EP3428331B1 - Nonwoven fabric - Google Patents

Nonwoven fabric Download PDF

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Publication number
EP3428331B1
EP3428331B1 EP17763153.8A EP17763153A EP3428331B1 EP 3428331 B1 EP3428331 B1 EP 3428331B1 EP 17763153 A EP17763153 A EP 17763153A EP 3428331 B1 EP3428331 B1 EP 3428331B1
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EP
European Patent Office
Prior art keywords
fluorine
nonwoven fabric
monomer
weight
copolymer
Prior art date
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EP17763153.8A
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German (de)
English (en)
French (fr)
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EP3428331A1 (en
EP3428331A4 (en
Inventor
Eiji Masuda
Kazuki SAKAMI
Kazuya Kawahara
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Daikin Industries Ltd
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Daikin Industries Ltd
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Classifications

    • 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
    • D04H1/4291—Olefin series
    • 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
    • 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
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • D04H1/565—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres by melt-blowing
    • 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
    • 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
    • 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)
    • 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
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/544—Olefin series
    • 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
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • 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]
    • 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
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • 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
    • D10B2509/00—Medical; Hygiene

Definitions

  • the present invention relates to a nonwoven fabric formed from a resin composition comprising a thermoplastic resin and a fluorine-containing copolymer.
  • thermoplastic resin Hitherto, disclosed is a technology of nonwoven fabric which adding a fluorine-containing polymer to a thermoplastic resin.
  • WO 01/053585A discloses a nonwoven fabric prepared by adding a lubricant comprising a vinylidene fluoride/hexafluoropropylene copolymer as processing aid to polypropylene. However, there is no surface modification effect in this nonwoven fabric comprising the fluorine-containing copolymer.
  • JP H09-511700A discloses a method of increasing a head-of-water pressure and an intensity to a nonwoven fabric having an average fiber diameter of at least 10 micrometers comprising a specific fluorocarbon.
  • JP 2002-521586A discloses a method of giving water repellency and alcohol repellency to a nonwoven fabric surface by adding a fluorine-containing additive agent to a specific region. These methods have a surface modification effect, but other effects cannot be seen.
  • JP 2006-37085A discloses a method of mixing a fluorine-containing copolymer with a thermoplastic resin to performing a surface modification.
  • a fluorine-containing copolymer with a thermoplastic resin to performing a surface modification.
  • water- and oil-repellency specialized in alcohol repellency is indicated as an effect, but other effects cannot be seen.
  • An object of the present invention is to provide a nonwoven fabric formed from a resin composition having improved antifouling property, sound insulation property, friction coefficient and touch feeling property.
  • the present invention relates to a nonwoven fabric formed from a resin composition comprising (1) a thermoplastic resin, and (2) a fluorine-containing copolymer.
  • the present invention provides a nonwoven fabric which is a meltblown nonwoven fabric, comprising fibers which are spun from a resin composition, the resin composition comprising:
  • the present invention provides a method of producing a nonwoven fabric, comprising steps of:
  • the resin composition (or the antifouling resin composition) can be processed into a nonwoven fabric with high processing characteristics.
  • a melt flow rate (MFR) of the resin composition is improved. Further, processing stability at the time of preparation of the nonwoven fabric is high, and the productivity of the nonwoven fabric is high.
  • a surface-modified nonwoven fabric is obtained.
  • the nonwoven fabric of the present invention has excellent antifouling properties, sound insulation properties, and water-proof pressure. Furthermore, the nonwoven fabric of the present invention has excellent wiping easiness and scratch resistance. In addition, the nonwoven fabric has a good touch feeling due to a decrease in a coefficient of friction.
  • a nonwoven fabric having a small fiber diameter and a high density can be obtained.
  • the thermoplastic resin is polypropylene.
  • polypropylene examples include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, and amorphous polypropylene.
  • the isotactic polypropylene is a highly crystalline polypropylene based on isotactic polypropylene prepared by a Ziegler-Natta catalyst or a metallocene catalyst.
  • the amorphous polypropylene is, for example, propylene having extremely low crystallinity prepared by using a metallocene catalyst.
  • the amorphous polypropylene may be a mixture of polypropylene having extremely low crystallinity (for example, at least 50 wt% of a total amount of the mixture) produced by using a metallocene catalyst, with other propylene.
  • the amorphous polypropylene is available as, for example, TAFTHREN T-3512 and T-3522 manufactured by Sumitomo Chemical Co., Ltd., and L-MODU S-400, S-600 and S-901 manufactured by Idemitsu Kosan Co., Ltd.
  • thermoplastic resin may be one or a combination of at least two.
  • the fluorine-containing copolymer (2) is a copolymer having a repeating unit formed from the fluorine-containing monomer (a) and a repeating unit formed from the fluorine-free monomer (b).
  • the fluorine-containing monomer (a) is a monomer containing a fluoroalkyl group having 4 to 6 carbon atoms.
  • the fluorine-free monomer (b) is a monomer containing a non-cyclic or cyclic hydrocarbon group having at least 14 carbon atoms, which may contain a nitrogen, oxygen and/or sulfur atom.
  • the fluorine-containing copolymer (2) may have a repeating unit formed from another monomer (c) other than the fluorine-containing monomer (a) and the fluorine-free monomer (b).
  • X is, for example, a hydrogen atom, a methyl group, a halogen atom, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX 1 X 2 group (where each of X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or unsubstituted phenyl group.
  • X is preferably a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.
  • X is especially a methyl group, since antifouling property is high.
  • Y is preferably -O-.
  • Z is, for example, a direct bond, a linear alkylene group or branched alkylene group having 1-20 carbon atoms, such as a group represented by the formula -(CH 2 ) x - wherein x is 1 to 10, a group represented by the formula -SO 2 N(R 1 )R 2 - or the formula -CON(R 1 )R 2 -- wherein R 1 is an alkyl group having 1 to 10 carbon atoms and R 2 is a linear alkylene group or branched alkylene group having 1 to 10 carbon atoms, a group represented by the formula -CH 2 CH(OR 3 )CH 2 - wherein R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, a formyl group or an acetyl group), -Ar-(CH 2 ) r - wherein Ar is an arylene group optionally having a substituent group, and r is 0 to 10, or a -(CH
  • Z is preferably a direct bond, an alkylene group having 1-20 carbon atoms, or -SO 2 N(R 1 )R 2 -, particularly preferably -(CH 2 ) 2 -.
  • the Rf group is preferably a perfluoroalkyl group, but may be a fluoroalkyl group having a hydrogen atom.
  • the carbon number of the Rf group is preferably 4 or 6.
  • the carbon number of the Rf group is particularly preferably 6. Examples of the Rf group include -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 ,-(CF 2 ) 5 CF 3 and -(CF 2 ) 3 CF(CF 3 ) 2 .
  • fluorine-containing monomer (a) examples include, but are not limited to, the followings:
  • the fluorine-containing copolymer has the repeating unit formed from the fluorine-free monomer (b) in addition to the repeating unit formed from the fluorine-containing monomer (a).
  • the fluorine-free monomer (b) is a monomer which contains a hydrocarbon group (a non-cyclic hydrocarbon group or a cyclic hydrocarbon group) having at least 14 carbon atoms.
  • the lower limit of the number of carbon atoms may be 16 or 17.
  • the upper limit of the number of carbon atoms of the hydrocarbon group may be 30, for example 25, especially 20.
  • the fluorine-free monomer (b) is preferably a (meth)acrylate.
  • the fluorine-free monomer (b) is preferably a (meth)acrylate ester wherein an acryloyloxy group is bonded to a monovalent hydrocarbon group.
  • the fluorine-free monomer (b) is an acrylate ester in which an alpha-position is a hydrogen atom.
  • the fluorine-free monomer (b) may be a fluorine-free non-crosslinkable monomer (b1).
  • hydrocarbon group having 14-30 carbon atoms examples include a linear or branched saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon group having 14 to 30 carbon atoms, a saturated or unsaturated (for example, ethylenically unsaturated) cycloaliphatic hydrocarbon group having 14 to 30 carbon atoms, an aromatic hydrocarbon group having 14-30 carbon atoms, and an araliphatic hydrocarbon group having 14-30 carbon atoms.
  • Q is a linear or branched saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon group having 14 to 30 carbon atoms, a saturated or unsaturated (for example, ethylenically unsaturated) cycloaliphatic hydrocarbon group having 14 to 30 carbon atoms, an aromatic hydrocarbon group having
  • the fluorine-free non-crosslinkable monomer (b1) may be a (meth)acrylate ester monomer.
  • a 21 is preferably a hydrogen atom, a methyl group or a chlorine atom.
  • a 22 (hydrocarbon group) may be a non-cyclic hydrocarbon group having 14 to 30 carbon atoms and a cyclic hydrocarbon group having 14 to 30 carbon atoms.
  • a 22 (hydrocarbon group) is preferably a non-cyclic hydrocarbon group, particularly a chain hydrocarbon group having 14 to 30 carbon atoms.
  • (meth)acrylate ester monomer having a non-cyclic hydrocarbon group examples include cetyl (meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate.
  • the fluorine-containing copolymer according to the present invention may consist of the fluorine-containing monomer (a) and the fluorine-free monomer (b) or may comprise another monomer (c) other than the fluorine-containing monomer (a) and the fluorine-free monomer (b).
  • the other monomer (c) is preferably free from a fluorine atom. Examples of the other monomer (c) are (c1) a fluorine-free crosslinkable monomer or (c2) a halogenated olefin monomer.
  • the fluorine-free crosslinkable monomer (c1) is a monomer free from a fluorine atom.
  • the fluorine-free crosslinkable monomer may be a fluorine-free compound having at least one reactive group and/or olefinic carbon-carbon double bond (preferably a (meth)acrylate group).
  • the fluorine-free crosslinkable monomer may be a compound which has at least two olefinic carbon-carbon double bonds (preferably (meth)acrylate groups) or a compound which has at least one olefinic carbon-carbon double bond and at least one reactive group.
  • the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group and a glycidyl group.
  • the fluorine-free crosslinkable monomer may be a mono(meth)acrylate, di(meth)acrylate, or mono(meth)acrylamide having a reactive group.
  • the fluorine-free crosslinkable monomer may be di(meth)acrylate.
  • fluorine-free crosslinkable monomer examples include, but are not limited to, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, monochlorovinyl acetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentylglycol di(meth)acrylate.
  • the fluorine-free crosslinkable monomer may be, for example, an isocyanatoacrylate monomer.
  • isocyanatoacrylate monomer include 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate, a pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, a 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, an epsilon-caprolactam adduct of 2-isocyanatoethyl (meth)acrylate, 2-butanone oxime adduct of 3-is
  • the halogenated olefin monomer (c2) is a monomer free from a fluorine atom.
  • the halogenated olefin monomer may be an olefin having 2-20 carbon atoms and substituted by 1-10 chlorine atoms, bromine atoms or iodine atoms.
  • the halogenated olefin monomer is a chlorinated olefin having 2-20 carbon atoms, particularly an olefin having 2-5 carbon atoms and having 1-5 chlorine atoms.
  • the halogenated olefin monomer are a vinyl halide such as vinyl chloride, vinyl bromide and vinyl iodide, and a vinylidene halide such as vinylidene chloride, vinylidene bromide and vinylidene iodide.
  • (meth)acrylate as used herein means an acrylate or methacrylate
  • (meth)acrylamide as used herein means an acrylamide or methacrylamide
  • Each of the monomers (a)-(c) may be used one alone or in a combination of at least two.
  • the fluorine-containing copolymers (2) may be one alone or in a combination of at least two.
  • the fluorine-containing copolymer (2) of the present invention is preferably free from a repeating unit formed from a fluorine-free monomer containing a hydrocarbon group having at most 13 carbon atoms, for example, a (meth)acrylate ester containing a hydrocarbon group having at most 13 carbon atoms, particularly a (meth)acrylate ester containing a non-cyclic hydrocarbon group having at most 13 carbon atoms.
  • the fluorine-containing copolymer (2) of the present invention is preferably free from a repeat unit formed from lauryl acrylate. High water- and oil-repellency is obtained by being free from these repeat units.
  • a weight ratio of the fluorine-containing monomer (a) to the fluorine-free monomer (b) in the fluorine-containing copolymer (2) is preferably 35:65 to 70:30, more preferably 40:60 to 60:40, particularly 42.5:57.5 to 58:42.
  • the amount of the fluorine-containing monomer (a) may be at least 25% by weight, for example, at least 35% by weight, particularly 35 to 60 % by weight, based on the fluorine-containing copolymer.
  • the amount of the monomer (c) may be at most 100 parts by weight, for example, 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the total of the monomer (a) and the monomer (b).
  • the weight-average molecular weight of the fluorine-containing polymer may be 2,500 to 20,000, preferably 3,000 to 15,000, for example, 5,000 to 12,000 in terms of polystyrene, as measured by GPC (gel permeation chromatography).
  • the polymer of the present invention may be a random copolymer or a block copolymer, but is generally a random copolymer.
  • the amount of the fluorine-containing copolymer (2) may be 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, particularly 0.2 to 10 parts by weight, for example, 1.0 to 8 parts by weight, more preferably 1.2 to 5.0 parts by weight, based on 100 parts by weight of the thermoplastic resin (1).
  • the fluorine-containing copolymer may be obtained by polymerizing by a known method using a polymerization initiator, a solvent, and optionally a chain transfer agent.
  • the fluorine-containing copolymer and the fluorine-free polymer in the present invention can be produced by any of conventional polymerization methods and the polymerization condition can be optionally selected.
  • the polymerization method includes, for example, a solution polymerization, a suspension polymerization and an emulsion polymerization.
  • the solution polymerization there can be used a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating at the temperature within the range from 30°C to 120°C for 1 hour to 10 hours.
  • a polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of total of the monomers.
  • the organic solvent is inert to the monomer, and dissolves the monomer
  • examples of the organic solvent include an ester (for example, an ester having 2-30 carbon atoms, specifically ethyl acetate and butyl acetate), a ketone (for example, a ketone of 2-30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and an alcohol (for example, an alcohol having 1-30 carbon atoms, specifically isopropyl alcohol).
  • organic solvent examples include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane.
  • the organic solvent may be used in the amount within the range from 10 to 2,000 parts by weight, for example, from 50 to 1,000 parts by weight, based on 100 parts by weight of total
  • emulsion polymerization there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 50°C to 80°C for 1 hour to 10 hours.
  • polymerization initiator for example, water-soluble initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate can be used.
  • the polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight, based on 100 parts by weight of the monomers.
  • the monomers are dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a highpressure homogenizer and an ultrasonic homogenizer) and then polymerized.
  • an emulsifying device capable of applying a strong shearing energy (e.g., a highpressure homogenizer and an ultrasonic homogenizer) and then polymerized.
  • a strong shearing energy e.g., a highpressure homogenizer and an ultrasonic homogenizer
  • various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight, based on 100 parts by weight of the monomers.
  • the anionic emulsifying agent and/or the cationic emulsifying agent and/or the nonionic emulsifying agent are preferable.
  • a compatibilizing agent capable of sufficiently compatibilizing them e.g., a water-soluble organic solvent and a low-molecular weight monomer
  • the emulsifiability and polymerizability can be improved.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol.
  • the water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water.
  • Examples of the low-molecular weight monomer are methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate.
  • the low-molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
  • a chain transfer agent may be used in the polymerization.
  • the molecular weight of the polymer can be changed according to the amount of the chain transfer agent used.
  • the chain transfer agent include a mercaptan group-containing compound (especially alkyl mercaptan (for example, having 1-30 carbon atoms)), such as lauryl mercaptan, thioglycol, and thioglycerol, and an inorganic salt such as sodium hypophosphite and sodium hydrogen sulfite.
  • the amount of the chain transfer agent may be within the range from 0.01 to 10 parts by weight, for example, from 0.1 to 5 parts by weight, based on 100 parts by weight of total of the monomers.
  • a liquid medium is removed from a liquid (solution or dispersion) containing the fluorine-containing copolymer to obtain the fluorine-containing copolymer.
  • a dispersion of fluorine-containing copolymer an aqueous dispersion or an organic solvent-dispersion
  • the resin composition may consist of the thermoplastic resin (1) and the fluorine-containing copolymer (2), or may comprise another component.
  • the other component include additives (that is, auxiliary agents) such as a dye, a pigment, an antistatic agent, an antioxidant, a light stabilizer, an ultraviolet light-absorbing agent, a neutralizing agent, a nucleating agent, an epoxy stabilizer, a lubricant, an antibacterial agent, a flame retardant and plasticizer.
  • the resin composition can be obtained by kneading (for example, melt-kneading) the thermoplastic resin (1) and the fluorine-containing copolymer (2).
  • the thermoplastic resin (1) and the fluorine-containing copolymer (2) are heated at a temperature of 100-320°C, for example, 200-300°C to produce the nonwoven fabric.
  • the resin composition is heated to spin the fiber.
  • the method for producing the nonwoven fabric is a melt-blow method.
  • a molten material of the resin composition pressure-fed to the die is spun from a nozzle having a large number of arranged small holes to give fibers.
  • a discharge amount in the single hole is 0.1 to 20 g/minute, and a high-speed air amount may be 10 to 1000 Nm 3 /hr/m.
  • Polypropylene as a base of the nonwoven fabric of the present invention may have a melt flow rate (MFR) of at least 600 g/10 min, preferably 650 to 2,500 g/10 min, more preferably 700 to 2,200 g/10 min, for example, 800 to 1,800 g/10 min.
  • MFR melt flow rate
  • the MFR is measured under a load of 2.16 kg at a temperature of 230°C in accordance with ASTM D1238.
  • the addition of the fluorine-containing copolymer to the polypropylene according to the present invention has the effect of giving a higher MFR.
  • a method of thinning the fiber diameter includes a method of improving a shape of a nozzle or reducing a nozzle diameter, a method of increasing the MFR of polypropylene as the base.
  • the addition of the fluorine-containing copolymer according to the present invention can increase the resin fluidity and can give a nonwoven fabric having a decreased fiber diameter.
  • An average fiber diameter of fibers in the nonwoven fabric is 0.1 to 5 micrometers, preferably 0.2 to 3 micrometers, more preferably 0.2 to 2.6 micrometers.
  • the fiber diameter of the nonwoven fabric can be thin, since a surface-modified resin composition is used.
  • a basis weight of the nonwoven fabric may be 5 to 300 g/m 2 , for example, 10 to 200 g/m 2 .
  • the basis weight is a value showing a weight per 1 m 2 of the nonwoven fabric prepared.
  • the nonwoven fabric of the present invention can be used for a clothes and health material such as operation clothes, paper diaper, sanitary napkin; a filter such as a cell filter, a dust-proof mask filter, a filter of an air cleaner and air conditioner; a separator for battery; a packaging material; a nonwoven fabric wiper; and an exterior material and interior material of automobile such as a door trim, an instrument panel, a tire house, a bumper, a floor cover, a hood cover and a roof cover; and a building material.
  • the nonwoven fabric of the present invention is suitable for a medical use.
  • the nonwoven fabric can be used for a surgical gown, a surgical drape, a sheet, a bandage, a wiping cloth, a pillow cover, a mask, and a covering cloth.
  • a fluorine-containing polymer (0.1 g) and tetrahydrofuran (THF) (19.9 g) were mixed and then filtered by a filter after standing for one hour to prepare a THF solution of the fluorine-containing polymer.
  • This sample was measured by a gel permeation chromatograph (GPC) set to the following device and condition.
  • a weight and an area of a nonwoven fabric were measured to determine a weight per 1 m 2 of the nonwoven fabric.
  • An electron microscope was used to prepare a picture of a nonwoven fabric taken by a magnification of 5,000x. 200 fibers were chosen at random from the fibers of the nonwoven fabric in the picture, and the diameters of the fibers were measured and an average value was calculated to give an average fiber diameter.
  • test liquid Mustard Ketchup Canned coffee Milky lotion
  • a nonwoven fabric was touched by an index finger to evaluate a feel.
  • a surface measuring instrument was used by using a steel ball as a friction element to measure a static friction coefficient, according to ASTM D1894.
  • a water penetration test machine was used so that water adjusted to 25°C was pressurized from a back of a nonwoven fabric kept at a ring. A height (cm) of a column of water was measured at the time of three liquid droplets appearing on the surface.
  • Discharge pressure A pressure applied at a tip of an extrusion machine was measured at the time of a nonwoven fabric processing. The evaluation is “unstable” if a pressure value is gradually changed in 10 seconds or less, and “stable” if a pressure value is not changed in more than 10 seconds.
  • Rolling-up property When a prepared nonwoven fabric was rolled-up from a wire part, the evaluation is "unstable” if the nonwoven fabric remains on a wire without separating smoothly from the wire part, and “stable” if the nonwoven fabric is separated smoothly from the wire part.
  • a pressure applied to a gear pump controlling a discharge amount of the resin from a tip of an extrusion machine was measured at the time of producing a nonwoven fabric.
  • a device for generating a sound by vibration was surrounded by a sound-insulated box having an opening part of a 10 cm x 10 cm, and the opening part was closed by a three-sheet pile of a nonwoven fabric.
  • the sound was generated by the vibration, a noise meter was placed at a distance of 5 cm from the nonwoven fabric closing the opening part, to measure a degree of noise (dB).
  • a tensile test was conducted according to JIS L1913.
  • a tensile strength for example, was measured under the conditions of a width of a nonwoven fabric test piece of 50 mm, a distance between chucks of 200 mm and a tensile speed of 100 mm/min.
  • IPA isopropyl alcohol
  • a fluorine-containing copolymer was obtained in the same manner as in Preparation Example 1 except that C6SFMA was 28.81 g, StA was 38.19 g, IPA was 102.51 g and AIBN was 0.47 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparation Example 1 except that C6SFMA was 30.15 g, StA was 36.85 g, IPA was 102.51 g and AIBN was 0.74 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparative Example 1 except that C6SFMA was 33.50 g, StA was 33.50 g, IPA was 101.84 g and AIBN was 0.60 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparative Example 1 except that C6SFMA was 38.86 g, StA was 28.14 g, IPA was 89.11 g and AIBN was 0.47 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparative Example 1 except that C6SFMA was 43.55 g, StA was 23.45 g, IPA was 100.50 g and AIBN was 0.67 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparation Example 1 except that C6SFMA was 32.16 g, StA was 34.84 g, IPA was 134.00 g and AIBN was 1.34 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparation Example 1 except that IPA was 67.00 g and AIBN was 0.47 g.
  • a fluorine-containing copolymer was obtained in the same manner as in Preparation Example 1 except that C6SFMA was 32.16 g, lauryl acrylate (hereinafter referred to as "LA") was 34.84 g, IPA was 93.80 g and AIBN was 0.54 g.
  • C6SFMA was 32.16 g
  • lauryl acrylate hereinafter referred to as "LA”
  • IPA 93.80 g
  • AIBN 0.54 g.
  • a monomer ratio and molecular weight of the fluorine-containing polymer obtained in Preparative Examples 1-6 and Comparative Preparative Examples 1-3 are shown in Table 1.
  • Table 1 Monomer Ratio Molecular weight Fluorine-containing monomer Fluorine-free monomer Fluorine-containing monomer Fluorine-free monomer
  • Each fluorine-containing copolymer obtained in Preparative Examples 1 to 6 was melt-mixed with polypropylene (hereinafter referred to as "PP800") having MFR of 800 at a temperature of 160°C by a twin screw extruder to give a fluorine-containing copolymer content of 20%, and the mixture was cooled with water and cut by a cutting machine to obtain pellets.
  • PP800 polypropylene
  • the polypropylene containing 20% of the fluorine-containing copolymer (hereinafter referred to as "fluorine-containing PP") was further mixed with PP800 in a pellet mix amount shown in Table 2, to give a target content of the fluorine-containing copolymer.
  • This mixture was melt-mixed by a nonwoven fabric processing machine set at 240°C, and discharged on a wire part by a gear pump adjusting an amount of discharge which was set at 15 rpm equipped with a nozzle having a caliber of 0.25 mm, to obtain a nonwoven fabric.
  • a target basis weight amount was set by changing a rolling-up speed of the wire part under the same discharge condition.
  • PP800 was melt-mixed by a nonwoven fabric processing machine set at 240°C, and discharged on a wire part by a nozzle having a caliber of 0.25 mm, to obtain a nonwoven fabric having a basis weight of 30 g/m 2 .
  • Each fluorine-containing copolymer of Preparative Comparative Examples 1 to 3 was melt-mixed with polypropylene (hereinafter referred to as "PP800") having MFR of 800 at a temperature of 160°C by a twin screw extruder to give a fluorine-containing copolymer content of 20%, and the mixture was cooled with water and cut by a cutting machine to obtain pellets.
  • PP800 polypropylene
  • a nonwoven fabric was obtained in the same manner as in Examples 1 to 8 except the above.
  • a fluorine-containing copolymer of Preparative Example 3 was melt-mixed with PP800 at a temperature of 160°C by a twin screw extruder to give a fluorine-containing copolymer content of 20%, and the mixture was cooled with water and cut by a cutting machine to obtain pellets.
  • fluorine-containing PP The polypropylene containing 20% of the fluorine-containing copolymer (hereinafter referred to as "fluorine-containing PP”) was further mixed with polypropylene (hereinafter referred to as "PP1800”) having MFR of 1800 in a pellet mix amount shown in Table 2, to give a target content of the fluorine-containing copolymer.
  • This mixture was melt-mixed by a nonwoven fabric processing machine set at 240°C, and discharged on a wire part by a gear pump adjusting an amount of discharge which was set at 15 rpm equipped with a nozzle having a caliber of 0.25 mm with adjusting a rolling-up speed in the wire part, to obtain a nonwoven fabric having a basis weight of 30 g/m 2 or 5 g/m 2 .
  • PP1800 was melt-mixed by a nonwoven fabric processing machine set at 240°C, and discharged on a wire part by a nozzle having a caliber of 0.25 mm, to obtain a nonwoven fabric having a basis weight of 30 g/m 2 .
  • Table 2 PP Fluorine-containing copolymer Pellet mix amount (kg) Ratio Basis weight g/m 2 PP Fluorine-containing PP PP Fluorine-containing copolymer Com.
  • Ex. 2 PP800 Pre. Ex. 2 100 25 100 5 30
  • Each fluorine-containing copolymer of Preparative Examples 3 and 4 was melt-mixed with PP800 at a temperature of 160°C by a twin screw extruder to give a fluorine-containing copolymer content of 20%, and the mixture was cooled with water and cut by a cutting machine to obtain pellets.
  • the polypropylene containing 20% of the fluorine-containing copolymer (hereinafter referred to as "fluorine-containing PP") was further mixed with PP800 in a pellet mix amount shown in Table 4, to give a target content of the fluorine-containing copolymer.
  • This mixture was melt-mixed by a nonwoven fabric processing machine set at 240°C, and discharged on a wire part by a gear pump adjusting an amount of discharge was set at 15 rpm equipped with a nozzle having a caliber of 0.25 mm with adjusting a rolling-up speed in the wire part, to obtain a nonwoven fabric having a basis weight of 15 g/m 2 .
  • a nonwoven fabric was obtained in the same manner as in Comparative Example 1 except a basis weight was 15 g/m 2 .
  • a nonwoven fabric was obtained in the same manner as in Comparative Example 5 except a basis weight was 15 g/m 2 .
  • Table 4 PP Fluorine-containing copolymer Pellet mix amount (kg) Ratio PP Fluorine-containing PP PP Fluorine-containing copolymer Com.
  • Ex. 6 PP800 - 100 - 100 - Ex. 10 PP800 Pre. Ex. 3 100 2.5 100 0.5 Ex. 11 PP800 Pre. Ex. 3 100 6.0 100 1.2 Ex. 12 PP800 Pre. Ex. 3 100 15.0 100 3 Ex. 13 PP800 Pre. Ex. 3 100 25.0 100 5 Ex. 14 PP800 Pre. Ex. 3 100 40.0 100 8 Ex. 15 PP800 Pre. Ex. 6 100 2.5 100 0.5 Ex.
  • a nonwoven fabric was obtained in the same manner as in Example 3 and Comparative Example 1 except a basis weight was 5 g/m 2 .
  • a pellet mix amount and test results are shown in Table 6.
  • Table 6 PP Fluorine-containing copolymer Pellet mix amount Flowability Basis weight (g/m 2 ) Average Fiber diameter (micrometer) PP Fluorine-containing PP Gear pump (rpm) Pressure (Mpa) Com.
  • a nonwoven fabric was obtained in the same manner as in Example 9 and Comparative Example 5 except a basis weight was 3 g/m 2 .
  • a pellet mix amount and test results are shown in Table 7.
  • Table 7 PP Fluorine-containing Copolymer Pellet mix amount Flowability Basis weight (g/m 2 ) Average Fiber diameter (micrometer) PP Fluorine-containing PP Gear pump (rpm) Pressure (Mpa) Com.
  • Ex. 3 100 25 15 0.52 3 0.7
  • a nonwoven fabric was obtained in the same manner as in Example 22 and Comparative Example 9 except a nozzle diameter was 0.15 mm.
  • a pellet mix amount and test results are shown in Table 8.
  • Table 8 PP Fluorine-containing Copolymer Pellet mix amount Flowability Basis weight (g/m 2 ) Average Fiber diameter (micrometer) PP Fluorine-containing PP Gear pump (rpm) Pressure (Mpa) Com.
  • Ex. 23 PP800 Pre. Ex. 3 100 25 15 0.58 3 0.3
  • the fiber diameter can be thin by increasing the MFR of polypropylene used as a base, and also by decreasing the nozzle caliber. It is shown that the fiber diameter is thinner by adding the fluorine-containing copolymer according to the present invention.
  • the nonwoven fabric of the present invention can be used as, for example, a clothes and sanitary material (for example, operation clothes, a paper diaper, a sanitary napkin), a filter (for example, a battery filter, a filter of a dust-proof mask, a filter of an air-conditioner or an air purifier), a separator for batteries, a packaging material, a nonwoven fabric wiper, an automotive interior material or exterior material (for example, a door trim, an instrument panel, a tire house, a bumper, a floor cover, a bonnet cover, a roof cover), and a building material.
  • the nonwoven fabric of the present invention is suitable for a medical use.
  • the nonwoven fabric can be used for a surgical gown, an operation drape, a sheet, a bandage, a wiping cloth, a pillow cover, a mask and a covering cloth.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
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US20190062969A1 (en) 2019-02-28

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