WO2018062529A1

WO2018062529A1 - Antimicrobial agent containing polymer having maleimide structure unit

Info

Publication number: WO2018062529A1
Application number: PCT/JP2017/035639
Authority: WO
Inventors: 勇介宮▲崎▼; 勇樹牧野
Original assignee: 株式会社日本触媒
Priority date: 2016-09-29
Filing date: 2017-09-29
Publication date: 2018-04-05
Also published as: JPWO2018062529A1; JP6730439B2

Abstract

The purpose of the present invention is to provide a molded article that has high antimicrobial capability (antibacterial capability and anti-mold capability), and that contains a polymer-type antimicrobial agent, wherein elution of the polymer can be suppressed and the polymer-type antimicrobial agent has excellent antibacterial durability. The present invention is an antimicrobial agent containing a polymer having the structure unit represented by formula (1), where: R₁ is a C3-24 alkylene group; R₂ is selected from the group comprising a C2-24 alkyl group, a C3-12 alicyclic hydrocarbon group, and a C6-24 aryl group; and a secondary amino group represented by -NHR₂ may be a neutralized salt.

Description

Antimicrobial agent comprising a polymer having a maleimide structural unit

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.

In recent years, 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.

As a polymer type antibacterial agent, 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)

However, the polymer type antibacterial agent described in 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.

Accordingly, 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). And

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.

In the formula (1), 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.

According to one aspect of the present invention, there is provided an antimicrobial agent comprising a polymer having a structural unit represented by the above formula (1). With such a structure, the antimicrobial performance (antifungal performance and antibacterial 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.

According to one embodiment of the present invention, (a) 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 And (b) at least one step selected from the step of bringing the polymer having the structural unit represented by the formula (1) or the antimicrobial agent into contact with a resin or an article. Provide a method for suppressing

According to one aspect of the present invention, there is provided use of a polymer having a structural unit represented by the above formula (1) as an antimicrobial agent.

In this specification, a 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. On the other hand, 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.

In the polymer having a maleimide structure of the present invention, when R ₁ is an alkylene group having 3 or more carbon atoms, the degree of freedom of the secondary amino group is increased in the polymer structure. As a result, 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. In addition, when 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.

In addition, 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.

Furthermore, 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.

Hereinafter, modes for carrying out the present invention will be described. However, the present invention is not limited to this embodiment. In addition, the form which combined two or more each preferable form of this invention described below is also a preferable form of this invention.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

<Antimicrobial agent>
[Polymer having maleimide structural unit]
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.

In the above formula (1), R ₁ is an alkylene group having 3 to 24 carbon atoms. In addition, 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. Examples of the alkylene group having 3 to 24 carbon atoms include propylene group, trimethylene group, butylene group, pentylene group, hexylene group (hexamethylene group), heptylene group, octylene group (octamethylene group), nonylene group, and decylene group. , Undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.

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.

In the above formula (1), 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), nonadecyl group, icosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group and the like.

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.

Examples of 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.

In R ₂ , 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. Group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, hexyl group, heptyl group or octyl group, more preferably isopropyl group, tert-butyl group, 2- An ethylhexyl group or a hexyl group;

In R ₂ , 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.

In R ₂ , 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. , An adamantyl group or a dicyclopentanyl group, and most preferably a cyclohexyl group.

In R ₂ , 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.

In one embodiment of the present invention, 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. When 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.

In a preferred embodiment of the present invention, R ₁ is an alkylene group having 3 to 18 carbon atoms, and 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.

In a more preferred embodiment of the present invention, 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. Selected from the group consisting of alkyl groups of ˜8 and alicyclic hydrocarbon groups of 6 to 10 carbon atoms, particularly preferably 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.

In the above formula (1), 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. Examples of 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. For example, a structural unit derived from styrene CH ₂ ═CH (C ₆ H ₅ ) can be represented by —CH ₂ CH (C ₆ H ₅ ) —. Here, 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.

As the monomer from which the structural unit of the above formula (1) is derived, maleimide, maleic anhydride, or the like can be used.

When 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. Examples of the copolymerizable monomer include a styrene monomer, an α-olefin monomer having 1 to 24 carbon atoms, a vinyl ester, an alkyl vinyl ether, and a (meth) acrylic acid ester.

Examples of styrene monomers include styrene, α-methyl styrene, vinyl toluene, p-methyl styrene, chloromethyl styrene, ethyl vinyl benzene, and the like.

Examples of the α-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.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl formate, vinyl benzoate and the like.

Examples of alkyl vinyl ethers include ethyl vinyl ether and methyl vinyl ether.

Examples of (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.

1 type or 2 types or more can be used for the said monomer.

In this specification, “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”. Further, “(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 α-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.

That is, in one embodiment of the present invention, 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 α-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. . When the weight average molecular weight is 1,000 or more, moldability can be improved. 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).

In one embodiment according to the present invention, the antimicrobial agent may contain other components in addition to the polymer having the structural unit of the above formula (1). As other components, a solvent, an additive, and the like can be used.

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.

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 and antifungal properties]
In the present invention, “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.

Examples of the bacteria 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.

Examples of 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. Examples of fungi other than molds include the genus Saccharomyces such as Saccharomyces cerevisiae, the genus Candida such as Candida albicans, and the genus Rhodotorula rubura and others. .

Although 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.

(Evaluation method for antibacterial and antifungal properties)
In the antimicrobial agent of the present invention, antibacterial performance can be evaluated according to JIS Z2801: 2012 (antibacterial processed product-antibacterial evaluation method / antibacterial effect). In the evaluation method using 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.

Also, the fungicidal performance can be evaluated with reference to JIS Z2911: 2010 (mold resistance test method). In the evaluation method using JIS Z2911: 2010, 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.

[Method for producing antimicrobial agent]
The manufacturing method of the antimicrobial agent of this invention is demonstrated.

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. In the production method, for example, 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.

Hereinafter, a method obtained by reacting an acid anhydride group of a maleic anhydride (co) polymer with a primary amino group of a diamine, ring-opening to form an amide bond, and then dehydrating ring-closing imidization reaction will be described. However, it is not limited only to the following forms.

Examples of the maleic anhydride (co) polymer 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.

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.

Further, 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”).

In the above formula (2), R ₁ and R ₂ in the formula (1) are applied to R ₁ and R ₂ . Examples of 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.

As described above, 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. For example, 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. 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. For example, 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. For example, the reaction temperature is 20 ° C. to 150 ° C., and the reaction time is 1 to 9 hours. Further, 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. For example, the temperature for vacuum drying is 40 to 95 ° C., and 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. For example, the temperature of the ring-closing imidization reaction is 100 to 250 ° C., and the time of the ring-closing imidization reaction is 3 to 24 hours.

In the present invention, 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. Here, 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%.

Regarding the introduction of the secondary amino group into the maleic anhydride structural unit, that is, 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.

When 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. Alternatively, 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 | purification process and a post-processing process.

<Composition>
As one embodiment of the present invention, there is provided a composition comprising the antimicrobial agent and a resin (excluding the polymer having the maleimide structural unit). As the resin, 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.

The thermoplastic resin used in the present invention is not particularly limited. For example, (meth) acrylic resin, styrene resin, polyester resin, polycarbonate resin, polyvinyl chloride resin, olefin resin (polyethylene, low density polyethylene, polypropylene, etc .; Cyclic olefin resins), polyamide resins, halogen-containing resins (polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, etc.), polyvinyl ester resins such as polyvinyl acetate, ethylene-vinyl acetate copolymers, ethylene- Examples thereof include vinyl acetate-vinyl chloride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), and polyacetal resin. A thermoplastic resin can be used individually or in combination of 2 or more types.

The 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. . In a preferred embodiment, 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. For example, 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. For example, (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.

The above thermoplastic resin, thermosetting resin, elastomer, and photocurable resin may be a synthetic product or a commercially available product. The 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.

In addition to the antimicrobial agent and the resin, the composition may contain other components, various additives, a solvent, and the like as desired. Examples of 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.

In the composition of the present invention, 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. As a more preferred form, 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.

In the composition of the present invention, 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). As a more preferred form, 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. For example, 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.

When 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 (for example, one to be used for the following applications) 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.

<Method for inhibiting the growth of microorganisms>
According to one aspect of the present invention, (a) 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. There is 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.

Description of the polymer having the structural unit represented by the above formula (1) in the present embodiment is the same as the description in [Polymer having maleimide structural unit], and thus the description thereof is omitted.

In this specification, “suppressing the growth of microorganisms” includes not only suppressing the growth of microorganisms but also killing microorganisms.

In the step (a), 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. For example, 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.

In the step (b), 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. Further, 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. For example, 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. In addition, 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. 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.

Therefore, 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.

In one embodiment of the present embodiment, in the steps (a) and (b), the polymer having the maleimide structure or the antimicrobial agent contains a resin (excluding the polymer having the maleimide structural unit). Included in things.

In this embodiment, as the resin, the resin exemplified in the <Composition> section is exemplified. In addition, the description of the composition is the same as the description in <Composition>, and the description is omitted.

In the method for suppressing the growth of microorganisms of the present invention, 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 In a preferred form, 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.

<Use of polymer having maleimide structural unit as antimicrobial agent>
According to one aspect of the present invention, there is provided use of a polymer having a structural unit represented by the above formula (1) (a polymer having a maleimide structural unit) as an antimicrobial agent.

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.

In the use as the antimicrobial agent of the present invention, 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>. Moreover, as resin used for use of this invention, resin illustrated by said <composition> is illustrated preferably. As the article to be used, the resin exemplified in the above <resin molding> is preferably exemplified. Moreover, as an aspect of the use as an antimicrobial agent of the present invention, the aspect exemplified in the above <Method for inhibiting the growth of microorganisms> is preferably exemplified.

In one embodiment of the present embodiment, 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.

In the composition according to this embodiment, 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). As a more preferred form, 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.

In one embodiment of the present embodiment, the polymer having the maleimide structural unit is contained in a resin molded body.

Description of the resin molded body including a polymer having a maleimide structural unit in the present embodiment is the same as that described in the above <Resin molded body>, and thus the description is omitted.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

In the antimicrobial agent containing a polymer having a maleimide structural unit, the antimicrobial performance (antibacterial and antifungal performance) was measured by the following method.

[Antimicrobial evaluation method]
The antibacterial evaluation test was conducted according to JIS Z2801: 2012 (antibacterial processed product-antibacterial evaluation method / antibacterial effect). First, 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. After culturing, the bacterial solution was collected from between the films, and the viable cell count was calculated by the agar plate culture method. At the same time, 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).

[Method for evaluating antifungal properties]
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. In accordance with the method described in JIS Z2911: 2010, Pesilomyces variotti (Paecilomyces variotii, NBRC33284 strain), Aspergillus niger (Aspergillus niger, NBRC105649 strain), Penicillium pinorum 28 (Aureobasidium pullulans, NBRC6353 strain), Cladosporium cladosporioides (Cladosporium cladosporoides, NBRC6348 strain), Trichoderma virens (Trichoderma virens, NBRC6355 strain) um globosum, NBRC6347 strain), preparing a spore solution of each mold or a mixture of spores of a plurality of molds (selected from the above molds), and placing the spore solution on the test piece and the surrounding agar medium And inoculated. After inoculation, 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.

The imidization of maleic anhydride and the weight average molecular weights of the following polymers 1 to 23 were analyzed by the following method.

[Imidation analysis]
In the following polymers 1 to 23, imidation was analyzed by analyzing the carbonyl group of the acid anhydride in the spectrum obtained with a Fourier transform infrared spectroscopy (FT-IR) analyzer (product name: Spectrum one) manufactured by PerkinElmer. and disappearance of the absorption peak (1775 cm ^-1) and the absorption peak of the carbonyl group of the amide (1550 cm ^-1) of was determined based on the detection of the absorption peak (1700 cm ^-1) of carbonyl group of the imide.

[Analysis of weight average molecular weight]
Using a gel permeation chromatography (GPC) apparatus (product name: HLC-8320GPC EcoSEC, column: TSKgel superHM-M, molecular weight standard: PSt Quick MP MP-M) manufactured by Tosoh Corporation, maleic anhydride before diamine modification The weight average molecular weight of the polymers 1 to 23 was calculated by measuring the weight average molecular weight of the polymer and multiplying the measured value by the conversion factor. The conversion coefficient was calculated by [(molecular weight of copolymer unit after diamine modification) / (molecular weight of copolymer unit before diamine modification) × 100].

<Evaluation of antimicrobial properties>
(Example 1)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and 226.5 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 5.84 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40.70 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6.5 hours to remove the solvent. 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.

2 g of the obtained polymer 1 and 18 g of ethanol were mixed to prepare a 10 wt% polymer solution. A test in which a polymer film was coated with polymer 1 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Example 2)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) 212.5 g were charged and stirred to dissolve the copolymer. While stirring the solution, N-linear alkyl-1,3-propanediamine (Product name: Diamine R-86, manufactured by Kao Corporation, C14: C16: C18 = 5: 50: (Mixture of 45 (weight ratio)) 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. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6.5 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 8,800) (polymer 2). The obtained 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.

2 g of the obtained polymer 2 and 18 g of n-hexane were mixed to prepare a 10% by weight polymer solution. A test in which a polymer film was coated with polymer 2 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, and then air-dried overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Example 3)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.07 g of N-benzyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40.00 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6.5 hours to be dehydrated and cyclized to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours to obtain 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.

2 g of the obtained polymer 3 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm was dipped on the polymer solution, and then air-dried overnight to remove the solvent and coat the polymer 3 A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 1.

Example 4
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, an isobutylene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 6,000, isobutylene: maleic anhydride = 1: 1 (molar ratio) )) 7.5 g and 147.1 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, 6.23 g of N-isopropyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 19.76 g of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. Was added dropwise to the solution. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 85 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 9,800) (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.

2 g of the obtained polymer 4 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a polymer film was coated with a polymer 4 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Example 5)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, an isobutylene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 6,000, isobutylene: maleic anhydride = 1: 1 (molar ratio) )) 7.5 g and 151.4 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, 8.40 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 21.69 g of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. Was added dropwise to the solution. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 85 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration and cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 11,400) (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.

2 g of the obtained polymer 5 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a polymer film was coated with polymer 5 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Example 6)
In a 500 ml four-necked flask equipped with a thermometer and a stirrer, 1-octadecene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 40,000, 1-octadecene: maleic anhydride = 1: 1 (molar ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 229.2 g were charged and stirred to dissolve the copolymer. While stirring the solution, a solution of 4.03 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 37.90 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. as a solution It was dripped in. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 3 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours and dehydrated and cyclized to obtain a polymer having a maleimide structure (weight average molecular weight 55,800) (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.

1 g of the obtained polymer 6 is sandwiched between two PTFE sheets (manufactured by Tokyo Glass Instrument Co., Ltd., product code 0638817711, thickness of 50 μm on page 479 in the 2016 catalog), and further sandwiched between two stainless steel plates. A test film was produced by pressing (200 ° C., 20 MPa, 2 minutes) with a press machine (AH-2003, manufactured by ASONE CORPORATION). The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 1.

(Comparative Example 1)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.95 g of N, N-dibutyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.00 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. Was added dropwise to the solution. 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. Thereafter, the entire amount of the solution was dropped into n-hexane to precipitate a polymer, which was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 80 ° C. for 2.5 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration and cyclization to obtain an imide-modified product (weight average molecular weight 6,600) (polymer 7). The obtained polymer 7 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.

2 g of the obtained polymer 7 and 8 g of n-hexane were mixed to prepare a 10 wt% polymer solution. A test in which a polymer film was coated with a polymer 7 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution and then air-dried overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Comparative Example 2)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.41 g of N, N-diisopropylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40.00 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration and cyclization to obtain an imide-modified product (weight average molecular weight 5,900) (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.

2 g of the obtained polymer 8 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a polymer film was coated with a polymer 8 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Comparative Example 3)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.05 g of N-phenylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40.00 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours to cause dehydration and cyclization to obtain 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.

2 g of the obtained polymer 9 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a polymer film was coated with a polymer 9 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Comparative Example 4)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.67 g of N-benzylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 40.00 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours to cause dehydration and cyclization to obtain an imide-modified product (weight average molecular weight 6,000) (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.

2 g of the obtained polymer 10 and 8 g of acetone were mixed to prepare a 20 wt% polymer solution. A test in which a polymer film was coated with a polymer 10 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 7 cm with respect to the polymer solution, followed by air drying overnight. A film was prepared. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Comparative Example 5)
In a 500 ml four-necked flask equipped with a thermometer and a stirrer, maleic anhydride (Wako Pure Chemical Industries, Ltd.) 18.77 g, styrene (Wako Pure Chemical Industries, Ltd.) 20.03 g, methyl ethyl ketone 202.90 g (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and stirred to obtain a uniform solution. 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). After the collected polymer was collected by filtration, the solvent was removed with a vacuum dryer at 100 ° C. to obtain 33.7 g of a dried styrene-maleic anhydride copolymer. The weight average molecular weight of the obtained styrene-maleic anhydride copolymer was calculated to be 450,000 by GPC analysis. 7.48 g of the synthesized styrene-maleic anhydride copolymer was dissolved in 50.26 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) to prepare Solution 1. Separately, 6.03 g of p-aminophenol (manufactured by Kanto Chemical Co., Inc.) and 49.62 g of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and dissolved to prepare Solution 2. 57.74 g of Solution 1 and 55.65 g of Solution 2 were mixed in a 300 mL round bottom flask, and 7.5 g of triethylamine (manufactured by Kanto Chemical Co., Inc.) was added. The temperature was raised to 90 ° C. while purging the gas phase with nitrogen, and the reaction was carried out for a total of 13 hours. 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. for 72 hours to obtain an imide-modified product (polymer 11). The polymer 11 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.

2 g of the polymer 11 and 8 g of N, N-dimethylformamide were mixed to prepare a 20% by weight polymer solution. After dipping a PET film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) cut to 5 cm × 7 cm with respect to the polymer solution, the solvent was removed by air drying overnight to prepare a test film coated with polymer 11. . The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Pecilomyces variotii and Cladosporium cladosporioides. The results are shown in Table 1.

(Examples 7 to 10)
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.

As shown in Tables 1 and 2, in Examples 1 to 10, it can be seen that since R ₁ is a trimethylene group, excellent antimicrobial performance can be exhibited. On the other hand, in Comparative Examples 2 to 4, it can be seen that since R ₁ is an ethylene group, there is almost no antimicrobial performance.

Further, as shown in Tables 1 and 2, in Examples 1 to 10, it has a structural unit in which a secondary amino group is added to the maleimide structure, and thus it can be seen that excellent antimicrobial performance can be exhibited. On the other hand, 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 μm. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 μm. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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.

(Comparative Example 6)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and 253.1 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, 3.31 g of N, N-diethyl-1,3-propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 31.10 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. The mixture was added dropwise to the solution. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours for dehydration and cyclization to obtain an imide-modified product (weight average molecular weight 5,600) (polymer 12). The polymer 12 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.

1 g of the obtained polymer 12 and 19 g of polypropylene (PP) (Nippon Polypro Co., Ltd., Novatec (registered trademark) PP) were used, using a lab plast mill (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 μm. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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.

As shown in Table 3, in Examples 11 to 12, excellent antimicrobial performance was obtained even when the content of the polymer having a maleimide structural unit according to the present invention was 5% by weight based on the resin. It can be seen that it can be demonstrated. On the other hand, in the case of Comparative Example 6, since it has a structural unit in which a tertiary amino group is added to the maleimide structure, when the content of the antimicrobial agent is 5% by weight with respect to the resin, the antimicrobial performance is I understand that there is no.

From the above, 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.

<Evaluation of dissolution>
[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. for 6 hours, and then 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. For the thickness measurement, a digital micrometer MCD130-25 manufactured by Niigata Seiki Co., Ltd. was used. 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.

(Examples 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 Example 7)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and 253.1 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 3.31 g of N, N-diethyl-1,3-propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 31.10 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) at 25 ° C. Was added dropwise to the solution. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 7 hours to effect dehydration to obtain an imide-modified product (weight average molecular weight 5,600) (polymer 13). The polymer 13 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.

1 g of the obtained polymer 13 and 4 g of acetone were mixed to prepare a 20 wt% polymer solution. A film coated with polymer 13 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 1 cm × 3 cm with respect to the polymer solution, and then air-dried overnight to remove the solvent. Was made. A film coated with the polymer 13 was cut into 1 cm × 1 cm to prepare a test film. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were irradiated with an ultraviolet lamp for 5 minutes per side to sterilize the test film. Sterilized test films were used for elution evaluation. The results are shown in Table 4.

(Comparative Example 8)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, an isobutylene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 6,000, isobutylene: maleic anhydride = 1: 1 (molar ratio) )) 10.0 g and N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) 190 g were charged and stirred to dissolve the copolymer. While stirring the solution, 8.5 g of N, N-diethyl-1,3-propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the solution at 25 ° C. After completion of the dropwise addition, a part of the reaction solution was dropped into acetone to precipitate the reaction product, and a part of the precipitate was recovered 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. Thereafter, the total amount of the solution was added dropwise to 438.5 g of acetone to precipitate a reaction product, which was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 50 ° C. for 6 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 16 hours for dehydration and cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 10,400) (polymer 14). The obtained polymer 14 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.

1 g of the obtained polymer 14 and 4 g of acetone were mixed to prepare a 20 wt% polymer solution. A film coated with polymer 14 after dipping a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 1 cm × 3 cm with respect to the polymer solution, and then air-dried overnight to remove the solvent. Was made. A film coated with the polymer 14 was cut into 1 cm × 1 cm to prepare a test film. The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were irradiated with an ultraviolet lamp for 5 minutes per side to sterilize the test film. Sterilized test films were used for elution evaluation. The results are shown in Table 4.

As shown in Table 4, in Examples 13 to 16, it has a structural unit in which a secondary amino group is added to the maleimide structure, so that elution of the polymer can be suppressed and the durability of antimicrobial performance is excellent. . On the other hand, 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.

(Example 17)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 5.1 g and 134.9 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 5.97 g of N-cyclohexyl-1,6-hexanediamine and 26.90 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 20 hours for dehydration and cyclization to obtain 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.

1 g of the resulting polymer 15 and 4 g of tetrahydrofuran were mixed to prepare a 20 wt% polymer solution. The prepared polymer solution was dropped onto the surface of a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 5 cm, and coated with a spin coater (Mikasa Co., Ltd.) overnight. The solvent was removed by air drying, and a test film coated with polymer 15 was produced. In a clean bench, the 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 antifungal property was evaluated for Aspergillus niger, Penicillium pinofilm, and Paecilomyces variotii. The results are shown in Table 5.

(Example 18)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 5.1 g and 134.9 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 6.82 g of N-cyclohexyl-1,8-octanediamine and 26.90 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 20 hours and subjected to dehydration cyclization to obtain 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.

(Example 19)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 7.5 g and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200.0 g were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 5.86 g of N- (tert-butyl) -1,3-propanediamine and 40.00 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 10 hours and subjected to dehydration cyclization to obtain 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.

(Example 20)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 5.1 g and 134.9 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 5.69 g of N- (2-ethylhexyl) -1,3-propanediamine and 26.90 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 10 hours and subjected to dehydration cyclization to obtain a polymer having a maleimide structure (weight average molecular weight 6,600) (polymer 18). The polymer 18 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 18 obtained above was used in place of the polymer 15, and an antifungal property was evaluated. The results are shown in Table 5.

(Example 21)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 5.1 g and 134.9 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 5.00 g of N-normalhexyl-1,3-propanediamine and 26.90 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 10 hours and subjected to dehydration cyclization to obtain 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.

1.5 g of the obtained polymer 19 is sandwiched between two PTFE sheets (manufactured by Tokyo Glass Instrument Co., Ltd., product code 0638817711, thickness of 50 μm on page 479 of the 2016 catalog), and further sandwiched between two stainless plates Then, a test film was produced by pressing (220 ° C., 20 MPa, 15 minutes) with a hot press machine (AH-2003, manufactured by ASONE CORPORATION). The test film was wiped with Kimwipe (registered trademark) and then wiped dry with Kimwipe (registered trademark). Thereafter, in the clean bench, both sides of the test film were 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 Aspergillus niger, Penicillium pinofilm, and Paecilomyces variotii. The results are shown in Table 5.

(Example 22)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, an ethylene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 100,000, ethylene: maleic anhydride = 1: 1 (molar ratio) )) 10.0 g and 27,0 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 13.9 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 86.0 g of N, N-dimethylformamide was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 100 ° C. for 6 hours to remove the solvent. 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.

(Example 23)
To a 500 ml four-necked flask equipped with a thermometer and a stirrer, an isobutylene-maleic anhydride copolymer (Isoban # 06, Kuraray Co., Ltd., weight average molecular weight 80,000, isobutylene: maleic anhydride = 1: 1 ( Mole ratio)) 10.0 g and 27,0 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 11.4 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 70.0 g of N, N-dimethylformamide was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 100 ° C. for 6 hours to remove the solvent. 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.

(Example 24)
To a 500 ml four-necked flask equipped with a thermometer and a stirrer, an isobutylene-maleic anhydride copolymer (Isoban # 10 manufactured by Kuraray Co., Ltd., weight average molecular weight 160,000, isobutylene: maleic anhydride = 1: 1 ( Mole ratio)) 10.0 g and 27,0 g of N, N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 11.4 g of N-cyclohexyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 70.0 g of N, N-dimethylformamide was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was collected by filtration with a vacuum filter, and the filter cake was vacuum-dried at 100 ° C. for 6 hours to remove the solvent. 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.

(Comparative Example 9)
Into a 500 ml four-necked flask equipped with a thermometer and a stirrer, a styrene-maleic anhydride copolymer (manufactured by Sigma-Aldrich, weight average molecular weight 3,600, styrene: maleic anhydride = 1: 1 (mol) Ratio)) 5.1 g and 134.9 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred to dissolve the copolymer. While stirring the solution, a mixture of 4.33 g of N-cyclohexylethylenediamine and 26.90 g of tetrahydrofuran was added dropwise to the solution at 25 ° C. 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. Thereafter, the entire amount of the solution was recovered by filtration with a vacuum filter, and the filter cake was vacuum dried at 50 ° C. for 4 hours to remove the solvent. The dried cake was vacuum-dried at 150 ° C. for 10 hours and subjected to dehydration cyclization to obtain 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.

As can be seen from Table 5, in Examples 17 to 24, R ₁ is an alkylene group having 3 to 8 carbon atoms, so that excellent antimicrobial performance can be exhibited. In contrast, in 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. A 20% by weight mixed polymer solution (polymer 17: AS resin = 12.5: 87.5 (weight ratio)) was prepared. The prepared mixed polymer solution was dropped on the surface of a PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) cut to 5 cm × 5 cm, and coated with a spin coater (Mikasa Co., Ltd.). The solvent was removed by air drying overnight, and a test film coated with a mixture of polymer 17 and AS resin was produced. In a clean bench, the 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.

As shown in Table 6, it can be seen that 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. Next, 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- A coating solution in which 0.08 g of pentanediol monoisobutyrate (CS-12, manufactured by JNC Corporation) is mixed and the concentration of the neutralized salt of polymer 1 is 7.9% by weight with respect to the entire coating solution. Was prepared. A PET film (Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm) 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 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 μm) 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. Aspergillus niger (Aspergillus niger), Penicillium pinofilm (Pecilomyces variotium), Trichoderma bilomis (Trichoderma bilomis) It implemented using the liquid mixture. The results are shown in Table 7.

(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. Was mixed with 0.29 g of a 10% by weight neutralized salt aqueous solution of polymer 1 prepared in Example 28 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 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.

As shown in Table 7, it can be seen that 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.

This application is based on Japanese Patent Application No. 2016-191846 filed on Sep. 29, 2016, the disclosure of which is incorporated by reference in its entirety.

Claims

Following formula (1):

In the formula (1), 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. A secondary amino group selected from the group consisting of 6 to 24 aryl groups and represented by —NHR 2 may be a neutralized salt;
The antimicrobial agent containing the polymer which has a structural unit represented by these.
A composition comprising the antimicrobial agent according to claim 1 and a resin.
A resin molded article comprising the antimicrobial agent according to claim 1 or the composition according to claim 2.
(A) The following formula (1):

In the formula (1), 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. A secondary amino group selected from the group consisting of 6 to 24 aryl groups and represented by —NHR 2 may be a neutralized salt;
A step of contacting a microorganism with an antimicrobial agent comprising a polymer having a structural unit represented by formula (1) or a polymer having a structural unit represented by formula (1), and (b) represented by formula (1) A method for inhibiting microbial growth, comprising at least one step selected from a step of bringing a polymer having a structural unit or the antimicrobial agent into contact with a resin or an article.
The method according to claim 4, wherein in the steps (a) and (b), the polymer represented by the formula (1) is contained in a composition containing a resin.
6. The method of claim 5, wherein the resin is selected from a thermoplastic resin, an elastomer, and a photocurable resin.
Following formula (1):

In the formula (1), 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. A secondary amino group selected from the group consisting of 6 to 24 aryl groups and represented by —NHR 2 may be a neutralized salt;
Use of a polymer having a structural unit represented by the formula:
The use according to claim 7, wherein the polymer represented by the formula (1) is contained in a composition containing a resin.
Use according to claim 8, wherein the resin is selected from thermoplastic resins, elastomers and photo-curable resins.
The use according to claim 7, wherein the polymer represented by the formula (1) is contained in a resin molded body.
The use according to claim 10, wherein the resin molding includes a resin selected from the group consisting of a thermoplastic resin, an elastomer, and a photocurable resin.