Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
  • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
  • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/321—Starch; Starch derivatives
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4209—Inorganic fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
  • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
  • D21H13/38—Inorganic fibres or flakes siliceous
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
  • D21H13/38—Inorganic fibres or flakes siliceous
  • D21H13/44—Flakes, e.g. mica, vermiculite

Definitions

• the invention relates to an inorganic fibrous shaped product that can be used as a sealing agent or a packing agent and a method for adjusting the hardness thereof.
• Inorganic fiber is light in weight, easy to handle, and has excellent heat resistance. Therefore, inorganic fiber is used as a heat-insulating sealing material, for example.
• inorganic fiber is inhaled by a human body and the inhaled fiber invades the lung. Therefore, biosoluble inorganic fiber that does not cause or hardly cause problems even if inhaled by a human body has been developed (Patent Documents 1 and 2, for example).
• biosoluble inorganic fiber is not only used as the raw material of textiles such as a rope, a yarn and a cloth, but also secondarily processed to and used as a shaped product such as a blanket, a board and a felt or an unshaped product such as a coating material and mortar.
• a shaped product When a shaped product is used as a joint filler in a heat-treatment apparatus, an industrial furnace or an incinerator, a joint filler that fills a gap of refractory tiles, heat-insulating bricks, shells and refractory mortars, a sealing material, and a packing material, flexibility and cushion properties are required such that construction of joints can be conducted without forming gaps.
• flexibility and cushion properties are required such that construction of joints can be conducted without forming gaps.
• a conventional shaped product such as a board contains an inorganic binder (colloidal silica) in order to allow it to be hard.
• colloidal silica is contained, when a shaped product is used at high temperatures, a problem arises that strength is lowered or cushion properties are deteriorated due to advancement in crystallization. Further, there is a problem that, due to deterioration in flexibility, a shaped product cannot retain its shape after construction, and as a result, it drops from the location of construction or a gap is formed between the location of construction and the shaped product.
• An object of the invention is to provide an inorganic fibrous shaped product that does not contain colloidal silica and has various degrees of flexibility and hardness, and heat resistance, and a method for adjusting the hardness thereof.
• the following method for adjusting the hardness of an inorganic fibrous shaped product can be provided.
• SiO 2 70 to 82 wt %
• MgO 1 wt % or less
• Al 2 O 3 less than 5 wt %
• the total of SiO 2 , CaO, MgO and Al 2 O 3 exceeds 98 wt %.
• an inorganic fibrous shaped product that does not contain colloidal silica and has various degrees of flexibility and hardness, and heat resistance, and to provide a method for adjusting the hardness thereof.
• the inorganic fibrous shaped product of the invention at least comprises prescribed inorganic fiber (hereinafter may often referred to as the “specific inorganic fiber”) and an organic thickener.
• the inorganic fibrous shaped product of the invention does not contain colloidal silica.
• the inorganic fibrous shaped product of the invention does not have to contain a metal alkoxide, a glass raw material composition (borosilicate glass, frit 3249 (manufactured by Ferro Corporation: 3.5% CaO; 12.2% MgO; 28.9% B 2 O 3 ; 13.3% Al 2 O 3 ; and 42.1% SiO 2 ) or the like), a sol (alumina borate sol or the like), and an inorganic binder such as an acid alumina phosphate does not have to be contained. Further, a thermosetting resin such as a phenol resin and an epoxy resin does not have to be contained.
• a glass raw material composition borosilicate glass, frit 3249 (manufactured by Ferro Corporation: 3.5% CaO; 12.2% MgO; 28.9% B 2 O 3 ; 13.3% Al 2 O 3 ; and 42.1% SiO 2 ) or the like
• a sol alumina borate sol or the like
• an inorganic binder such as an acid a
• Organic thickeners include a natural thickener and its derivative or a vinyl-based, vinylidene-based, polyester-based, polyamide-based, polyether-based, polyglycol-based, polyvinyl alcohol-based, polyalkylene oxide-based and polyacrylic acid-based thickeners.
• Specific examples thereof include cellulose-based thickeners such as CMC (carboxymethyl cellulose), MC (methyl cellulose), albumin, casein, alginic acid, agar, starch, polysaccharide, PVA (polyvinyl alcohol), PVB (polyvinyl butyral), acrylic emulsion or the like. These may be used alone or in combination of two or more.
• a polyacrylic acid-based thickener, a cellulose-based thickener and starch are preferable.
• the shaped product of the invention may contain an organic thickener in a substantially un-molten state.
• the inorganic fibrous shaped product of the invention may further contain a fixing agent in order to allow an organic thickener to be fixed to fibers.
• a fixing agent sulfates, nitrates, acetates and hydrochlorides of each of aluminum, magnesium, calcium, sodium and potassium can be given.
• a flocculant may be contained.
• a general-purpose flocculant may be used, and the type and amount may appropriately be selected according to the state of the resulting flocs. Flocculants are not necessarily be contained.
• the specific inorganic fiber used in the invention has the following composition.
• the fiber having the following composition has excellent biosolubility and fire resistance after heating.
• the total of SiO 2 , CaO, MgO and Al 2 O 3 exceeds 98 wt %.
• composition can preferably be exemplified.
• SiO 2 66 to 82 wt % (it can be 68 to 80 wt %, 70 to 80 wt %, 71 to 80 wt % or 71 to 76 wt %, for example)
• CaO 10 to 34 wt % (it can be 20 to 30 wt % or 21 to 26 wt %, for example)
• Al 2 O 3 5 wt % or less (it can be 3.5 wt % or less or 3 wt % or less, or it can be 1 wt % or more or 2 wt % or more, for example)
• the inorganic fiber has excellent heat resistance. If CaO and MgO are contained in the above-mentioned amount range, the inorganic fiber has excellent biosolubility before and after heating.
• the Al 2 O 3 content can be 3.4 wt % or less or 3.0 wt % or less, for example, or it can be 1.1 wt % or more and 2.0 wt % or more.
• the Al 2 O 3 content is preferably 0 to 3 wt %, more preferably 1 to 3 wt %. If Al 2 O 3 is contained in this amount range, a higher strength can be achieved.
• the above-mentioned inorganic fiber may contain, as other oxides, one or more selected from alkali metal oxides (K 2 O, Na 2 O or the like), Fe 2 O 3 , ZrO 2 , P 2 O 5 , B 2 O 3 , TiO 2 , MnO, R 2 O 3 (R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or a mixture thereof) or the like. They need not be contained.
• the content of each of other oxides may be less than 1.0 wt %, 0.2 wt % or less or 0.1 wt % or less.
• the content of each oxide may be less than 1.0 wt % or 0.2 wt % or less, and the total of alkali metal oxides may be less than 1.0 wt % or 0.2 wt % or less.
• the total content of SiO 2 , CaO, MgO and Al 2 O 3 may exceed 99 wt %.
• biosoluble fiber is fiber having a physiological saline dissolution ratio at 40° C. of 1% or more.
• the physiological saline dissolution ratio is measured by the following method, for example. Specifically, first, 1 g of the sample obtained by pulverizing inorganic fibers to 200 meshes or less and 150 mL of physiological saline are put in a conical flask (volume: 300 mL). This flask is placed in an incubator of 40° C., and a horizontal vibration (120 rpm) is continuously applied for 50 hours. Thereafter, the concentration (mg/L) of each element contained in a filtrate obtained by filtration is measured by an ICP emission spectrometry apparatus. Based on the measured concentration of each element and the content (wt %) of each element in inorganic fiber before dissolution, the physiological saline dissolution ratio (%) is calculated.
• a1, a2, a3 and a4 are respectively the measured concentration (mg/L) of silicon, magnesium, calcium and aluminum
• b1, b2, b3 and b4 are respectively the content (wt %) of silicon, magnesium, calcium and aluminum in the inorganic fiber before dissolution.
• the inorganic fibrous shaped product may contain other inorganic fiber in addition to the above-mentioned specific inorganic fiber.
• the content of the specific inorganic fiber may be 50 wt % or more, 60 wt % or more, 80 wt % or more or 100 wt %.
• Refractory fiber composed mainly of silica and alumina (silica: 4 to 60 wt %, alumina: 40 to 96 wt %), rock wool (for example, the SiO 2 content is 30 to 50 mass %, the Al 2 O 3 content is 10 to 20 mass %, the MgO content is 1 to 10 mass %, the CaO content is 20 to 40 mass %, the Fe 2 O 3 content is 0 to 3 mass % and the MnO content is 0 to 1 mass %), carbon fiber, slag wool, glass wool, silica fiber, silicon carbide fiber, boron nitride fiber, zirconia fiber, calcium silicate fiber, and other natural mineral fiber can be given.
• rock wool for example, the SiO 2 content is 30 to 50 mass %, the Al 2 O 3 content is 10 to 20 mass %, the MgO content is 1 to 10 mass %, the CaO content is 20 to 40 mass %, the Fe 2 O 3 content is 0 to 3 mass % and
• the inorganic fibrous shaped product may contain inorganic powder, anti-foaming agents, pH-adjusting agents or the like.
• the content of an organic thickener is normally 0.01 to 60 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and further preferably 1 to 15 parts by weight, when the total content of all of the inorganic fiber contained in the shaped product is taken as 100 parts by weight. If the content of an organic thickener is 60 parts by weight or more, dehydration forming becomes difficult. If the shaped product is used at high temperatures, organic components may cause a gas to be generated. Therefore, the content of an organic thickener may be appropriately adjusted such that the inorganic fibrous shaped product can exhibit its function or can satisfy required properties according to applications.
• a fixing agent may normally be contained in an amount of 0 to 10, preferably 0.5 to 10, and more preferably 1 to 7, if the content of an organic thickener is taken as 1.
• a fixing agent is normally contained in an amount of 0 to 20 parts by weight, preferably 0.01 to 15 parts by weight, more preferably 0.5 to 10 parts by weight and further preferably 1 to 10 parts by weight, if the total content of the inorganic fiber is taken as 100 parts by weight.
• the total of an organic thickener and a fixing agent is preferably 0.1 to 30 wt %, preferably 1 to 20 wt %, preferably 1 to 15 wt % and preferably 1 to 10 wt %.
• the organic fibrous shaped product may be configured such that the total content of the inorganic fiber and the organic thickener (if organic powder and/or a fixing agent are contained, the total content of the inorganic fiber, the organic thickener, the inorganic powder and the fixing agent) becomes 90 wt % or more, 95 wt % or more, 98 wt % or more, 99 wt % or more or 100 wt %.
• the inorganic fibrous shaped product is preferably in the shape of a fabric such as a felt or in the shape of a flexible sheet.
• the shaped product such as a felt can be used as a single body without the need of scattering, applying or stacking other materials on the surface thereof.
• the shaped product having flexibility or cushion properties can change its form easily, and therefore, can be pushed into a gap between joints easily, for example.
• the thickness is not particularly restricted, but is normally 5 mm or more, preferably 10 to 50 mm.
• the hardness and flexural strength of the inorganic fibrous shaped product of the invention can be appropriately adjusted according to applications by changing the amount of an organic thickener and/or a fixing agent. With an increase in the amount of an organic thickener and a fixing agent, the organic fibrous shaped product has higher hardness.
• the surface hardness of the inorganic fibrous shaped product in the normal state (unheated) varies depending on the application, but is normally 1 to 60°.
• the method for measuring the surface hardness is described in the Examples.
• a flexural strength in the normal state of 0.03 to 0.6 Mpa is preferable since the handling properties and the working accuracy of the inorganic fibrous shaped product are improved.
• the method for measuring the flexural strength is described in the Examples.
• the heat shrinkage of the inorganic fibrous shaped product after heating at 1100° C. for 24 hours is preferably 2% or less, more preferably 1% or less.
• the heat shrinkage can be further lowered by using the above-mentioned specific inorganic fiber having a low heat shrinkage and by appropriately combining an organic thickener and a fixing agent.
• the method for measuring the heat shrinkage is described in the Examples.
• the shaped product can be produced by a known method such as dehydration forming or the like.
• it can be produced by a method in which a raw material containing the inorganic fiber and an organic thickener and a dispersion medium are mixed to form a slurry, the slurry is flown in a die to conduct forming, and the formed product is dried. Drying is preferably conducted at a temperature that is not higher than the melting temperature.
• the shaped product of the invention can be produced by using a used shaped product. However, since it is difficult to control the amount of an organic substance, normally, a used shaped product is not used. If the amount of an organic substance is large, a large amount of gas is generated when heating.
• a slurry is produced by mixing components with a solvent.
• the amount of a solvent is normally 1000 to 100000 parts by weight, preferably 1500 to 80000 parts by weight, and further preferably 2000 to 60000 parts by weight, when the total amount of all inorganic fiber contained in the shaped product is taken as 100 parts by weight.
• water is used as the solvent.
• a polar organic solvent may be used, or may be added partially, but water is preferable as the solvent.
• water one that is normally used on the industrial basis may be used, and examples of usable water include distilled water, ion exchange water, tap water, groundwater and industrial water.
• Inorganic fiber A comprising 73 mass % of SiO 2 , 24 mass % of CaO, 0.3 mass % of MgO and 2 mass % of Al 2 O 3 and an organic thickener selected from CMC (organic thickener), starch (organic thickener) and an acrylic emulsion (organic thickener) were mixed with water in amounts shown in Tables 1 to 3, whereby a raw material slurry was prepared.
• CMC organic thickener
• starch organic thickener
• acrylic emulsion organic thickener
• the amount is indicated in terms of part by weight when the amount of the inorganic fiber A is taken as 100 parts by weight.
• Water was used in an amount of 3000 parts by weight when the amount of the inorganic fiber A is taken as 100 parts by weight.
• This raw material slurry was flown in a forming die in which a net was provided in the bottom part thereof.
• the water contained in the raw material slurry was sucked and removed through the net of the forming die. Thereafter, the dehydrated raw material was dried by heating in a drier, whereby felts each having a thickness of 25 mm were obtained.
• a sample (length: 150 mm, width: 50 mm) taken out from the felt was fired at 1100° C. for 24 hours. Before and after the firing, the length in the longitudinal direction was measured, and the heat shrinkage was obtained according to the following formula:
• Bending strength (MPa) ⁇ 3 ⁇ maximum load (N) ⁇ distance (mm) between the centers of support rolls ⁇ / ⁇ 2 ⁇ width (mm) of insulating material ⁇ (thickness (mm) of insulating material) 2 ⁇
• Example 1 Example 2
• Example 3 Example 4
• Example 5 Example 6
• the inorganic fiber B comprises 53 mass % of SiO 2 and 47 mass % of Al 2 O 3 .
• Tables 5 and 6 The components shown in Tables 5 and 6 were mixed in amounts shown in Tables 5 and 6. Felts each having a thickness of 25 mm were produced and evaluated in the same manner as in Example 1. The results are shown in Tables 5 and 6.
• Example Example Composition 33 34 35 36 Inorganic fiber Inorganic fiber A 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Organic thickener CMC 5 5 5 3 Starch Acrylic emulsion Fixing agent Aluminum nitrate 1 2 3 2 Heat shrinkage 1100° C. ⁇ 24 hr 0.76 0.78 0.73 0.89 Flexural strength Unheated 0.12 0.31 0.49 0.14 Hardness Surface 19 38 45 21
• the felts of the Examples can have appropriate values of heat shrinkage, flexural strength and hardness without using an inorganic binder.
• the heat shrinkage of the felts is equivalent to or smaller than that of the boards, and the flexural strength (flexibility) of the felts is equivalent to or smaller than that of the boards.
• the hardness of the felt can be increased to a level that is equal to that of the board by increasing the amount of an organic thickener or the amount of a fixing agent and an organic thickener.
• the inorganic fibrous shaped product of the invention can be used in various applications as a joint filler in a heat treatment apparatus, an industrial kiln or an incinerator; a joint filler that fills a gap of refractory tiles, heat-insulting bricks, shells and refractory mortars, a sealing material, a packing material, a heat insulating material or an alternative to asbestos.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Fibers (AREA)
• Glass Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Nonwoven Fabrics (AREA)
• Ceramic Products (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=47469401

Family Applications (1)

Country Status (4)

Cited By (2)

Families Citing this family (1)

Citations (1)

Family Cites Families (9)

• 2012
  • 2012-01-24 JP JP2012011705A patent/JP5087709B1/ja active Active
  • 2012-12-04 US US14/374,146 patent/US20150033986A1/en not_active Abandoned
  • 2012-12-04 EP EP12866549.4A patent/EP2808314A4/en not_active Withdrawn
  • 2012-12-04 WO PCT/JP2012/007764 patent/WO2013111232A1/ja active Application Filing

Patent Citations (3)

Also Published As

Similar Documents

Legal Events