WO2014175380A1 - 黒色ポリテトラフルオロエチレン多孔質膜およびその製造方法と用途 - Google Patents
黒色ポリテトラフルオロエチレン多孔質膜およびその製造方法と用途 Download PDFInfo
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- WO2014175380A1 WO2014175380A1 PCT/JP2014/061570 JP2014061570W WO2014175380A1 WO 2014175380 A1 WO2014175380 A1 WO 2014175380A1 JP 2014061570 W JP2014061570 W JP 2014061570W WO 2014175380 A1 WO2014175380 A1 WO 2014175380A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
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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
- D01F1/04—Pigments
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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
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
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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
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
- D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
Definitions
- the present invention relates to a black polytetrafluoroethylene porous membrane and a production method and use thereof.
- Polytetrafluoroethylene has excellent chemical resistance, heat resistance, electrical insulation, and has properties such as self-lubricating and non-adhesive properties. Widely used in the field.
- PTFE is used after being processed into a porous membrane
- the PTFE porous membrane is used for a filter such as a vent filter, for example.
- the vent filter is used for, for example, an acoustic microphone or a cover of a mobile phone or the like, and is a filter that ensures ventilation inside the molded body and provides a waterproof and dustproof function to the molded body while maintaining a pressure adjusting function. It is.
- PTFE used for a vent filter
- PTFE PTFE
- ePTFE PTFE
- PTFE PTFE
- ePTFE is composed of a fibrous part and a nodule part of PTFE, and the light irradiated to ePTFE is substantially totally reflected by this unique structural feature, and thus the appearance of ePTFE is pure white. And is not suitable for applications that are not allowed to be white.
- Patent Document 1 Japanese Patent Laid-Open No. 7-289865.
- Patent Document 1 Japanese Patent Laid-Open No. 7-289865.
- Patent Document 1 discloses only a stretched porous PTFE membrane obtained from pre-colored PTFE using a colored paste-like PTFE obtained by mixing and stirring a colorant, PTFE fine powder, and a liquid lubricant as raw materials. It is taught that such a problem can be solved by a vent filter consisting of
- the vent filter described in Patent Document 1 is black (in this specification, “black” means that the lightness (V) represented by the Munsell symbol in accordance with JIS Z 8721 is N2.5 or less.
- black means that the lightness (V) represented by the Munsell symbol in accordance with JIS Z 8721 is N2.5 or less.
- Patent Document 1 is characterized by using a colored paste-like PTFE obtained by mixing and stirring a colorant, PTFE fine powder, and a liquid lubricant as a material for a vent filter, It is an invention characterized by the manufacturing process.
- Patent Document 2 Japanese Patent Publication No. 2012-515850 is taken up here as an invention for producing a PTFE molded body using a method other than the method described in Patent Document 1.
- Patent Document 2 describes a method of creating a PTFE mat by an electrospinning method (so-called electrospinning method). However, in the invention described in Patent Document 2, it is an object to provide an improved method for electrospinning PTFE, and the above-mentioned problem relating to the color of PTFE is not recognized. Therefore, Patent Document 2 does not teach any means for solving the problem related to the color of PTFE.
- Patent Document 3 (WO2009 / 031620 International Publication) describes a water-soluble electrospun sheet containing a water-soluble substrate, and examples of the water-soluble substrate include vinyl polymers and acrylic polymers. Also described is an embodiment in which the water-soluble electrospun sheet contains a colored component.
- Patent Document 4 Japanese Patent Laid-Open No. 2012-123359 describes a makeup sheet-like cosmetic having a nanofiber sheet of a polymer compound containing a color pigment, and the makeup sheet-like makeup. A production method for producing the material by electrospinning is also described.
- Patent Document 3 and Patent Document 4 describe a method for coloring a polymer compound using an electrospinning method
- PTFE is blackened.
- the problem of not being able to color is not recognized. Therefore, Patent Document 3 and Patent Document 4 do not teach any means for solving the problems related to the color of PTFE.
- Patent Document 3 and Patent Document 4 do not describe any use of a filter such as a vent filter.
- the black PTFE porous membrane whose brightness (V) is N2.5 or less has not been conventionally known.
- An object of the present invention is to provide a black PTFE porous membrane having a lightness (V) of N2.5 or less without impairing performance such as strength as compared with a conventional PTFE porous membrane.
- the carbon-containing polytetrafluoroethylene (PTFE) nanofiber (d), the lightness (V) represented by the Munsell symbol according to JIS Z 8721 is N2.5 or less, and the carbon-containing PTFE nanofiber (
- a black PTFE porous membrane obtained by subjecting a spinning solution containing at least carbon (b) powder and PTFE or modified PTFE (A) to an electrospinning method.
- the spinning solution containing PTFE or modified PTFE serving as a binder resin plays an important role, and the PTFE porous membrane according to the present invention is obtained by the electrospinning method.
- PTFE nanofibers colored with a black colorant black (lightness) with the excellent physical properties of PTFE (chemical resistance, heat resistance, electrical insulation, self-lubrication, non-adhesiveness, etc.) Is N2.5 or less).
- the black colorant is carbon
- a spinning solution containing PTFE or modified PTFE as a binder resin and carbon powder as a colorant may be subjected to an electrospinning method to form carbon-containing PTFE nanofibers.
- the brightness described above can be obtained by mixing PTFE, which is a binder resin, and carbon, which is a colorant, into a film by extrusion.
- a black PTFE porous membrane having (V) of N2.5 or less cannot be obtained). That is, the present invention is as follows.
- the black PTFE porous membrane according to the present invention includes polytetrafluoroethylene (PTFE) nanofibers (E) and black colorant-containing PTFE nanofibers (D) including a black colorant (B), and conforms to JIS Z 8721.
- the spinning (V) expressed by the Munsell symbol is N2.5 or less, and the black colorant-containing PTFE nanofiber (D) is subjected to an electrospinning method using a spinning solution containing at least PTFE or modified PTFE (A). It is characterized by being obtained.
- the black colorant-containing polytetrafluoroethylene (PTFE) nanofiber (D) is a carbon-containing polytetrafluoroethylene (PTFE) nanofiber (d), and the black colorant (B) is carbon (b), and the carbon-containing PTFE nanofiber (d) is obtained by subjecting a spinning solution containing at least PTFE or modified PTFE (A) and carbon (b) powder to an electrospinning method. It is preferable from the standpoint that the brightness (V) of the black PTFE porous membrane can be made smaller than before.
- the amount of the black coloring material (B) is 3 to 20 parts by weight with respect to 100 parts by weight of the PTFE (A), or PTFE or modified PTFE (A). It is preferable from the viewpoint that the lightness (V) of the black PTFE porous membrane can be made smaller than before without impairing the physical properties derived from the above.
- the filter which concerns on this invention comprises the said black PTFE porous membrane, It is characterized by the above-mentioned.
- the filter is a black PTFE porous membrane provided with a support, a protective layer and the like unless the necessary characteristics as a filter such as air permeability and filtration performance are greatly impaired. May be.
- the vent filter which concerns on this invention consists of said filter, It is characterized by the above-mentioned.
- the method for producing a black PTFE porous membrane according to the present invention comprises at least 3 to 20 parts by weight of polytetrafluoroethylene (PTFE) or modified PTFE (A) and 100 parts by weight of the PTFE or modified PTFE (A).
- a carbon (b) powder and a viscosity adjusting polymer (C) are dispersed in water and / or an organic solvent to prepare a spinning solution, and the spinning solution is subjected to an electrospinning method.
- the resulting carbon-containing PTFE is obtained.
- the nanofiber (d) is deposited in a sheet form, the sheet-like deposit of the carbon-containing PTFE nanofiber (d) is heated, and the water and / or organic solvent remaining in the sheet-form deposit and The viscosity adjusting polymer (C) is removed.
- the black PTFE porous membrane according to the present invention includes polytetrafluoroethylene (PTFE) nanofibers (E) and black colorant-containing PTFE nanofibers (D) including a black colorant (B), and conforms to JIS Z 8721.
- the spinning (V) expressed by the Munsell symbol is N2.5 or less
- the black colorant-containing PTFE nanofiber (D) is subjected to an electrospinning method using a spinning solution containing at least PTFE or modified PTFE (A). Therefore, the lightness (V) represented by the Munsell symbol according to JIS Z 8721 is N2.5 or less, and the blackness is excellent.
- the black PTFE porous membrane according to the present invention includes carbon-containing PTFE nanofibers, and the carbon-containing PTFE nanofibers are carbon powder and polytetrafluoroethylene (PTFE) or Since the spinning solution containing the modified PTFE is obtained by subjecting it to an electrospinning method, the lightness (V) represented by the Munsell symbol is N2.5 or less according to JIS Z 8721, and the blackness is excellent.
- PTFE polytetrafluoroethylene
- the black PTFE porous membrane according to the present invention can be suitably used for applications that are required to be black, for example, a black mobile phone or a speaker vent filter. it can.
- the black PTFE porous membrane according to the present invention in order to increase the blackness, it is not necessary to add a large amount of black coloring material such as carbon powder until the performance of the PTFE porous membrane is impaired. Excellent in water and tensile strength.
- a black PTFE porous membrane or an electrospinning method obtained by subjecting a spinning solution containing a black coloring material such as carbon powder in an amount of 3 to 20 parts by weight to 100 parts by weight of the PTFE for electrospinning.
- black PTFE porous membrane can be suitably used for applications that require air permeability, water repellency, tensile strength, and the like, for example, filters, and in particular, vent filters.
- the black PTFE porous membrane according to the present invention is required to have air permeability, water repellency, tensile strength, etc. in addition to being black as in the case of a black cellular phone vent filter, among other applications. It can be very suitably used for applications.
- the black PTFE porous membrane as described above can be produced efficiently and with good productivity.
- FIG. 1 is a diagram illustrating an example of an electrospinning apparatus and the principle of electrospinning.
- FIG. 2 is a graph showing the relationship between carbon (CB) parts by weight with respect to 100 parts by weight of PTFE in the black PTFE porous membrane and the brightness (V) of the black PTFE porous membrane according to the present invention.
- FIG. 3 is a graph showing the relationship between carbon (CB) parts by weight with respect to 100 parts by weight of PTFE and Gurley values (sec / 100 cc) per 25 ⁇ m thickness of the black PTFE porous membrane according to the present invention.
- FIG. 4 is a graph showing the relationship between carbon (CB) parts by weight with respect to 100 parts by weight of PTFE and the contact angle of the black PTFE porous membrane according to the present invention.
- the amount of PTFE and modified PTFE in the black PTFE porous membrane and the amount of black coloring material such as carbon are the same as the amount of PTFE and modified PTFE used as a raw material for the production of the black PTFE porous membrane and the black powder such as carbon powder. Treated as substantially the same amount of colorant.
- blackness means whether the lightness is in the range of black (the lightness is N2.5 or less) in the range from white having the lightness of N9.5 to black having the lightness of N1 ( It is a term representing whether the blackness is high) or black (the brightness is N2.5 or less) or not (blackness is low). “High blackness” indicates that the brightness is black of N2.5 or less. “Low blackness” represents a color (gray or white with a lightness exceeding N2.5 and up to N9.5) separated from black (the lightness is N2.5 or less).
- the black polytetrafluoroethylene (PTFE) porous membrane according to the present invention contains a polytetrafluoroethylene (PTFE) nanofiber (E) and a black colorant-containing PTFE nanofiber containing a black colorant (B).
- the brightness (V) represented by the Munsell symbol in accordance with JIS Z 8721 is (N) 2.5 or less
- the black colorant-containing PTFE nanofiber (D) is at least PTFE or modified PTFE (A ) Is obtained by subjecting it to an electrospinning method.
- the black polytetrafluoroethylene (PTFE) porous membrane according to the present invention includes carbon-containing polytetrafluoroethylene (PTFE) nanofibers (d), and has a lightness (V) represented by a Munsell symbol in accordance with JIS Z8721. N2.5 or less, and the carbon-containing PTFE nanofiber (d) is obtained by subjecting a spinning solution containing the powder of carbon (b) and PTFE or modified PTFE (A) to an electrospinning method. This is preferable from the standpoint that the brightness (V) of the black PTFE porous membrane can be made smaller than before.
- Nonwoven fabric porous membrane containing nanofibers obtained by electrospinning PTFE or modified PTFE is a fiber compared to ePTFE in which fiber structures with different thicknesses such as a fibrous portion and a binding portion are mixed. Since the uniformity of the diameter is very high, it can be suitably used for filter performance such as air permeability. In addition, since shrinkage due to heating is less likely to occur compared to ePTFE, there is an advantage that characteristics hardly change depending on a manufacturing process including heating such as a reflow process.
- the black PTFE nanofiber (D) contained in the black PTFE porous membrane is obtained by subjecting a spinning solution containing at least PTFE or modified PTFE (A) to an electrospinning method.
- the carbon-containing PTFE nanofiber (d) contained in the black PTFE porous membrane can be a carbon-containing PTFE nanofiber (d), and the brightness (V) of the black PTFE porous membrane can be made smaller than before. From the viewpoint of the above.
- the carbon-containing PTFE nanofiber (d) is obtained, for example, by subjecting a spinning solution containing at least carbon (b) powder and PTFE or modified PTFE (A) to an electrospinning method.
- modified PTFE is obtained by copolymerizing a tetrafluoroethylene homopolymer and a small amount (for example, 0.5 mol% or less) of other monomers.
- PTFE or modified PTFE is contained in an amount of 80 to 97 parts by weight in 100 parts by weight of the porous film from the viewpoint of preventing the performance of the PTFE resin applied to the black PTFE porous film from being impaired as much as possible. Is preferred.
- the colorant for coloring PTFE or modified PTFE may be a colorant other than black, but it is a black colorant from the viewpoint of practical use.
- the black colorant (B) is not limited as long as it is a material capable of coloring and dyeing PTFE nanofibers to N2.5 or less, and examples thereof include inorganic pigments such as carbon, iron oxide, and metal complex compounds, and azine compounds. And organic dyes.
- inorganic pigments are preferable from the viewpoint that they can be integrated with PTFE nanofibers and hardly fall off from PTFE fibers, and can maintain the black color of black PTFE nanofibers over a long period of time.
- Carbon is a PTFE nanofiber.
- black coloring materials (B) may be blended with black PTFE nanofibers alone or in a mixture of two or more.
- black coloring materials (B) may be blended with black PTFE nanofibers alone or in a mixture of two or more.
- carbon in a case where a black PTFE porous membrane is obtained by subjecting a spinning solution containing PTFE or modified PTFE and carbon powder to an electrospinning method, which is a particularly preferable form, will be described in detail.
- the black coloring material is carbon powder
- the carbon-containing PTFE nanofibers, and thus the PTFE porous membrane can be colored to a black color with lower brightness.
- carbon in the case of obtaining a black PTFE porous membrane by subjecting a spinning solution containing carbon powder and PTFE or modified PTFE to an electrospinning method refers to a spinning solution subjected to an electrospinning method, which will be described later. It is a component derived from powder of carbon (b) used when coloring PTFE or modified PTFE nanofibers that have been spun or spun.
- the carbon-containing PTFE nanofibers, and thus the PTFE-based porous membrane are colored black so that the lightness (V) represented by the Munsell symbol is N2.5 or less according to JIS Z8721. It is preferable that the lightness (V) represented by the Munsell symbol in accordance with JIS Z 8721 is a component derived from carbon powder (carbon powder) of N2.5 or less, preferably N2.0 to 1.
- the black PTFE porous membrane according to the present invention includes PTFE nanofibers colored black by carbon, it is colored black.
- Carbon is a component derived from carbon powder such as carbon black, graphite, carbon nanotube, carbon nanofiber, fullerene, and the like.
- a component derived from carbon black is preferable from the viewpoint of efficiently coloring the carbon-containing PTFE nanofibers, and thus the black PTFE porous membrane, efficiently and inexpensively to black.
- These carbons may be blended singly or in combination with two or more carbon-containing PTFE nanofibers.
- black PTFE nanofibers such as carbon-containing PTFE nanofibers, and thus the PTFE porous membrane black, without damaging the performance of the PTFE resin as much as possible, with respect to 100 parts by weight of PTFE.
- it is preferably contained in an amount of 3 to 20 parts by weight with respect to 100 parts by weight of PTFE in the black PTFE porous membrane.
- the amount of black coloring material such as carbon is the amount of black coloring material such as carbon in the spinning solution used for the electrospinning method, carbon used when coloring the spun PTFE or modified PTFE nanofibers, etc.
- the amount of the black colorant can be adjusted.
- the black colorant can also serve as a filler, for example, carbon
- the amount of carbon relative to 100 parts by weight of PTFE or modified PTFE depends on the average fiber diameter of the carbon-containing PTFE nanofibers and the thickness of the black PTFE porous membrane. It affects the basis weight, voids, pore diameter, and air permeability, and also affects the appearance of the carbon-containing PTFE nanofiber and the black PTFE porous film, such as the blackness, water repellency, and tensile strength. This is presumably because carbon plays a role not only as a coloring material but also as a filler in the present invention.
- black coloring material such as carbon
- PTFE or modified PTFE depends on properties desired for black coloring material-containing PTFE nanofibers such as carbon-containing PTFE nanofibers and black PTFE porous membranes. This will be described in detail with reference to data in the item of an example described later.
- the black colorant-containing PTFE nanofibers such as carbon-containing PTFE nanofibers may contain other fillers and other fluororesin materials as long as the object of the present invention is not impaired.
- the black colorant-containing PTFE nanofibers such as carbon-containing PTFE nanofibers are described later. After the heat treatment, it is preferable that only the black colorant such as PTFE or modified PTFE and carbon is contained in the amount ratio as described above.
- the blackness of the black PTFE porous membrane according to the present invention is evaluated by the brightness (V) represented by the Munsell symbol according to JIS Z 8721.
- the brightness (V) of the black PTFE porous membrane of the present invention is usually N2. 0.5 or less, preferably 1.8 or less, particularly preferably 1.3 or less, and the lower limit is 1.0 in each case (Table 2).
- the blackness (the brightness (V)) of the black PTFE porous membrane according to the present invention can be adjusted to the above range by adjusting the amount of black coloring material such as carbon with respect to PTFE or modified PTFE, for example. .
- the amount of black coloring material such as carbon (the state in the black PTFE porous membrane) relative to PTFE or modified PTFE in the black PTFE porous membrane is the amount of black coloring material such as carbon powder relative to PTFE or modified PTFE in the electrospinning solution. It is substantially equal to the amount of (raw material state).
- the adjustment of the black coloring material such as the amount of carbon relative to PTFE or modified PTFE in the black PTFE porous membrane was adjusted according to the amount of the black coloring material such as carbon powder relative to PTFE or modified PTFE in the electrospinning solution or the electrospun. What is necessary is just to adjust by adjusting the quantity of black coloring materials, such as carbon powder with respect to PTFE nanofiber (the following is same).
- the black PTFE porous membrane according to the present invention has a lightness (V) of N2.5 or less, and unlike the conventional expanded PTFE porous membrane having a lightness (V) of at least about N5.5, Since the degree is high, for example, it can be suitably used for applications requiring a black color, such as a vent filter for a black mobile phone.
- N2.5 or less those whose brightness (V) is N2.5 or less are referred to as black
- those whose brightness (V) is greater than N2.5 and less than N8 are referred to as gray
- a lightness (V) of N8 to N10 is called white.
- the said brightness (V) is similarly applied not only to black coloring material containing PTFE nanofibers, such as carbon containing PTFE nanofiber, but to other materials.
- the lightness (V) expressed in Munsell symbols in accordance with JIS Z 8721 is an achromatic color (white color such as white, gray, or black), for example, N ( Unlike the case of chromatic colors (colors such as red, blue, and yellow), the hue is represented by an achromatic color (indicating symbol) and a numerical value (representing the brightness of the color, or lightness). , Saturation is not displayed.
- the brightness indicates the brightness of the color, and is usually determined by comparing the color of the evaluation object with the color sample.
- white that totally reflects light is white having the highest brightness (ie, N10)
- black that totally absorbs light is black having the lowest brightness (ie, N0). Since it is impossible to realize such white and black in (color sample) and the like, normally, a value of N9.5 is used for white with the highest brightness, and a value of 1 is used for black with the lowest brightness.
- black colorants such as carbon black can be selectively exposed on the surface of PTFE nanofibers containing black colorants such as carbon-containing nanofibers. It is assumed that high blackness can be exhibited.
- the black colorant-containing PTFE nanofibers such as carbon-containing nanofibers are obtained by subjecting a spinning solution containing PTFE or modified PTFE and, for example, carbon powder to an electrospinning method, Compared to the carbon support on the surface, it has the advantage that there is no powdering of carbon (carbon contamination), peeling and color fading.
- the average fiber diameter of black colorant-containing PTFE nanofibers such as carbon-containing PTFE nanofibers is preferably 400 to 3000 nm from the viewpoint of imparting excellent air permeability and water repellency to the black PTFE porous membrane.
- the thickness is more preferably 400 to 1500 nm, and further preferably 400 to 1000 nm.
- the thickness of the black PTFE porous membrane according to the present invention is preferably 10 ⁇ m or more, and more preferably 30 to 300 ⁇ m, from the viewpoint of the tensile strength and air permeability of the porous membrane.
- the average flow diameter (measurement method: bubble point method) of the black PTFE porous membrane according to the present invention is preferably 0.5 to 5.0 ⁇ m from the viewpoint of imparting excellent air permeability. It is more preferably 0 to 3.0 ⁇ m, and further preferably 1.0 to 2.0 ⁇ m.
- the air permeability of the black PTFE porous membrane according to the present invention is evaluated by an average Gurley value.
- the average Gurley measured according to JIS P8117 of the black PTFE porous membrane according to the present invention is 25 ⁇ m equivalent air permeability by multiplying the air permeability (sec / 100 cc) by 25 ( ⁇ m) / film thickness ( ⁇ m). Degree (sec / 100 cc).
- it is preferably 0.3 to 10.0 s / 100 cc, more preferably 0.3 to 3.0 s / 100 cc. Particularly preferred is 0.3 to 2.0 s / 100 cc.
- the water repellency of the black PTFE porous membrane according to the present invention is evaluated by the water contact angle.
- the water contact angle of the black PTFE porous membrane according to the present invention is preferably 110 to 150 °, and preferably 130 to 150 ° from the viewpoint of imparting excellent water repellency to the black PTFE porous membrane. More preferred.
- the black PTFE porous membrane according to the present invention is excellent in water repellency and the like, and can be suitably used for applications requiring water repellency, for example, a vent filter for a mobile phone. it can.
- the tensile strength of the black PTFE porous membrane according to the present invention is preferably 0.3 to 20 N / mm 2 , more preferably 0.5 to 10 N / mm 2 , and 1.2 to 1.7 N. More preferably, it is / mm 2 .
- the tensile strength of the black PTFE porous membrane according to the present invention is in the above range, it is not easily broken even if it is used for a filter or the like.
- the black PTFE porous membrane according to the present invention is made of, for example, carbon-containing PTFE nano material by electrospinning (electrospinning method) using black colorant such as PTFE or modified PTFE and carbon powder as raw materials. It can be produced by forming (or producing) a black colorant-containing PTFE nanofiber such as a fiber, and then heat-treating the obtained black colorant-containing PTFE nanofiber such as a carbon-containing PTFE nanofiber under specific conditions.
- the spinning solution only needs to contain at least PTFE or modified PTFE, but in the following, the black coloring material is carbon, and a spinning solution containing at least carbon powder and PTFE or modified PTFE is subjected to the electrospinning method.
- the black coloring material is carbon
- a spinning solution containing at least carbon powder and PTFE or modified PTFE is subjected to the electrospinning method.
- a case will be described as an example, and will be explained step by step.
- the following manufacturing method can be similarly applied when the black colorant is other than carbon powder.
- a form in which PTFE particles or modified PTFE particles and carbon powder are added in the form of a dispersion dispersed in water and / or an organic solvent is previously integrated with PTFE particles or modified PTFE particles and carbon powder ( It is also possible to change to a form in which the particles obtained by the (coloring) treatment are added in the state of dispersion dispersed in water and / or an organic solvent.
- a spinning solution is prepared for providing the electrospinning (electrospinning).
- PTFE or modified PTFE and carbon powder for the spinning solution, PTFE or modified PTFE and carbon powder, water and / or organic solvent (eg, chloroform, methanol, formic acid, N, N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, methyl ethyl ketone, etc.)
- a viscosity adjusting polymer (C) is added as necessary to prepare a spinning solution.
- the viscosity adjusting polymer (C) is used in electrospinning of a material insoluble in a solvent such as PTFE, and is used for adjusting the viscosity of the spinning solution to a desired range and molding a desired carbon-containing PTFE nanofiber. It is removed by subsequent heat treatment.
- viscosity adjusting polymer (C) examples include polyethylene oxide, dextran, alginic acid, chitosan, starch, polyvinyl pyridine compound, cellulose compound, cellulose ether, hydrolyzed polyacrylamide, polyacrylate, polycarboxylate, polyvinyl alcohol, polyethylene glycol, Examples include polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyitaconic acid and the like.
- the solvent examples include water, chloroform, methanol, formic acid, N, N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, methyl ethyl ketone and the like.
- water is preferable as a medium for dispersing PTFE, carbon and the like from the viewpoints of reduction of environmental load, cost reduction, ease of handling, volatility of the medium during electrospinning, and the like.
- PTFE, modified PTFE or carbon powder may be added to the spinning solution in any form as long as the spinning solution can be prepared. From the standpoint of uniform dispersion and enabling desired spinning, it is preferable to add in a dispersion state dispersed in water and / or an organic solvent.
- a stirring process, a heating / cooling process, a charge (pH) adjusting process, or the like may be performed in a dispersion state.
- the carbon-containing PTFE nanofibers and thus the porous membrane can be obtained by integrating the PTFE nanofibers and the carbon without greatly increasing the fiber diameter of the nanofibers and without impairing the performance of the PTFE resin as much as possible.
- the average secondary particle diameter of the carbon powder is preferably 50 to 1000 nm, more preferably 80 to 550 nm, and further preferably 80 to 280 nm.
- the average secondary particle diameter indicates an average diameter of secondary particles that are aggregates of primary particles that are single particles (minimum particles that cannot be divided). It is observed as the measured particle size in liquids.
- the preferable average primary particle diameter of the carbon powder is preferably 1 to 100 nm, more preferably 5 to 80 nm, and more preferably 8 to 20 nm from the viewpoint of efficiently coloring the PTFE nanofibers black. More preferably. From the above viewpoint, the size of the primary particles of the carbon powder is preferably 1/5 to 1/50, more preferably 1/10 to 1/20 with respect to the size of the primary particles of the PTFE particles.
- the average secondary particle diameter is measured by a laser diffraction method.
- the average primary particles of the PTFE particles are preferably 10 to 500 nm, more preferably 30 to 400 nm, and even more preferably 50 to 300 nm.
- the content of the carbon powder in the dispersion is preferably 1 to 20 parts by weight, more preferably 30 parts by weight or less from the viewpoint of the viscosity of the spinning solution, the fiber diameter of the carbon-containing PTFE nanofibers, the tensile strength, and the like. It is preferably 3 to 20 parts by weight.
- Carbon powder dispersions include Aqua Black 162 (hydrophilic carbon black, manufactured by Tokai Carbon Co., Ltd., average secondary particle size 110 nm, carbon black concentration 20% by weight), Aqua Black 001, and the like. It is done.
- PTFE and modified PTFE may be manufactured according to a conventional method or may be commercially available.
- examples of the dispersion of commercially available PTFE or modified PTFE include D210-C (manufactured by Daikin Industries, Ltd., PTFE content 60% by weight, average particle size 230 nm).
- the viscosity of the spinning solution is preferably 500 to 300,000 mPa ⁇ s, because it affects the shape and properties (eg, fiber diameter, tensile strength, etc.) of the carbon-containing PTFE nanofibers to be obtained, and preferably 500 to 50000 mPa ⁇ s. s is more preferable, and in particular, 1000 to 30000 mPa ⁇ s is preferable.
- the viscosity of the spinning solution may be adjusted to the above range by adding a viscosity modifier in an appropriate amount to the spinning solution.
- a viscosity modifier in an appropriate amount to the spinning solution.
- it may be adjusted to the above range by adding water and / or an organic solvent to the spinning solution.
- Electrospinning electrospinning
- the spinning solution prepared as described above is supplied to an electrospinning apparatus, and then electrospinning is performed.
- Electrospinning can be carried out, for example, by the method described in US 2010/0193999 A1.
- FIG. 1 is taken as an example of the electrospinning method, and an outline of the electrospinning method will be described with reference to this.
- the electrospinning apparatus 1 is provided with a container 2 storing a spinning solution and a target electrode connected to a DC voltage power source 4.
- a spinneret 3 capable of discharging the spinning solution is provided at the tip (lower end) of the container 2.
- PTFE, carbon, etc. are electrostatically charged when the spinning solution passes through the spinneret 3.
- fibers nanofibers 6
- the nonwoven fabric 7 is formed (see also the electron micrograph 8 of the nanofiber nonwoven fabric).
- Examples of the collector 5 include a sheet type, a drum type, and a moving belt type.
- Examples of the material constituting the collector 5 include iron, metals such as aluminum and copper.
- the type and material type of the collector 5 are not particularly limited as long as the electrospinning can be performed, and may be appropriately selected according to the purpose. If necessary, the spinneret 3 is provided with a spinning solution heating mechanism for improving the spinning efficiency.
- the carbon-containing PTFE nanofibers are spun by performing electrospinning using such an electrospinning apparatus (for example, ES-2300, manufactured by Huence Co., Ltd.).
- the spun carbon-containing PTFE nanofibers are usually accumulated on a collector installed in advance to form a sheet-like deposit made of carbon-containing PTFE nanofibers.
- the heat treatment is usually performed by heat treating a sheet-like deposit of carbon-containing PTFE nanofiber (D) at 200 to 390 ° C. for 30 to 300 minutes.
- Sheet-like deposits of carbon-containing PTFE-based nanofibers are obtained at room temperature (usually 25 ° C. at a temperature rising rate of 1 to 10 ° C./min in an electric furnace such as DRH453WA (manufactured by Advantech Toyo Co., Ltd.). Temperature) to about 200 to 390 ° C. When the temperature reaches about 200 to 390 ° C., the temperature is maintained for 30 to 300 minutes.
- the heating time at 200 to 390 ° C. to be 300 minutes or less as a whole.
- the water and / or organic solvent and the viscosity adjusting polymer remaining in the sheet-like deposit are removed.
- a PTFE porous membrane (PTFE nonwoven fabric) containing carbon-containing PTFE nanofibers can be produced.
- Example 1 A spinning solution was prepared by adding 4.2 parts by weight of hydrophilic carbon black dispersion and 2.3 parts by weight of polyethylene oxide to 45 parts by weight of PTFE dispersion. The obtained spinning solution was subjected to an electrospinning apparatus (ES-2300, manufactured by Huence Co., Ltd.), electrospun under the conditions described in Table 1 below, and electrospun black carbon black-containing PTFE nanofibers were obtained. The sheet-like deposit was obtained by accumulating on the collector.
- ES-2300 manufactured by Huence Co., Ltd.
- PTFE dispersion product number D210-C, manufactured by Daikin Industries, Ltd., PTFE content 60% by weight, average primary particle size 220 nm (catalog value).
- Hydrophilic carbon black dispersion Product name Aqua Black 162, manufactured by Tokai Carbon Co., Ltd., average secondary particle size 110 nm (catalog value), carbon black (CB) concentration 20% by weight.
- Polyethylene oxide (PEO) manufactured by SIGMA-ALDRICH Co., molecular weight 300,000.
- the obtained carbon black-containing PTFE nanofiber deposit was subjected to an electric furnace (DRH453WA, manufactured by Advantech Toyo Co., Ltd.) and heated from room temperature to 360 ° C. at a heating rate of 2 ° C./min. Maintaining for 30 minutes, a black PTFE porous membrane made of a carbon black-containing PTFE nanofiber nonwoven fabric was produced.
- the obtained black PTFE porous membrane was evaluated as follows, and various evaluation results are shown in Table 2.
- the amount of PTFE and the amount of carbon powder in the spinning solution are the same as the amount of PTFE and the amount of carbon powder in the obtained porous PTFE membrane. It was assumed that The amount of CB is obtained from (Amount of hydrophilic carbon black dispersion ⁇ weight% concentration of carbon black in the hydrophilic carbon black dispersion) / 100, and the amount of PTFE is (amount of PTFE dispersion ⁇ PTFE content% concentration in the PTFE dispersion) / 100.
- Viscosity measurement of spinning solution Viscosity was measured at 25 ° C using a viscometer (TVB-10H) manufactured by Toki Sangyo Co., Ltd. and a small amount of sample adapter.
- TVB-10H viscometer
- B-10H viscometer
- CR-400 color difference meter
- Konica Minolta Co., Ltd. brightness (Munsell symbol notation) was measured for the PTFE porous film.
- Porosity (%) ⁇ 1 ⁇ weight per unit area (g / m 2 ) / specific gravity (g / cm 3 ) / thickness (mm) / 1000) ⁇ ⁇ 100 (7)
- Average flow pore size of PTFE porous membrane According to ASTM F316-86, measured by bubble point method with Palm Porometer (CFP-1200-AEL porous material automatic pore size distribution measurement system) manufactured by Porous Materials Inc. went. The air permeability is evaluated and measured according to JIS P-8117, and the air permeability (sec / 100cc) is multiplied by 25 ( ⁇ m) / film thickness ( ⁇ m) to obtain a 25 ⁇ m equivalent air permeability (sec / 100cc). It was.
- Example 2 Comparative Examples 1 to 3
- a PTFE porous membrane was produced in the same manner as in Example 1 except that the amounts of PTFE dispersion, CB dispersion, and PEO were changed as shown in Table 2, and various measurements were performed. The results are shown in Table 2.
- the CB weight part relative to 100 weight parts of PTFE is 1. It was 5 parts by weight of gray with a lightness of 5.5.
- the average fiber diameter of the CB-containing PTFE nanofibers hardly changes when the CB weight is from 0 to 10 parts by weight with respect to 100 parts by weight of PTFE, and the CB-containing PTFE nanofibers are more than 20 parts by weight with respect to 100 parts by weight of PTFE. It was confirmed that the average fiber diameter of the fiber became thinner. This is presumed that by adding CB to the spinning solution, the conductivity of the spinning solution is improved, so that finer nanofibers can be formed by the electrospinning method.
- the size of the CB primary particles is very small compared to the size of the PTFE primary particles (the particle size of the CB primary particles is considered to be about 1/10 to 1/20 with respect to the particle size of the PTFE primary particles).
- the particle size of the CB primary particles is considered to be about 1/10 to 1/20 with respect to the particle size of the PTFE primary particles.
- FIG. 3 shows the results of evaluating the air permeability of CB parts by weight and PTFE porous membrane with respect to 100 parts by weight of PTFE.
- the air permeability improves as the CB part by weight with respect to 100 parts by weight of PTFE increases. It can be evaluated that this is due to an increase in porosity due to an increase in the amount of CB in the PTFE porous membrane and the formation of fine fibers.
- FIG. 4 shows changes in the contact angle between CB parts by weight and PTFE porous membrane with respect to 100 parts by weight of PTFE.
- the contact angle of the PTFE porous membrane was about 144 to 145 °, which was higher than that of the CB-free PTFE porous membrane. This is considered that the water repellency is improved by increasing the porosity and making the fibers finer.
- the black PTFE porous membrane according to the present invention is black while maintaining excellent water repellency, heat resistance, chemical resistance, air permeability, tensile strength, etc. derived from PTFE, a filter such as a vent filter (particularly black) Can be suitably used.
- Electrospinning device 2 Container storing spinning solution 3: Spinneret 4: DC voltage power supply 5: Collector 6: Nanofiber 7: Nanofiber deposit 8: Electron micrograph of nanofiber nonwoven fabric
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Abstract
Description
ベントフィルターは、例えば、携帯電話などの音響用マイクやカバーなどに用いられ、成形体内部の通気を確保し、かつ、圧力調整機能を保持しながら防水、防塵機能を該成形体に付与するフィルターである。
しかし、ePTFEは、PTFEの繊維状部分と結節部分とからなり、この独特の構造的特徴によってePTFEに照射された光線は実質的に全反射されるため、ePTFEの外観は真白色であるという特徴を有しており、白色であることが許容されない用途には向いていない。
このように、上記明度(V)がN2.5以下である黒色のPTFE多孔質膜は、従来知られていなかった。
例えば、カーボン含有ポリテトラフルオロエチレン(PTFE)ナノファイバー(d)を含み、JIS Z 8721に準じてマンセル記号であらわした明度(V)が、N2.5以下であり、前記カーボン含有PTFEナノファイバー(d)が、少なくともカーボン(b)の粉末とPTFEまたは変性PTFE(A)とを含む紡糸液を電界紡糸法に供して得られるものである黒色PTFE多孔質膜により上記課題が解決される。
例えば、黒色着色材がカーボンである場合は、バインダー樹脂であるPTFEまたは変性PTFEと着色材であるカーボン粉末とを含む紡糸液を、電界紡糸法に供してカーボン含有PTFEナノファイバーに成形することが重要な役割を果たしているものと推察される(後述の比較例が示すように、バインダー樹脂であるPTFEと着色材であるカーボンを混錬して押出法によって膜状に成形しても、上記明度(V)がN2.5以下である黒色のPTFE多孔質膜は得られない)。
すなわち、本発明は、以下の通りである。
本発明に係る黒色PTFE多孔質膜は、上記黒色着色材含有ポリテトラフルオロエチレン(PTFE)ナノファイバー(D)がカーボン含有ポリテトラフルオロエチレン(PTFE)ナノファイバー(d)であり、前記黒色着色材(B)が、カーボン(b)であり、前記カーボン含有PTFEナノファイバー(d)が、少なくともPTFEまたは変性PTFE(A)およびカーボン(b)の粉末を含む紡糸液を電界紡糸法に供して得られることが、黒色PTFE多孔質膜の明度(V)を従来に比してより小さくできるなどの観点から好ましい。
上記黒色PTFE多孔膜をフィルターとして用いる際には、通気性やろ過性能などフィルターとしての必要な特性を大きく損ねない限り、該フィルターは支持体や保護層などを具備する上記黒色PTFE多孔膜であってもよい。
本発明に係るベントフィルターは、上記フィルターからなることを特徴とする。
本発明に係る黒色PTFE多孔質膜の製造方法は、少なくともポリテトラフルオロエチレン(PTFE)または変性PTFE(A)と、該PTFEまたは変性PTFE(A)100重量部に対して3~20重量部のカーボン(b)の粉末と、粘度調整ポリマー(C)とを、水および/または有機溶媒中に分散して紡糸液を調製し、該紡糸液を電界紡糸法に供し、得られたカーボン含有PTFEナノファイバー(d)をシート状に堆積し、該カーボン含有PTFEナノファイバー(d)のシート状の堆積物を加熱して、シート状の堆積物に残留している前記水および/または有機溶媒および前記粘度調整ポリマー(C)を除去することを特徴とする。
例えば、本発明に係る黒色PTFE多孔質膜は、上記黒色着色材がカーボンである場合、カーボン含有PTFEナノファイバーを含み、該カーボン含有PTFEナノファイバーがカーボンの粉末とポリテトラフルオロエチレン(PTFE)または変性PTFEとを含む紡糸液を電界紡糸法に供して得られたものであるので、JIS Z 8721に準じてマンセル記号で表した明度(V)がN2.5以下であり、黒色度に優れる。
なお、黒色PTFE多孔質膜中のPTFEや変性PTFEの量およびカーボン等の黒色着色材の量は、黒色PTFE多孔質膜の製造に原料として用いたPTFEや変性PTFEの量およびカーボン粉末等の黒色着色材の量に実質的に同じとして扱った。
本発明に係る黒色ポリテトラフルオロエチレン(PTFE)多孔質膜は、ポリテトラフルオロエチレン(PTFE)ナノファイバー(E)および黒色着色材(B)を含む黒色着色材含有PTFEナノファイバー(D)を含み、JIS Z 8721に準じてマンセル記号であらわした明度(V)が、N2.5以下であり、前記黒色着色材含有PTFEナノファイバー(D)が、少なくともPTFEまたは変性PTFE(A)を含む紡糸液を電界紡糸法に供して得られることを特徴とする。
本発明に係る黒色ポリテトラフルオロエチレン(PTFE)多孔質膜は、カーボン含有ポリテトラフルオロエチレン(PTFE)ナノファイバー(d)を含み、JIS Z 8721に準じてマンセル記号であらわした明度(V)が、N2.5以下であり、前記カーボン含有PTFEナノファイバー(d)が、カーボン(b)の粉末とPTFEまたは変性PTFE(A)とを含む紡糸液を電界紡糸法に供して得られることが、黒色PTFE多孔質膜の明度(V)を従来に比してより小さくできるなどの観点から好ましい。
PTFEまたは変性PTFEを電界紡糸して得られるナノファイバーを含む不織布状の多孔質膜は、繊維状部分と結束部分のような太さの異なる繊維構造が混在しているePTFEと比較して、繊維径の均一性が非常に高いため、通気性などのフィルター性能に好適に用いることができる。また、ePTFEと比較して、加熱による収縮が生じにくいため、リフロー工程などの加熱を含む製造過程によって特性がほとんど変化しないという利点を有する。
黒色PTFE多孔質膜に含まれる黒色PTFEナノファイバー(D)は、少なくともPTFEまたは変性PTFE(A)を含む紡糸液を電界紡糸法に供して得られる。
(カーボン含有PTFEナノファイバー(d))
黒色PTFE多孔質膜に含まれるカーボン含有PTFEナノファイバー(D)は、カーボン含有PTFEナノファイバー(d)であることが、黒色PTFE多孔質膜の明度(V)を従来に比してより小さくできるなどの観点から好ましい。
カーボン含有PTFEナノファイバー(d)は、例えば、少なくともカーボン(b)の粉末とPTFEまたは変性PTFE(A)とを含む紡糸液を電界紡糸法に供して得られる。
本明細書において、変性PTFEとは、テトラフルオロエチレンの単重合体および少量(たとえば0.5モル%以下)の他の単量体を共重合させて得られる。
PTFEまたは変性PTFEを着色する着色材は、黒色以外の着色材であってもよいが、実用面等の観点から黒色着色材とする。
黒色着色材(B)としては、PTFEナノファイバーをN2.5以下に着色・染色できる材料であれば限定されず、例えば、カーボン、酸化鉄および金属錯体化合物などの無機系顔料やアジン系化合物などの有機系染料が挙げられる。
これら黒色着色材の中でも、無機系顔料が、PTFEナノファイバーと一体化してPTFEファイバーから脱落しにくく、長期に亘って黒色PTFEナノファイバーの黒色を維持できるという観点から好ましく、カーボンが、PTFEナノファイバーを効率よく黒色に着色できるという観点から特に好ましい。
これら黒色着色材(B)は、黒色PTFEナノファイバーに、1種単独で配合されてもよいし、2種以上が混合されて配合されてもよい。
以下、特に好ましい形態である、PTFEまたは変性PTFEおよびカーボン粉末を含む紡糸液を電界紡糸法に供して黒色PTFE多孔質膜を得る場合における、カーボンについて詳細に記載する。
黒色着色材がカーボン粉末であると、カーボン含有PTFEナノファイバー、ひいては、PTFE系多孔質膜をより明度の低い黒色に着色することが可能となる。
(カーボン(b))
本明細書において、カーボンの粉末とPTFEまたは変性PTFEとを含む紡糸液を電界紡糸法に供して黒色PTFE多孔質膜を得る場合におけるカーボンとは、後述する、電界紡糸法に供された紡糸液中や紡糸されたPTFEまたは変性PTFEナノファイバーを着色する際に用いられるカーボン(b)の粉末に由来する成分である。
カーボンは、例えば、カーボンブラック、グラファイト、カーボンナノチューブ、カーボンナノファイバー、フラーレンなどのカーボン粉末に由来する成分である。カーボン含有PTFEナノファイバー、ひいては、黒色PTFE多孔質膜を効率よく安価に黒色に着色するなどの観点からは、これらカーボンの中でも、カーボンブラックに由来する成分が好ましい。
カーボン等の黒色着色材は、PTFE樹脂の性能を極力損なわずにカーボン含有PTFEナノファイバー等の黒色PTFEナノファイバー、ひいては、PTFE系多孔質膜を黒色に着色するという観点から、PTFE100重量部に対して3重量部以上であることが好ましく、特に、膜の諸物性の観点から黒色PTFE多孔質膜中のPTFE100重量部に対して3~20重量部含まれていることが好ましい。カーボン等の黒色着色材の量は、後述するように、電界紡糸法に供する紡糸液中のカーボン等の黒色着色材の量や紡糸されたPTFEまたは変性PTFEナノファイバーを着色する際に用いるカーボン等の黒色着色材の量により調整できる。
以下に、本発明に係る黒色PTFE系多孔質膜の性状について述べるが、各種項目の測定方法、評価方法は、後述の実施例に記載された測定方法、評価方法に準ずればよい。
本発明に係る黒色PTFE多孔質膜の黒色度は、JIS Z 8721に準じてマンセル記号で表した明度(V)で評価され、本発明の黒色PTFE多孔質膜の該明度(V)は通常N2.5以下、好ましくは、1.8以下、特に好ましくは、1.3以下であり、その下限値はいずれの場合も1.0である(表2)。
JIS Z 8721に準じてマンセル記号で表した明度(V)は、無彩色(白、灰色、黒のように色味のない色)の場合、例えば、「N2.5」のように、N(無彩色であることを表す表示記号)と数値(色の明るさ、すなわち明度を表す)で表され、有彩色(赤、青、黄のように色味のある色)の場合と異なり、色相、彩度は表示されない。
カーボン含有PTFEナノファイバー等の黒色着色材含有PTFEナノファイバーの平均繊維径は、黒色PTFE多孔質膜に優れた通気性、撥水性などを付与するという観点から、400~3000nmであることが好ましく、400~1500nmであることがより好ましく、400~1000nmであることがさらに好ましい。
本発明に係る黒色PTFE多孔質膜の厚みは、該多孔質膜の引っ張り強度、通気性などの観点から、10μm以上であることが好ましく、30~300μmであることがより好ましい。
本発明に係る黒色PTFE系多孔質膜の平均流量径(測定方法:バブルポイント法)は、優れた通気性を付与するという観点から、0.5~5.0μmであることが好ましく、1.0~3.0μmであることがより好ましく、1.0~2.0μmであることがさらに好ましい。
本発明に係る黒色PTFE系多孔質膜の通気性は、平均ガーレー値によって評価される。
本発明に係る黒色PTFE系多孔質膜のJIS P8117に準じて測定した平均ガーレーは、透気度(sec/100cc)に25(μm)/膜厚(μm)を乗じる事によって、25μm換算透気度(sec/100cc)とした。その黒色PTFE系多孔質膜に優れた通気性を付与するという観点から、0.3~10.0s/100ccであることが好ましく、0.3~3.0s/100ccであることがより好ましく、特に0.3~2.0s/100ccであることがさらに好ましい。
本発明に係る黒色PTFE多孔質膜の撥水性は、水接触角によって評価される。
本発明に係る黒色PTFE多孔質膜の水接触角は、黒色PTFE多孔質膜に優れた撥水性を付与するという観点から、110~150°であることが好ましく、130~150°であることがより好ましい。
本発明に係る黒色PTFE多孔質膜の引っ張り強度は、0.3~20N/mm2であることが好ましく、0.5~10N/mm2であることがより好ましく、1.2~1.7N/mm2であることがさらに好ましい。
本発明に係る黒色PTFE多孔質膜は、引っ張り強度が上記範囲にあると、フィルターなどの用途に供しても、容易に破壊されたりしない。
本発明に係る黒色PTFE多孔質膜は、例えば、PTFEまたは変性PTFEおよびカーボン粉末等の黒色着色材を原料として、エレクトロスピニング法(電界紡糸法)によりカーボン含有PTFEナノファイバー等の黒色着色材含有PTFEナノファイバーを形成(あるいは製造)し、次いで、得られたカーボン含有PTFEナノファイバー等の黒色着色材含有PTFEナノファイバーを特定の条件下で熱処理することで製造できる。
紡糸液には、少なくともPTFEまたは変性PTFEが含まれていればよいが、以下では、黒色着色材がカーボンであり、少なくともカーボンの粉末とPTFEまたは変性PTFEとを含む紡糸液を電界紡糸法に供する場合を例に挙げて、順を追って説明する。
下記製造方法は、黒色着色材がカーボン粉末以外である場合にも、同様に適用できる。
また、例えば、PTFE粒子または変性PTFE粒子およびカーボン粉末が水および/または有機溶媒に分散されたディスパージョンの状態で添加された形態を、あらかじめPTFE粒子または変性PTFE粒子とカーボン粉末とを一体化(着色)処理して得られた粒子が水および/または有機溶媒に分散されたディスパージョンの状態で添加された形態に変えて応用することもできる。
まず、エレクトロスピニング(電界紡糸)に供するための紡糸液を調製する。
紡糸液には、PTFEまたは変性PTFEおよびカーボン粉末を、水および/または有機溶媒(例:クロロホルム、メタノール、ギ酸、N,N-ジメチルホルムアミド、テトラヒドロフラン、1,2-ジクロロエタン、酢酸エチル、メチルエチルケトンなど)に添加し、さらに粘度調整ポリマー(C)を必要に応じて添加して、紡糸液を調製する。
なお、本明細書において、平均2次粒子径とは、単一の粒子である一次粒子(分割することのできない最小粒子)の凝集体である2次粒子の平均直径を示すものであり、分散液等における実測の粒子径として観測される。またカーボン粉末の好ましい平均一次粒子径は、PTFEナノファイバーを効率よく黒色に着色するなどの観点から、1~100nmであることが好ましく、5~80nmであることがより好ましく、8~20nmであることが更に好ましい。
カーボン粉末の一次粒子の大きさは、上記観点からPTFE粒子の一次粒子の大きさに対して、1/5~1/50が好ましく、1/10~1/20がより好ましい。
上記平均2次粒子径は、レーザー回折法で測定する。
なお、PTFE粒子の平均一次粒子は、10~500nmであることが好ましく、30~400nmであることがより好ましく、50~300nmであることが更に好ましい。
また、市販されているPTFEまたは変性PTFEのディスパージョンとしては、D210-C(ダイキン工業株式会社製、PTFE含有量60重量%、平均粒子径230nm)などが挙げられる。
上記のように調製された紡糸液は、電界紡糸装置に供されて、次いで、電界紡糸が実施される。
ここで、図1を電界紡糸法の一例として取り挙げ、これを参照しながら電界紡糸法の概略を説明する。
上記のようにして得られたカーボン含有PTFEナノファイバーのシート状の堆積物を以下のように加熱処理すると、本発明に係る黒色PTFE多孔質膜を得ることができる。
カーボン含有PTFE系ナノファイバーのシート状の堆積物は、例えば、DRH453WA(アドバンテック東洋株式会社製)のような電気炉などの中で、昇温速度1~10℃/分で、室温(通常25℃程度)から200~390℃程度まで昇温し、該200~390℃程度に達したら、該温度で30~300分間維持する。
この加熱処理により、シート状の堆積物に残留している前記水および/または有機溶媒および前記粘度調整ポリマーが除去される。
このようにして、カーボン含有PTFE系ナノファイバーを含むPTFE多孔質膜(PTFE不織布)を製造することができる。
[実施例1]
PTFEディスパージョン45重量部に、親水性カーボンブラックディスパージョン4.2重量部、ポリエチレンオキサイド2.3重量部を添加して紡糸液を調製した。得られた紡糸液を電界紡糸装置(ES-2300、株式会社ヒューエンス製)に供して、下記表1に記載された条件で電界紡糸を行い、電界紡糸された黒色のカーボンブラック含有PTFEナノファイバーをコレクター上に集積させて、シート状の堆積物を得た。
・PTFEディスパージョン:製品番号D210-C、ダイキン工業株式会社製、PTFE含有量60重量%、平均1次粒子径220nm(カタログ値)。
・親水性カーボンブラックディスパージョン:製品名アクアブラック162、東海カーボン株式会社製、平均2次粒子径110nm(カタログ値)、カーボンブラック(CB)濃度20重量%。
・ポリエチレンオキサイド(PEO):SIGMA-ALDRICH Co.社製、分子量300000。
粘度測定は、東機産業株式会社製粘度計(TVB-10H)及び少量サンプルアダプターを利用し、25℃で測定を行った。
(2)PTFE多孔膜の明度測定
コニカミノルタ株式会社製色彩色差計(CR-400)を使用して、PTFE多孔膜について明度(マンセル記号表記)の測定を行った。
(3)PTFE多孔膜の外観観察
デジタルカメラで撮影し、PTFE多孔膜の外観と色を評価した。
(4)PTFEナノファイバーの平均繊維径
株式会社日立ハイテクノロジーズ製走査型電子顕微鏡(S-3400N)を用い、測定対象となるPTFE多孔膜について、無作為にSEM観察の領域を選択し、この領域をSEM観察(倍率:10,000倍)して無作為に10本のPTFEナノファイバーを選択し、それらナノファイバーの断面を観察し、繊維径の平均値を算出して得られた値を平均繊維径とした。
(5)厚み
株式会社ミツトヨ社製高精度デジタル測長機(LITEMATIC VL-50)を用いて、測定力0.01Nの条件で膜厚の測定を実施した。
(6)空孔率
測定した厚み、目付け、及び使用した各素材の比重より次式より算出した。
空孔率(%)={1-目付け(g/m2)/比重(g/cm3)/厚み(mm)/1000)}×100
(7)PTFE多孔膜の平均流量孔径
ASTM F316-86に準じて、Porous Materials Inc.社製パームポロメーター(CFP-1200-AEL 多孔質材料自動細孔径分布測定システム)でバブルポイント法により測定を行った。
透気度はJIS P-8117に準拠した評価測定を行い、透気度(sec/100cc)に25(μm)/膜厚(μm)を乗じる事によって、25μm換算透気度(sec/100cc)とした。
(8)PTFE多孔膜の撥水性
撥水性評価としての水接触角はJIS R3257に準拠し、協和界面化学株式会社製接触角計(CA-X)を用いて、PTFE多孔膜の膜表面を評価した。
(9)PTFE多孔膜の引っ張り強度
引張強度測定はJIS K7161に準拠し、株式会社島津製作所社製引張試験機(EZ-TEST)にて評価した。
PTFEディスパージョン、CBディスパージョン、PEOの量を表2に記載の通りに替えた以外は、実施例1と同様に、PTFE多孔膜を製造し、各種測定を行った。
結果を表2に示す。
PTFEファインパウダーにカーボンブラックを1.5wt%添加混合し、次に液状潤滑剤を混合し予備成形し、予備成形体をペースト押出しして、テープ状に形成したものを、2軸方向に延伸して多孔化されて得られた、厚み32μm、空孔率80%のグレー色のePTFE膜について各種測定を行った。
図2から分かるように、PTFEの量に対するカーボンブラック(CB)の量を増加させる(即ち「PTFE100重量部に対するCB重量部を増加させる)ことで、CB含有PTFEナノファイバーの黒色化が進行し、PTFE多孔質膜の黒色化も進行した。CB不含有PTFEナノファイバー(PTFE100重量部に対してCB0重量部)は白色であり、PTFE100重量部に対するCB重量部が1.5であるCB含有PTFEナノファイバーは明度3.2のグレーであった。PTFE100重量部に対するカーボン(CB)重量部が3.0重量部以上であるCB含有PTFEナノファイバーは黒色(明度がN2.5以下)であることが確認された。
PTFE100重量部に対するCB重量部が0~10重量部までは、CB含有PTFEナノファイバーの平均繊維径はほとんど変化せず、PTFE100重量部に対するCB重量部が20重量部以上では、CB含有PTFEナノファイバーの平均繊維径が細くなることが確認された。これは、CBが紡糸液に添加されることにより紡糸液の導電性が向上することで、電界紡糸法によってより細いナノファイバーの形成が可能となったと推察される。また、CB一次粒子の大きさがPTFE一次粒子の大きさに比べて非常に小さい(CB一次粒子の粒子径がPTFE一次粒子の粒子径に対して約1/10~1/20と考えられる)と考えられ、PTFE粒子及びCB粒子を電界紡糸法に供すると、CB粒子の一部がPTFEナノファイバーを形成しているPTFE粒子間の隙間に入り込むことが可能となり、CB含有PTFEナノファイバーの繊維径が大きく増加しなかったと推測される。
図3にPTFE100重量部に対するCB重量部とPTFE多孔質膜の通気性評価結果を示した。
図4に、PTFE100重量部に対するCB重量部とPTFE多孔質膜の接触角の変化を示した。
PTFE100重量部に対するCB重量部が20重量部までの範囲では、CB不含有PTFEナノファイバーからなるPTFE多孔質膜と同程度もしくは優れた引っ張り強度を示したが、PTFE100重量部に対するCB重量部が30重量部の黒色PTFE多孔質膜では、引っ張り強度が大きく低下していた。
2: 紡糸液を貯留した容器
3: スピナレット
4:直流電圧電源
5: コレクター
6:ナノファイバー
7:ナノファイバー堆積物
8: ナノファイバー不織布の電子顕微鏡写真
Claims (6)
- ポリテトラフルオロエチレン(PTFE)ナノファイバー(E)および黒色着色材(B)を含む黒色着色材含有PTFEナノファイバー(D)を含み、
JIS Z 8721に準じてマンセル記号であらわした明度(V)が、N2.5以下であり、
前記黒色着色材含有PTFEナノファイバー(D)が、少なくともPTFEまたは変性PTFE(A)を含む紡糸液を電界紡糸法に供して得られる
ことを特徴とする黒色PTFE多孔質膜。 - 前記黒色着色材含有PTFEナノファイバー(D)が、カーボン含有ポリテトラフルオロエチレン(PTFE)ナノファイバー(d)であり、
前記黒色着色材(B)が、カーボン(b)であり、
前記カーボン含有PTFEナノファイバー(d)が、少なくともカーボン(b)の粉末とPTFEまたは変性PTFE(A)とを含む紡糸液を電界紡糸法に供して得られることを特徴とする請求項1に記載の黒色PTFE多孔質膜。 - 前記黒色着色材(B)の量が、前記PTFEまたは変性PTFE(A)100重量部に対して3~20重量部であることを特徴とする請求項1または2に記載の黒色PTFE多孔質膜。
- 請求項1~3のいずれか1項に記載の黒色PTFE多孔質膜を具備することを特徴とするフィルター。
- 請求項4に記載のフィルターからなることを特徴とするベントフィルター。
- ポリテトラフルオロエチレン(PTFE)または変性PTFE(A)と、該PTFEまたは変性PTFE(A)100重量部に対して3~20重量部のカーボン(b)の粉末と、粘度調整ポリマー(C)とを、水および/または有機溶媒中に分散して紡糸液を調製し、
該紡糸液を電界紡糸法に供し、
得られたカーボン含有PTFEナノファイバー(d)のシート状の堆積物を、加熱して、シート状の堆積物に残留している前記水および/または有機溶媒および前記粘度調整ポリマー(C)を除去することを特徴とする黒色PTFE多孔質膜の製造方法。
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WO2017080475A1 (zh) * | 2015-11-11 | 2017-05-18 | 重庆润泽医药有限公司 | 一种聚四氟乙烯纤维膜 |
WO2018062113A1 (ja) * | 2016-09-30 | 2018-04-05 | 日東電工株式会社 | エアフィルタ濾材、エアフィルタパック及びエアフィルタユニット |
JP2019173221A (ja) * | 2018-03-28 | 2019-10-10 | 大豊精機株式会社 | 導電性ナノファイバー、燃料電池用部材、及び燃料電池 |
JP2019183295A (ja) * | 2018-04-02 | 2019-10-24 | 株式会社豊田中央研究所 | 不織布 |
WO2022004885A1 (ja) * | 2020-07-03 | 2022-01-06 | 日東電工株式会社 | ポリテトラフルオロエチレン多孔質膜、通気膜及び通気部材 |
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TWI636189B (zh) * | 2017-08-21 | 2018-09-21 | 研能科技股份有限公司 | 微型氣體控制裝置 |
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JP2022013925A (ja) * | 2020-07-03 | 2022-01-18 | 日東電工株式会社 | ポリテトラフルオロエチレン多孔質膜、通気膜及び通気部材 |
JP7106726B2 (ja) | 2020-07-03 | 2022-07-26 | 日東電工株式会社 | ポリテトラフルオロエチレン多孔質膜、通気膜及び通気部材 |
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Also Published As
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US20160075838A1 (en) | 2016-03-17 |
JP6378672B2 (ja) | 2018-08-22 |
JPWO2014175380A1 (ja) | 2017-02-23 |
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