WO2020022260A1 - スパンボンド不織布、および、スパンボンド不織布から構成されるエアフィルター - Google Patents
スパンボンド不織布、および、スパンボンド不織布から構成されるエアフィルター Download PDFInfo
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- WO2020022260A1 WO2020022260A1 PCT/JP2019/028646 JP2019028646W WO2020022260A1 WO 2020022260 A1 WO2020022260 A1 WO 2020022260A1 JP 2019028646 W JP2019028646 W JP 2019028646W WO 2020022260 A1 WO2020022260 A1 WO 2020022260A1
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- nonwoven fabric
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- spunbonded nonwoven
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
- B01D39/163—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin sintered or bonded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
- B03C3/28—Plant or installations without electricity supply, e.g. using electrets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
- D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
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- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0627—Spun-bonded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1233—Fibre diameter
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- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
Definitions
- the present invention relates to a spunbonded nonwoven fabric.
- the present invention relates to a spunbonded nonwoven fabric which has low pressure loss and high trapping performance when used as an air filter and has excellent workability, and an air filter composed of the spunbonded nonwoven fabric.
- an air filter has been used to remove pollen, dust, and the like in a gas, and a fiber sheet is often used as a filter medium.
- the performance required of the air filter is that a large amount of micro dust can be collected (high collection performance), and that the resistance when a gas passes through the inside of the air filter is low (low pressure loss characteristic).
- the collection mechanism of the air filter is mainly based on physical effects such as brown diffusion, shielding, and inertial collisions.
- the fiber sheet to be formed must be relatively fine. It is suitable that there is.
- the fiber density in the sheet must be increased, in other words, the pore size must be reduced, resulting in a high pressure loss.
- the constituent fiber sheet may have a relatively large fineness, but the gap between the fibers in the sheet is widened, and the collecting performance is reduced. I will.
- the fineness of the constituent fibers is generally such as a non-woven fabric sheet made of fine fibers for applications where high collection performance is important, and a non-woven fabric sheet made of large fibers for applications where low pressure loss characteristics are important. It is used for different purposes.
- the fiber sheet described in the example of Patent Document 1 is a melt-blown nonwoven fabric that has been electretized by applying a high pressure.
- a fine-sized sheet such as a melt-blown nonwoven fabric is included per unit volume as compared with a large-sized fine sheet. Since the total surface area of the fibers is large and a larger charging effect is obtained, the collection performance can be further improved, and the fiber can be used for applications that place more importance on high collection.
- the melt-blown nonwoven fabric as disclosed in Patent Document 1 has a high collection efficiency, but is inferior in strength, and has a problem that tearing occurs in a processing stage or a product stage.
- the spunbonded nonwoven fabric disclosed in Patent Documents 2 and 3 since the single fiber fineness (average single fiber diameter) of the fibers used in the examples is in a general range, when the air filter is used. Although there was no problem with the strength of the powder, the trapping performance was not sufficient.
- an object of the present invention is to provide a spunbonded nonwoven fabric which has low pressure loss and high collecting performance and is excellent in processability, and an air filter using the spunbonded nonwoven fabric.
- the present inventors attempted to further improve the trapping performance by increasing the amount of fibers, but as a result, the pressure loss increased due to the increase in the basis weight. . Then, in order to achieve the above object, as a result of further studies by the present inventors, the melt flow rate of the spunbonded nonwoven fabric was set to a specific range, and the average single fiber diameter of the fibers constituting the spunbonded nonwoven fabric It has been found that, by setting the value in a specific range, it is possible to obtain a spunbonded nonwoven fabric having low pressure loss and high collection efficiency.
- the spunbonded nonwoven fabric of the present invention is composed of a fiber made of a polyolefin resin, has an average single fiber diameter of 6.5 ⁇ m or more and 22.0 ⁇ m or less, and contains a hindered amine compound of 0.1% by mass or more and 5% by mass or less.
- a spunbonded nonwoven fabric comprising: a nonwoven fabric having a melt flow rate (MFR) of 32 g / 10 min or more and 850 g / 10 min or less; and the nonwoven fabric is electret-processed.
- MFR melt flow rate
- the hindered amine compound is a compound represented by the following general formula (1).
- the basis weight of the spunbonded nonwoven fabric is 5 g / m 2 or more and 60 g / m 2 or less.
- the spunbonded nonwoven fabric has a thickness of 0.05 mm or more and 1.0 mm or less.
- the tensile strength in the machine direction is 0.3 (N / 5 cm) / (g / m 2 ) or more.
- the nucleating agent is contained in an amount of 0.001% by mass or more and 1.0% by mass or less.
- the filter medium for an air filter of the present invention uses the above spunbonded nonwoven fabric.
- the present invention can provide a spunbonded nonwoven fabric having low pressure loss and high trapping performance and excellent workability, and an air filter using the spunbonded nonwoven fabric.
- FIG. 1 is a schematic side view showing a device for measuring a collection efficiency and a pressure loss.
- the spunbonded nonwoven fabric of the present invention is composed of fibers made of a polyolefin resin, has an average single fiber diameter of 6.5 ⁇ m or more and 22.0 ⁇ m or less, and is represented by a hindered amine compound, preferably represented by the following general formula (1).
- MFR melt flow rate
- R 1 to R 3 are hydrogen or an alkyl group having 1 to 2 carbon atoms
- R 4 is hydrogen or an alkyl group having 1 to 6 carbon atoms
- the fibers constituting the spunbonded nonwoven fabric used in the present invention are made of a polyolefin resin.
- the polyolefin resin include a polypropylene resin and a polyethylene resin.
- the polypropylene resin include a homopolymer of propylene or a copolymer of propylene and various ⁇ -olefins.
- the polyethylene resin include a homopolymer of ethylene or a copolymer of ethylene and various ⁇ -olefins. Polymers and the like can be mentioned, and among these materials, those mainly composed of polypropylene are preferable because they exhibit particularly excellent electret performance. Other components may be copolymerized as long as the properties of the polymer are not impaired.
- the polyolefin resin used in the present invention may be a mixture of two or more kinds, or a resin composition containing other polyolefin resin, thermoplastic elastomer, or the like.
- the MFR can be adjusted by blending two or more kinds of thermoplastic resins having different MFRs at an arbitrary ratio.
- polypropylene is measured at a load of 2.16 kg and a temperature of 230 ° C.
- polyethylene is measured at a load of 2.16 kg and a temperature of 190 ° C.
- the measurement is performed at the highest temperature among the measurement temperatures of the respective polyolefin-based resins.
- the polyolefin resin preferably has an MFR of 32 g / 10 min or more and 850 g / 10 min or less.
- the lower limit of the MFR is preferably 32 g / 10 min or more, more preferably 60 g / 10 min or more, further preferably 80 g / 10 min or more, particularly preferably 120 g / 10 min or more, and most preferably 155 g / 10 min. More than a minute.
- the upper limit is preferably 850 g / 10 minutes or less, more preferably 600 g / 10 minutes or less, and even more preferably 400 g / 10 minutes or less.
- the fiber thinning behavior when spinning the fibers constituting the spunbonded nonwoven fabric is stable, and even if drawing at a high spinning speed to increase productivity, stable spinning is possible. Become.
- the yarn sway is suppressed, and unevenness when collecting in a sheet shape is less likely to occur.
- the ratio is equal to or less than the upper limit, it is possible to stably draw at a high spinning speed, so that oriented crystallization of the fiber can be promoted, and a fiber having high mechanical strength can be obtained.
- the melting point of the polyolefin resin used in the present invention is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 180 ° C.
- the melting point is preferably 80 ° C. or higher, more preferably 100 ° C. or higher.
- heat resistance that can withstand practical use is easily obtained.
- the melting point is a value measured using a differential scanning calorimeter DSC-2 manufactured by Perkin Elmer under the condition of a temperature rising rate of 20 ° C./min.
- the polyolefin resin used in the present invention also includes, as long as the effects of the present invention are not impaired, antioxidants, weather stabilizers, light stabilizers, antistatic agents, antifogging agents, antiblocking agents, lubricants which are generally used. , Nucleating agents, additives such as pigments, or other polymers can be added as necessary.
- the spunbonded nonwoven fabric of the present invention can be added with additives such as a heat stabilizer, a weathering agent and a polymerization inhibitor, and from the viewpoint of improving the chargeability and charge retention when the nonwoven fabric is electret-treated. It is important that the fiber material contains a hindered amine compound, preferably a compound represented by the general formula (1) (hindered amine compound).
- the hindered amine compound is contained in an amount of 0.1 to 5% by mass, and the lower limit is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass or more. It is particularly preferred to do so. Further, the content is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2.5% by mass or less.
- hindered amine compound for example, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ((2,2,6, 6-Tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)] ("Chimasorb” (registered trademark) 944LD, manufactured by BASF Japan Ltd.) ), Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate (“Tinuvin” (registered trademark) 622LD, manufactured by BASF Japan Ltd.) , And bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate (BAS Japan Co., Ltd., "Tinuvin" (
- the compound (hindered amine-based additive) represented by the above general formula (1) is preferred from the viewpoint of chargeability and charge retention when the spunbonded nonwoven fabric is electret-treated, and specifically, poly [(6-(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino Hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)] ("Chimasorb” (registered trademark) 944LD, manufactured by BASF Japan Ltd.), dibutylamine 1,3,5- Polycondensate of triazine.N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine ( "Kimasorb” (registered trademark) 2020FDL manufactured by BASF
- the hindered amine compound such as a compound having a structure represented by the following general formula (1) may be used singly or as a mixture of plural kinds.
- R 1 to R 3 are hydrogen or an alkyl group having 1 to 2 carbon atoms
- R 4 is hydrogen or an alkyl group having 1 to 6 carbon atoms
- the fibers constituting the spunbonded nonwoven fabric of the present invention can contain a nucleating agent in addition to the compound represented by the general formula (1).
- crystal nucleating agent examples include a sorbitol-based nucleating agent, a nonitol-based nucleating agent, a kyrisitol-based nucleating agent, a phosphate-based nucleating agent, a triaminobenzene derivative nucleating agent, and a carboxylic acid metal salt nucleating agent.
- Sorbitol nucleating agents include dibenzylidene sorbitol (DBS), monomethyldibenzylidene sorbitol (eg, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol (p-MDBS)), dimethyldibenzylidene sorbitol (eg, , 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol (3,4-DMDBS)) and the like, “Millad” (registered trademark) # 3988 (manufactured by Milliken Japan KK), And “Gelall” (registered trademark) E-200 (manufactured by Shin Nippon Rika Co., Ltd.).
- DBS dibenzylidene sorbitol
- p-MDBS monomethyldibenzylidene sorbitol
- p-MDBS dimethyldibenzylidene sorbitol
- Nonitol-based nucleating agents include, for example, 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol, and “Millad” (registered trademark). NX8000 (manufactured by Milliken Japan KK) and the like.
- the xylitol-based nucleating agent includes, for example, bis-1,3: 2,4- (5 ', 6', 7 ', 8'-tetrahydro-2-naphthaldehydebenzylidene) 1-allylxylitol.
- the phosphoric acid-based nucleating agent includes, for example, aluminum-bis (4,4 ′, 6,6′-tetra-tert-butyl-2,2′-methylenediphenyl-phosphate) -hydroxide, and the like, “ADK STAB” (registered trademark) NA-11 (manufactured by ADEKA Corporation), “ADK STAB” (registered trademark) NA-21 (manufactured by ADEKA Corporation) and the like can be mentioned.
- the triaminobenzene derivative nucleating agent includes, for example, 1,3,5-tris (2,2-dimethylpropanamido) benzene and the like, and is represented by the following general formula (2), “Irgclear” (registered trademark) ) XT386 "(manufactured by BASF Japan Ltd.).
- examples of the metal carboxylate nucleating agent include sodium benzoate and calcium 1,2-cyclohexanedicarboxylate.
- R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms. , A cycloalkenyl group having 5 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- the content of the crystal nucleating agent in the fibers constituting the nonwoven fabric is preferably from 0.001% by mass to 1.0% by mass.
- the content of the crystal nucleating agent is 0.001% by mass or more, more preferably 0.005% by mass or more, the effect of dust collection characteristics can be effectively enhanced. In addition, fusion between fibers can be suppressed, and the amount of ventilation can be increased.
- the content of the crystal nucleating agent is 1.0% by mass or less, more preferably 0.5% by mass or less, the spinnability is stable and the cost is superior.
- the spunbonded nonwoven fabric of the present invention is composed of a polymer containing the compound as described above.
- the polymer is used as a resin material such as an antioxidant, a light stabilizer, and a heat stabilizer. It may contain stabilizers normally contained.
- the content here can be determined, for example, as follows. After the nonwoven fabric was subjected to Soxhlet extraction with a methanol / chloroform mixed solution, the extract was subjected to HPLC fractionation, and each fraction was subjected to IR measurement, GC measurement, GC / MS measurement, MALDI-MS measurement, 1 H-NMR measurement, and The structure is confirmed by 13 C-NMR measurement. The masses of the fractions containing the crystal nucleating agent are totaled to determine the ratio to the entire nonwoven fabric, and this is defined as the content of the crystal nucleating agent. Similarly, for the compound represented by the general formula (1), the masses of the fractions contained in the compound are also summed, and the ratio to the entire nonwoven fabric is determined, which is defined as the content of the compound.
- conjugated fibers can also be used.
- the composite form of the composite fiber include composite forms such as concentric core-sheath type, eccentric core-sheath type and sea-island type.
- Monocomponent fibers, core-in-sheath type, multi-component fibers such as sea-island type, etc. are not particularly limited, but in the case of multi-component fibers, depending on the choice of the resin, the charge is higher than the difference in electric resistance between the resins. In a preferred embodiment, it is a monocomponent fiber because of the possibility of leakage.
- the fibers constituting the spunbonded nonwoven fabric used in the present invention have an average single fiber diameter of 6.5 or more and 22.0 ⁇ m or less.
- the average single fiber diameter By controlling the average single fiber diameter to be preferably 6.5 ⁇ m or more, more preferably 7.5 ⁇ m or more, and still more preferably 8.4 ⁇ m or more, a decrease in spinnability is prevented, and a stable high-quality nonwoven fabric is produced. can do.
- the average single fiber diameter is preferably 22.0 ⁇ m or less, more preferably 13.0 ⁇ m or less, further preferably 11.2 ⁇ m or less, and particularly preferably 10.0 ⁇ m or less, denseness and uniformity are improved.
- the spunbonded nonwoven fabric is used as an air filter, so that a high collection efficiency can be achieved.
- the cross-sectional shape of the fibers constituting the spunbonded nonwoven fabric of the present invention is not particularly limited as long as the obtained spunbonded nonwoven fabric is suitable for filter applications, but is circular, hollow circular, elliptical, flat, or X-type, Y-type and other irregular shapes, polygonal shapes, multi-leaf shapes, and the like are preferred modes.
- the fiber diameter of the non-circular fiber is obtained by taking an circumscribed circle and an inscribed circle with respect to the fiber cross section, and calculating the average value of the diameters as the fiber diameter.
- the MFR of the spunbonded nonwoven fabric of the present invention is not less than 32 g / 10 min and not more than 850 g / 10 min. It is at least 32 g / 10 min, preferably at least 60 g / 10 min, more preferably at least 80 g / 10 min, even more preferably at least 120 g / 10 min, most preferably at least 155 g / 10 min. Thereby, thinning progresses and a nonwoven fabric having a high collection efficiency can be obtained.
- the fiber thinning behavior during spinning becomes stable and the productivity is increased. Even if the drawing is performed at a very high spinning speed, stable spinning is possible.
- MFR of the spunbonded nonwoven fabric of the present invention a value measured by ASTM D1238 (Method A) is adopted.
- ASTM D1238 Method A
- polypropylene is measured at a load of 2.16 kg and a temperature of 230 ° C.
- polyethylene is measured at a load of 2.16 kg and a temperature of 190 ° C.
- a polyolefin resin constituting the resin and a resin constituting the other nonwoven fabric are different, and when a plurality of types of resins are used, It is measured at the highest temperature among the measurement temperatures of the polyolefin resin constituting the spunbond nonwoven fabric.
- the spunbonded nonwoven fabric of the present invention is charged, and by using a charged spunbonded nonwoven fabric, it is possible to obtain high collection performance while maintaining low pressure loss characteristics by an electrostatic adsorption effect. You can.
- the pressure loss and the collection efficiency in the present invention are measured by the following measuring method or a measuring method that can obtain a result equivalent thereto. That is, five measurement samples of 15 cm ⁇ 15 cm were collected from an arbitrary portion of the spunbonded nonwoven fabric, and the collection efficiency and pressure loss of each sample were measured by a collection performance measuring device schematically shown in FIG. I do.
- the basis weight of the spunbonded nonwoven fabric of the present invention is not particularly limited as long as it is suitable for a filter use, but is preferably 5 g / m 2 or more, more preferably 8 g / m 2 or more. It is particularly preferable that the amount is 10 g / m 2 or more. By doing so, the strength and rigidity of the nonwoven fabric can be increased. Further, it is preferably at most 60 g / m 2, more preferably at most 50 g / m 2 , particularly preferably at most 40 g / m 2 . By doing so, the pressure loss can be reduced and the cost can be kept in a preferable range.
- the spunbonded nonwoven fabric of the present invention may be laminated with another sheet to form a laminated fiber sheet.
- a spunbonded nonwoven fabric and a sheet having higher rigidity than the spunbonded nonwoven fabric to improve the product strength, or to use a sheet having a functional property such as deodorization and antibacterial.
- the spunbonded nonwoven fabric of the present invention preferably has a tensile strength in the longitudinal direction per unit weight of 0.3 (N / 5 cm) / (g / m 2 ) or more.
- the tensile strength in the machine direction is 0.3 (N / 5 cm) / (g / m 2 ) or more, preferably 0.5 (N / 5 cm) / (g / m 2 ) or more, more preferably 1 (N / cm 2 ) or more.
- the longitudinal tensile strength per unit weight can be adjusted by the spinning speed and average single fiber diameter of the fibers constituting the spunbonded nonwoven fabric layer, and the thermocompression bonding conditions (compression ratio, temperature and linear pressure) of the spunbonded nonwoven fabric. it can.
- the longitudinal direction is the longitudinal direction of the nonwoven fabric.
- the tensile elongation at the maximum tensile strength is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more. Since processing is possible, excellent workability can be obtained.
- the spunbonded nonwoven fabric of the present invention preferably has a thickness of 0.05 to 1.0 mm.
- the thickness is preferably 0.05 to 1.0 mm, more preferably 0.08 to 0.8 mm, and still more preferably 0.10 to 0.5 mm.
- the thickness is preferably in the above range in order to suppress an increase in pressure loss due to the pleat shape when the air filter is used. If the thickness is less than the lower limit, it is difficult to obtain the shape retention of the filter medium when processing air with a high air volume, so it is not preferable, and if the thickness exceeds the upper limit, the storability when used as an air filter decreases. Therefore, it is not preferable.
- the spunbonded nonwoven fabric of the present invention preferably has a pressure loss per unit area of not less than 0.10 (Pa) / (g / m 2 ) and not more than 0.50 (Pa) / (g / m 2 ).
- the lower limit of pressure loss per unit weight is preferably 0.10 (Pa) / (g / m 2 ), more preferably 0.15 (Pa) / (g / m 2 ) or more, and further preferably 0 or more.
- the number of fibers per unit weight is increased or the total surface area is increased, so that it is not broken at the time of processing, and strength excellent in processability can be obtained.
- the amount is not more than the upper limit, the number of fibers per unit weight or the total surface area becomes appropriate, and a low pressure loss can be obtained.
- the spunbonded nonwoven fabric according to the present invention is as follows: first, a melted polyolefin resin is spun out as a long fiber from a spinneret, which is drawn by suction with compressed air by an ejector, and then the fibers are collected on a moving net to obtain a nonwoven fabric. And
- Various shapes such as a round shape and a rectangular shape can be adopted as the shape of the spinneret or the ejector.
- the combination of a rectangular die and a rectangular ejector is preferred because the amount of compressed air used is relatively small and the energy cost is excellent, the fusion and rubbing of the yarns do not easily occur, and the yarns are easily opened. It is preferably used.
- the polyolefin-based resin is melted in an extruder, measured and supplied to a spinneret to be spun as a long fiber.
- the spinning temperature when the polyolefin resin is melted and spun is preferably 200 ° C. or more and 270 ° C.
- the spinning temperature is 200 ° C or higher, more preferably 210 ° C or higher, further preferably 220 ° C or higher, or 270 ° C or lower, more preferably 260 ° C or lower, further preferably 250 ° C or lower.
- a stable molten state, and excellent spinning stability can be obtained.
- the spun filaments are then cooled.
- a method of cooling the spun yarn for example, a method of forcibly blowing cold air to the yarn, a method of naturally cooling at ambient temperature around the yarn, and a method of adjusting the distance between the spinneret and the ejector Or a method combining these methods.
- the cooling conditions can be appropriately adjusted and adopted in consideration of the discharge amount per single hole of the spinneret, the spinning temperature, the ambient temperature, and the like.
- the cooled and solidified yarn is drawn and drawn by the compressed air injected from the ejector.
- the spinning speed is preferably from 3000 m / min to 6500 m / min. Having a high spinning speed of 3000 m / min to 6500 m / min, more preferably 3500 m / min to 6500 m / min, and still more preferably 4000 m / min to 6500 m / min.
- oriented crystallization of the fiber proceeds, and a high-strength long fiber can be obtained.
- the spinnability deteriorates and the filament cannot be stably produced.
- the intended polyolefin fiber can be obtained. Can be stably spun.
- the obtained long fibers are collected on a moving net to form a nonwoven fiber web.
- the nonwoven fiber web is temporarily bonded to the nonwoven fiber web by abutting a heat flat roll on one side of the net.
- the surface temperature of the thermal flat roll at the time of thermal temporary bonding is -60 to -25 ° C with respect to the melting point of the polyolefin resin used.
- the lower limit of the surface temperature of the heat flat roll is preferably ⁇ 60 ° C. or more, more preferably ⁇ 55 ° C. or more, with respect to the melting point of the polyolefin resin.
- the upper limit of the surface temperature of the heat flat roll is preferably -25 ° C or lower, more preferably -30 ° C or lower with respect to the melting point of the polyolefin resin.
- the content is preferably -25 ° C or lower, more preferably -30 ° C or lower with respect to the melting point of the polyolefin resin.
- a hot embossed roll in which a pair of upper and lower roll surfaces are respectively engraved (uneven portions), and one of the roll surfaces is flat (smooth).
- Various types of rolls are used, such as a hot embossing roll composed of a combination of a roll and a roll having an engraved (uneven portion) on the surface of the other roll, and a hot calender roll composed of a combination of a pair of upper and lower flat (smooth) rolls.
- a method such as ultrasonic bonding in which heat welding is performed by ultrasonic vibration of a horn.
- a hot embossing roll composed of a combination of a roll having one flat roll surface (smooth) and a roll having an engraved (uneven portion) formed on the other roll surface is used. It is an aspect.
- a metal roll and a metal roll are used in order to obtain a sufficient thermocompression bonding effect and to prevent the engraving (uneven portion) of one embossing roll from being transferred to the other roll surface. Pairing is the preferred embodiment.
- the emboss bonding area ratio by such a hot embossing roll is preferably 3% or more and 30% or less.
- the bonding area is preferably 3% or more, more preferably 5% or more, and still more preferably 8% or more, it is possible to obtain strength that can be practically used as a nonwoven fabric.
- the bonding area is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less, it is possible to secure appropriate air permeability particularly suitable for use in an air filter application. it can. Even when ultrasonic bonding is used, the bonding area ratio is preferably in the same range.
- adheresive area refers to the ratio of the adhesive portion to the entire spunbonded nonwoven fabric. Specifically, when heat bonding is performed using a pair of rolls having irregularities, the convex portion of the upper roll and the convex portion of the lower roll overlap and abut on the nonwoven fabric layer (adhesive portion) to the entire spunbonded nonwoven fabric. It refers to the percentage of the account. Further, in the case of thermally bonding with a roll having irregularities and a flat roll, it refers to a ratio of a portion (adhesive portion) of the convex portion of the roll having irregularities in contact with the nonwoven fabric layer to the entire spunbonded nonwoven fabric. In the case of ultrasonic bonding, it refers to the ratio of the portion (bonded portion) thermally welded by ultrasonic processing to the entire spunbonded nonwoven fabric.
- a circle, an ellipse, a square, a rectangle, a parallelogram, a diamond, a regular hexagon, a regular octagon, or the like can be used.
- the adhesive portions are uniformly present at regular intervals in the longitudinal direction (transport direction) and the width direction of the spunbonded nonwoven fabric. By doing so, the variation in the strength of the spunbonded nonwoven fabric can be reduced.
- the surface temperature of the hot embossing roll at the time of heat bonding is ⁇ 50 to ⁇ 15 ° C. with respect to the melting point of the polyolefin resin used.
- the surface temperature of the heat roll is preferably ⁇ 50 ° C. or more, more preferably ⁇ 45 ° C. or more with respect to the melting point of the polyolefin-based resin.
- the surface temperature of the hot embossing roll is preferably ⁇ 15 ° C. or lower, more preferably ⁇ 20 ° C. or lower with respect to the melting point of the polyolefin resin, excessive thermal adhesion is suppressed, and as a spunbond nonwoven fabric, Suitable air permeability and workability suitable for use in air filters can be obtained.
- the temperature is adjusted so as to fall within the above range with respect to the lowest temperature among the melting points of the respective polyolefin resins.
- the linear pressure of the hot embossing roll during thermal bonding is preferably 10 N / cm or more and 500 N / cm or less.
- the linear pressure of the roll is preferably 10 N / cm or more, more preferably 50 N / cm or more, still more preferably 100 N / cm or more, and particularly preferably 150 N / cm, the heat is moderately heat-bonded and put to practical use. It is possible to obtain a spunbonded nonwoven fabric having a high strength.
- the linear pressure of the hot embossing roll is set to preferably 500 N / cm or less, more preferably 400 N / cm or less, and still more preferably 300 N / cm or less, it is used as a spunbonded nonwoven fabric, particularly for an air filter. Suitable air permeability and workability suitable for the sintering process can be obtained.
- thermocompression bonding is performed by a hot calender roll composed of a pair of upper and lower flat rolls.
- a pair of upper and lower flat rolls is a metal roll or an elastic roll having no irregularities on the surface of the roll, such as a pair of a metal roll and a metal roll, or a pair of a metal roll and an elastic roll. Can be used.
- the elastic roll is a roll made of a material having elasticity as compared with a metal roll.
- the elastic roll include so-called paper rolls such as paper, cotton, and aramid paper, and urethane-based resins, epoxy-based resins, silicone-based resins, polyester-based resins and hard rubbers, and resin-made rolls including a mixture thereof.
- paper rolls such as paper, cotton, and aramid paper, and urethane-based resins, epoxy-based resins, silicone-based resins, polyester-based resins and hard rubbers, and resin-made rolls including a mixture thereof.
- the charging method is not particularly limited, but according to various findings of the present inventors, in particular, corona charging method, drying after applying water to the nonwoven fabric sheet.
- a method of charging by charging for example, a method described in JP-A-9-501604, JP-A-2002-249978, etc.
- a thermal electret method, and the like are preferably used.
- an electric field strength of preferably 15 kV / cm or more, more preferably 20 kV / cm or more is suitable.
- the charging process may be performed continuously during the production of the nonwoven fabric, or the produced nonwoven fabric may be once wound up and processed in another process.
- Measurement method Unless otherwise specified, the measurement method is assumed to be measured by the method described above.
- the electret fiber sheet of the present invention will be described based on examples.
- the characteristics and performance in the present invention were obtained by the following methods.
- Average single fiber diameter Regarding the average single fiber diameter, 10 measurement samples of 3 mm x 3 mm were collected from an arbitrary position on the sheet, and the magnification was adjusted to 200 to 3000 times with a scanning electron microscope. Were photographed one by one, for a total of 10 pictures. The single fiber diameter was measured for the fiber in which the fiber diameter (single fiber diameter) in the photograph was clearly confirmed, and the average value was rounded off to the second decimal place of the average value.
- Sheet thickness The thickness of the sheet was measured at equal intervals in the width direction at 10 points using a thickness gauge (“TECLOCK” (registered trademark) SM-114, manufactured by TECLOCK Co., Ltd.), and the average value was rounded to the third decimal place.
- TECLOCK registered trademark
- a 10% solution of polystyrene 0.309U (manufactured by Nacalai Tesque, Inc.) is diluted up to 200 times with distilled water and filled in the dust storage box 2.
- the measurement sample M is set in the sample holder 1, and the air volume is adjusted by the flow rate adjustment valve 4 so that the filter passage speed becomes 6.5 m / min, and the dust concentration is 10,000 / (2.83).
- the number D of dust upstream and the number d of downstream dust of the measurement sample M were measured three times per one measurement sample using a particle counter 6 (manufactured by Rion, KC-01D), and the measurement was carried out according to JIS K 0901 (1991), Based on the following formula, the collection efficiency (%) of particles having a particle size of 0.3 ⁇ m or more and 0.5 ⁇ m or less was determined based on “the shape, size, and performance test method of the filter material for collecting dust samples”.
- Collection efficiency (%) [1- (d / D)] ⁇ 100 (However, d represents the total number of three times of downstream dust, and D represents the total number of three times of upstream dust.)
- the pressure loss was obtained by reading the static pressure difference between the upstream and downstream of the measurement sample M at the time of measuring the collection efficiency with the pressure gauge 8. The average value of the five measurement samples was defined as the final pressure loss.
- the pressure loss was 25 Pa or less and the QF value, which is an index of the trapping performance calculated according to the following equation, was 0.13 Pa -1 or more, it was determined to be acceptable.
- Sheet Density The sheet density is calculated by dividing the basis weight measured in (1) by the thickness measured in (3). The obtained value was rounded off to the fourth decimal place to calculate the sheet density (g / cm 3 ).
- Example 1 Extrusion of a polyolefin resin containing 1% by mass of a hindered amine compound “Kimasorb” (registered trademark) 944LD (manufactured by BASF Japan Ltd.) in a polypropylene resin composed of a homopolymer having an MFR of 200 g / 10 minutes and represented by Compound A. After being melted by a machine, a yarn spun at a spinning temperature of 235 ° C. and a single hole discharge rate of 0.32 g / min from a rectangular die having a hole diameter ⁇ of 0.30 mm and a hole depth of 2 mm is cooled and solidified.
- a hindered amine compound “Kimasorb” registered trademark 944LD
- the obtained non-woven fiber web was heat-temporarily bonded at a temperature of 120 ° C. using a flat roll, and the obtained heat-temporarily bonded non-woven web was engraved with a metal polka dot pattern on the upper roll.
- an embossing roll having an adhesion area ratio of 16% and using a pair of upper and lower hot embossing rolls composed of a metal flat roll as a lower roll, heat is applied at a linear pressure of 30 N / cm and a thermal bonding temperature of 130 ° C.
- a spunbond nonwoven fabric having a basis weight of 30 g / m 2 was obtained.
- the average single fiber diameter of the obtained spunbonded nonwoven fabric was 10.1 ⁇ m.
- the spinnability was good with no yarn breakage after 1 hour of spinning.
- Example 2 An electret nonwoven fabric was obtained in the same manner as in Example 1, except that the MFR was 800 g / 10 min and the single hole discharge rate was 0.21 g / min. The basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 7.2 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 3 An electret nonwoven fabric was obtained in the same manner as in Example 1, except that the MFR was 155 g / 10 min and the single hole discharge rate was 0.24 g / min. The basis weight of the nonwoven fabric was 45 g / m 2 , and the average single fiber diameter was 8.9 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 4 A hindered amine compound A "Kimasorb” (registered trademark) 944LD (manufactured by BASF Japan Ltd.) 1% by mass and a crystal nucleating agent "Irgclear” represented by compound B are added to a polypropylene resin composed of a homopolymer having an MFR of 200 g / 10 minutes.
- a polyolefin resin containing 0.05% by mass of (registered trademark) XT386 manufactured by BASF Japan Co., Ltd.
- a hole having a diameter ⁇ of 0.30 mm and a hole depth of 2 mm is cut from a rectangular die.
- the yarn spun at a spinning temperature of 235 ° C. and a single hole ejection rate of 0.32 g / min is cooled and solidified, and then pulled and stretched by a rectangular ejector with compressed air at an ejector pressure of 0.35 MPa, and then trapped. Collected on the collection net. Except for the above, an electret nonwoven fabric was obtained in the same manner as in Example 1.
- the basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 9.8 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 5 A polyolefin resin containing 1% by mass of a hindered amine compound “Kimasorb” (registered trademark) 2020 (manufactured by BASF Japan Ltd.) represented by Compound C is extruded from a homopolymer polypropylene resin having an MFR of 200 g / 10 min. After being melted by a machine, a yarn spun at a spinning temperature of 235 ° C. and a single hole discharge rate of 0.32 g / min from a rectangular die having a hole diameter ⁇ of 0.30 mm and a hole depth of 2 mm is cooled and solidified.
- a hindered amine compound “Kimasorb” (registered trademark) 2020 manufactured by BASF Japan Ltd.
- the obtained non-woven fiber web was thermally pre-bonded at a temperature of 145 ° C. using a flat roll, and the obtained hot-temporarily bonded non-woven web was engraved with a metal polka dot pattern on the upper roll.
- an embossing roll having an adhesion area ratio of 16% and using a pair of upper and lower hot embossing rolls composed of a metal flat roll as a lower roll, heat is applied at a linear pressure of 30 N / cm and a thermal bonding temperature of 145 ° C.
- a spunbond nonwoven fabric having a basis weight of 60 g / m 2 was obtained. The average single fiber diameter was 11.8 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Example 1 An electret nonwoven fabric was obtained in the same manner as in Example 1 except for the above. Table 1 shows measured values and calculated values of the obtained electret nonwoven fabric.
- Example 6 An electret nonwoven fabric was obtained in the same manner as in Example 5, except that the MFR was 155 g / 10 min, the single hole discharge rate was 0.37 g / min, and the ejector pressure was 0.20 MPa. The basis weight of the nonwoven fabric was 20 g / m 2 , and the average single fiber diameter was 11.8 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 7 An electret nonwoven fabric was obtained in the same manner as in Example 2.
- the basis weight of the nonwoven fabric was 10 g / m 2 , and the average single fiber diameter was 6.6 ⁇ m.
- the spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 8 An electret nonwoven fabric was obtained in the same manner as in Example 1, except that the MFR was 39 g / 10 min and the single hole discharge rate was 0.65 g / min.
- the basis weight of the nonwoven fabric was 23 g / m 2 , and the average single fiber diameter was 21.5 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 9 An electret nonwoven fabric was obtained in the same manner as in Example 4, except that the addition rate of the crystal nucleating agent “Irgclear” (registered trademark) XT386 (manufactured by BASF Japan Ltd.) represented by the compound B was changed to 0.005% by mass.
- the basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 9.8 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 10 A spunbonded nonwoven fabric was prepared in the same manner as in Example 4 except that the addition rate of the crystal nucleating agent “Irgclear” (registered trademark) XT386 (manufactured by BASF Japan Ltd.) represented by the compound B was 0.5% by mass. Obtained.
- the basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 10.1 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 11 An electret nonwoven fabric was obtained in the same manner as in Example 1, except that the MFR was 60 g / 10 min, the single hole discharge amount was 0.43 g / min, and the ejector pressure was 0.15 MPa. The basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 14.0 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured and calculated values of the obtained electret nonwoven fabric.
- Example 12 The non-woven fiber web is thermally pre-bonded at a temperature of 110 ° C. using a flat roll, and the resulting non-woven web that has been thermally pre-bonded is bonded to the upper roll using a metal polka dot pattern engraved area ratio.
- a 16% embossing roll and a pair of upper and lower hot embossing rolls composed of a metal flat roll as the lower roll heat bonding at a linear pressure of 10 N / cm and a heat bonding temperature of 120 ° C.
- An electret nonwoven fabric was obtained in the same manner as in Example 11, except that a spunbond nonwoven fabric having a basis weight of 200 g / m2 was obtained.
- the average single fiber diameter of the obtained spunbonded nonwoven fabric was 14.0 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- Table 1 shows the measured values and calculated values of the electret nonwoven fabric.
- the obtained nonwoven fabric had very good collection efficiency, but was inferior in tensile strength, high in pressure loss, and could not be used for air filters.
- Example 2 A spunbonded nonwoven fabric was obtained in the same manner as in Example 1, except that the addition ratio of the hindered amine compound A “Kimasorb” (registered trademark) 944LD (manufactured by BASF Japan Ltd.) was 1% by mass.
- the basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 10.1 ⁇ m.
- the spinnability was good with no yarn breakage after 1 hour of spinning.
- the obtained nonwoven fabric had a low collection efficiency, and did not reach the range where it could be used for air filters.
- Example 3 A spunbonded nonwoven fabric was obtained in the same manner as in Example 1, except that the MFR was 30 g / 10 min and the single hole discharge rate was 0.70 g / min. The basis weight of the nonwoven fabric was 30 g / m 2 , and the average single fiber diameter was 22.5 ⁇ m. The spinnability was good with no yarn breakage after 1 hour of spinning.
- the obtained nonwoven fabric had a low collection efficiency, and did not reach the range where it could be used for air filters.
- a nonwoven fabric comprising fibers made of a polyolefin resin, having an average single fiber diameter of 6.5 ⁇ m or more and 22.0 ⁇ m or less, and containing a hindered amine compound at 0.1% by mass or more and 5% by mass or less.
- MFR melt flow rate
- the spunbonded nonwoven fabrics of Examples 1 to 10 have a large tensile strength per unit area. In addition, high collection performance has been achieved.
- Comparative Example 1 has a high weight per unit area due to a high weight per unit area
- Comparative Example 2 has a low nonwoven fabric tensile strength per unit area per unit area because of a meltblown nonwoven cloth
- Comparative Example 3 has a low hindered amine compound A addition rate. Therefore, the electretization was insufficient and the collection efficiency was low.
- Comparative Example 4 was a result that the average single fiber diameter was large and the collection efficiency was low.
- a high-performance spunbond having a low pressure loss and high trapping performance is obtained, and this spunbond nonwoven fabric can be preferably used for an air filter as a filter material, but its application range is not limited to these. Absent.
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Abstract
Description
本発明のスパンボンド不織布の好ましい態様によれば、前記スパンボンド不織布の目付が、5g/m2以上60g/m2以下である。
以下に、その構成要素について詳細に説明するが、本発明はその要旨を超えない限り、以下に説明する範囲に何ら限定されるものではない。
本発明で用いられるスパンボンド不織布を構成する繊維は、ポリオレフィン系樹脂からなる。このポリオレフィン系樹脂としては、ポリプロピレン系樹脂、ポリエチレン系樹脂などが挙げられる。ポリプロピレン系樹脂としては、プロピレンの単独重合体もしくはプロピレンと各種α-オレフィンとの共重合体などが挙げられ、また、ポリエチレン樹脂としては、エチレンの単独重合体もしくはエチレンと各種α-オレフィンとの共重合体などが挙げられるが、これらの材料の中でも、ポリプロピレンを主体とするものはエレクトレット性能を特に発揮する点から好ましい。またポリマーの性質を損なわない範囲で他の成分が共重合されていてもよい。
該化合物をスパンボンド不織布に存在させることにより、帯電により付与された電荷をより効果的に安定化できるため、該スパンボンド不織布をエアフィルターの濾材に使用した場合には、捕集性能が向上し、低い圧力損失で高捕集性能を有したエアフィルターを実現できるのである。
また、本発明のスパンボンド不織布を構成する繊維は、複合型繊維も用いることができる。複合型繊維の複合形態としては、例えば、同心芯鞘型、偏心芯鞘型および海島型などの複合形態を挙げることができる。単成分繊維や、芯鞘型、海島型といった複合成分型繊維等、特に限定されるものではないが、複合成分型繊維の場合、樹脂の選択次第では、樹脂間の電気抵抗の相違より電荷が漏洩する可能性があるため、単成分繊維であることが好ましい態様である。
本発明のスパンボンド不織布のMFRは、32g/10分以上850g/10分以下であることが重要である。32g/10分以上、好ましくは60g/10分以上、より好ましくは、80g/10分以上、さらに好ましくは、特に好ましくは120g/10分以上、最も好ましくは155g/10分以上である。これにより、細化が進み、捕集効率の高い不織布とすることができる。一方、850g/10分以下、好ましくは、600g/10分以下、より好ましくは、400g/10分以下とすることにより、紡糸する際の繊維の細化挙動が安定し、生産性を高くするために速い紡糸速度で延伸したとしても、安定した紡糸が可能となる。
次に、本発明のスパンボンド不織布を製造する方法の一例を説明する。
測定方法について、特段、記載のないものについては、前記された方法によって測定されたものとする。
タテ×ヨコ=5cm×5cmのシートの質量を、1サンプルについて3枚測定した。得られた値を1m2当たりの値に換算し、小数点以下第1位を四捨五入して、シート目付(g/m2)を算出した。
平均単繊維直径については、シートの任意の場所から、3mm×3mmの測定サンプルを10個採取し、走査型電子顕微鏡で倍率を200~3000倍に調節して、採取した測定サンプルから繊維表面写真を各1枚ずつ、計10枚を撮影した。写真の中の繊維直径(単繊維径)がはっきり確認できる繊維について単繊維径を測定し、平均した値の小数点以下第2位を四捨五入して平均単繊維径とした。
厚み計(テクロック社製“TECLOCK”(登録商標)SM-114)を使用して、シートの厚みを幅方向等間隔に10点測定し、その平均値から小数点以下第3位を四捨五入し、厚みとした。
シートの幅方向5カ所で、タテ×ヨコ=15cm×15cmの測定用サンプルを採取し、それぞれのサンプルについて、図1に示す捕集効率測定装置を用いて捕集効率を測定した。この図1の捕集効率測定装置には、測定サンプルMをセットするサンプルホルダー1の上流側に、ダスト収納箱2を連結し、下流側に流量計3、流量調整バルブ4およびブロワ5が連結されている。また、サンプルホルダー1にパーティクルカウンター6を使用し、切替コック7を介して、測定サンプルMの上流側のダスト個数と下流側のダスト個数とをそれぞれ測定することができる。さらに、サンプルホルダー1は圧力計8を備え、測定サンプルMの上流と下流での静圧差を読み取ることができる。
・捕集効率(%)=〔1-(d/D)〕×100
(ただし、dは下流ダストの3回測定トータル個数を表し、Dは上流のダストの3回測定トータル個数を表す。)。
なお、圧力損失が25Pa以下であり、かつ、下記式に従って算出される捕集性能の指数であるQF値が0.13Pa-1以上である場合に合格と判定した。
・QF値(Pa-1)=-ln(1-捕集効率(%)/100)/圧力損失(Pa)
(5)単位目付当たりの不織布の引張強度(N/5cm)/(g/m2);
縦方向の引張強度は、JIS L1913(2010年)の6.3.1に準じ、以下のように測定される値を採用するものとする。
(A)積層不織布から幅5cm×30cmの試験片を2枚採取する。
(B)試験片をつかみ間隔20cmで引張試験機にセットする。
(C)引張速度10cm/分で引張試験を行い、サンプルが破断したときの強度を引張強度(N/5cm)とし、3点の平均値を、小数点以下第二位を四捨五入して算出する。ここで得られた引張強度を上記(1)で測定した目付で除することで単位目付当たりの不織布の引張強度を算出する。なお、0.3(N/5cm)/(g/m2)以上の場合に、引張強度があるとした。
上記(4)で測定した圧力損失を上記(1)で測定した目付で除することで単位目付当たりの不織布の圧力損失を算出し、得られた値を、小数点以下第3位を四捨五入する。なお、単位目付当たりの不織布の圧力損失は0.10(Pa)/(g/m2)以上0.50(Pa)/(g/m2)以下である場合に合格と判定した。
上記(1)で測定した目付を上記(3)で測定した厚みで除することでシートの密度を算出する。得られた値を、小数点以下第4位を四捨五入して、シートの密度(g/cm3)を算出した。
MFRが200g/10分のホモポリマーからなるポリプロピレン樹脂に化合物Aで表されるヒンダードアミン系化合物“キマソーブ”(登録商標)944LD(BASFジャパン(株)製)を1質量%含むポリオレフィン系樹脂を、押出機で溶融し、孔径φが0.30mm、孔深度が2mmの矩形口金から、紡糸温度が235℃、単孔吐出量が0.32g/分で紡出した糸条を、冷却固化した後、矩形エジェクターでエジェクターの圧力を0.35MPaとした圧縮エアによって牽引、延伸し、捕集ネット上に捕集した。得られた不織繊維ウェブを、フラットロールを用いて120℃の温度で熱仮接着し、得られた熱仮接着された不織ウェブを、上ロールに金属製で水玉柄の彫刻がなされた接着面積率16%のエンボスロールを用い、下ロールに金属製フラットロールで構成される上下一対の熱エンボスロールを用いて、線圧が30N/cmで、熱接着温度が130℃の温度で熱接着し、目付が30g/m2のスパンボンド不織布を得た。得られたスパンボンド不織布の平均単繊維直径は10.1μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを800g/10分とし、単孔吐出量が0.21g/分とした以外は、実施例1と同様にしてエレクトレット不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は7.2μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを155g/10分とし、単孔吐出量が0.24g/分とした以外は、実施例1と同様にしてエレクトレット不織布を得た。不織布の目付は45g/m2であり、平均単繊維直径は8.9μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRが200g/10分のホモポリマーからなるポリプロピレン樹脂にヒンダードアミン系化合物A“キマソーブ”(登録商標)944LD(BASFジャパン(株)製)1質量%と、化合物Bで表される結晶核剤“Irgaclear”(登録商標)XT386(BASFジャパン(株)製)を0.05質量%とを含むポリオレフィン系樹脂を、押出機で溶融し、孔径φが0.30mm、孔深度が2mmの矩形口金から、紡糸温度が235℃、単孔吐出量が0.32g/分で紡出した糸条を、冷却固化した後、矩形エジェクターでエジェクターの圧力を0.35MPaとした圧縮エアによって牽引、延伸し、捕集ネット上に捕集した。前記以外は、実施例1と同様にしてエレクトレット不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は9.8μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRが200g/10分のホモポリマーからなるポリプロピレン樹脂に化合物Cで表されるヒンダードアミン系化合物“キマソーブ”(登録商標)2020(BASFジャパン(株)製)1質量%を含むポリオレフィン系樹脂を、押出機で溶融し、孔径φが0.30mm、孔深度が2mmの矩形口金から、紡糸温度が235℃、単孔吐出量が0.32g/分で紡出した糸条を、冷却固化した後、矩形エジェクターでエジェクターの圧力を0.35MPaとした圧縮エアによって牽引、延伸し、捕集ネット上に捕集した。得られた不織繊維ウェブを、フラットロールを用いて145℃の温度で熱仮接着し、得られた熱仮接着された不織ウェブを、上ロールに金属製で水玉柄の彫刻がなされた接着面積率16%のエンボスロールを用い、下ロールに金属製フラットロールで構成される上下一対の熱エンボスロールを用いて、線圧が30N/cmで、熱接着温度が145℃の温度で熱接着し、目付が60g/m2のスパンボンド不織布を得た。平均単繊維直径は11.8μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを155g/10分とし、単孔吐出量が0.37g/分とし、エジェクターの圧力を0.20MPaとした以外は、実施例5と同様にしてエレクトレット不織布を得た。不織布の目付は20g/m2であり、平均単繊維直径は11.8μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
実施例2と同様にしてエレクトレット不織布を得た。不織布の目付は10g/m2であり、平均単繊維直径は6.6μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを39g/10分とし、単孔吐出量が0.65g/分とした以外は、実施例1と同様にしてエレクトレット不織布を得た。不織布の目付は23g/m2であり、平均単繊維直径は21.5μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
化合物Bで表される結晶核剤“Irgaclear”(登録商標)XT386(BASFジャパン(株)製)の添加率を0.005質量%とした以外は、実施例4と同様にしてエレクトレット不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は9.8μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
化合物Bで表される結晶核剤“Irgaclear”(登録商標)XT386(BASFジャパン(株)製)の添加率を0.5質量%とした以外は、実施例4と同様にしてスパンボンド不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は10.1μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを60g/10分とし、単孔吐出量を0.43g/分、エジェクターの圧力を0.15MPaとした以外は実施例1と同様にエレクトレット不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は14.0μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
不織繊維ウェブを、フラットロールを用いて110℃の温度で熱仮接着し、得られた熱仮接着された不織ウェブを、上ロールに金属製で水玉柄の彫刻がなされた接着面積率16%のエンボスロールを用い、下ロールに金属製フラットロールで構成される上下一対の熱エンボスロールを用いて、線圧が10N/cmで、熱接着温度が120℃の温度で熱接着し、不織布の目付が200g/m2のスパンボンド不織布を得たこと以外は、実施例11と同様にエレクトレット不織布を得た。得られたスパンボンド不織布の平均単繊維直径は14.0μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRが800g/分のホモポリマーからなるポリプロピレン樹脂を押出機で溶融し、孔径φが0.25mmの口金から、紡糸温度が260℃、単孔吐出量が0.10g/分で紡出した。その後、エア温度が290℃、エア圧力が0.10MPaの条件でエアを糸条に噴射し、前記の熱融着性不織布層上に捕集し、メルトブロー不織布を形成した。不織布の目付は20g/m2であり、平均繊維径平均単繊維直径は4μmであった。
ヒンダードアミン系化合物A“キマソーブ”(登録商標)944LD(BASFジャパン(株)製)の添加率を1質量%とした以外は、実施例1と同様にしてスパンボンド不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は10.1μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
MFRを30g/10分とし、単孔吐出量が0.70g/分とした以外は、実施例1と同様にしてスパンボンド不織布を得た。不織布の目付は30g/m2であり、平均単繊維直径は22.5μmであった。紡糸性については、1時間の紡糸において糸切れは見られず良好であった。
2:ダスト収納箱
3:流量計
4:流量調整バルブ
5:ブロワ
6:パーティクルカウンター
7:切替コック
8:圧力計
M:測定サンプル
Claims (9)
- ポリオレフィン系樹脂からなる繊維で構成され、その平均単繊維直径が6.5μm以上22.0μm以下であり、ヒンダードアミン系化合物が0.1質量%以上5質量%以下含有されてなるスパンボンド不織布であって、前記不織布のメルトフローレート(MFR)が、32g/10分以上850g/10分以下であり、該不織布がエレクトレット加工されてなる、スパンボンド不織布。
- ポリオレフィン系樹脂からなる繊維で構成され、その平均単繊維直径が6.5μm以上13.0μm以下であり、下記一般式(1)で表される化合物が0.1質量%以上5質量%以下含有する不織布であって、前記不織布のメルトフローレート(MFR)が、80g/10分以上850g/10分以下であり、該不織布がエレクトレット加工されてなる、スパンボンド不織布。
- 前記不織布の目付が、5g/m2以上60g/m2以下である、請求項1~3のいずれかに記載のスパンボンド不織布。
- 前記不織布の厚みが、0.05mm以上1.0mm以下である、請求項1~4のいずれかに記載のスパンボンド不織布。
- 単位目付当たりの縦方向の引張強度が0.3(N/5cm)/(g/m2)以上である、請求項1~5のいずれかに記載のスパンボンド不織布。
- 単位目付あたりの圧力損失が0.10~0.50(Pa)/(g/m2)以下である、請求項1~6のいずれかに記載のスパンボンド不織布。
- 前記不織布に、結晶核剤が0.001質量%以上1.0質量%以下含有されてなる、請求項1~7のいずれかに記載のスパンボンド不織布。
- 請求項1~8のいずれかに記載の不織布を用いてなる、エアフィルター用濾材。
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| WO2021153296A1 (ja) * | 2020-01-27 | 2021-08-05 | 東レ株式会社 | 積層エレクトレット不織布ならびにこれを用いてなるエアフィルターユニット、空気清浄機 |
| WO2022101203A1 (en) * | 2020-11-10 | 2022-05-19 | Neenah Gessner Gmbh | Filter medium comprising a nonwoven electret |
| WO2023276484A1 (ja) * | 2021-07-02 | 2023-01-05 | 東レ株式会社 | エレクトレット繊維シートおよび積層シート、エアフィルター、エレクトレット繊維シートの製造方法 |
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| JPWO2023058516A1 (ja) * | 2021-10-08 | 2023-04-13 | ||
| WO2023167053A1 (ja) * | 2022-03-03 | 2023-09-07 | 東レ株式会社 | エレクトレットメルトブロー不織布、および、これを用いてなるエアフィルター濾材 |
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- 2019-07-22 WO PCT/JP2019/028646 patent/WO2020022260A1/ja not_active Ceased
- 2019-07-22 US US17/261,352 patent/US11975281B2/en active Active
- 2019-07-22 JP JP2020532381A patent/JPWO2020022260A1/ja active Pending
- 2019-07-22 KR KR1020207037807A patent/KR102801606B1/ko active Active
- 2019-07-22 CN CN201980048655.7A patent/CN112424410A/zh active Pending
- 2019-07-25 TW TW108126384A patent/TW202015781A/zh unknown
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| WO2021153296A1 (ja) * | 2020-01-27 | 2021-08-05 | 東レ株式会社 | 積層エレクトレット不織布ならびにこれを用いてなるエアフィルターユニット、空気清浄機 |
| WO2022101203A1 (en) * | 2020-11-10 | 2022-05-19 | Neenah Gessner Gmbh | Filter medium comprising a nonwoven electret |
| JP2023551393A (ja) * | 2020-11-10 | 2023-12-08 | ネーナー・ゲッスナー・ゲーエムベーハー | 不織布エレクトレットを含む濾材 |
| WO2023276484A1 (ja) * | 2021-07-02 | 2023-01-05 | 東レ株式会社 | エレクトレット繊維シートおよび積層シート、エアフィルター、エレクトレット繊維シートの製造方法 |
| JP7226655B1 (ja) * | 2021-07-02 | 2023-02-21 | 東レ株式会社 | エレクトレット繊維シートおよび積層シート、エアフィルター、エレクトレット繊維シートの製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US11975281B2 (en) | 2024-05-07 |
| KR102801606B1 (ko) | 2025-04-25 |
| TW202015781A (zh) | 2020-05-01 |
| JPWO2020022260A1 (ja) | 2021-08-05 |
| US20210283541A1 (en) | 2021-09-16 |
| KR20210035099A (ko) | 2021-03-31 |
| CN112424410A (zh) | 2021-02-26 |
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