WO2023100655A1 - Composition et membrane - Google Patents

Composition et membrane Download PDF

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WO2023100655A1
WO2023100655A1 PCT/JP2022/042524 JP2022042524W WO2023100655A1 WO 2023100655 A1 WO2023100655 A1 WO 2023100655A1 JP 2022042524 W JP2022042524 W JP 2022042524W WO 2023100655 A1 WO2023100655 A1 WO 2023100655A1
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polymer
resin
powder
mass
parts
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PCT/JP2022/042524
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English (en)
Japanese (ja)
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俊輔 千葉
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住友化学株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • 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
    • C08K3/08—Metals
    • 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
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the present invention relates to compositions and films.
  • PVDF polyvinylidene fluoride resin
  • PMMA polymethyl methacrylic acid resin
  • PVDF containing 0.05% by mass or more and 5% by mass or less of an organic antimicrobial agent, 0.05% by mass or more and 5% by mass or less of an inorganic antimicrobial agent, and 0.05% by mass or more and 5% by mass or less of an inorganic-organic composite antimicrobial agent Antimicrobial films are described.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel composition and membrane that are excellent in antibacterial and antiviral properties.
  • a composition containing a thermoplastic resin A, a polymer B, and a powder C containing a metal element Q The polymer B has a structural unit represented by formula (1) or formula (2),
  • the value of the standard electrode potential E at 25 ° C. of the single metal element Q in the aqueous solution system is -1.5 V 2.0 V or less
  • the median diameter D50 of the powder C measured by the laser diffraction method is 0.5 to 30 ⁇ m and With respect to a total of 100 parts by mass of the resin A and the polymer B, the content of the resin A is 1 to
  • the content of the polymer B is 1 to 99 parts by mass, and the content of the powder C is 0.01 to 25 parts by mass.
  • R 1 to R 3 are each independently a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group. At least one hydrogen atom in each alkyl group and each alkoxy group is They may be independently substituted with halogen atoms.
  • the value of the standard electrode potential E at 25 ° C. of the simple substance of the metal element Q in the aqueous solution system is 0 V
  • [3] The composition according to [1] or [2], wherein the median diameter D50 of the powder C is 1 to 25 ⁇ m.
  • the resin A is 10 to 100 parts by mass with respect to the total of 100 parts by mass of the resin A and the polymer B 85 parts by mass, and the polymer B is 15 to 90 parts by mass, the composition according to any one of [1] to [3].
  • a film containing a resin M and a powder C containing a metal element Q, The value of the standard electrode potential E at 25 ° C. of the single metal element Q in the aqueous solution system is -1.5 V 2.0 V or less.
  • the surface of the film has a sea region of the resin M and an island region of the powder C. As shown in FIG. A ratio of the island region to the total area of the sea region and the island region on the surface of the film is 0.05% or more and less than 49%.
  • FIG. 1 is an enlarged schematic diagram of the surface of a film according to one embodiment.
  • FIG. 2 is an enlarged schematic diagram of a cross section near the surface of a film according to one embodiment.
  • composition is a composition containing a thermoplastic resin A, a polymer B, and a powder C containing a metal element Q.
  • the content of resin A is 1 with respect to a total of 100 parts by mass of resin A and polymer B to 99 parts by mass, the content of polymer B is 1 to 99 parts by mass, and the content of powder C is 0.99 parts by mass. 01 to 25 parts by mass.
  • thermoplastic resin A examples include olefin-based polymers, styrene-based polymers, methacrylic-based resins, acrylic-based resins, ester-based resins, amide-based resins, and vinyl-based polymers.
  • Thermoplastic resin A may be a single resin or a mixture of two or more resins.
  • the olefinic polymer of the present invention is a polymer containing 51% by weight or more of constituent units derived from an olefin having 2 to 10 carbon atoms (provided that the total amount of the olefinic polymer is 100 % by weight).
  • olefins having 2 to 10 carbon atoms include ethylene, 1-propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1- Decene and the like can be mentioned, and any plural kinds thereof may be included.
  • the olefinic polymer may also contain structural units derived from monomers other than olefins having 2 to 10 carbon atoms.
  • monomers other than olefins having 2 to 10 carbon atoms include aromatic vinyl monomers such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, acrylic Unsaturated carboxylic acid esters such as butyl acid, methyl methacrylate and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene); non-conjugated dienes such as cyclopentadiene and 5-ethylidene-2-norbornene; and propylene.
  • aromatic vinyl monomers such as styrene
  • unsaturated carboxylic acids such as acrylic acid and methacrylic acid
  • the olefinic polymer may have two or more types of structural units derived from other monomers.
  • the olefin-based polymer can be at least one selected from the group consisting of an ethylene-based polymer, a propylene-based polymer, and a butene-based polymer, or a combination of any two or more thereof.
  • the ethylene copolymer is a polymer containing 50% by mass or more of structural units derived from ethylene, examples of which include ethylene homopolymer, ethylene-1-butene copolymer, ethylene- 1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene copolymer.
  • the ethylene-based copolymer may be a combination of two or more ethylene-based copolymers.
  • a propylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from propylene, and examples thereof include propylene homopolymers, propylene-ethylene copolymers, and propylene-1-butene copolymers. , propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene- 1-hexene copolymer and propylene-ethylene-1-octene copolymer.
  • the propylene-based copolymer may be a combination of two or more propylene-based copolymers. It is preferred that the olefin-based polymer is a propylene-based copolymer.
  • the butene-based copolymer is a polymer containing 50% by mass or more of structural units derived from 1-butene, examples of which include 1-butene homopolymer, 1-butene-ethylene copolymer, 1- Butene-propylene copolymer, 1-butene-1-hexene copolymer, 1-butene-1-octene copolymer, 1-butene-ethylene-propylene copolymer, 1-butene-ethylene-1- A hexene copolymer, a 1-butene-ethylene-1-octene copolymer, a 1-butene-propylene-1-hexene copolymer, and a 1-butene-propylene-1-octene copolymer.
  • the butene-based copolymer may be a combination of two or more butene-based copolymers.
  • a styrenic polymer is a polymer containing 51% by weight or more of constitutional units derived from styrene or a styrene derivative.
  • styrene derivatives include p-methylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene and p-methoxystyrene.
  • the styrene polymer may contain structural units derived from monomers other than styrene or styrene derivatives, such as olefins having 2 to 10 carbon atoms; Unsaturated carboxylic acids such as acrylic acid and methacrylic acid; Unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate; Vinyl ester compounds such as vinyl acetate; conjugated dienes such as -butadiene and 2-methyl-1,3-butadiene (isoprene); and non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.
  • monomers other than styrene or styrene derivatives such as olefins having 2 to 10 carbon atoms
  • Unsaturated carboxylic acids such as acrylic acid and methacrylic
  • a methacrylic resin is a polymer containing 51% by weight or more of structural units derived from a methacrylate ester. (2-ethylhexyl methacrylate) and the like.
  • the methacrylic resin of the present invention preferably comprises 50 to 100% by weight of a methacrylic acid alkyl ester having an alkyl group of 1 to 4 carbon atoms, 0 to 50% by weight of an acrylic ester, and other copolymerizable copolymers thereof. from 0 to 49% by weight of at least one of the organic monomers.
  • Thermoplastic polymers having a glass transition temperature of 40° C. or higher are preferred.
  • the acrylic acid ester is more preferably used in the range of 0.1 to 50% by weight, and the copolymerization ratio of the methacrylic acid alkyl ester is more preferably 50 to 99.9%. % range by weight.
  • the glass transition temperature of this methacrylic resin is more preferably 60° C. or higher.
  • methacrylic acid alkyl esters examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid.
  • Methacrylic acid alkyl esters in which the alkyl group has 1 to 8 carbon atoms such as cyclohexyl acid and 2-hydroxyethyl methacrylate are included. The number of carbon atoms in the alkyl group is preferably 1-4.
  • methyl methacrylate is particularly preferably used from the viewpoint of durability.
  • Methacrylic acid alkyl esters may be used alone or in combination of two or more.
  • polymerizable monomers copolymerizable with methacrylic acid alkyl esters include various monomers conventionally known in the art. Examples of such monomers include monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule, and polyfunctional monomers having at least two polymerizable carbon-carbon double bonds in the molecule. monomers and the like, and monofunctional monomers are preferably used.
  • monofunctional monomers include styrene-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, halogenated styrene, and hydroxystyrene; vinyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; , unsaturated acids such as methacrylic acid, maleic anhydride, itaconic anhydride, etc.; maleimides such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide; Unsaturated alcohols such as methallyl alcohol and allyl alcohol; vinyl acetate, vinyl chloride, ethylene, propylene, 4-methyl-1-pentene, 2-hydroxymethyl-1- Other monomers such as butene, methyl vinyl ketone, N-vinylpyrrolidone, N-vinylcarbazole, and the like are included.
  • Other polymerizable monomers copolymerizable with
  • An acrylic resin is a polymer containing 51% by weight or more of structural units derived from an acrylic ester, and examples thereof include poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), poly (2-ethylhexyl acrylate) and the like.
  • an acrylic acid alkyl ester is usually used.
  • alkyl acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid alkyl esters having 1 to 8 carbon atoms in the alkyl group such as cyclohexyl acid and 2-hydroxyethyl acrylate can be mentioned.
  • the number of carbon atoms in the alkyl group is preferably 1-4. Only one type of acrylic acid ester may be used, or two or more types may be used in combination.
  • polymerizable monomers copolymerizable with acrylic acid alkyl esters include various monomers conventionally known in the art. Such monomers include, for example, monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule, polymerizable carbon- Examples include polyfunctional monomers having at least two carbon double bonds, and monofunctional monomers are preferably used.
  • monofunctional monomers include styrene-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, halogenated styrene, and hydroxystyrene; vinyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; , methacrylic acid, maleic anhydride, itaconic anhydride, etc.; maleimides such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide; unsaturated alcohols such as methallyl alcohol, allyl alcohol other monomers such as vinyl acetate, vinyl chloride, ethylene, propylene, 4-methyl-1-pentene, 2-hydroxymethyl-1-butene, methyl vinyl ketone, N-vinylpyrrolidone, N-vinylcarbazole; be done.
  • These other polymerizable monomers copolymerizable with alkyl acrylates may be used alone
  • An ester resin is a polymer containing 51% by weight or more of structural units derived from an ester of a polyhydric carboxylic acid and a polyhydric alcohol. Examples thereof include polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. , polybutylene naphthalate, and the like.
  • An amide resin is a polymer containing 51% by weight or more of structural units repeating amide bonds. methylene dodecaneamide), poly(p-phenylene terephthalamide), poly(m-phenylene terephthalamide) and the like.
  • the vinyl-based polymer of the present invention contains 51% by weight of structural units derived from a monomer having a vinyl group.
  • Polymers containing the above include, for example, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, and polyvinylidene chloride.
  • acrylic resins and methacrylic resins are preferable because of their high transparency.
  • the glass transition temperature (Tg) of the thermoplastic resin A is preferably 0° C. or higher, more preferably 50° C. or higher, and even more preferably 80° C. or higher, from the viewpoint of snow sliding properties in wet snow. The higher the glass transition temperature (Tg), the more excellent the snow sliding properties of the composition on wet snow.
  • the glass transition temperature (Tg) of thermoplastic resin A is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.
  • the melt mass flow rate (MFR) of thermoplastic resin A measured at a temperature of 190°C or 230°C and a load of 2.16 kgf or 3.80 kgf (37.3 N) is 0.01 g/10 minutes or more. can be 200 g/10 minutes or less.
  • the upper limit of MFR can be 100 g/10 min, 50 g/10 min, 30 g/10 min. The smaller the melt mass flow rate of the thermoplastic resin A, the more excellent the moldability of the composition tends to be.
  • thermoplastic resin A As a method for producing the thermoplastic resin A, a known polymerization method using a known polymerization catalyst is used.
  • Polymer B of the present invention is a polymer having a structural unit represented by formula (1) or formula (2).
  • R 1 to R 3 are each independently selected from hydrogen atoms, halogen atoms, alkoxy groups and alkyl groups.
  • halogen atoms are F, Cl, Br, I.
  • the number of carbon atoms in the alkoxy group or alkyl group of R 1 to R 3 in formulas (1) and (2) is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less. is.
  • the alkyl groups and alkoxy groups of R 1 to R 3 may be linear, branched or cyclic, but preferably linear.
  • At least one hydrogen atom in each alkyl group and each alkoxy group of R 1 to R 3 may be independently substituted with a halogen atom such as fluorine. It is preferred that all hydrogen atoms in each alkyl group and each alkoxy group are replaced with halogen atoms such as fluorine.
  • Polymer B is preferably a polymer containing 51% by weight or more of structural units of formula (1) and/or (2), for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride , tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoroethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, perfluoroalkoxyalkane (e.g. tetrafluoroethylene/perfluoroalkoxyethylene copolymer polymerization), ethylene-tetrafluoroethylene copolymer, and the like.
  • polytetrafluoroethylene polychlorotrifluoroethylene
  • polyvinylidene fluoride polyvinyl fluoride
  • tetrafluoroethylene/hexafluoropropylene copolymer ethylene/tetrafluoroethylene
  • the polymer B is preferably polychlorotrifluoroethylene, polyvinylidene fluoride, or perfluoroalkoxyalkane.
  • a vinylidene fluoride-based polymer When a vinylidene fluoride-based polymer is used as the polymer B, it may be a resin containing vinylidene fluoride units.
  • a copolymer containing The content of vinylidene fluoride units in the vinylidene fluoride polymer is preferably 50% by mass or more, and 70% by mass. 90% by mass or more is more preferable.
  • vinyl monomers copolymerizable with vinylidene fluoride include, for example, vinyl fluoride, Fluorinated vinyl monomers such as tetrafluoroethylene, trifluoroethylene chloride, and hexafluoropropylene; and vinyl monomers such as styrene, ethylene, butadiene, and propylene.
  • a known polymerization method using a known polymerization catalyst is used as a method for producing the polymer B.
  • the melting point of polymer B determined by DSC is not particularly limited, but from the viewpoint of processability, it is preferably less than 300°C, more preferably less than 280°C, and even more preferably less than 260°C. be.
  • the melting point (Tm) of polymer B determined by DSC is the melting temperature of the crystalline phase contained in polymer B. Specifically, in the DSC curve obtained when polymer B is heated, It is the peak top temperature in the endothermic peak on the high temperature side.
  • this melting point is measured under the following conditions.
  • MFR of polymer B Polymer B at a temperature of 230° C., or a temperature of 190° C. or 300° C., and a load2.
  • Melt mass flow rate (MFR) measured under conditions of 16 kgf or 5 kgf is 0.0 It can be 1 g/10 min or more and can be 200 g/10 min or less. MFR can be 100 g/10 min, 50 g/10 min, 30 g/10 min. The smaller the melt mass flow rate of the polymer B, the more excellent the moldability of the composition tends to be.
  • a known polymerization method using a known polymerization catalyst is used as a method for producing the polymer B.
  • the powder C contains the metal element Q.
  • the powder C may contain the metal element Q in a nonionic state (either singly or in a mixture such as an alloy) or in an ionic state (including compounds).
  • the standard electrode potential E at 25° C. of a single metal element Q in an aqueous solution system is ⁇ 1.5 V or higher.2. It is 0 V or less, may be 0 V or more and 1.5 V or less, preferably 0 V or more and 1.0 V or less.
  • the standard electrode potential E is a potential expressed on the basis of a standard hydrogen electrode under an environment of 1 atm and 25°C.
  • the standard electrode potential E of a simple substance of the metal element Q in an aqueous solution system is an electrode potential related to the electrochemical reaction between the simple substance of the metal element Q and the hydrated ion of the metal element, Corresponds to the ionization tendency of the metal element Q. This value is described in Kagaku Binran Basic Edition Revised 4th Edition, Maruzen Co., Ltd., II-464 (1993), 12, 2, 1, f.
  • Hg 0.8535 V (Hg 2+ )
  • Ag 0.799 V (Ag + )
  • Au 1 . 52 V (Au 3+ ) and 1.83 V (Au + )
  • Pd 0.915 V (Pd 2+ )
  • Pt 1.118 V (Pt 2+ )
  • Cd ⁇ 0.4025 V (Cd 2+ )
  • Co ⁇ 0.
  • the metal element Q is preferably silver or copper.
  • the powder C can contain one or more of the metal elements Q described above.
  • the powder C can be a powder of a metal element Q alone or an alloy. Examples of such powder C are copper powder, silver powder and the like.
  • the powder C can be a powder of a compound of the metal element Q.
  • compounds are metal halides such as chlorides, fluorides, bromides, iodides.
  • Specific examples are CuF, CuI, AgCl, AgI and the like.
  • oxides are copper oxide (Cu 2 O, CuO), Silver oxide ( Ag2O , AgO, Ag2O3 ).
  • the powder C contains a single substance, an alloy, and/or ions of the metal element Q in the matrix material, Alternatively, a form in which a compound of the metal element Q is supported may be used.
  • matrix materials are crystalline aluminosilicates, amorphous aluminosilicates, silica gel, activated alumina, diatomaceous earth, activated carbon, zirconium phosphate, hydroxyapatite, They are magnesium oxide, magnesium perchlorate, glass, silicone resin, and carbon materials.
  • glasses are e.g. elemental glasses, hydrogen bonding glasses, oxide glasses, silicate glasses, Silicate glass, alkali silicate glass, soda lime glass, lead (alkali) glass, barium glass, borosilicate glass, phosphate glass, borate glass, fluoride glass, chloride glass, sulfide glass, carbonate glass, nitrate glass, sulfate glass, fusible glass, crystallized glass.
  • glass supporting metal ions such as Ag and Cu is suitable.
  • methods for supporting the metal element Q on glass or the like include a melting method, a CDC method, a sol-gel method, an ion exchange method, and an ion implantation method.
  • the silicone resin contains structural units represented by formula (3).
  • R 4 and R 5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. ]
  • the number of carbon atoms in the alkoxy group or alkyl group of R 4 and R 5 is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less.
  • Alkyl groups and alkyl groups may be linear, branched, or cyclic, but are preferably linear.
  • thermosetting resins examples include thermosetting resins, diamond, graphite, fullerenes, and the like.
  • the median diameter D50 of Powder C measured by a laser diffraction method is 0.5 ⁇ m or more, and may be 1 ⁇ m or more, from the viewpoint of antibacterial and antiviral properties.
  • the median diameter D50 is 30 ⁇ m or less, may be 25 ⁇ m or less, may be 20 ⁇ m or less, and may be 10 ⁇ m or less. It may be ⁇ m or less. If the D50 is too large, the moldability tends to deteriorate, and if the particle size is too small, the transparency tends to deteriorate.
  • the median diameter D50 is determined by measuring the weight-based particle size distribution according to JISR1629 using a laser diffraction particle size distribution analyzer, and the cumulative amount 5 read from the obtained particle size cumulative distribution curve. It can be determined from a particle size value of 0% by weight.
  • the laser diffraction particle size distribution analyzer include MT-3300EX-II manufactured by Nikkiso Co., Ltd.
  • the powder C in the present invention preferably exhibits solid particulate properties even at a temperature of 100°C.
  • the method for producing the above inorganic compound is not particularly limited, and known gas phase methods such as PVD method and CVD method, coprecipitation method, alkoxide method, sol-gel method, hydrothermal synthesis method, polymerization method and spray drying method. and a liquid phase method such as a freeze-drying method, a resin kneading method, various pulverization methods, a mechanical alloying method, and the like can be applied.
  • gas phase methods such as PVD method and CVD method, coprecipitation method, alkoxide method, sol-gel method, hydrothermal synthesis method, polymerization method and spray drying method.
  • a liquid phase method such as a freeze-drying method, a resin kneading method, various pulverization methods, a mechanical alloying method, and the like can be applied.
  • the composition of the present invention is a composition containing a thermoplastic resin A, a polymer B having a structural unit represented by formula (1) or formula (2), and powder C, wherein the resin A
  • the content of the resin A is 1 to 99 parts by mass
  • the content of the polymer B is 1 to 99 parts by mass, based on the total of 100 parts by mass of the resin and the polymer B.
  • the content of resin A is preferably 10 to 90 parts by mass
  • the content of polymer B is preferably 10 to 90 parts by mass
  • the content of resin A is 10 to 85 parts by mass.
  • the content of polymer B is more preferably 15 to 90 parts by mass, the content of resin A is 10 to 80 parts by mass, and the content of polymer B is 20 to 90 parts by mass. More preferably, the content of resin A is 10 to 70 parts by mass, the content of polymer B is even more preferably 30 to 90 parts by mass, and the content of resin A is 20 to 70 parts by mass, and the content of polymer B is even more preferably 30 to 80 parts by mass.
  • the amount of powder C is 0.01 to 25 parts by mass with respect to 100 parts by mass of resin A and polymer B in total.
  • the content of powder C is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 15 parts by mass. It is even more preferable that the content of the substance C is 0.01 to 10 parts by mass, and it is even more preferable that the content of the powder C is 0.5 to 10 parts by mass.
  • the number of peaks in the glass transition temperature of the composition of the present invention is preferably unimodal.
  • the thermoplastic resin A and the polymer B are preferably completely compatible.
  • the composition may contain additives other than the thermoplastic resin A, the polymer B, and the powder C, if necessary.
  • Additives include stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, inorganic fibers, organic fibers, composite fibers, inorganic whiskers, and fillers.
  • stabilizers include lubricants, antioxidants, heat stabilizers, light stabilizers, weather stabilizers, metal deactivators, ultraviolet absorbers, light stabilizers, and copper damage inhibitors.
  • Examples of light stabilizers include hindered amine light stabilizers
  • examples of colorants include titanium oxide, carbon black and organic pigments
  • examples of metal powders include ferrite
  • examples of inorganic fibers include glass fibers
  • examples of organic fibers include carbon fibers and aramid fibers.
  • examples of inorganic whiskers include potassium titanate whiskers.
  • fillers include glass beads, glass balloons, glass flakes, asbestos and mica. , calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, Diatomaceous Earth, Graphite, Pumice, Evo Powder, Cotton Flock, Cork Powder, Barium Sulfate, Fluororesins, cellulose powders, and wood flours can be mentioned.
  • the additive may be contained in the dispersed phase of the resin A, may be contained in the dispersed phase of the polymer B, or the resin A and the polymer B may form separate dispersed phases.
  • Method for producing composition As a method for producing the composition according to the present invention, there is a method of melt-kneading the thermoplastic resin A, the polymer B and the powder C, and a thermoplastic resin in the presence of the thermoplastic resin A, the polymer B and the powder C.
  • a method of polymerizing various monomer components constituting the resin A and the polymer B can be mentioned. From the viewpoint of workability, the method of melt-kneading the thermoplastic resin A, the polymer B and the powder C is preferable.
  • the melt-kneading described above can be performed by a known method using a known apparatus.
  • the thermoplastic resin A, the polymer B and the powder C are mixed using a mixing device such as a Henschel mixer, a ribbon blender, or a tumble mixer, and then further melt-kneaded.
  • Thermoplastic resin A, polymer B, powder C, and, if necessary, various additives are continuously supplied at a constant rate to obtain a mixture, and then the mixture is uniaxially or biaxially or more A method of melt-kneading using an extruder, a Banbury mixer, a roll-type kneader, or the like.
  • the melt-kneading temperature is preferably 80° C. or higher, more preferably 100° C. to 300° C., more preferably 120° C. to 280° C., still more preferably 14 0°C to 260°C. (action)
  • the molded body of the composition A powder C containing a predetermined metal element Q can be selectively arranged on the surface. Therefore, articles such as various films having specific surfaces, which will be described later, can be favorably molded.
  • the surface of the membrane is likely to have antibacterial and/or antiviral properties.
  • a film according to one embodiment of the present invention is a film containing a resin M and a powder C containing a metal element Q,
  • the value of the standard electrode potential E at 25 ° C. of the single metal element Q in the aqueous solution system is -1.5 V 2.0 V or less
  • the surface of the film has a sea region of the resin M and an island region of the powder C, A ratio of the island region to the total area of the sea region and the island region on the surface of the film is 0.05% or more and less than 49%.
  • Resin M is not particularly limited.
  • Resin M may be a mixture of thermoplastic resin A and polymer B in the composition described above.
  • the surface of the film 10 has a sea region S of resin M and an island region I of powder C. As shown in FIG. That is, on the surface of the film, a large number of island regions I of the powder C are dispersed in the sea region S of the resin.
  • the powder C protrudes from the resin M on the surface of the film.
  • the resin M forms a sea region S
  • the powder C forms an island region I.
  • the ratio of the area of the island region I to the sum of the sea region S and the island region I on the surface of the film is From the viewpoint of enhancing antibacterial and antiviral properties, it is 0.05% or more and less than 49%. This proportion is preferably 0.05% or more and 15% or less, more preferably 0.05% or more and 10% or less, and more preferably 0.05% or more and 5% or less. The lower limit of the area ratio is 0 . 07%, 0.1%, 0.2%, 0.3%, 0.5%.
  • the area of the island region I on the surface of the film is calculated based on the image taken from the direction perpendicular to the surface. For example, by elemental analysis such as SEM-EDS, the island region I and the sea region S are separated, Area can be calculated.
  • the average equivalent circle diameter of the island regions can be 0.001 to 25 ⁇ m.
  • the thickness of the film is not limited, it can be, for example, 1 ⁇ m or more. There is no particular upper limit, but it can be 150 mm.
  • the film of the present embodiment can be obtained by melting and molding the above composition.
  • molding methods are extrusion, compression molding, injection molding.
  • Extrusion methods include, for example, a T-die molding method, a single-layer extrusion molding method by an inflation molding method, a multilayer extrusion molding method by a T-die molding method or a single-layer extrusion molding method by an inflation molding method, and a spinning extrusion method. mentioned.
  • Known methods such as a feed block method and a multi-manifold method can be used as the multilayer extrusion method.
  • injection molding methods include general injection molding, injection foam molding, supercritical injection foam molding, ultra-high speed injection molding, injection compression molding, gas-assisted injection molding, sandwich molding, and sandwich foam.
  • a molding method, an insert/outsert molding method, and the like can be mentioned.
  • extrusion molding and compression molding are preferable as the above molded article.
  • the film of the present invention may be used alone, or laminated with other resin members, metal members, paper, leather or the like to form a multi-layer article.
  • a surface treatment may be applied to the surface of the film of the present invention.
  • Examples of surface treatment methods include embossing, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.
  • the film of the present invention include transparent optical members, fiber materials, agricultural materials, exterior members, furniture and interior decoration members, house members, toy members, gardening members, automobile members, and packaging materials.
  • transparent optical members include solar panel members, lens members, and the like.
  • Fiber materials include, for example, clothing fabric members, interior fabric members, and industrial fiber members. film members, house members, and net members; Post members, cycle port members, deck members, sunroom members, roof members, terrace members, handrail members, shade members, awning members, etc.
  • furniture and interior decoration members include sofa members, table members, and chair members.
  • household appliance members include watch members, Examples include mobile phone members, home appliance members, etc.
  • Toy members include, for example, plastic model members, diorama members, and video game main body members.
  • Gardening members include, for example, planter members, vase members, and flowerpot members.
  • Examples of automobile members include bumper materials and instrument panel materials
  • examples of packaging materials include food packaging materials, fiber packaging materials, miscellaneous goods packaging materials, and the like.
  • other uses include, for example, monitor members, office automation (OA) equipment members, medical members, drainage pans, toiletry members, bottles, containers, snow removal product members, and various construction members.
  • OA office automation
  • the island regions I of the powder C containing the metal element Q are dispersed in the sea region S of the resin at a suitable area ratio. Excellent in nature.
  • thermoplastic resin A thermoplastic resin A, polymer B and powder C used in Examples and Comparative Examples are shown below.
  • Thermoplastic resin A (A-1) Polymethyl methacrylate (trade name) Sumipex LG (manufactured by Sumitomo Chemical) MFR (230°C 3.80 kgf (37.3 N)): 10.0 g/10 minutes
  • thermoplastic resin each thermoplastic resin
  • polymer each polymer
  • component each component
  • composition were measured according to the methods shown below.
  • Melt mass flow rate (MFR, unit: g/10 minutes) It was measured according to the method specified in JIS K7210-2014. Measured temperature is 230 °C or 300 °C, and the load was 2.16 kgf, 3.80 kgf or 5.00 kgf.
  • SEM-EDS analysis is performed by coating the surface of the sample with 4 nm thick osmium, and using the osmium-coated sample with JSM-7900F manufactured by JEOL Ltd. at an acceleration voltage of 3.5 kV. , and measured by EDS analysis of the sample surface at an observation magnification of ⁇ 1000. Observation area is 1.3mm 2.
  • the obtained analysis image was binarized using the image analysis software Azo-kun manufactured by Asahi Engineering Co., Ltd., and the area ratio of the island portion was evaluated from the obtained binarized image.
  • antibacterial activity value (R) [Resin A-1 containing no powder C and polymer B after 24 hours of culture Number of viable bacteria on the control test piece] - [Number of viable bacteria on the test piece using the composition of each example or comparative example after 24 hours of culture] ... (E2) Antibacterial activity is understood to be present when the antibacterial activity value (R) is 0.1 or more. Antibacterial activity value (R ), the higher the antibacterial property.
  • Antiviral activity value (R) Influenza A virus (A/Hong Kong/8/68; TC adapt ed) Using (ATCC VR-1679), the antiviral activity value (R) obtained by the following formula (E3) was evaluated based on the results measured according to ISO21702.
  • Antiviral activity value (R) [the number of residual viruses in the control test piece of resin A-1 containing no powder C and polymer B after 24 hours of culture] - [after 24 hours of culture, each example or Number of residual viruses in test piece using composition of comparative example] (E3)
  • Antiviral activity value (R) of 0.1 or more is understood to have antiviral activity. The higher the antiviral activity value (R), the better the antiviral properties.
  • Example ⁇ 1 30 parts by mass of thermoplastic resin (A-1), 70 parts by mass of polymer (B-1), and 3 parts by mass of powder (C-1) are uniformly mixed, and a twin-screw kneader with an inner diameter of 15 mm is used.
  • a twin-screw kneader with an inner diameter of 15 mm is used.
  • the composition was extruded using a single-screw extruder with an inner diameter of 20 mm ⁇ (VS20-14 manufactured by Tanabe Plastics Co., Ltd.) at a set temperature of 210 ° C. to a thickness of 50.
  • a film was obtained as an extruded body shaped into a sheet of ⁇ m.
  • the antibacterial activity value and antiviral activity value of the obtained membrane were evaluated.
  • Example ⁇ 2 The procedure was the same as in Example ⁇ 1, except that 70 parts by mass of the thermoplastic resin (A-1), 30 parts by mass of the polymer (B-1), and 3 parts by mass of the powder (C-1) were used.
  • Example ⁇ 3 The procedure was the same as in Example ⁇ 1, except that 0.5 parts by mass of powder (C-1) was used.
  • Example ⁇ 4 The procedure was the same as in Example ⁇ 1, except that 5 parts by mass of powder (C-1) was used.
  • Example ⁇ 5 The procedure was the same as in Example ⁇ 1, except that 3 parts by mass of powder (C-2) was used instead of powder (C-1).
  • Example ⁇ 1 The procedure of Example ⁇ 1 was repeated except that 100 parts by mass of the thermoplastic resin (A-1) and 3 parts by mass of the powder (C-1) were used, and the polymer B was not added.
  • Example ⁇ 2 The procedure was the same as in Example ⁇ 1, except that 30 parts by mass of the thermoplastic resin (A-1) and 70 parts by mass of the polymer (B-1) were used, and the powder C was not added. Table 1 shows the conditions and results.
  • Example ⁇ 3 The procedure was the same as in Example ⁇ 1, except that 3 parts by mass of powder (C-3) was used instead of powder (C-1).
  • composition having a predetermined composition yields a molded article having excellent antibacterial and/or antiviral properties.
  • the composition was using a single-screw extruder (VS20-14 manufactured by Tanabe Plastics Co., Ltd.) at a set temperature of 210° C. to form a sheet having a thickness of 50 ⁇ m. A 5% membranous extrudate was obtained.
  • the antibacterial activity value and antiviral activity value of the molded article were evaluated.
  • Example ⁇ 2 The procedure was the same as in Example ⁇ 1, except that the amount of powder (C-1) was changed to 3 parts by mass.
  • the area ratio of powder C on the surface of the film was 2%.
  • Example ⁇ 1 The procedure was the same as in Example ⁇ 2, except that the resin A was 100 parts by mass and the polymer B was not added. The area ratio of powder C on the surface of the film was 0%.
  • Table 2 shows the conditions and results.
  • membranes having a given surface structure have improved antibacterial and/or antiviral properties.

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Abstract

L'invention concerne une composition contenant: une résine thermoplastique A, un polymère B, et une poudre C qui contient un élément métallique Q. Le polymère B possède une unité structurelle représentée par la formule (1) ou la formule (2). La valeur du potentiel E d'électrode standard à 25℃ pour un élément simple de l'élément métallique Q dans un système de solution aqueuse est comprise entre -1,5 V et 2,0 V. Le diamètre médian D50 de la poudre C tel que mesuré par diffraction laser est compris entre 5 et 30 μｍ. Pour 100 parties en poids du total de la teneur en résine A et en polymère B, la teneur en résine A représente 1 à 99 parties en poids, la teneur en polymère B représente 1 à 99 parties en poids, et la teneur en poudre C représente 0,01 à 25 parties en poids. Dans les formules, R1 à R3 représentent indépendamment un atome d'hydrogène, un atome d'halogène, un atome d'oxygène, un groupe alcoxy, ou un groupe alkyle. Au moins 1 atome d'hydrogène à l'intérieur de chaque groupe alkyle et chaque groupe alcoxy peut être indépendamment substitué à l'aide d'un atome d'halogène.
PCT/JP2022/042524 2021-11-30 2022-11-16 Composition et membrane WO2023100655A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384066A (ja) * 1989-08-25 1991-04-09 Toray Ind Inc 抗菌作用を有する樹脂組成物およびその製造方法
JPH07157666A (ja) * 1993-12-10 1995-06-20 Matsushita Electric Ind Co Ltd 耐汚染性に優れた樹脂組成物
JPH11343350A (ja) * 1998-06-01 1999-12-14 Matsushita Electric Ind Co Ltd 人工大理石成形体
JP2004269635A (ja) * 2003-03-07 2004-09-30 Kanbo Pras Corp 難燃性フィルム、不燃性積層体、および不燃性積層体構造体
JP2005132866A (ja) * 2003-10-28 2005-05-26 Narupura:Kk 抗菌剤入りのフィルム又はシート状プラスチック成形品
JP2006213885A (ja) * 2005-02-07 2006-08-17 Denki Kagaku Kogyo Kk フッ化ビニリデン系樹脂フィルム
JP2008239882A (ja) * 2007-03-28 2008-10-09 Du Pont Mitsui Fluorochem Co Ltd 抗菌性フッ素樹脂組成物
CN112250974A (zh) * 2020-10-21 2021-01-22 嘉兴高正新材料科技股份有限公司 一种透明聚偏氟乙烯耐候抗菌薄膜专用料及其制备方法
CN112280223A (zh) * 2020-09-29 2021-01-29 程凤娟 一种pvdf抗菌薄膜

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0384066A (ja) * 1989-08-25 1991-04-09 Toray Ind Inc 抗菌作用を有する樹脂組成物およびその製造方法
JPH07157666A (ja) * 1993-12-10 1995-06-20 Matsushita Electric Ind Co Ltd 耐汚染性に優れた樹脂組成物
JPH11343350A (ja) * 1998-06-01 1999-12-14 Matsushita Electric Ind Co Ltd 人工大理石成形体
JP2004269635A (ja) * 2003-03-07 2004-09-30 Kanbo Pras Corp 難燃性フィルム、不燃性積層体、および不燃性積層体構造体
JP2005132866A (ja) * 2003-10-28 2005-05-26 Narupura:Kk 抗菌剤入りのフィルム又はシート状プラスチック成形品
JP2006213885A (ja) * 2005-02-07 2006-08-17 Denki Kagaku Kogyo Kk フッ化ビニリデン系樹脂フィルム
JP2008239882A (ja) * 2007-03-28 2008-10-09 Du Pont Mitsui Fluorochem Co Ltd 抗菌性フッ素樹脂組成物
CN112280223A (zh) * 2020-09-29 2021-01-29 程凤娟 一种pvdf抗菌薄膜
CN112250974A (zh) * 2020-10-21 2021-01-22 嘉兴高正新材料科技股份有限公司 一种透明聚偏氟乙烯耐候抗菌薄膜专用料及其制备方法

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