This application is a national phase application based on PCT/EP2005/006260, filed Jun. 10, 2005, the content of which is incorporated herein by reference.
1. Field of the Invention
The present invention relates to a method for making a sound-insulating load-bearing floor.
In particular, the present invention relates to a method for making a sound-insulating load-bearing floor, said method comprising the step of applying onto said load-bearing floor a sound-insulating material including at least one rubber in a subdivided form and at least one binding agent.
In a further aspect, the present invention also relates to a sound-insulating material including at least one rubber in a subdivided form and at least one binding agent.
In a still further aspect, the present invention also relates to a building structure including at least one load-bearing floor, said load-bearing floor comprising a sound-insulating material including at least one rubber in a subdivided form and at least one binding agent.
2. Description of the Related Art
In building constructions, in particular in building constructions including two or more stories, it is known to include a sound-insulating material on the load-bearing floor of the upper floors. The sound-insulating material minimizes the pressure of sound generated into a room and traveling downward through the load-bearing floor. Sound-insulating material functions by reflecting sound waves, absorbing sound waves, and/or disrupting sound waves.
Conventional sound-insulating materials comprise pre-formed sheets of cork, asphalt, or other materials such as, for example, foamed polyethylene or foamed polyurethane.
However, said sound insulating materials may show some disadvantages.
For example, the asphalt typically comprises about 80% by weight of tar, the remainder including clay, solvents, and other fillers. One disadvantage of the asphalt is that upon aging, it tends to harden. It also hardens in cold weather. When asphalt hardens, it tends to crack if the floor expands or contracts (e.g. as a consequence of temperatures changes). Similarly, since cork comprises a matrix of particles pressed together, the cork also tends to develop cracks if the floor expands or contracts (e.g. as a consequence of temperatures changes).
Other sound-insulating materials have been already suggested in the art.
For example, International. Patent Application WO 02/48478 relates to a light soundproof floor-filling structure for filling the space between a floor surface and the level of the laying plane of the walking-on floor covering. Said soundproof floor-filling structure consists of a mixture of concrete as air-hardening binder and a given amount of grains of resin materials which may be selected from polyvinyl resins, polyethylene, polypropylene, polyvinylchloride, caoutchouc, rubbers in general, polycarbons, silicon resins, plastics of different kinds. Metal elements such as copper and tin may be present as either pure metal or alloys. The abovementioned structure is said to have the following features: lightness, soundproofing, compactness, workability, mechanical strength and environmental compatibility.
International Patent Application WO 00/26485 relates to an acoustic insulating material with a filler which is mainly made of granules of a sound-deadening component, mixed with a binding agent, such that an almost coherent mass is formed. Said filler mainly contains rubber granules. Said binding agent is made on the basis of polyurethane and preferably consists of a polyurethane glue. A sound-insulating sprung floor provided with the abovementioned insulating material and resting on a load-bearing floor, and a method for making such a floor, are also disclosed.
French Patent Application FR 2,221,465 relates to a material made from waste rubber particles, in particular waste rubber particles derived from tyres, and a synthetic elastomeric binding agent, preferably a moisture-hardening isocyanate or polyisocyanate or a two-component polyurethane. Said binding agent is of cellular structure and fills only partly the spaces between the rubber particles. The abovementioned material is said to be suitable as a floor underlay.
International Patent Application WO 00/50707 relates to a solid paste which can be applied with a trowel to form regularly spaced striae, comprising an adhesive-type elastomeric resin forming 50%-70% of the volume of the paste, 30-90 mesh rubber-granules forming 30%-50% of the volume of the paste, all of which is mixed with air to produce a foam. The adhesive is water-based. The rubber granules come from recycled tyres which are shredded into granules and ground. A method of application of said solid paste is also disclosed, said method comprising the following steps: take a container with the adhesive-type elastomeric resin superposed on rubber granules in a suspension in the air, insert a mechanical mixer and agitate for two to five minutes in order to form a homogeneous emulsion containing air, rubber and resin, apply the product to a hard surface using an adhesive comb in order to form said striae and wedge tiles on top of the striae. The abovementioned solid paste is said to have sound-insulating properties.
According to the Applicant, the sound-insulating materials as described above may have some disadvantages.
For example, when concrete is used as an air-hardening binder, the sound-insulating materials has low sound-insulating properties because of the stiffness of the concrete. On the other hand, the use of isocyanates or polyisocyanates as binding agents has to be avoided because of the toxicity of said substances which leads to risks for both the environment and the health of the operators. Moreover, in the case of fire, isocyanates, polyisocyanates or polyurethanes, may release cyanidric acid. Finally, when a water-based adhesive-type elastomeric resin is used, problems related to its stability may arise. The elastomeric resin may coagulate so forming a non-homogeneous adhesive mixture: the presence of coagulums may negatively affect the sound-insulating properties of said adhesive mixture.
The Applicant has now found that it is possible to make a sound-insulating load-bearing floor by applying onto said load-bearing floor a sound-insulating material including at least one rubber in a subdivided form and at least one binding agent, said binding agent comprising at least one water-dispersible polymer. Said sound-insulating material has good sound-insulating properties. Furthermore, said sound-insulating material maintains its sound-insulating properties upon aging. Moreover, said sound-insulating material has a reduced dynamic stiffness, in particular, a dynamic stiffness, measured according to standard ISO 9052-1:1989, lower than 150 MN/m3. Said sound-insulating material also shows vibration damping properties. Furthermore, said sound-insulating material shows a good compression resistance after drying. Additionally, the binding agent used in said sound-insulating material does not contain harmful substances and does not release harmful substances in the case of fire.
According to a first aspect, the present invention relates to a method for making a sound-insulating load-bearing floor, said method comprising the following steps:
Said glass transition temperature may be measured according to known techniques such as, for example, by Differential Scanning Calorimetry (DSC): further details regarding the DSC analysis will be described in the examples given hereinbelow.
According to one preferred embodiment, said step of applying a sound-insulating material, further comprises the step of making pre-formed sheets of said sound insulating material.
According to one preferred embodiment, said sound-insulating material is applied directly in contact with said load-bearing floor. Alternatively, at least one intermediate layer is interposed between the load-bearing floor and the sound-insulating material.
According to a further preferred embodiment, said method further comprises the step of applying a covering floor onto said load-bearing floor. Preferably, said covering floor is applied onto said sound-insulating material.
According to a further preferred embodiment, said sound-insulating material is applied onto said covering floor.
According to a further preferred embodiment, said method further comprises the step of applying a protective foil onto said sound-insulating material. Preferably, said step is carried out before the application of said covering floor onto said sound-insulating material. Said protective foil may be selected, for example, from: polyethylene sheets, paper sheets, nylon sheets, woven-nonwoven sheets.
According to a further aspect, the present invention also relates to a sound-insulating material including:
According to a further aspect, the present invention also relates to a building structure including at least one load-bearing floor, said load-bearing floor comprising a sound-insulating material including:
According to one preferred embodiment, said sound insulating material has, in a dry form, a dynamic stiffness measured according to standard ISO 9052-1:1989, lower than 150 MN/m3, preferably lower than 100 MN/m3, more preferably of from 10 MN/m3 to 80 MN/m3.
According to a further preferred embodiment, said sound-insulating material has, in a dry form, a noise index (L), which is a measure of its sound-insulating properties, measured according to standard ISO 140-8:1997, on a sample of said sound-insulating material having a 10 mm thickness, not higher than 65 dB, preferably not higher than 63 dB.
According to one preferred embodiment, said sound-insulating material form a substantially continuous coating layer having a thickness of from 5 mm to 50 mm, preferably of from 7 mm to 30 mm.
For the purpose of the present description and of the claims which follow, except where otherwise indicated, all numbers expressing amounts, quantities, percentages, and so forth, are to be understood as being modified in all instances by the term “about”. Also, all ranges include any combination of the maximum and minimum points disclosed and include any intermediate ranges therein, which may or may not be specifically enumerated herein.
Said sound-insulating material may be made according to different processes.
According to one preferred embodiment, the process for making a sound-insulating material is carried out by mixing, at a temperature of from −20° C. to +60° C., preferably of from +5° C. to +40° C., for a time of from 10 seconds to 4 hours, preferably of from 60 seconds to 30 minutes, said at least one rubber in a subdivided form with said binding agent, obtaining a homogeneous sound-insulating material. The obtained homogeneous sound-insulating material may be collected in hermetic buckets or tanks and stored for further use.
In the case in which the obtained homogeneous sound-insulating material is not stored, preferably, in order to avoid its pre-drying, the above reported mixing step is carried out not more than 48 hours, preferably from 5 minutes to 24 hours, before the step of applying said sound-insulating material.
Said mixing step may be carried out manually for example in a bucket, or in different mixing devices such as, for example, concrete mixer, cement mixer, concrete pump, cement pump, plaster sprayer.
The step of applying a sound-insulating material may be carried according to different ways.
According to one preferred embodiment, the step of applying a sound-insulating material is carried out by spreading (for example, by means of a trowel) said sound-insulating material onto said load-bearing floor.
According to a further preferred embodiment, the step of applying a sound-insulating material is carried out by spraying said sound-insulating material onto said load-bearing floor.
According to a further preferred embodiment, said sound-insulating material is made and applied “in situ” by:
According to one preferred embodiment, said continuous coating layer has a drying time, at 23° C., of from 10 minutes to 72 hours, preferably of from 30 minutes to 24 hours.
According to a further preferred embodiment, as reported above, said sound-insulating material may be previously shaped as pre-formed sheets which will be subsequently applied onto said load-bearing floor. Said pre-formed sheets may be obtained by means of different processes. For example, said pre-formed sheets may be obtained by means of a process comprising:
In order to obtain a substantially continuous coating layer of a sound-insulating material, after having applied said pre-formed sheets onto said load-bearing floor, the gaps optionally present between adjacent pre-formed sheets may be filled with suitable materials, e.g. with a binding agent or with a sound-insulating material, preferably the same used to make the pre-formed sheets according to the present invention.
According to one preferred embodiment, the rubber in a subdivided form which may be used in the present invention, is in the form of powder or granules having a particle size in the range of from 0.1 mm to 15 mm, preferably of from 1.0 mm to 10 mm.
According to one preferred embodiment, the rubber in a subdivided form may be selected, for example, from diene elastomeric polymers or copolymers which may be of natural origin or may be obtained by solution polymerization, emulsion polymerization or gas-phase polymerization of one or more conjugated diolefins, optionally blended with at least one comonomer selected from monovinylarenes and/or polar comonomers in an amount of not more than 60% by weight.
Preferably, the diene elastomeric polymers or copolymers may be selected, for example, from: cis-1,4-polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene, polybutadiene (in particular polybutadiene with a high 1,4-cis content), optionally halogenated isoprene/isobutene copolymers, 1,3-butadiene/acrylonitrile copolymers, styrene/1,3-butadiene copolymers, styrene/isoprene/1,3-butadiene copolymers, styrene/1,3-butadiene/acrylonitrile copolymers, or mixtures thereof.
Alternatively, the rubber in a subdivided form may be selected from elastomeric polymers of one or more monoolefins with olefinic comonomers or derivatives thereof. Preferably, said elastomeric polymers may be selected, for example, from: ethylene/propylene copolymers (EPR) or ethylene/propylene/diene copolymers (EPDM); polyisobutene; butyl rubbers; halobutyl rubbers, in particular chlorobutyl or bromobutyl rubbers; or mixtures thereof.
Preferably, said rubber in a subdivided form may be obtained from a waste rubber derived from the rubber manufacturing processes. More preferably, said rubber in a subdivided form is a vulcanized rubber which may be obtained by grinding or otherwise comminuting any source of vulcanized rubber compound such as, for example, tyres, roofing membranes, hoses, gaskets, and the like, and is preferably obtained from reclaimed or scrap tyres using any conventional method. For example, the vulcanized rubber in a subdivided form may be obtained by mechanical grinding at ambient temperature or in the presence of a cryogenic coolant (i.e. liquid nitrogen). Said vulcanized rubber in a subdivided form may comprise at least one crosslinked diene elastomeric polymer or copolymer, said diene elastomeric polymer or copolymer being selected from those above reported; or at least one crosslinked elastomeric polymer of one or more monoolefins with an olefinic comonomer or derivatives thereof, said elastomeric polymer being selected from those above reported; or mixtures thereof.
According to one preferred embodiment, said water-dispersible polymer is used in the form of an aqueous dispersion. Preferably, said aqueous dispersion comprises from 30% by weight to 90% by weight, preferably from 40% by weight to 70% by weight, with respect to the total weight of the aqueous dispersion, of at least one water-dispersible polymer.
According to a further preferred embodiment, said aqueous dispersion has a Brookfield viscosity, measured at 23° C. and at 250 rpm, of from 0.2 Pa·s to 60 Pa·s, preferably of from 0.5 Pa·s to 30 Pa·s.
Said Brookfield viscosity is measured using a viscosimeter of Brookfield type, model DV3, equipped with a RV6 spindle.
According to a further preferred embodiment, said aqueous dispersion has a minimum film-forming temperature lower than or equal to 10° C., preferably of from −10° C. to +5° C.
Said minimum film-forming temperature is measured according to standard ISO 2115:1996.
According to one preferred embodiment, said water-dispersible polymer may be selected from polymers having a main hydrocarbon chain to which hydrophilic groups are linked.
In the present description and in the claims which follow, by the expression “polymers having a main hydrocarbon chain to which hydrophilic groups are linked” it is meant a polymer wherein hydrophilic groups, either directly or through side groups, are linked to the main hydrocarbon chain, which may be either linear or branched.
In the present description and in the claims which follow, by the expression “hydrophylic groups” it is meant groups which are able to bind water molecules by means of hydrogen bonds.
With regard to said polymers having a main hydrocarbon chain to which hydrophilic groups are linked, said hydrophylic groups, are preferably selected from:
According to a further preferred embodiment, said polymers having a main hydrocarbon chain to which hydrophilic groups are linked may be selected from:
Preferably, the ethylenically unsaturated carboxylic acid monomer or a derivative thereof may be selected, for example, from: (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonic acid, citraconic, acid cinnamic acid, maleic anhydride, methyl hydrogen fumarate, benzyl hydrogen maleate, butyl hydrogen maleate, octyl hydrogen itaconate, dodecyl hydrogen citraconate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, butyl fumarate, butyl maleate, octyl maleate, or mixtures thereof. Acrylic acid, methacrylic acid, or a derivative thereof, or mixtures thereof, are particularly preferred.
Other (meth)acrylic esters monomers which may be used according to the present invention are multifunctional (meth)acrylates which may be selected, for example, from: ethylene glycol monoester of (meth)acrylic acid, propylene glycol monoester of (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, esters of (meth)acrylic acid with polyoxyethylene glycol or polyoxypropylene glycol, (meth)acryloyl compounds having a polyoxyalkylene structure, or mixtures thereof.
Preferably, the aliphatic vinyl ester monomer may be selected, for example, from: vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl octylate, vinyl heptanoate, vinyl pelargonate, vinyl-3,6-dioxaheptanoate, vinyl-3,6,9-trioxaundecanoate, vinyl ester of versatic acid, or mixtures thereof. Vinyl acetate is particularly preferred.
Preferably, the aliphatic vinyl ether monomer may be selected, for example, from: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, t-amyl vinyl ether, or mixtures thereof. Methyl vinyl ether is particularly preferred.
Preferably, the aliphatic or aromatic olefinic monomer may be selected, for example, from:
Other comonomers which may optionally be used according to the present invention, may be selected from polar monomers such as, for example: vinyl chloride, vinyl sulfonate, vinyl silane, vinylidene chloride, nitriles or amides such as, for example, acrylonitrile, acrylamide, or mixtures thereof. When used, said comonomers are present in the polymer in an amount not higher than or equal to 5% by weight, with respect to the total weight of the polymer.
Specific examples of homopolymers (i) which may be advantageously used according to the present invention are: poly(meth)acrylic acid, polyalkylacrylamide, polyhydroxyalkylate, polyalkylacrylate, polyvinylacetate, polyvinylalcohol, or mixtures thereof.
Specific examples of copolymers (ii) which may be advantageously used according to the present invention are: vinylacetate/ethylene copolymers, vinylacetate/alkylacrylate copolymers, ethylene/alkylacrylate copolymers, vinylacetate/vinylversatate copolymers, vinylacetate/butylmaleate copolymers, styrene/acrylate copolymers, styrene/acrylic acid/copolymers, or mixtures thereof.
Specific examples of terpolymers (iii) which may be advantageously used according to the present invention are: vinylacetate/ethylene/acrylate terpolymers, vinylalcohol/ethylene/vinylacetate terpolymers, or mixtures thereof.
The aqueous dispersion according to the present invention, may be prepared by polymerization of monomers emulsified in water using conventional emulsion polymerization procedures.
The aqueous dispersion according to the present invention, may further comprise protective colloids such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl pirrolidone, polyethylene-glycol distearate, hydroxypropyl methylcellulose, hydroxyethyl cellulose, or mixtures thereof. The polyvinyl alcohol which may be advantageously used according to the present invention, may be a modified polyvinylalcohol (such as, acetoacetylated polyvinyl alcohol), a partially or completely saponified polyvinyl alcohol, or mixtures thereof.
Said aqueous dispersion may further comprise surfactants. Suitable surfactants include non-ionic, anionic, cationic, surfactants, or mixtures thereof. Said surfactants may be selected, for example, from: octylphenoxy polyethoxy ethanol, polysiloxane copolymers, acetylenic alcohol or glycols or their ethoxylated derivatives; ethylene oxide/propylene oxide copolymers; or mixtures thereof.
Said aqueous dispersion may comprise other commonly used additives which may be selected, for example, from: plasticizers such as, for example, polyethylene glycol, dibutyl phthalate, butyl benzyl phthalate, propylene glycol dibenzoate, triethylene glycol polyester of benzoic acid and phthalic acid, alkyd resin plasticizers; humectants such as, for example, glycerin, ethylene glycol, triethylene glycol, propylene glycol, urea, or mixtures thereof; filming aids and coalescing agents such as, for example, esters of lactic acid, 2-butoxy ethanol, esters of phthalic acid (for example, butyl octyl phathalate), 2-(2-butoxy ethoxy)ethanol, ethylene glycol, dyethylene glycol, propylene glycol, diacetone alcohol, or mixtures thereof; or mixtures thereof.
Said aqueous dispersion may further comprise inorganic fillers such as, for example, sand, silica, calcium carbonate, calcium silicates, barium sulfates, talc, mica, carbon black, or mixtures thereof; pigments; dyes; antiseptic agents; antifoaming agents; or mixtures thereof.
In order to speed up the drying of said aqueous dispersion, solvents such as, for example, acetone, ethanol, or mixtures thereof, may be added.
Examples of aqueous dispersions of homopolymers (i), or copolymers (ii), or terpolymers (iii), which may be used according to the present invention and which are commercially available, are the products known as Vinavil®, Ravemul® or Crilat®, from Vinavil, or Airflex® from Air Products.
The present invention will now be illustrated in further detail by means of the attached
A sprung floor 1 is provided on top of a load-bearing floor 2 associated with the walls 5. Said sprung floor 1 comprises a covering floor 3 which rests on a coating layer 4 made from the sound-insulating material according to the present invention and which does not have any direct contact with said load-bearing floor 2 or with the walls 5. Preferably, said coating layer 4 has a thickness of from 5 mm to 50 mm, more preferably of from 7 mm to 30 mm.
According to
Alternatively, said coating layer 4 horizontally extends over the load-bearing floor 2 up against the surrounding walls 5 (not represented in
Alternatively, the coating layer 4 extends both horizontally and vertically over the load-bearing floor 2 up against the surrounding walls 5 (not represented in
Preferably, the stranding strip 6 vertically extends from the load-bearing floor 2 up to the covering floor 3 and it has a thickness of from 2 mm to 20 mm, preferably of from 3 mm to 10 mm.
Optionally, in order to protect the coating layer 4 during the manufacturing of the sprung floor 1, a protective foil 7 is provided over said coating layer 4 and it is folded up against the walls 5 on the edges of the sprung floor 1.
The covering floor 3 is usually made from a hardened composition mainly comprising sand and cement, as is generally known for making fixed floors.
Further, a metal spot-welded wire netting (not represented in
Said covering floor 3 extends up to under the top edge of the above-mentioned standing strip 6 so that, consequently, there is no contact between the surrounding walls 5 and the covering floor 3.
Preferably, said covering floor has a thickness of from 2 cm to 10 cm, more preferably of from 4 cm to 6 cm. Depending on the expected load of the floor, this thickness may possibly be adjusted.
To sum up, the sprung-floor 1 comprises a covering floor 3 in the shape of a rigid plate whose perimeter is practically entirely enclosed by said standing strip 6 and a coating layer 4, whereby the whole rests on the fixed load-bearing floor 2.
Usually, over said covering floor 3, after it has been hardened, a layer of a finishing material 8 (such as, tiles, wood), is placed.
The present invention will be further illustrated below by means of a number of preparation examples, which are given for purely indicative purposes and without any limitation of this invention.
80% by weight (% by weight with respect to the total weight of the sound-insulating material) of a vulcanized rubber (ground waste rubber from scrap tyres having an average diameter of from 4 mm to 7 mm commercialized by Transeco s.r.l.) was mixed, under stirring, in a 5 liters becker, with 20% by weight (% by weight with respect to the total weight of the sound-insulating material) of the binding agent (the binding agent components are reported in Table 1—the amounts are expressed in % by weight with respect to the total weight of the binding agent), at room temperature (23° C.), until a homogeneous dispersion was obtained.
The mixtures of Example 2 and 3 were subjected to the following measurement.
Brookfield Viscosity
The Brookfield viscosity was measured at 23° C. and at 250 rpm using a viscosimeter of Brookfield type, model DV3, equipped with a RV6 spindle. The obtained data are the following:
The minimum filming temperature was measured according to standard ISO 2115:1996. The obtained data are the following:
The mixture of Examples 2 and 3 were subjected to Differential Scanning Calorimetry (DSC) analysis in order to measure the glass transition temperatures. The DSC analysis was conducted as follows.
First Step:
The so obtained sound-insulating material was subjected to the following tests.
Dynamic Stiffness
The dynamic stiffness was measured according to standard ISO 9052-1:1989.
To this aim, the so obtained sound-insulating material was spreaded over a polyethylene sheet and was allowed drying at room temperature (23° C.), for 48 hours. A sample of the sound-insulating material having the following dimensions: 20 cm×20 cm×1 cm was removed from the above polyethylene sheet and was subjected to the dynamic stiffness measurement.
The obtained sample was placed between two metal plates which were maintained at the following conditions: 23° C., 50% of humidity. The upper plate was a 8 kg load plate corresponding to a load of 200 kg/m2 that is the typical weight of the load bearing floor. The plate was subjected to an impulse frequency of from 50 Hz to 200 Hz: said impulse was generated by a generator and transferred to the upper plate by a shaker. The vibrational acceleration was measured by an accelerometer placed on the upper plate.
The dynamic stiffness was calculated according to the standard ISO 9052-1:1989 above reported and the obtained data, expressed in MN/m3, were given in Table 2.
Sound-Insulation Performance Test
The test was performed according to standard ISO 140-8:1997.
To this aim the sound-insulating material obtained as disclosed above was spreaded over a 10 m2 of a standard load bearing floor to obtain a layer having 10 mm thickness and was let to harden at room temperature (23° C.). After 24 hours the standard cement covering floor was applied. The acoustic measurements were performed after 28 days and the obtained data, expressed as a noise index (L), were given in Table 2.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2005/006260 | 6/10/2005 | WO | 00 | 7/24/2009 |
Publishing Document | Publishing Date | Country | Kind |
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WO2006/131138 | 12/14/2006 | WO | A |
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Number | Date | Country | |
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20090293413 A1 | Dec 2009 | US |