiation curable material which is partially radiation cured with just enough dose to create a tacky surface. A glass fibre mesh is applied to the tacky surface and a subsequent layer of radiation curable material is applied over the glass fibre mesh, and fully cured with a suitable radiation source.
In another embodiment the radiation curable material is a pressure sensitive adhesive. Such pressure sensitive adhesives which are radiation curable are known but have not been used for the purpose described. Suitable formulations include:
While the methods and apparatus detailed herein are ideally suited to achieving simultaneous sealing and reinforcing of the substrate, it will be appreciated that in the broadest form sealing of the substrate need not be achieved. Accordingly, the invention in at least one aspect is intended to include all methods by which a reinforcing material is adhered to a rigid substrate using a radiation curable resin. For example, rather than applying a full sealing coating of the resin to the substrate, a pattern of resin may be applied sufficient only to bond the reinforcing material to the substrate. Alternatively, the resin may be applied to the reinforcing material by methods such as dipping, rolling or spraying, prior to the reinforcing material being brought into bonding contact with the board. Such methods may include the steps of applying multiple layers of resin, with or without intermediate partial cure or gel cure steps along the lines outlined herein.
The invention in one of its broadest forms provides a simple but effective method of providing a building element with enhanced strength characteristics achieved by adhering a reinforcing material to a rigid substrate using a radiation curable resin. The use of a radiation curable resin as the adhesive makes the manufacturing process easy to automate as a continuous process and is readily adapted for most substrates and particularly suited for use with the preferred substrate fibre reinforced cement.
Similar advantages are obtained with that form of the invention that uses a meltable and resettable polymer solely to adhere the reinforcing material to the rigid substrate.
The invention in its preferred forms provides a very simple cost and time effective means of both sealing and simultaneously reinforcing building materials so as to improve their water resistance and strength characteristics.
This can result on the one hand, in products of only slightly increased thickness having substantially improved strength characteristics, which increases their potential range of applications, in that the products are potentially less brittle, easier to handle and more durable in terms of improved weather resistance and impact resistance.
Alternatively, the invention can be used to provide products having at least equivalent or potentially better strength characteristics to existing products, but in a form that is lighter in weight and easier to transport and handle.
The invention has particular advantages when applied to the specific field of structural flooring for use in wet area flooring and external decking. In this regard, fibre cement materials are potentially suited to such applications in terms of their durability and resistance to rot but the brittle nature of fibre cement and its reduced load bearing capabilities when wet, does in many ways limit its applications. However, as can be seen from the example above, modification of these basic flooring substrates in accordance with the invention, dramatically improves the strength characteristics of these boards. This also facilitates extended use of fibre cement products in decking applications where there may be some current resistance due to the brittleness of the base product. By having an integral reinforcing material, the product will be less prone to brittle type failure, but where this does occur the reinforcing may act to retain the fragments of the substrate in a similar manner to laminated glass products.
As mentioned above the building element of the present invention is particularly suitable for structural flooring as it does not require a tile backerboard to adhere tires to the structural flooring. Similarly, the element is suitable for external decking due to the inventive synergistic combination of moisture resistance and increased structural integrity.
The invention also allows more conventional fibre cement products to be readily adapted for use in impact resistant walling applications such as is required in hospitals and schools.
Another advantage of the invention is that the applied reinforcing helps to resist edge break out when nailing the perimeter of a building sheet, or when the fastened sheet is exposed to shear or racking forcing when fastened to framing.
It should be mentioned, that while the invention was developed primarily for use with fibre cement substrate materials, it can clearly be seen that it will have useful application with a variety of other base materials including manufactured wood, plywood etc.
Similarly, while the invention has been described in relation to the preferred application to building sheets and building panels, the invention can be applied to non-planar building elements made from similar materials such as trim components and the like, the reinforcing elements serving to increase bending strength and thereby improve handle-ability etc.
Although the invention has been described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.
Number | Date | Country | Kind |
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2006901936 | Apr 2006 | AU | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/AU2007/000487 | 4/12/2007 | WO | 00 | 4/10/2009 |
Publishing Document | Publishing Date | Country | Kind |
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WO2007/115379 | 10/18/2007 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
369216 | Temple | Aug 1887 | A |
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1399023 | Murray | Dec 1921 | A |
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1630801 | Parsons | May 1927 | A |
1634809 | Weiss | Jul 1927 | A |
1698557 | O'Brien | Jan 1929 | A |
1819093 | Hardinge | Aug 1931 | A |
1856932 | Shaw | May 1932 | A |
1856936 | Turner | May 1932 | A |
1871843 | Ericson | Aug 1932 | A |
1914163 | Randall | Jun 1933 | A |
1930024 | Varden | Oct 1933 | A |
1943663 | Ericson | Jan 1934 | A |
1959519 | Black | May 1934 | A |
1976684 | Munroe et al. | Oct 1934 | A |
1976984 | Condon et al. | Oct 1934 | A |
1978519 | Willock et al. | Oct 1934 | A |
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1997939 | Loucks | Apr 1935 | A |
2009619 | Huffine | Jul 1935 | A |
2024689 | Walter et al. | Dec 1935 | A |
2030383 | Luth et al. | Feb 1936 | A |
2054854 | Dreyfus | Sep 1936 | A |
2062149 | Stark et al. | Nov 1936 | A |
2156308 | Schuh | May 1939 | A |
2156311 | Schuh | May 1939 | A |
2175568 | Haustein | Oct 1939 | A |
2175569 | Kennedy | Oct 1939 | A |
2176668 | Egeberg et al. | Oct 1939 | A |
2182372 | Cox et al. | Dec 1939 | A |
2224351 | Kaye | Dec 1940 | A |
2253753 | Black | Aug 1941 | A |
2276170 | Elmendorf | Mar 1942 | A |
2317634 | Olsen | Apr 1943 | A |
2320702 | Marchese et al. | Jun 1943 | A |
2323230 | McAvoy | Jun 1943 | A |
2324325 | Schuh | Jul 1943 | A |
2354639 | Seymour | Jul 1944 | A |
2377484 | Elmendorf | Jun 1945 | A |
2400357 | Krajci | May 1946 | A |
2413794 | Small | Jan 1947 | A |
2447275 | Price | Aug 1948 | A |
2511083 | Small | Jun 1950 | A |
2517122 | Lockwood | Aug 1950 | A |
2518281 | Camp et al. | Aug 1950 | A |
2619776 | Potters | Dec 1952 | A |
2624298 | Farren | Jan 1953 | A |
2645576 | Bate et al. | Jul 1953 | A |
2676892 | McLaughlin | Apr 1954 | A |
2694025 | Slayter et al. | Nov 1954 | A |
2724872 | Herbes | Nov 1955 | A |
2746735 | Bradford | May 1956 | A |
2762619 | Booth | Sep 1956 | A |
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2797201 | Veatch | Jun 1957 | A |
2838881 | Plumat | Jun 1958 | A |
2879171 | Kullenberg | Mar 1959 | A |
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2928143 | Newton | Mar 1960 | A |
2945326 | Wood | Jul 1960 | A |
2947115 | Wood | Aug 1960 | A |
2978339 | Veatch et al. | Apr 1961 | A |
2978340 | Veatch et al. | Apr 1961 | A |
2987408 | Minnick | Jun 1961 | A |
2997403 | Searight | Aug 1961 | A |
3010177 | Thompson et al. | Nov 1961 | A |
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3047985 | Murphy | Aug 1962 | A |
3081179 | Charvat et al. | Mar 1963 | A |
3106503 | Randall et al. | Oct 1963 | A |
3150947 | Bland | Sep 1964 | A |
3173229 | Weber | Mar 1965 | A |
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3215505 | Schmalfeld et al. | Nov 1965 | A |
3235039 | O'Donnell | Feb 1966 | A |
3236932 | Grigas et al. | Feb 1966 | A |
3256105 | Alford | Jun 1966 | A |
3264125 | Bourlin | Aug 1966 | A |
3274743 | Blum, Jr. | Sep 1966 | A |
3279905 | Wood et al. | Oct 1966 | A |
3284980 | Dinkel | Nov 1966 | A |
3293014 | Callender et al. | Dec 1966 | A |
3297411 | Dear | Jan 1967 | A |
3321414 | Vieli | May 1967 | A |
3333379 | Harris | Aug 1967 | A |
3336710 | Raynes | Aug 1967 | A |
3341314 | Vukasovich et al. | Sep 1967 | A |
3348956 | Ekdahl | Oct 1967 | A |
3360392 | Mod et al. | Dec 1967 | A |
3365315 | Beck et al. | Jan 1968 | A |
3408786 | Snyker | Nov 1968 | A |
3415019 | Andersen | Dec 1968 | A |
3416275 | Van Loghem et al. | Dec 1968 | A |
3421281 | Harris | Jan 1969 | A |
3481093 | Davidson | Dec 1969 | A |
3495961 | Lange | Feb 1970 | A |
3501324 | Kubo | Mar 1970 | A |
3527004 | Sorenson | Sep 1970 | A |
3560185 | Nylander | Feb 1971 | A |
3560186 | Nylander | Feb 1971 | A |
3574113 | Shannon | Apr 1971 | A |
3582377 | Hays et al. | Jun 1971 | A |
3606720 | Cookson | Sep 1971 | A |
3616173 | Green et al. | Oct 1971 | A |
3625808 | Martin | Dec 1971 | A |
3634567 | Yang | Jan 1972 | A |
3635742 | Fujimasu et al. | Jan 1972 | A |
3660955 | Simon et al. | May 1972 | A |
3663341 | Veneziale, Jr. | May 1972 | A |
3663353 | Long et al. | May 1972 | A |
3679446 | Kubo | Jul 1972 | A |
3703795 | Mattes | Nov 1972 | A |
3708943 | Thomas et al. | Jan 1973 | A |
3716386 | Kempster | Feb 1973 | A |
3729368 | Ingham et al. | Apr 1973 | A |
3736162 | Chvalovsky et al. | May 1973 | A |
3748100 | Forseth | Jul 1973 | A |
3748160 | Carbajal | Jul 1973 | A |
3752685 | Honda et al. | Aug 1973 | A |
3753749 | Nutt | Aug 1973 | A |
3754365 | Carrick et al. | Aug 1973 | A |
3780483 | Mattes | Dec 1973 | A |
3782985 | Gebhardt | Jan 1974 | A |
3797179 | Jackson | Mar 1974 | A |
3797190 | Widdowson | Mar 1974 | A |
3804058 | Messenger | Apr 1974 | A |
3818668 | Charniga | Jun 1974 | A |
3835604 | Hoffmann, Jr. | Sep 1974 | A |
3836412 | Boustany et al. | Sep 1974 | A |
3838998 | Matthews et al. | Oct 1974 | A |
3843380 | Beyn | Oct 1974 | A |
3847633 | Race | Nov 1974 | A |
3865779 | Oya et al. | Feb 1975 | A |
3866378 | Kessler | Feb 1975 | A |
3869295 | Bowles et al. | Mar 1975 | A |
3873025 | Qvarnstrom et al. | Mar 1975 | A |
3873475 | Pechacek et al. | Mar 1975 | A |
3877918 | Cerbo | Apr 1975 | A |
3887386 | Majumdar et al. | Jun 1975 | A |
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3888957 | Netting | Jun 1975 | A |
3902911 | Messenger | Sep 1975 | A |
3904377 | Honda et al. | Sep 1975 | A |
3904424 | Aoki et al. | Sep 1975 | A |
3909283 | Warnke | Sep 1975 | A |
3918981 | Long | Nov 1975 | A |
3921346 | Sauer et al. | Nov 1975 | A |
3924901 | Phillips | Dec 1975 | A |
3928701 | Roehner | Dec 1975 | A |
3931069 | Lundin | Jan 1976 | A |
3932275 | Mewes et al. | Jan 1976 | A |
3935364 | Proksch et al. | Jan 1976 | A |
3954390 | Akhundov et al. | May 1976 | A |
3965633 | Carroll | Jun 1976 | A |
3969567 | Occleshaw et al. | Jul 1976 | A |
3974024 | Yano et al. | Aug 1976 | A |
3986312 | Calhoun et al. | Oct 1976 | A |
3992845 | Grzesiek et al. | Nov 1976 | A |
3998651 | Baudouin et al. | Dec 1976 | A |
3998944 | Long | Dec 1976 | A |
4002482 | Coenen et al. | Jan 1977 | A |
4003752 | Isohata et al. | Jan 1977 | A |
4009135 | Harreus et al. | Feb 1977 | A |
4010587 | Larsen | Mar 1977 | A |
4010589 | Gross et al. | Mar 1977 | A |
4013480 | Chumbley et al. | Mar 1977 | A |
4015392 | Eaton | Apr 1977 | A |
4028859 | Bellagamba et al. | Jun 1977 | A |
4034528 | Sanders et al. | Jul 1977 | A |
4040851 | Ziegler | Aug 1977 | A |
4046548 | Wood et al. | Sep 1977 | A |
4047355 | Knorr | Sep 1977 | A |
4052220 | Turpin, Jr. | Oct 1977 | A |
4052829 | Chapman | Oct 1977 | A |
4057908 | Mirliss et al. | Nov 1977 | A |
4058944 | Rieger | Nov 1977 | A |
4059423 | De Vos et al. | Nov 1977 | A |
4063393 | Toti | Dec 1977 | A |
4065899 | Kirkhuff | Jan 1978 | A |
4066723 | King et al. | Jan 1978 | A |
4070199 | Downing et al. | Jan 1978 | A |
4070843 | Leggiere et al. | Jan 1978 | A |
4076884 | Riley et al. | Feb 1978 | A |
4079562 | Englert et al. | Mar 1978 | A |
4088804 | Cornwell et al. | May 1978 | A |
4098701 | Burrill et al. | Jul 1978 | A |
4101335 | Barrable et al. | Jul 1978 | A |
4102106 | Golder et al. | Jul 1978 | A |
4102697 | Fukuba et al. | Jul 1978 | A |
4102773 | Green et al. | Jul 1978 | A |
4104103 | Tarullo | Aug 1978 | A |
4104840 | Heintz et al. | Aug 1978 | A |
4110507 | Colledge | Aug 1978 | A |
4111713 | Beck | Sep 1978 | A |
4112647 | Scheid | Sep 1978 | A |
4118236 | Erskine et al. | Oct 1978 | A |
4128696 | Goebel et al. | Dec 1978 | A |
4131480 | McCurrich et al. | Dec 1978 | A |
4131638 | Whitaker et al. | Dec 1978 | A |
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4133928 | Riley et al. | Jan 1979 | A |
4134773 | Simeonov et al. | Jan 1979 | A |
4138313 | Hillstrom et al. | Feb 1979 | A |
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4153439 | Tomic et al. | May 1979 | A |
4161389 | Staffin et al. | Jul 1979 | A |
4162924 | Kubo et al. | Jul 1979 | A |
4166749 | Sterrett et al. | Sep 1979 | A |
4177176 | Burrill et al. | Dec 1979 | A |
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4203788 | Clear | May 1980 | A |
4204644 | Kozuka et al. | May 1980 | A |
4205992 | Mogensen et al. | Jun 1980 | A |
4211525 | Vetter et al. | Jul 1980 | A |
4217335 | Sasaki et al. | Aug 1980 | A |
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4225383 | McReynolds | Sep 1980 | A |
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4234344 | Tinsley et al. | Nov 1980 | A |
4235753 | Brown et al. | Nov 1980 | A |
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4240840 | Downing et al. | Dec 1980 | A |
4243421 | Kume et al. | Jan 1981 | A |
4250134 | Minnick | Feb 1981 | A |
4252193 | Powers et al. | Feb 1981 | A |
4256504 | Dunstan, Jr. | Mar 1981 | A |
4256584 | Lord et al. | Mar 1981 | A |
4258090 | Moraru | Mar 1981 | A |
4261286 | Kupfer et al. | Apr 1981 | A |
4261754 | Krenchel et al. | Apr 1981 | A |
4265674 | Debus et al. | May 1981 | A |
4268316 | Wills, Jr. | May 1981 | A |
4268317 | Rayl | May 1981 | A |
4274239 | Carroll | Jun 1981 | A |
4274913 | Kikuiri et al. | Jun 1981 | A |
4292206 | Barnes, Jr. et al. | Sep 1981 | A |
4292364 | Wesch et al. | Sep 1981 | A |
4295907 | Cordts et al. | Oct 1981 | A |
4298413 | Teare | Nov 1981 | A |
4298647 | Cancio et al. | Nov 1981 | A |
4303732 | Torobin | Dec 1981 | A |
4304604 | Daerr et al. | Dec 1981 | A |
4305758 | Powers et al. | Dec 1981 | A |
4306911 | Gordon et al. | Dec 1981 | A |
4307142 | Blitstein et al. | Dec 1981 | A |
4307551 | Crandell | Dec 1981 | A |
4321780 | Hooper et al. | Mar 1982 | A |
4327528 | Fritz | May 1982 | A |
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4330634 | Rodaway | May 1982 | A |
4332618 | Ballard | Jun 1982 | A |
4336338 | Downs et al. | Jun 1982 | A |
4337290 | Kelly et al. | Jun 1982 | A |
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4339489 | Barker et al. | Jul 1982 | A |
4340407 | Anderson et al. | Jul 1982 | A |
4343127 | Greve et al. | Aug 1982 | A |
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4347155 | Jenkins | Aug 1982 | A |
4350567 | Moorehead et al. | Sep 1982 | A |
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4361616 | Bomers et al. | Nov 1982 | A |
4362566 | Hinterwaldner et al. | Dec 1982 | A |
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4370166 | Powers et al. | Jan 1983 | A |
4373955 | Bouchard et al. | Feb 1983 | A |
4373957 | Pedersen et al. | Feb 1983 | A |
4374672 | Funston et al. | Feb 1983 | A |
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4379553 | Kelly | Apr 1983 | A |
4379729 | Cross et al. | Apr 1983 | A |
4380564 | Cancio et al. | Apr 1983 | A |
4383960 | Delcoigne et al. | May 1983 | A |
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4394175 | Cheriton et al. | Jul 1983 | A |
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4465729 | Cancio et al. | Aug 1984 | A |
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4487620 | Neusy et al. | Dec 1984 | A |
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4498913 | Tank et al. | Feb 1985 | A |
4501830 | Miller et al. | Feb 1985 | A |
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4504320 | Rizer et al. | Mar 1985 | A |
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4506486 | Culpepper, Jr. et al. | Mar 1985 | A |
4507154 | Burge et al. | Mar 1985 | A |
4510020 | Green et al. | Apr 1985 | A |
4512736 | Wader et al. | Apr 1985 | A |
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4517375 | Schmidt et al. | May 1985 | A |
4519777 | Akhtyamov et al. | May 1985 | A |
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4538530 | Whitman | Sep 1985 | A |
4540629 | Sands et al. | Sep 1985 | A |
4543159 | Johnson et al. | Sep 1985 | A |
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4590884 | Kreeger et al. | May 1986 | A |
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4621024 | Wright | Nov 1986 | A |
4623390 | Delmonico | Nov 1986 | A |
4624798 | Gindrup et al. | Nov 1986 | A |
4626398 | Vetter et al. | Dec 1986 | A |
4629413 | Michelson et al. | Dec 1986 | A |
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4640715 | Heitzmann et al. | Feb 1987 | A |
4641469 | Wood | Feb 1987 | A |
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4643920 | McEntee et al. | Feb 1987 | A |
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4647505 | Blackie et al. | Mar 1987 | A |
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4652535 | Mackenzie et al. | Mar 1987 | A |
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4659386 | Nagai et al. | Apr 1987 | A |
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4737191 | Meynardi et al. | Apr 1988 | A |
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227376 | Oct 1982 | AR |
228671 | Mar 1983 | AR |
291.988 | Jan 1984 | AR |
240667 | Aug 1990 | AR |
250022 | Jul 1996 | AR |
015457 | Sep 1998 | AR |
014046 | Nov 1998 | AR |
014702 | Mar 1999 | AR |
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4494885 | Jan 1986 | AU |
0552930 | Jun 1986 | AU |
5592986 | Oct 1986 | AU |
94035 | Nov 1986 | AU |
95878 | Mar 1987 | AU |
98800 | Dec 1987 | AU |
99683 | Feb 1988 | AU |
572111 | May 1988 | AU |
102662 | Jan 1989 | AU |
606344 | Jan 1989 | AU |
103840 | May 1989 | AU |
104552 | Aug 1989 | AU |
108078 | Jul 1990 | AU |
616088 | Jul 1990 | AU |
198946878 | Jul 1990 | AU |
110320 | Feb 1991 | AU |
199176201 | Jun 1992 | AU |
1306792 | Sep 1992 | AU |
199215903 | Apr 1993 | AU |
117138 | May 1993 | AU |
118448 | Oct 1993 | AU |
118862 | Nov 1993 | AU |
643726 | Nov 1993 | AU |
199340398 | Nov 1993 | AU |
686135 | Nov 1994 | AU |
677649 | Dec 1994 | AU |
122634 | Feb 1995 | AU |
123141 | Apr 1995 | AU |
123142 | Apr 1995 | AU |
659400 | May 1995 | AU |
681049 | Sep 1996 | AU |
702630 | Nov 1996 | AU |
130941 | Aug 1997 | AU |
132812 | Feb 1998 | AU |
732998 | May 1998 | AU |
6292698 | Aug 1998 | AU |
135097 | Sep 1998 | AU |
199869111 | Oct 1998 | AU |
135557 | Nov 1998 | AU |
199879922 | Feb 1999 | AU |
734095 | Mar 1999 | AU |
137291 | May 1999 | AU |
9768198 | May 1999 | AU |
199886116 | May 1999 | AU |
137791 | Jul 1999 | AU |
9926061 | Sep 1999 | AU |
714529 | Jan 2000 | AU |
9952711 | Mar 2000 | AU |
1137300-1137300 | May 2000 | AU |
140607 | May 2000 | AU |
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200078752 | May 2001 | AU |
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200111200 | May 2001 | AU |
746655 | Jun 2001 | AU |
783430 | Jun 2001 | AU |
200072012 | Jun 2001 | AU |
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735352 | Jul 2001 | AU |
3768301 | Sep 2001 | AU |
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200053659 | Mar 2002 | AU |
147568 | Apr 2002 | AU |
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148485 | Jul 2002 | AU |
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152915 | Aug 2003 | AU |
153491 | Oct 2003 | AU |
153493 | Oct 2003 | AU |
153494 | Oct 2003 | AU |
153495 | Oct 2003 | AU |
153496 | Oct 2003 | AU |
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730345 | Mar 1966 | CA |
1040859 | Oct 1978 | CA |
1080601 | Jul 1980 | CA |
1084230 | Aug 1980 | CA |
1177205 | Nov 1984 | CA |
2242749 | Feb 1999 | CA |
2313456 | Jun 1999 | CA |
2405354 | Nov 2001 | CA |
368918 | Apr 1963 | CH |
606674 | Nov 1978 | CH |
678882 | Nov 1991 | CH |
684285 | Aug 1994 | CH |
32972 | Feb 1980 | CL |
2346-01 | Sep 2001 | CL |
2347-01 | Sep 2001 | CL |
2352-01 | Sep 2001 | CL |
2353-01 | Sep 2001 | CL |
461-02 | Mar 2002 | CL |
693-2004 | Jan 2005 | CL |
1032332 | Apr 1989 | CN |
1052519 | Jun 1991 | CN |
2149444 | Dec 1993 | CN |
1081168 | Jan 1994 | CN |
1087885 | Jun 1994 | CN |
2170342 | Jun 1994 | CN |
1099089 | Feb 1995 | CN |
1160070 | Sep 1997 | CN |
1178202 | Apr 1998 | CN |
2281378 | May 1998 | CN |
1199116 | Nov 1998 | CN |
1224701 | Aug 1999 | CN |
1251358 | Apr 2000 | CN |
1061328 | Jan 2001 | CN |
2435455 | Jun 2001 | CN |
1394167 | Jan 2003 | CN |
1500038 | May 2004 | CN |
222361 | Jun 1983 | CS |
283459 | Apr 1998 | CZ |
1952082 | Dec 1966 | DE |
2421380 | Jan 1975 | DE |
2344773 | Mar 1975 | DE |
2460879 | Jun 1976 | DE |
2460880 | Jun 1976 | DE |
2610998 | Sep 1977 | DE |
143936 | Sep 1980 | DE |
3037220 | Apr 1982 | DE |
3046405 | Sep 1982 | DE |
3213521 | Jun 1983 | DE |
3210326 | Sep 1983 | DE |
3232106 | Mar 1984 | DE |
3308917 | Sep 1984 | DE |
3314796 | Oct 1984 | DE |
3324671 | Jan 1985 | DE |
3505335 | Aug 1986 | DE |
3601736 | Jul 1987 | DE |
3711549 | Oct 1987 | DE |
3621010 | Jan 1988 | DE |
3743467 | Jul 1989 | DE |
3932176 | Jun 1990 | DE |
3908172 | Sep 1990 | DE |
3923800 | Jan 1991 | DE |
4004103 | Aug 1991 | DE |
4104919 | Aug 1992 | DE |
4229572 | Mar 1993 | DE |
4209834 | Sep 1993 | DE |
4228338 | Oct 1993 | DE |
9403018 | May 1994 | DE |
4316666 | Dec 1994 | DE |
4410020 | Sep 1995 | DE |
19607081 | Aug 1997 | DE |
19654836 | Jun 1998 | DE |
19858342 | Feb 2000 | DE |
20006112 | Jul 2000 | DE |
19549535 | Jan 2001 | DE |
19962137 | Jun 2001 | DE |
20105063 | Aug 2001 | DE |
10044641 | Mar 2002 | DE |
10106888 | Sep 2002 | DE |
0007585 | Feb 1980 | EP |
0012546 | Jun 1980 | EP |
0021362 | Jan 1981 | EP |
0033133 | Aug 1981 | EP |
0036275 | Sep 1981 | EP |
0049365 | Apr 1982 | EP |
0055504 | Jul 1982 | EP |
0056263 | Jul 1982 | EP |
0069095 | Jan 1983 | EP |
0084951 | Aug 1983 | EP |
0102092 | Mar 1984 | EP |
0103097 | Mar 1984 | EP |
0104540 | Apr 1984 | EP |
0127960 | Dec 1984 | EP |
0136790 | Apr 1985 | EP |
0147429 | Jul 1985 | EP |
0159046 | Oct 1985 | EP |
0159173 | Oct 1985 | EP |
0173553 | Mar 1986 | EP |
0184477 | Jun 1986 | EP |
0188471 | Jul 1986 | EP |
0220073 | Apr 1987 | EP |
0222339 | May 1987 | EP |
0242872 | Oct 1987 | EP |
0247817 | Dec 1987 | EP |
0263723 | Apr 1988 | EP |
0287962 | Oct 1988 | EP |
0297186 | Jan 1989 | EP |
0305209 | Mar 1989 | EP |
0314242 | May 1989 | EP |
0327351 | Aug 1989 | EP |
0328431 | Aug 1989 | EP |
0347092 | Dec 1989 | EP |
0359362 | Mar 1990 | EP |
0376334 | Jul 1990 | EP |
0419657 | Apr 1991 | EP |
0428431 | May 1991 | EP |
0430667 | Jun 1991 | EP |
0430995 | Jun 1991 | EP |
0482810 | Apr 1992 | EP |
0484283 | May 1992 | EP |
0558239 | Sep 1993 | EP |
0564447 | Oct 1993 | EP |
0593779 | Apr 1994 | EP |
0601594 | Jun 1994 | EP |
0619227 | Oct 1994 | EP |
0619277 | Oct 1994 | EP |
0625618 | Nov 1994 | EP |
0678488 | Oct 1995 | EP |
0683282 | Nov 1995 | EP |
0708213 | Apr 1996 | EP |
0717675 | Jun 1996 | EP |
0725044 | Aug 1996 | EP |
0754663 | Jan 1997 | EP |
0801037 | Oct 1997 | EP |
0803484 | Oct 1997 | EP |
0846666 | Jun 1998 | EP |
0846668 | Jun 1998 | EP |
0891954 | Jan 1999 | EP |
0931778 | Jul 1999 | EP |
0999232 | May 2000 | EP |
1052262 | Nov 2000 | EP |
1088800 | Apr 2001 | EP |
1094165 | Apr 2001 | EP |
1106236 | Jun 2001 | EP |
1144129 | Oct 2001 | EP |
1155794 | Nov 2001 | EP |
1156021 | Nov 2001 | EP |
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990242 | Sep 1951 | FR |
1557348 | Feb 1969 | FR |
2248246 | May 1975 | FR |
2405908 | May 1979 | FR |
2451428 | Oct 1980 | FR |
2451428 | Nov 1980 | FR |
2512440 | Mar 1983 | FR |
2540160 | Aug 1984 | FR |
2562591 | Oct 1985 | FR |
2611432 | Sep 1988 | FR |
2624870 | Jun 1989 | FR |
2628775 | Sep 1989 | FR |
2671072 | Jul 1992 | FR |
2702790 | Sep 1994 | FR |
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119182 | Sep 1918 | GB |
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558584 | Jan 1944 | GB |
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1515521 | Jun 1978 | GB |
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1543460 | Apr 1979 | GB |
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Number | Date | Country | |
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20090272058 A1 | Nov 2009 | US |