WO2018062529A1 - Agent antimicrobien contenant un polymère ayant un motif structural maléimide - Google Patents

Agent antimicrobien contenant un polymère ayant un motif structural maléimide Download PDF

Info

Publication number
WO2018062529A1
WO2018062529A1 PCT/JP2017/035639 JP2017035639W WO2018062529A1 WO 2018062529 A1 WO2018062529 A1 WO 2018062529A1 JP 2017035639 W JP2017035639 W JP 2017035639W WO 2018062529 A1 WO2018062529 A1 WO 2018062529A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
group
resin
structural unit
antimicrobial agent
Prior art date
Application number
PCT/JP2017/035639
Other languages
English (en)
Japanese (ja)
Inventor
勇介 宮▲崎▼
勇樹 牧野
Original Assignee
株式会社日本触媒
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日本触媒 filed Critical 株式会社日本触媒
Priority to JP2018542960A priority Critical patent/JP6730439B2/ja
Publication of WO2018062529A1 publication Critical patent/WO2018062529A1/fr

Links

Classifications

    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • 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
    • C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and 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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the present invention relates to an antimicrobial agent comprising a polymer having a structural unit in which a secondary amino group is added to a maleimide structure.
  • antimicrobial agents against bacteria, molds, and the like have been used in various fields such as resins, molded articles, paints, and the like from the viewpoint of increasing cleanliness and hygiene. Used to impart microbial properties. These antimicrobial agents are required to have safety as well as antimicrobial performance, and polymer-type antimicrobial agents have low volatility and are difficult to elute from the base material in the environment of use. It has been attracting attention as a highly safe antimicrobial agent.
  • Polymeric antimicrobial agents are said to act by destroying cell membranes such as bacteria and mold. As described above, it is considered that the method of targeting the cell membrane of a microorganism as a target of attack makes it difficult for the microorganism to acquire resistance as compared with a conventional antimicrobial agent that targets a specific protein as a target of attack.
  • Patent Document 1 discloses that a styrene-maleic anhydride copolymer such as styrene-dimethylaminopropylmaleimide is modified with a tertiary amine N, N-dimethyl-1,3-propanediamine. Antibacterial agents are described.
  • JP 2013-518964 A (corresponding to US Patent Application Publication No. 2012/0316305)
  • Patent Document 1 does not have sufficient antimicrobial performance (antifungal performance and antibacterial performance), and particularly when added to a resin or the like, the antibacterial performance is not exhibited if the addition amount is small. There was a problem.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a polymer-type antimicrobial agent that can exhibit excellent antimicrobial performance (antifungal performance and antimicrobial performance).
  • the present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by an antimicrobial agent containing a polymer having a structural unit represented by the following formula (1), and have completed the present invention.
  • R 1 is an alkylene group having 3 to 24 carbon atoms
  • R 2 is an alkyl group having 2 to 24 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a carbon number.
  • the secondary amino group selected from the group consisting of 6 to 24 aryl groups and represented by —NHR 2 may be a neutralized salt.
  • an antimicrobial agent comprising a polymer having a structural unit represented by the above formula (1).
  • the antimicrobial performance is high, and in a molded article containing a polymeric antimicrobial agent, the elution of the polymer can be suppressed, and the antimicrobial performance excellent in antimicrobial performance is achieved. It becomes possible to provide an antimicrobial agent. Therefore, the antimicrobial agent of the present invention can be applied to various product forms such as resins, molded articles, paints, pressure-sensitive adhesives, and adhesives.
  • an antimicrobial agent comprising a polymer having a structural unit represented by the above formula (1) or a polymer having a structural unit represented by the above formula (1) and a microorganism
  • polymer having a structural unit of the above formula (1) in which a secondary amino group is added to a maleimide structure is also simply referred to as “polymer having a maleimide structural unit”.
  • the antimicrobial agent according to the present invention contains a polymer having the maleimide structural unit and can exhibit excellent antimicrobial performance.
  • Cell membranes such as bacteria and fungi are bilayers composed mainly of phospholipids and are negatively charged.
  • the secondary amino group added to the maleimide structural unit is easily positively charged. This is because there is one functional group bonded to the nitrogen of the secondary amino group, so the nitrogen atoms of the amino group in the polymer are different from each other in the tertiary amino group in which two functional groups are bonded. It is likely that the cells are densely packed, and due to the concentration of nitrogen atoms, the positive charge is partially increased, the affinity to the negatively charged cell membrane is improved, and the effect of destroying cell membranes such as bacteria and fungi is further improved.
  • the degree of freedom of the secondary amino group is increased in the polymer structure.
  • the permeability to the cell wall is increased, and it is considered that the cell membrane can be more effectively destroyed against mold having a thick cell wall.
  • R 1 is an alkylene group having 3 or more carbon atoms
  • nitrogen atoms of the amino group tend to be densely packed, and due to the denseness of the nitrogen atoms, a positive charge is partially increased, and as described above, negatively charged. It is considered that the affinity for the cell membrane is improved, and the effect of destroying cell membranes of bacteria and molds is further improved.
  • the polymer having the maleimide structure of the present invention since the polymer having the maleimide structure of the present invention has an imide ring structure in the polymer main chain, the main chain mobility is suppressed to some extent, and it is important for the polymer chain to be intertwined in a complex manner and exhibit antimicrobial performance. It is possible to prevent an amino group from being buried inside the polymer. Therefore, since the secondary amino group added to the maleimide structure can be effectively exposed on the polymer surface, it is considered that cell membranes such as bacteria and fungi can be more effectively destroyed.
  • the antimicrobial agent according to the present invention is characterized by excellent durability of antimicrobial performance.
  • the antimicrobial agent according to the present invention can suppress elution of a polymer in a molded article containing the antimicrobial agent by adding a secondary amino group to the maleimide structure. This is considered to be because the secondary amino group is more likely to be densely packed in the polymer than the tertiary amino group, and the molecular entanglement between the polymers causes the elution to be suppressed.
  • the above action mechanism is speculation, and the present invention is not limited to the above action mechanism.
  • X to Y indicating a range means “X or more and Y or less”.
  • operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.
  • the antimicrobial agent of this invention contains the polymer which has a structural unit of the said Formula (1) which added the secondary amino group to the maleimide structure.
  • R 1 is an alkylene group having 3 to 24 carbon atoms.
  • R 1 is preferably an alkylene group having 18 or less carbon atoms, more preferably an alkylene group having 12 or less carbon atoms, and particularly preferably an alkylene group having 8 or less carbon atoms, from the viewpoint of easy availability of synthetic raw materials. It is a group.
  • the alkylene group may be linear or branched.
  • alkylene group having 3 to 24 carbon atoms examples include propylene group, trimethylene group, butylene group, pentylene group, hexylene group (hexamethylene group), heptylene group, octylene group (octamethylene group), nonylene group, and decylene group.
  • R 1 may be the same or different between maleimide structural units.
  • R 1 is preferably a linear alkylene group having 3 to 8 carbon atoms, more preferably a trimethylene group, a butylene group, a pentylene group, a hexylene group, or a heptylene group, from the viewpoint of exhibiting more antimicrobial performance. Or it is an octylene group, More preferably, it is a trimethylene group, a hexylene group, or an octylene group, Most preferably, it is a trimethylene group.
  • R 2 is selected from the group consisting of an alkyl group having 2 to 24 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aryl group having 6 to 24 carbon atoms.
  • the alkyl group having 2 to 24 carbon atoms may be linear or branched.
  • Examples of the alkyl group having 2 to 24 carbon atoms include ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 2 -Ethylhexyl group, hexyl group (normal hexyl group), heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), Examples include heptadecyl group, octadecyl group (stearyl group),
  • Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group, isobornyl group, adamantyl group, A dicyclopentanyl group etc. are mentioned.
  • aryl groups having 6 to 24 carbon atoms include phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group , Anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, pyrenyl group and the like.
  • R 2 may be the same or different between maleimide structural units.
  • the alkyl group is preferably an alkyl group having 2 to 8 carbon atoms, more preferably an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, from the viewpoint of exhibiting more antimicrobial performance.
  • the alkyl group is preferably an alkyl group having 9 to 20 carbon atoms, more preferably an alkyl group having 12 to 18 carbon atoms, from the viewpoint of more exerting antimicrobial performance and durability. And more preferably a dodecyl group, a tridecyl group, a tetradecyl group (myristyl group), a pentadecyl group, a hexadecyl group (palmityl group), a heptadecyl group or an octadecyl group (stearyl group).
  • the alkyl group may be a mixture of alkyl groups having different carbon numbers.
  • R 2 may be a mixture of the above alkyl groups having different carbon numbers.
  • the mixed alkyl group is preferably a tetradecyl group (myristyl group), a hexadecyl group (palmityl group), and an octadecyl group (stearyl group) from the viewpoint of more exerting antimicrobial performance and durability.
  • the alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 4 to 10 carbon atoms, more preferably an alicyclic hydrocarbon group having 6 to 10 carbon atoms, from the viewpoint of exhibiting more antimicrobial performance.
  • a cyclic hydrocarbon group more preferably a cyclohexyl group, an adamantyl group, a dicyclopentanyl group, a dicyclopentenyl group, an isobornyl group, an adamantyl group and a dicyclopentanyl group, particularly preferably a cyclohexyl group, an isobornyl group.
  • the aryl group is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group, a benzyl group, a phenethyl group, o-, m- or A p-tolyl group, a 2,3- or 2,4-xylyl group and a mesityl group, more preferably a benzyl group.
  • R 2 is preferably an alkyl group having 2 to 24 carbon atoms and an alicyclic hydrocarbon having 3 to 12 carbon atoms from the viewpoint that antimicrobial performance and durability thereof can be further improved. Selected from the group consisting of groups.
  • R 2 is selected from the group consisting of an alkyl group having 2 to 24 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, when the structure of R 2 is invaded into the cell membrane of a microorganism, the cell membrane It is speculated that higher antimicrobial performance can be exerted because large pores are formed in the cell, thereby promoting the outflow of the intracellular fluid.
  • R 1 is an alkylene group having 3 to 18 carbon atoms
  • R 2 is an alkyl group having 2 to 24 carbon atoms from the viewpoint that the antimicrobial performance and its durability can be further improved. Selected from the group consisting of a group and an alicyclic hydrocarbon group having 3 to 12 carbon atoms.
  • R 1 is an alkylene group having 3 to 8 carbon atoms and R 2 is 2 to 24 carbon atoms from the viewpoint that the antimicrobial performance and its durability can be further improved. More preferably, R 1 is an alkylene group having 3 to 8 carbon atoms, and R 2 is a group having 2 carbon atoms.
  • R 1 is selected from the group consisting of trimethylene group, hexylene group and octylene group
  • 2 is selected from the group consisting of isopropyl, tert-butyl, 2-ethylhexyl, hexyl and cyclohexyl.
  • the secondary amino group represented by —NHR 2 may be a neutralized salt with an acid. Since the secondary amino group is a neutralized salt, the polarity is increased, so that it can be applied to products using a polar solvent such as an aqueous emulsion.
  • the acid used for neutralization include organic acids such as acetic acid, formic acid, propionic acid, succinic acid, citric acid and malic acid; and inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.
  • the acid used for neutralization may be used alone or in combination of two or more.
  • the neutralization of the secondary amino group represented by —NHR 2 can be appropriately performed in consideration of the polar solvent used.
  • the addition amount of the acid used for neutralization is 25 mol% or more, preferably 50 mol% or more, based on the secondary amino group contained in the polymer having a maleimide structure.
  • the polymer main chain having a maleimide structural unit of the present invention can have a structural unit derived from a monomer copolymerizable with the monomer from which the maleimide structural unit is derived. That is, the polymer main chain having the maleimide structural unit may be a copolymer of a monomer derived from the structural unit of the above formula (1) and a monomer copolymerizable with the monomer. Good.
  • the structure of the copolymer is not particularly limited, and may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer.
  • the “structural unit derived from a copolymerizable monomer” is a structure having a structure formed by polymerization of a copolymerizable monomer (hereinafter also referred to as “other monomer”).
  • a unit typically a structural unit in which at least one carbon-carbon double bond of the other monomer is replaced with a carbon-carbon single bond.
  • a structural unit derived from styrene CH 2 ⁇ CH (C 6 H 5 ) can be represented by —CH 2 CH (C 6 H 5 ) —.
  • the “structural unit having a structure formed by polymerizing other monomers” is not limited to a structural unit formed by actually polymerizing other monomers, and has the same structure. If present, it means that structural units formed by other methods are also included.
  • maleimide As the monomer from which the structural unit of the above formula (1) is derived, maleimide, maleic anhydride, or the like can be used.
  • the polymer main chain having a maleimide structural unit of the present invention includes a structural unit derived from a monomer copolymerizable with the monomer from which the maleimide structural unit is derived, the structural unit derived from the copolymerizable monomer
  • the proportion is, for example, 1 to 95 mol%, and preferably 1 to 80 mol%, more preferably 1 to 60 mol% from the viewpoint of exhibiting antimicrobial performance with a small addition amount (provided that The total amount of maleimide structural units and the copolymerizable structural units is 100 mol%).
  • the monomer that can be copolymerized with the monomer from which the structural unit of the above formula (1) is derived is not particularly limited and can be appropriately selected depending on the intended use.
  • the copolymerizable monomer include a styrene monomer, an ⁇ -olefin monomer having 1 to 24 carbon atoms, a vinyl ester, an alkyl vinyl ether, and a (meth) acrylic acid ester.
  • styrene monomers include styrene, ⁇ -methyl styrene, vinyl toluene, p-methyl styrene, chloromethyl styrene, ethyl vinyl benzene, and the like.
  • Examples of the ⁇ -olefin monomer having 1 to 24 carbon atoms include ethylene, propylene, isobutylene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-hexene Examples include octadecene and 1-eicosene.
  • vinyl esters examples include vinyl acetate, vinyl propionate, vinyl formate, vinyl benzoate and the like.
  • alkyl vinyl ethers examples include ethyl vinyl ether and methyl vinyl ether.
  • (meth) acrylic acid esters include: (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tertiary butyl (meth) acrylate, (meth) Amyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, ( Examples thereof include hydroxypropyl methacrylate and polyethylene glycol mono (meth) acrylate.
  • (meth) acrylic acid means both “acrylic acid” and “methacrylic acid”.
  • (meth) acrylate means both “acrylate” and “methacrylate”.
  • the copolymerizable monomer described above is preferably at least one selected from the group consisting of a styrene monomer and an ⁇ -olefin monomer from the viewpoint that durability of antimicrobial performance can be maintained. It is. More preferably, it is at least one selected from the group consisting of styrene, ethylene, isobutylene and 1-octadecene.
  • the polymer having a maleimide structural unit is selected from the group consisting of the structural unit represented by the above formula (1), a styrene monomer, and an ⁇ -olefin monomer. And at least one copolymer.
  • the polymer having a maleimide structural unit is preferably a copolymer of the structural unit represented by the above formula (1) and at least one selected from the group consisting of styrene, ethylene, isobutylene and 1-octadecene. .
  • the weight average molecular weight of the polymer having a maleimide structural unit of the present invention is 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and particularly preferably 4,000 or more. .
  • the upper limit of the weight average molecular weight is not particularly limited, but from the viewpoint of moldability, it is 1,000,000 or less, preferably 500,000 or less, more preferably 400,000 or less, and still more preferably. 100,000 or less, particularly preferably 60,000 or less.
  • the range of the weight average molecular weight of the polymer having a maleimide structural unit of the present invention is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and still more preferably 3,000. To 400,000, more preferably 3,000 to 100,000, and particularly preferably 4,000 to 60,000.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC), and is a value measured by the method described in the examples in detail.
  • One embodiment of the antimicrobial agent of the present invention is an antimicrobial agent comprising a polymer having the structural unit of the above formula (1).
  • the antimicrobial agent may contain other components in addition to the polymer having the structural unit of the above formula (1).
  • a solvent, an additive, and the like can be used as other components.
  • the solvent is not particularly limited, and for example, amides such as N, N-dimethylformamide and N-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran and dioxane; lower alcohols such as methanol, ethanol and isopropyl alcohol; ethyl acetate, Esters such as butyl acetate, ethyl butyrate and butyl butyrate; water and the like can be used.
  • the solvent may be used alone or in the form of a mixture of two or more.
  • Additives are not particularly limited, and for example, film-forming aids, plasticizers, stabilizers (antioxidants, UV absorbers, etc.), lubricants (silica, wax, fatty acid amides, etc.), inorganic fillers (glass fiber oxidation) Titanium, calcium carbide, etc.), flame retardants (bromine compounds, aluminum hydroxide, etc.), dispersants (surfactants, metal soaps, waxes, etc.), dyes, pigments, etc. can be used.
  • film-forming aids plasticizers, stabilizers (antioxidants, UV absorbers, etc.), lubricants (silica, wax, fatty acid amides, etc.), inorganic fillers (glass fiber oxidation) Titanium, calcium carbide, etc.), flame retardants (bromine compounds, aluminum hydroxide, etc.), dispersants (surfactants, metal soaps, waxes, etc.), dyes, pigments, etc. can be used.
  • the content of the polymer having a maleimide structural unit in the antimicrobial agent of the present invention is not particularly limited, but is 0.1% by weight or more and 100% by weight or less with respect to the whole antimicrobial agent (100% by weight). It is preferable.
  • antimicrobial agent refers to an agent having antibacterial and antifungal properties.
  • Antibacterial performance and fungicidal performance refer to having at least one of the ability to kill microorganisms and the ability to suppress the growth of microorganisms.
  • bacteria examples include Escherichia such as Escherichia coli; Pseudomonas such as Pseudomonas aeruginosa; Salmonella cholera Switzerland such as Salmonella choleraesu; Moraxella x Genus; Gram negative bacteria such as Legionella pneumophila such as Legionella pneumophila, Staphylococcus such as Staphylococcus aureus; Clostridium botulinum, cerfuridum cerf ), And the like Gram-positive bacteria such as Clostridium, such as.
  • molds include Aspergillus genus such as Aspergillus niger and Aspergillus penicilloids; Penicillium genus such as Penicillium citrinum; Trichoderma genus such as Trichoderma virens; Ketomium genus such as Chaetomium globosum; Eurotium tonoturum E Europium genus such as Tonophilum; Rhizopus oryzae genus Rhizopus; Cladosporium cladosporioides and other genus Cladosporia ulid Aureobas pulid au les Examples include the genus Obacidium; the genus Milotesium such as Myrothecium verrucaria.
  • fungi other than molds examples include the genus Saccharomyces such as Saccharomyces cerevisiae, the genus Candida such as Candida albicans, and the genus Rhodotorula rubura and others. .
  • the antimicrobial agent of the present invention can exhibit antimicrobial performance regardless of the type of bacteria, molds, etc., among them, the antimicrobial agent of the present invention can destroy the cell membrane of microorganisms, It can also be suitably used as an antimicrobial agent against gram-negative bacteria, molds such as Aspergillus, Pesilomyces, and Penicillium.
  • antibacterial performance can be evaluated according to JIS Z2801: 2012 (antibacterial processed product-antibacterial evaluation method / antibacterial effect).
  • JIS Z2801: 2012 the value of the difference in the number of viable cells with the addition of the antimicrobial agent as a logarithm (log 10 ) with respect to the viable cell count of the control (without adding the antimicrobial agent) That is, the value indicating the difference in the logarithmic value of the number of viable bacteria after bacterial inoculation culture is shown as the antibacterial activity value. If the antibacterial activity value is 2.0 or more, it can be evaluated as having antibacterial properties.
  • the fungicidal performance can be evaluated with reference to JIS Z2911: 2010 (mold resistance test method).
  • JIS Z2911: 2010 mold resistance test method
  • a test film containing an antimicrobial agent is placed on the surface of a solid medium, and the mold spore solution is inoculated and cultured on the solid medium and the test film, and the mold surface is exposed to mold.
  • Those with no growth (breeding) can be evaluated as having antifungal properties.
  • the method for producing a polymer having a maleimide structural unit contained in the antimicrobial agent of the present invention is not particularly limited, and a conventionally known method can be used.
  • an acid anhydride group of a maleic anhydride (co) polymer is reacted with a primary amino group of a diamine, ring-opened to form an amide bond, and then subjected to a dehydrating ring-closing imidization reaction.
  • a method obtained by imidating maleic anhydride with diamine to synthesize a maleimide monomer, and polymerizing the maleimide monomer alone or with a monomer copolymerizable with the maleimide monomer. Can be mentioned.
  • the neutralized salt of a polymer having a maleimide structural unit can be obtained by mixing the produced polymer having a maleimide structural unit and the acid used for the neutralization.
  • maleic anhydride (co) polymer examples include styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, 1-octadecene-maleic anhydride copolymer, and ethylene-maleic anhydride copolymer. Commercial products may be used or synthesized.
  • a maleic anhydride (co) polymer When a maleic anhydride (co) polymer is synthesized, it can be produced by a conventionally known method such as radical (co) polymerization using a suitable initiator. Examples of the production method include a method of copolymerizing maleic anhydride and a monomer copolymerizable with maleic anhydride in a solvent such as benzene and acetone.
  • the structure of the copolymer is not particularly limited, and may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer.
  • the weight average molecular weight of the maleic anhydride (co) polymer used in the present invention is 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more.
  • the upper limit of the weight average molecular weight is 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less.
  • a polymer having a maleimide structural unit can be produced by reacting the maleic anhydride (co) polymer with a diamine of the following formula (2) (hereinafter also simply referred to as “diamine”).
  • R 1 and R 2 in the formula (1) are applied to R 1 and R 2 .
  • the diamine used in the present invention include N-cyclohexyl-1,3-propanediamine and N-linear alkyl-1,3-propanediamine (the linear alkyl includes, for example, those having 14, 16 and 18 carbon atoms.
  • a mixture of linear alkyl N-isopropyl-1,3-propanediamine, N-benzyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-cyclohexyl-1,6-hexanediamine N-cyclohexyl-1,8-octanediamine, N-normalhexyl-1,3-propanediamine, N- (tert-butyl) -1,3-propanediamine, N- (2-ethylhexyl) -1,3 -Propanediamine, N-isobornyl-1,3-propanediamine, N-adamantyl-1,3-propanedia Emissions, such as N- dicyclopentenyl-1,3-propane diamine.
  • the reaction between the maleic anhydride (co) polymer and the diamine of the above formula (2) occurs when the acid anhydride group of the maleic anhydride (co) polymer reacts with the primary amino group of the diamine. It can be produced by forming an amide bond by ring-opening, followed by dehydration ring-closing imidization reaction. More specifically, maleic anhydride (co) polymer is added to a solvent and dissolved, and a mixture of the diamine and the solvent or diamine alone is dropped into the solution. The acid anhydride group of the maleic anhydride (co) polymer reacts with the primary amino group of the diamine and opens to form an amide bond, resulting in a precipitate.
  • the precipitate is collected by filtration, the solvent is removed from the filter cake by vacuum drying, and then the filter cake is vacuum dried again, whereby an imide, that is, a polymer having a maleimide structural unit can be obtained by a dehydrating ring-closing imidization reaction.
  • the polymer having a maleimide structural unit is prepared by dissolving a maleic anhydride (co) polymer and a diamine in a solvent and reacting them at 100 to 150 ° C. to carry out from amidation to imidation in solution. It can also be obtained by a method of performing amidation and imidization by kneading maleic anhydride (co) polymer and diamine in the absence of a solvent in a screw extruder.
  • the amounts of maleic anhydride (co) polymer and diamine used as raw materials are not particularly limited.
  • diamine is added in an amount of 0.1 to 0.1% with respect to the maleic anhydride residue in the maleic anhydride (co) polymer.
  • Three molar equivalents can be used.
  • the solvent to be used is not particularly limited, but a solvent that does not hinder the above reaction and can dissolve the maleic anhydride (co) polymer and diamine as raw materials is preferable.
  • a solvent that does not hinder the above reaction and can dissolve the maleic anhydride (co) polymer and diamine as raw materials is preferable.
  • examples thereof include amides such as N, N-dimethylformamide and N-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran and dioxane; lower alcohols such as methanol, ethanol and isopropyl alcohol; water and the like.
  • the solvent may be used alone or in the form of a mixture of two or more.
  • the maleic anhydride (co) polymer and diamine may be dissolved in the same solvent or in different solvents, but are preferably dissolved in the same solvent.
  • the amount of the solvent used is not particularly limited as long as the raw material maleic anhydride (co) polymer or diamine can be dissolved.
  • the amount of the solvent used is 1 to 40 times (weight) with respect to maleic anhydride and 1 to 15 times (weight) with respect to diamine.
  • the conditions for reacting the diamine with the maleic anhydride (co) polymer are not particularly limited.
  • the reaction temperature is 20 ° C. to 150 ° C.
  • the reaction time is 1 to 9 hours.
  • the reaction may be carried out under stirring or standing, but is preferably carried out under stirring.
  • the filter cake may be dried before the ring-closing imidization reaction, and examples of the drying method include vacuum drying.
  • the vacuum drying conditions are not particularly limited as long as the solvent can be removed.
  • the temperature for vacuum drying is 40 to 95 ° C.
  • the time for vacuum drying is 2 to 8 hours.
  • the conditions for the ring-closing imidization reaction are not particularly limited as long as the conditions for the ring-closing imidization reaction proceed.
  • the temperature of the ring-closing imidization reaction is 100 to 250 ° C.
  • the time of the ring-closing imidization reaction is 3 to 24 hours.
  • the ratio (imidation ratio) of introducing a secondary amino group into the maleic anhydride structural unit of the maleic anhydride (co) polymer to form a maleimide structural unit is not particularly limited, and is, for example, 100% or less. It is.
  • the lower limit of the imidization rate is preferably 25 mol% or more, more preferably 50 mol% or more. Within the above range, the effect of cell membrane destruction by the secondary amino group added to the maleimide structural unit is sufficient, and the antibacterial performance and antifungal performance can be enhanced.
  • the “imidation ratio” is the ratio of the structural unit having a secondary amino group introduced when the maleic anhydride structural unit contained in the maleic anhydride (co) polymer is 100%.
  • the analysis of imidization for example, by the Fourier transform infrared spectroscopy (FT-IR) analysis, the disappearance of absorption peaks derived from acid anhydrides and amides and The determination can be made based on detection of an absorption peak derived from imide.
  • FT-IR Fourier transform infrared spectroscopy
  • the antimicrobial agent of the present invention contains components other than the polymer having the maleimide structural unit
  • the antimicrobial agent of the present invention is produced by mixing other components after the production of the polymer having the maleimide structural unit.
  • it may be produced by adding to a raw material before production of a polymer having a maleimide structural unit, a reaction solution or an intermediate during production.
  • the manufacturing method of the antimicrobial agent of this invention may include arbitrary processes, such as a refinement
  • composition comprising the antimicrobial agent and a resin (excluding the polymer having the maleimide structural unit).
  • a resin excluding the polymer having the maleimide structural unit.
  • a thermoplastic resin, a thermosetting resin, an elastomer, a photocurable resin, or the like can be used, preferably selected from a thermoplastic resin, an elastomer, and a photocurable resin, and more preferably a thermoplastic resin or It is an elastomer, and a thermoplastic resin is particularly preferable.
  • thermoplastic resin used in the present invention is not particularly limited.
  • a thermoplastic resin can be used individually or in combination of 2 or more types.
  • thermosetting resin used in the present invention is not particularly limited, and examples thereof include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, urethane resin, and thermosetting polyimide resin. .
  • the thermosetting resin is not an epoxy resin.
  • a thermosetting resin can be used individually or in combination of 2 or more types.
  • the elastomer used in the present invention is not particularly limited.
  • natural rubber ethylene-propylene rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, fluorine rubber, silicon rubber, urethane rubber, polysulfide rubber, Examples include acrylic rubber, butyl rubber, and epichlorohydrin rubber.
  • Elastomers can be used alone or in combination of two or more.
  • the photocurable resin used in the present invention is not particularly limited.
  • (meth) acrylate resins such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and acrylic (meth) acrylate, Saturated polyester resin, polyene / polythiol resin, epoxy resin, diallyl phthalate resin and the like can be mentioned.
  • a photocurable resin can be used individually or in combination of 2 or more types.
  • thermoplastic resin, thermosetting resin, elastomer, and photocurable resin may be a synthetic product or a commercially available product.
  • thermoplastic resin, thermosetting resin, elastomer and photocurable resin may be a resin emulsion.
  • the composition of the present embodiment may include unreacted monomers and oligomers related to the thermosetting resin and the photocurable resin.
  • Preferred examples of the resin emulsion include (meth) acrylic resin emulsion (acrylic emulsion), ethylene-vinyl acetate resin emulsion, urethane resin emulsion, and the like.
  • Anionic acrylic emulsion, nonionic acrylic emulsion, ethylene-vinyl acetate A resin emulsion, a weak anionic urethane emulsion, and a nonionic urethane emulsion are more preferable, and it is more preferable that these are aqueous emulsions.
  • the composition may contain other components, various additives, a solvent, and the like as desired.
  • additives include film-forming aids, plasticizers, stabilizers (antioxidants, UV absorbers, etc.), lubricants (silica, wax, fatty acid amides, etc.), inorganic fillers (glass fiber titanium oxide, calcium carbide, etc.) Etc.), flame retardants (bromine compounds, aluminum hydroxide, etc.), dispersants (surfactants, metal soaps, waxes, etc.), dyes, pigments and the like.
  • the solvent is not particularly limited, and for example, amides such as N, N-dimethylformamide and N-methylpyrrolidone; ethers such as diethyl ether, tetrahydrofuran and dioxane; lower alcohols such as methanol, ethanol and isopropyl alcohol; ethyl acetate, Esters such as butyl acetate, ethyl butyrate and butyl butyrate; water and the like can be used.
  • the solvent may be used alone or in the form of a mixture of two or more.
  • the content of the antimicrobial agent is 0.5 to 25.0% by weight with respect to the whole composition (100% by weight), and the resin content is 100% by weight. To 99.5 to 75.0% by weight.
  • the lower limit of the content of the antimicrobial agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the resin from the viewpoint of antimicrobial performance. More preferably 3 parts by weight or more.
  • the upper limit of the content is 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the resin, from the viewpoint of influence on the mechanical properties of the resin composition. It is as follows.
  • the content of the polymer having the structural unit represented by the above formula (1) is 0.5 to 25.0% by weight with respect to the entire composition (100% by weight),
  • the resin content is 99.5 to 75.0% by weight based on the entire composition (100% by weight).
  • the lower limit of the content of the antimicrobial agent is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more with respect to 100 parts by weight of the resin from the viewpoint of antimicrobial performance. More preferably 3 parts by weight or more.
  • the upper limit of the content is 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the resin, from the viewpoint of influence on the mechanical properties of the resin composition. It is as follows.
  • the composition of the present invention can be obtained by a known method for producing a resin composition using an antimicrobial agent, a resin and, if necessary, other additives and a solvent.
  • the mixing conditions are not particularly limited and may be known conditions.
  • ⁇ Resin molding> As one embodiment of the present invention, there is provided a resin molded article containing the antimicrobial agent or the composition.
  • the molded product containing the antimicrobial agent or composition of the present invention can be obtained using a conventionally known method.
  • the method for obtaining the molded body is a method of dissolving the antimicrobial agent or composition of the present invention in an organic solvent and removing the solvent, a method of mixing a UV curable monomer and an antimicrobial agent, and then irradiating with UV.
  • Examples include a method of molding an antimicrobial agent and resin pellets or powder with a kneading / extrusion molding machine.
  • the composition contains a polymer having a maleimide structural unit and a resin emulsion (preferably an aqueous emulsion)
  • the polymer having the maleimide structure and the emulsion are mixed to prepare a coating liquid, and the coating liquid
  • a method of forming a coating film by coating the substrate on a substrate is also a preferable method.
  • Examples of the shape of the obtained molded body include a block shape, a plate shape, a sheet shape, a film shape, and a thread shape.
  • Uses of molded products include, for example, sanitary items such as bathtubs, washstands and toilet seats; household appliances such as refrigerators, washing machines and air conditioners; household items such as washbasins and cutting boards; PVC pipes, wallpaper, flooring, etc.
  • Building supplies Fibers and textile products such as polypropylene fibers, polyester fibers, nylon fibers, spandex; Packaging materials such as foamed polystyrene and polyethylene sheets; Sealing materials such as silicone sealants and rubber packings; Medical supplies such as catheters and wound dressings And various uses.
  • a polymer having a structural unit represented by the above formula (1) (a polymer having a maleimide structural unit) or an antimicrobial agent containing a polymer having the maleimide structure and a microorganism are provided.
  • a method for suppressing the growth of microorganisms comprising: a step of contacting, and (b) at least one step selected from the step of contacting the polymer having the maleimide structure or the antimicrobial agent with a resin or an article.
  • “suppressing the growth of microorganisms” includes not only suppressing the growth of microorganisms but also killing microorganisms.
  • the contacting is not particularly limited as long as the polymer or the antimicrobial agent having the maleimide structure can be brought into contact with the microorganism.
  • a polymer having a maleimide structure or the antimicrobial agent may be applied (applied, mixed, impregnated, coated, etc.) to an article or place that requires suppression of microbial growth.
  • the contact means that the polymer having the maleimide structure or the antimicrobial agent is added to a resin or an article (part component) to be controlled for microorganism growth, coating, impregnation, Although spraying etc. are illustrated, it is not limited to this.
  • the contact is preferably addition.
  • the contacting step preferably includes applying a polymer having a maleimide structure or the antimicrobial agent to the article, more preferably mixing the polymer having the maleimide structure or the antimicrobial agent containing the polymer into the article. Impregnation or coating.
  • Examples of the shape of the polymer having the structural unit represented by the above formula (1) or the article to which the antimicrobial agent is applied include a block shape, a plate shape, a sheet shape, a film shape, and a thread shape.
  • Uses of goods include sanitary items such as bathtubs, washstands and toilet seats; household appliances such as refrigerators, washing machines and air conditioners; household items such as washbasins and cutting boards; building supplies such as PVC pipes, wallpaper and flooring ; Polypropylene fiber, polyester fiber, nylon fiber, spandex and other fibers and fiber products; Foamed polystyrene, polyethylene sheet and other packaging products; Silicone sealant, rubber packing and other sealing materials; Catheter, wound dressing and other medical products It is done.
  • the method of applying the polymer having the structural unit represented by the above formula (1) or the antimicrobial agent to an article is not particularly limited, and a conventionally known method can be used.
  • the polymer having the maleimide structural unit or the antimicrobial agent is molded into a block shape, a plate shape, a sheet shape, a film shape, a thread shape or the like to obtain a molded product, and the molded product is used as an article, or the molded article is used as an article. It can be used as a material or part thereof.
  • a polymer having the maleimide structural unit or the antimicrobial agent is mixed into a material used for manufacturing an article, or an article or a material used for manufacturing the article is contained in a solution containing the polymer having the maleimide structural unit or the antimicrobial agent.
  • a solution containing the polymer having the maleimide structural unit or the antimicrobial agent for example, impregnation or coating of the polymer having the maleimide structural unit or the antimicrobial agent on the surface of the article or the material used for the production thereof may be mentioned.
  • one embodiment of the present embodiment is characterized in that an article is mixed, impregnated, or coated with a polymer having the structural unit represented by the formula (1) or the antimicrobial agent.
  • the polymer having the maleimide structure or the antimicrobial agent contains a resin (excluding the polymer having the maleimide structural unit). Included in things.
  • the resin As the resin, the resin exemplified in the ⁇ Composition> section is exemplified.
  • the description of the composition is the same as the description in ⁇ Composition>, and the description is omitted.
  • the amount of the polymer having a maleimide structure or the antimicrobial agent of the present invention is not particularly limited, but from the viewpoint of remarkably exhibiting the effect, the polymer having a maleimide structure and
  • the polymer having a maleimide structure is used in a preferred form of 0.5% by weight or more, more preferably 1% by weight or more, and even more preferably 3% by weight or more based on the total of the resin or article used for inhibiting the growth of microorganisms.
  • the upper limit of the amount used is not particularly limited, but is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably, based on the total of the polymer having a maleimide structure and the resin or article used for inhibiting the growth of microorganisms. Is 10% by weight or less.
  • Examples of usage as an antimicrobial agent include, for example, contacting the polymer having the maleimide structural unit or the antimicrobial agent with a resin or an article, but is not limited thereto. This makes it possible to suppress the growth of microorganisms in the interior or surface of the resin or article.
  • Examples of the contact include, but are not limited to, addition, coating, impregnation, and spraying. The contact is preferably addition.
  • the amount of the polymer having a maleimide structural unit or the antimicrobial agent of the present invention is the same as in the above ⁇ Method for inhibiting the growth of microorganisms>.
  • resin used for use of this invention resin illustrated by said ⁇ composition> is illustrated preferably.
  • the resin exemplified in the above ⁇ resin molding> is preferably exemplified.
  • the aspect exemplified in the above ⁇ Method for inhibiting the growth of microorganisms> is preferably exemplified.
  • the polymer having the maleimide structural unit is included in a composition containing a resin (excluding the polymer having the maleimide structural unit).
  • the description of the composition is the same as that described in ⁇ Composition>, and thus the description thereof is omitted.
  • the content of the polymer having a maleimide structural unit is 0.5 to 25.0% by weight relative to the whole composition (100% by weight), and other than the polymer having a maleimide structural unit.
  • the content of the resin is 99.5 to 75.0% by weight based on the entire composition (100% by weight).
  • the lower limit of the content of the polymer having a maleimide structural unit is preferably 0.5 parts by weight or more with respect to 100 parts by weight of the resin other than the polymer having a maleimide structural unit from the viewpoint of antimicrobial performance. More preferably, it is 1 part by weight or more, and more preferably 3 parts by weight or more.
  • the upper limit of the content is 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight with respect to 100 parts by weight of the resin, from the viewpoint of influence on the mechanical properties of the resin composition. It is as follows.
  • the polymer having the maleimide structural unit is contained in a resin molded body.
  • the antimicrobial performance was measured by the following method.
  • the antibacterial evaluation test was conducted according to JIS Z2801: 2012 (antibacterial processed product-antibacterial evaluation method / antibacterial effect).
  • 0.4 ml of E. coli (Escherichia coli, NBRC3982 strain) or Staphylococcus aureus (NBRC15035 strain) prepared according to the method described in JIS Z2801: 2012 was planted on the surface of a test film cut to 5 cm ⁇ 5 cm. Fungus. After covering with a polyethylene film cut to 4 cm ⁇ 4 cm so that the bacterial solution did not dry, it was cultured at 35 ° C. for 24 hours under conditions of relative humidity of 90% or more.
  • the bacterial solution was collected from between the films, and the viable cell count was calculated by the agar plate culture method.
  • the same operation was performed on an unprocessed film (non-added polyethylene; MZ-PE, manufactured by Maruai Co., Ltd.) not coated with the following polymers 1 to 12.
  • the number of viable bacteria after the culture was converted per 1 cm 2 of the film area, and the antibacterial activity value was obtained by subtracting the viable cell number of the test film from the log number of the raw film.
  • a test film having an antibacterial activity value of 2.0 or more based on JIS Z2801: 2012 has antibacterial properties (obtained by reducing the number of viable bacteria to 1/100 or less compared to the unprocessed film). Less than the test film was judged as having no antibacterial property (x).
  • the antifungal evaluation test was carried out with reference to JIS Z2911: 2010 (mold resistance test method). First, a test film cut to 1 cm ⁇ 1 cm was added to a glucose-added inorganic salt agar medium (glucose 30 g, sodium nitrate 2 g, potassium dihydrogen phosphate 0.7 g, dipotassium hydrogen phosphate 0.3 g, potassium chloride 0.5 g, agar 20 g, pure water 1000 mL, pH 6.0 to 6.5) and placed on the surface.
  • a glucose-added inorganic salt agar medium glucose-added inorganic salt agar medium (glucose 30 g, sodium nitrate 2 g, potassium dihydrogen phosphate 0.7 g, dipotassium hydrogen phosphate 0.3 g, potassium chloride 0.5 g, agar 20 g, pure water 1000 mL, pH 6.0 to 6.5) and placed on the surface.
  • the cells were cultured at 30 ° C. for 1 week under conditions of relative humidity of 90% or more. Observation of the film surface after culturing with a microscope, the test film with no mold growth is judged to be moldproof ( ⁇ ), and the test film with mold growth is judged to have no mold resistance ( ⁇ ) did.
  • 7.5 g and 226.5 g of tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • the dried cake was vacuum-dried at 150 ° C. for 7 hours and subjected to dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 6,100) (polymer 1).
  • the obtained polymer 1 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • a mixture of 11.52 g and 111.10 g of tetrahydrofuran was added dropwise to the solution.
  • C14, C16 and C18 mean straight alkyl groups having 14, 16 and 18 carbon atoms, respectively.
  • FT-IR analysis After completion of the dropping, a part of the precipitate was collected and subjected to FT-IR analysis. The disappearance of the absorption peak of the carbonyl group of the acid anhydride and the detection of the absorption peak of the carbonyl group of the amide were confirmed by FT-IR analysis.
  • polymer 2 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • polymer 3 a polymer having a maleimide structure (weight average molecular weight 6,200) (polymer 3).
  • the obtained polymer 3 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • polymer 4 The obtained polymer 4 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • polymer 5 The polymer 5 thus obtained was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide.
  • tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. 229.2 g were charged and stirred to dissolve the copolymer.
  • polymer 6 The polymer 6 thus obtained was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide carbonyl group and the detection of the absorption peak due to the carbonyl group of the imide.
  • polymer 8 The polymer 8 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • polymer 9 an imide-modified product (weight average molecular weight 5,700) (polymer 9).
  • the obtained polymer 9 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide carbonyl group and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • polymer 10 The polymer 10 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • the homogeneous solution prepared while purging the gas phase with nitrogen was heated to 60 ° C., 0.66 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.50 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.)
  • the solution dissolved in was added to the homogeneous solution to initiate the polymerization reaction. After 10 hours from the start of the reaction, the reaction solution was added dropwise to 720.3 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) to precipitate a polymer (styrene-maleic anhydride copolymer).
  • the reaction solution was cooled to room temperature and then added dropwise to 500 mL of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.). After completion of the dropwise addition, the precipitate was collected by filtration and dried in vacuo at 120 ° C. overnight to remove the solvent. The total amount of the dried product was dissolved in 100 mL of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.). The solution was dropped into 500 mL of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) to precipitate a polymer, and the precipitate was collected by filtration. The filtered product was dehydrated and cyclized by vacuum drying at 120 ° C.
  • polymer 11 was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide.
  • Example 7 The test films prepared in Examples 1, 2, 4 and 5 were evaluated for antifungal properties against Aspergillus niger, Penicillium pinofilm or Aureobasidium pullulans. It was. The results are shown in Table 2.
  • Comparative Example 1 has a structural unit in which a tertiary amino group is added to the maleimide structure, and thus it can be seen that the antimicrobial performance is low.
  • Example 11 1 g of the polymer 1 obtained in Example 1 and 19 g of low density polyethylene (LDPE) (manufactured by Sigma-Aldrich, MELT INDEX 25 g / 10 min), and Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd., 4C- 150) and kneaded at 200 ° C. for 5 minutes. The kneaded material was pressed at 200 ° C. and 2 MPa for 2 minutes to prepare a test film having a thickness of about 100 ⁇ m. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark).
  • LDPE low density polyethylene
  • test film was irradiated with an ultraviolet lamp for 5 minutes per side to sterilize the test film.
  • Sterilized test films were used for antibacterial evaluation and antifungal evaluation.
  • the antifungal property was evaluated for Paecilomyces variotii. The results are shown in Table 3.
  • Example 12 1 g of the polymer 2 obtained in Example 2 and 19 g of polypropylene (PP) (manufactured by Nippon Polypro Co., Ltd., Novatec (registered trademark) PP), Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd., 4C-150) ) And kneaded at 210 ° C. for 5 minutes. The kneaded material was pressed at 200 ° C. and 2 MPa for 2 minutes to prepare a test film having a thickness of about 100 ⁇ m. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark).
  • PP polypropylene
  • PP polypropylene
  • Labo Plast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd., 4C-150
  • test film was irradiated with an ultraviolet lamp for 5 minutes per side to sterilize the test film.
  • Sterilized test films were used for antibacterial evaluation and antifungal evaluation.
  • the antifungal property was evaluated for Paecilomyces variotii. The results are shown in Table 3.
  • test film was irradiated with an ultraviolet lamp for 5 minutes per side to sterilize the test film.
  • Sterilized test films were used for antibacterial evaluation and antifungal evaluation.
  • the antifungal property was evaluated with respect to Paecilomyces variotii. The results are shown in Table 3.
  • the antimicrobial agent of the present invention is a polymer having a structural unit in which a secondary amino group is added to the maleimide structure, or a structural unit in which a tertiary amino group is added to the maleimide structure by including the polymer. It turns out that it has the outstanding antimicrobial performance compared with the imide modified body which has.
  • Dissolution evaluation method Dissolution was evaluated using a test film cut to 1 cm ⁇ 1 cm. First, the thickness of the test film (thickness before immersion) was measured. Next, a test film and glucose-added inorganic salt medium (glucose 30.0 g, sodium nitrate 2.0 g, potassium dihydrogen phosphate 0.7 g, dipotassium hydrogen phosphate 0.3 g, potassium chloride 0.5 g, pure water 1000 mL; pH 6.0-6.5) and 5 mL were placed in a vial. The vial was allowed to stand in an incubator set at 35 ° C.
  • the test film was taken out of the vial and dried, and the thickness of the test film after drying (thickness after immersion) was measured.
  • a digital micrometer MCD130-25 manufactured by Niigata Seiki Co., Ltd. was used for the thickness measurement.
  • the measured value of the thickness of the test film before and after immersion which is obtained by subtracting the thickness of the PET film as the base material, is the film thickness before immersion and the film thickness after immersion. %) was calculated.
  • the dissolution rate (%) was calculated by ⁇ (film thickness before immersion ⁇ film thickness after immersion) / film thickness before immersion ⁇ ⁇ 100.
  • Example 13 to 16 The test films prepared in Examples 1, 2, 4 and 5 were evaluated for elution. The results are shown in Table 4.
  • Comparative Examples 7 to 8 have a structural unit in which a tertiary amino group is added to the maleimide structure, so that the elution of the polymer may result in insufficient antimicrobial performance durability. Recognize.
  • 5.1 g and 134.9 g of tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • polymer 15 a polymer having a maleimide structure (weight average molecular weight 6,800) (polymer 15).
  • the polymer 15 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • 5.1 g and 134.9 g of tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • polymer 16 a polymer having a maleimide structure (weight average molecular weight 7,300) (polymer 16).
  • the polymer 16 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of amide and the detection of the absorption peak due to the carbonyl group of imide were confirmed.
  • a test film was prepared in the same manner as in Example 17 except that the polymer 16 obtained above was used in place of the polymer 15, and an antifungal property was evaluated. The results are shown in Table 5.
  • tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
  • polymer 17 a polymer having a maleimide structure (weight average molecular weight 5,600) (polymer 17).
  • the polymer 17 thus obtained was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide group and the detection of the absorption peak due to the carbonyl group of the imide.
  • a test film was prepared in the same manner as in Example 17 except that the polymer 17 obtained above was used in place of the polymer 15, and an antifungal property was evaluated. The results are shown in Table 5.
  • a styrene-maleic anhydride copolymer manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride
  • polymer 18 was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide group and the detection of the absorption peak due to the carbonyl group of the imide.
  • a test film was prepared in the same manner as in Example 17 except that the polymer 18 obtained above was used in place of the polymer 15, and an antifungal property was evaluated. The results are shown in Table 5.
  • a styrene-maleic anhydride copolymer manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride
  • polymer 19 a polymer having a maleimide structure (weight average molecular weight 6,100) (polymer 19).
  • the obtained polymer 19 was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • the dried cake was vacuum-dried at 150 ° C. for 6 hours for dehydration and cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 209,600) (polymer 20).
  • the polymer 20 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide carbonyl group and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • a test film was prepared in the same manner as in Example 21 except that the polymer 20 obtained above was used in place of the polymer 19, and an antifungal property was evaluated. The results are shown in Table 5.
  • Isoban # 06 Kuraray Co., Ltd., weight average molecular weight 80,000
  • the dried cake was vacuum-dried at 150 ° C. for 6 hours and subjected to dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 151,800) (polymer 21).
  • the obtained polymer 21 was subjected to FT-IR analysis to confirm the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide.
  • a test film was prepared in the same manner as in Example 21 except that the polymer 21 obtained above was used in place of the polymer 19, and the antifungal property was evaluated. The results are shown in Table 5.
  • 10.0 g and 27,0 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer.
  • the dried cake was vacuum-dried at 150 ° C. for 6 hours for dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 303,500) (polymer 22).
  • the polymer 22 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • a test film was prepared in the same manner as in Example 21 except that the polymer 22 obtained above was used in place of the polymer 19, and an antifungal property was evaluated. The results are shown in Table 5.
  • polymer 23 a polymer having a maleimide structure (weight average molecular weight 5,800) (polymer 23).
  • the polymer 23 thus obtained was subjected to FT-IR analysis, and the disappearance of the absorption peak of the amide group of the amide and the detection of the absorption peak due to the carbonyl group of the imide were confirmed.
  • a test film was prepared in the same manner as in Example 21 except that the polymer 23 obtained above was used in place of the polymer 19, and the antifungal property was evaluated. The results are shown in Table 5.
  • R 1 is an alkylene group having 3 to 8 carbon atoms, so that excellent antimicrobial performance can be exhibited.
  • Comparative Example 9 since R 1 is an ethylene group, it can be seen that there is no antimicrobial.
  • Example 25 0.25 g of polymer 17 and 1.75 g of acrylonitrile-styrene (AS) resin (manufactured by Sigma-Aldrich, weight average molecular weight 165,000) and 8 g of tetrahydrofuran were mixed together, and polymer 17 and AS resin were mixed.
  • AS acrylonitrile-styrene
  • AS resin 12.5: 87.5 (weight ratio)
  • the prepared mixed polymer solution was dropped on the surface of a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 ⁇ m) cut to 5 cm ⁇ 5 cm, and coated with a spin coater (Mikasa Co., Ltd.).
  • test film coated with a mixture of polymer 17 and AS resin was produced.
  • test film was sterilized by irradiating both sides of the test film with an ultraviolet lamp for 5 minutes per side. A sterilized test film was used for evaluation of mold resistance.
  • the fungicidal evaluation was performed on Penicillium pinofilm, Pecilomyces variotti and Cladosporium cladosporioides. The results are shown in Table 6.
  • the resin molded body containing the polymer having a maleimide structure and a resin according to the present invention can exhibit excellent antimicrobial performance.
  • Example 26 5.0 g of the polymer 1 obtained in Example 1, 17.7 g of pure water, and 0.9 g of acetic acid were mixed to prepare a 25 wt% neutralized salt aqueous solution of the polymer 1.
  • 1.0 g of an anionic aqueous acrylic emulsion manufactured by Nippon Shokubai Co., Ltd., Acryset EF-165
  • 0.5 g of the above neutralized salt aqueous solution 2,2,4-trimethyl-1,3-
  • CS-12 pentanediol monoisobutyrate
  • a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 ⁇ m) cut to 5 cm ⁇ 10 cm is coated with a coating solution using a bar coater, and naturally dried for 6 hours in a hot air dryer set at 55 ° C.
  • the test film was produced by holding for 16 hours to solidify the coating film.
  • the content of the neutralized salt of polymer 1 contained in the test film was 20% by weight.
  • the test film was cut into 1 cm ⁇ 5 cm.
  • the cut test film was immersed in 40 ml of water overnight, then washed with pure water and then naturally dried.
  • the test film was sterilized by irradiating both sides of the film with an ultraviolet lamp for 5 minutes per side.
  • the coated surface of the sterilized test film was used for evaluation of mold resistance.
  • the antifungal evaluation is aspergillus niger (Penicillium pinophyllum), Paecilomyces variotium (Trichoderma bilomis) It implemented using the liquid mixture. The results are shown in Table 7.
  • Example 27 1.0 g of the polymer 1 obtained in Example 1, 1.8 g of pure water, and 0.18 g of acetic acid were mixed to prepare a 40% by weight neutralized salt aqueous solution of the polymer 1. Next, 1.0 g of a nonionic water-based acrylic emulsion (manufactured by Nippon Shokubai Co., Ltd., Acryset ES-970E) and 0.01 g of the above neutralized salt aqueous solution are mixed, and the concentration of the neutralized salt of the polymer 1 is mixed. was prepared to be 0.4% by weight based on the entire coating solution.
  • a nonionic water-based acrylic emulsion manufactured by Nippon Shokubai Co., Ltd., Acryset ES-970E
  • a test film was prepared in the same manner as in Example 26 except that the prepared coating liquid was used instead of the coating liquid used in Example 26, and the antifungal property was evaluated.
  • the content of the neutralized salt of polymer 1 contained in the test film was 1% by weight. The results are shown in Table 7.
  • Example 28 1.0 g of the polymer 1 obtained in Example 1, 10.62 g of pure water, and 0.18 g of acetic acid were mixed to prepare a 10% by weight neutralized aqueous salt solution of the polymer 1. Next, 1.0 g of a water-based ethylene-vinyl acetate copolymer emulsion (manufactured by Sumika Chemtex Co., Ltd., Sumikaflex 201HQ) and 0.29 g of the above neutralized salt aqueous solution are mixed, and the neutralized salt of polymer 1 is mixed. A coating solution having a concentration of 2.2% by weight with respect to the entire coating solution was prepared.
  • a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 ⁇ m) cut to 5 cm ⁇ 10 cm is coated with a coating solution using a bar coater, and air-dried overnight to solidify the coating.
  • a film was prepared. The content of the neutralized salt of polymer 1 contained in the test film was 5% by weight.
  • the test film was cut into 2 cm ⁇ 5 cm. The cut test film was immersed in 50 ml of warm water at 50 ° C. overnight, then washed with pure water and then naturally dried. The test film was sterilized by irradiating both sides of the film with an ultraviolet lamp for 5 minutes per side. The coated surface of the sterilized test film was used for evaluation of mold resistance.
  • Example 29 1.0 g of water-based ethylene-vinyl acetate copolymer emulsion (Sumikaflex 400HQ, manufactured by Sumika Chemtex Co., Ltd.) so that the concentration of the neutralized salt of polymer 1 is 2.2% by weight with respect to the entire coating solution.
  • 1.0 g of water-based ethylene-vinyl acetate copolymer emulsion (Sumikaflex 400HQ, manufactured by Sumika Chemtex Co., Ltd.) so that the concentration of the neutralized salt of polymer 1 is 2.2% by weight with respect to the entire coating solution.
  • a test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated.
  • the content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown
  • Example 30 1.0 g of an aqueous ethylene-vinyl acetate copolymer emulsion (Sumikaflex 752 manufactured by Sumika Chemtex Co., Ltd.) so that the concentration of the neutralized salt of polymer 1 is 2.1% by weight with respect to the entire coating solution. And 0.26 g of a 10% by weight neutralized aqueous solution of polymer 1 prepared in Example 28 were mixed to prepare a coating solution.
  • a test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated. The content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown in Table 7.
  • Example 31 Water-based ethylene-vinyl acetate-vinyl chloride copolymer emulsion (Sumikaflex 808HQ, manufactured by Sumika Chemtex Co., Ltd.) so that the concentration of the neutralized salt of polymer 1 is 2.1% by weight with respect to the entire coating solution.
  • a coating solution was prepared by mixing 1.0 g and 0.27 g of a 10 wt% polymer 1 neutralized salt aqueous solution prepared in Example 28.
  • a test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated.
  • the content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown in Table 7.
  • Example 32 1.0 g of weak anionic aqueous urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 300) so that the concentration of the neutralized salt of polymer 1 is 1.4% by weight with respect to the entire coating solution, A coating solution was prepared by mixing 0.16 g of the 10 wt% polymer 1 neutralized salt aqueous solution prepared in Example 28. A test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated. The content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown in Table 7.
  • Example 33 Implementation with 1.0 g of nonionic aqueous urethane emulsion (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 500M) so that the concentration of the neutralized salt of polymer 1 is 1.9% by weight with respect to the entire coating solution.
  • a coating solution was prepared by mixing 0.24 g of a 10 wt% polymer 1 neutralized salt aqueous solution prepared in Example 28.
  • a test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated.
  • the content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown in Table 7.
  • Example 34 1.0 g of nonionic water-based urethane emulsion (Superflex E-2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) so that the concentration of the neutralized salt of polymer 1 is 2.1% by weight with respect to the entire coating solution.
  • a coating solution was prepared by mixing 0.27 g of a 10 wt% polymer 1 neutralized salt aqueous solution prepared in Example 28.
  • a test film was produced in the same manner as in Example 28 except that the prepared coating liquid was used instead of the coating liquid used in Example 28, and the antifungal property was evaluated.
  • the content of the neutralized salt of polymer 1 contained in the test film was 5% by weight. The results are shown in Table 7.
  • the polymer having a maleimide structural unit according to the present invention can exert excellent antimicrobial activity even when the secondary amino group is a neutralized salt.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'objectif de la présente invention est de fournir un article moulé qui possède une activité antimicrobienne élevée (activité antibactérienne et activité anti-moisissures) et qui contient un agent antimicrobien de type polymère, l'élution du polymère pouvant être supprimée et l'agent antimicrobien de type polymère ayant une excellente durabilité antibactérienne. La présente invention est un agent antimicrobien contenant un polymère ayant le motif structural représenté par la formule (1), où : R1 est un groupe alkylène en C3 à 24 ; R2 est choisi dans le groupe comprenant un groupe alkyle en C2 à 24, un groupe hydrocarboné alicyclique en C3 à 12 et un groupe aryle en C6 à 24 ; et un groupe amino secondaire représenté par -NHR2 peut être un sel neutralisé.
PCT/JP2017/035639 2016-09-29 2017-09-29 Agent antimicrobien contenant un polymère ayant un motif structural maléimide WO2018062529A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018542960A JP6730439B2 (ja) 2016-09-29 2017-09-29 マレイミド構造単位を有するポリマーを含む抗微生物剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-191846 2016-09-29
JP2016191846 2016-09-29

Publications (1)

Publication Number Publication Date
WO2018062529A1 true WO2018062529A1 (fr) 2018-04-05

Family

ID=61759914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/035639 WO2018062529A1 (fr) 2016-09-29 2017-09-29 Agent antimicrobien contenant un polymère ayant un motif structural maléimide

Country Status (2)

Country Link
JP (1) JP6730439B2 (fr)
WO (1) WO2018062529A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023183954A1 (fr) * 2022-03-24 2023-09-28 Stellenbosch University Dispersion aqueuse de polymère antimicrobien

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416668A (en) * 1978-10-25 1983-11-22 Petrolite Corporation Antistatic agents for organic liquids
JPH06322259A (ja) * 1993-05-14 1994-11-22 Dai Ichi Kogyo Seiyaku Co Ltd 熱可塑性樹脂組成物
JPH0841262A (ja) * 1994-08-01 1996-02-13 Tonen Chem Corp 熱可塑性樹脂組成物
JPH09255843A (ja) * 1996-03-26 1997-09-30 Dai Ichi Kogyo Seiyaku Co Ltd 抗菌性樹脂組成物
JP2002510341A (ja) * 1997-04-25 2002-04-02 アイエスピー インヴェストメンツ インコーポレイテッド マレインアミド酸及び／又はその環状イミド反復ユニットを含む無水マレイン酸重合体の製造方法
JP2002517786A (ja) * 1998-06-03 2002-06-18 コダック ポリクロム グラフィックス カンパニー リミテッド リソグラフ印刷板前駆体
JP2006124592A (ja) * 2004-10-29 2006-05-18 Kaneka Corp イミド樹脂及びその樹脂組成物
JP2013518964A (ja) * 2010-02-04 2013-05-23 ステレンボッシュ ユニバーシティ 抗微生物性ポリマー化合物およびその繊維
JP2016014794A (ja) * 2014-07-02 2016-01-28 株式会社日本触媒 光学フィルムと、それを備える偏光板および画像表示装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416668A (en) * 1978-10-25 1983-11-22 Petrolite Corporation Antistatic agents for organic liquids
JPH06322259A (ja) * 1993-05-14 1994-11-22 Dai Ichi Kogyo Seiyaku Co Ltd 熱可塑性樹脂組成物
JPH0841262A (ja) * 1994-08-01 1996-02-13 Tonen Chem Corp 熱可塑性樹脂組成物
JPH09255843A (ja) * 1996-03-26 1997-09-30 Dai Ichi Kogyo Seiyaku Co Ltd 抗菌性樹脂組成物
JP2002510341A (ja) * 1997-04-25 2002-04-02 アイエスピー インヴェストメンツ インコーポレイテッド マレインアミド酸及び／又はその環状イミド反復ユニットを含む無水マレイン酸重合体の製造方法
JP2002517786A (ja) * 1998-06-03 2002-06-18 コダック ポリクロム グラフィックス カンパニー リミテッド リソグラフ印刷板前駆体
JP2006124592A (ja) * 2004-10-29 2006-05-18 Kaneka Corp イミド樹脂及びその樹脂組成物
JP2013518964A (ja) * 2010-02-04 2013-05-23 ステレンボッシュ ユニバーシティ 抗微生物性ポリマー化合物およびその繊維
JP2016014794A (ja) * 2014-07-02 2016-01-28 株式会社日本触媒 光学フィルムと、それを備える偏光板および画像表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023183954A1 (fr) * 2022-03-24 2023-09-28 Stellenbosch University Dispersion aqueuse de polymère antimicrobien

Also Published As

Publication number Publication date
JPWO2018062529A1 (ja) 2019-06-24
JP6730439B2 (ja) 2020-07-29

Similar Documents

Publication Publication Date Title
Lu et al. Tunable pH and temperature response of weak polyelectrolyte brushes: role of hydrogen bonding and monomer hydrophobicity
Gratzl et al. Antimicrobial activity of poly (acrylic acid) block copolymers
US11459445B2 (en) Composition and molded body
Shekh et al. Electrospun nanofibers of poly (NPEMA-co.-CMPMA): used as heavy metal ion remover and water sanitizer
Bedel et al. Antibacterial poly (ethylene terephthalate) surfaces obtained from thymyl methacrylate polymerization
KR20040002694A (ko) 항균성 또는 항응혈성 고분자 수지 및 그 제조방법
Lepoittevin et al. Antibacterial surfaces obtained through dopamine and fluorination functionalizations
Muhamad et al. Characterization and evaluation of antibacterial properties of polyacrylamide based hydrogel containing magnesium oxide nanoparticles
JP6730439B2 (ja) マレイミド構造単位を有するポリマーを含む抗微生物剤
Abudonia et al. Surface modification of polypropylene film by grafting with vinyl monomers for the attachment of chitosan
Chen et al. Cooperative enhancement of fungal repelling performance by surface photografting of stereochemical bi-molecules
JP4905980B2 (ja) 抗菌性フィルム
EP3927762A1 (fr) Matériaux polymères antibactériens actifs en cas de contact
JP2000506154A (ja) 重合体の殺虫剤としての用途
CN1361796A (zh) 制备固有杀微生物聚合物表面的方法
JP2003509546A (ja) アクリロイルアミノアルキル化合物のコポリマー
DE19921895A1 (de) Antimikrobielle Copolymere
Sadeghi et al. One-step UV-curable ligand copolymer coatings as non-migratory antioxidant packaging
US20040076674A1 (en) Method for thermally assisted antimicrobial surface treatment
AU7236300A (en) Microbicidal copolymers
Chen et al. Temperature responsive methacrylamide polymers with antibacterial activity
CN1360602A (zh) 生产固有杀微生物聚合物表面的方法
Sadeghi et al. Ultraviolet-cured p-phenylenediamine functionalized polypropylene film as a non-migratory antioxidant
WO2000069937A1 (fr) Copolymeres microbicides
Hyun et al. Surface characterization of 8‐quinolinyl acrylate‐grafted poly (ethylene terephthalate) prepared by plasma glow discharge and it's antibacterial activity

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17856476

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018542960

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17856476

Country of ref document: EP

Kind code of ref document: A1