JP2012092089A - Antibacterial agent and substrate surface treatment method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial agent which can be limited to the required location on the surface of a material without mixing, and has excellent antibacterial, antifungal and antiviral effects even at low concentrations of the active ingredient without elution, volatilization or the like.SOLUTION: The antibacterial agent contains as an active ingredient a resin having an organic group represented by general formula (1); wherein Rand Rare independently fluoroalkyl groups of 1 to 4 carbon atoms; C and A are joined by a covalent bond or an ionic bond; and A is a hydrogen atom or a positive ion.

Description

  The present invention relates to an antibacterial agent having antibacterial property, antifungal property, and antiviral property, a surface treatment method for a substrate using the same, and an antibacterial member thereof.

  The need for antibacterial agents is greatly expanding with the diversification of living environments and changes in living consciousness. At present, chemical technologies such as antibacterial and antifungal are applied in various industrial fields such as life-related fields, plastics industry, electronic parts industry, and the like.

  The antibacterial in the present invention is a series of techniques for continuously preventing the occurrence and development of microorganisms, particularly bacteria and fungi (molds), and preventing or avoiding the harm caused by them.

  There are various physical techniques for temporary sterilization, such as a method using ultraviolet rays or radiation, a heating method, a cooling method, and a pressurizing method. Antibacterial refers to microorganisms that, unlike temporary sterilization, have a level below sterilization and above bacteriostatic to continuously suppress the growth of microorganisms over a long period of time. Sterilization is a level at which microorganisms are killed or disappeared, and bacteriostasis is a level at which the growth of these microorganisms is suppressed.

  Bacteria whose antibacterial agents exhibit antibacterial activity include gram positive bacteria or gram negative bacteria. Gram positive bacteria include pathogens such as Staphylococcus aureus, Streptococcus pyogenes and Clostridium botulinum. On the other hand, Gram-negative bacteria include pathogens such as Salmonella, Escherichia coli, Klebsiella, Haemophilus, Pseudomonas aeruginosa and Proteus. In addition, some fungi parasitize humans and cause diseases, such as ringworm.

  Thus, antibacterial agents are widely used in order to continuously suppress the growth of microorganisms.

  Antibacterial agents are required to have both antifungal properties and antiviral properties such as virus disinfection.

  There are various molds or viruses in human living space.

  The main types of molds include blue mold, Aspergillus, mold, and spider mold. In general, there is a name of black mold, but it is difficult to specify the type of mold. In addition, red-knot mold is common in Europe, and the stain on the wall is often Cladosporium.

  On the other hand, the main types of viruses include norovirus, rotavirus, rhinovirus, coronavirus and respiratory syncytial virus. Viruses may or may not have an outer membrane, but in general, viruses with an outer membrane are more sensitive to germicidal disinfectants, whereas they do not have an outer membrane. Viruses are highly resistant. Major viruses that do not have an outer membrane are enteroviruses and reoviruses such as polio in RNA viruses, and adenoviruses, papovaviruses, and hepatitis B viruses in DNA viruses. Enteroviruses such as polio, coxsackie, and echo, which are RNA viruses that do not have an outer membrane, are generally resistant to various disinfectants, followed by adenovirus followed by herpes virus and vaccinia virus that have an outer membrane. And influenza viruses are very sensitive. Among the drugs, sodium hypochlorite is said to be an effective disinfectant at a relatively low concentration against any virus.

  In addition, there are various types of antibacterial agents, and various types are used depending on the purpose of use. Antibacterial agents can be classified into organic compound systems, inorganic compound systems, and natural product systems.

  Organic compound antibacterial agents include thiazole, imidazole, pyridine or triazine heterocyclic compounds, organic nitrogen compounds such as amines, quaternary ammonium compounds or nitrile compounds, phenols, cresols or halogenated phenols. Organic oxygen compounds such as thiols, organic sulfur compounds such as thiols, or organic phosphorus compounds such as thiophosphoric acid are known. Organic compound antibacterial agents are characterized by high antibacterial properties against molds. However, when added to a film or a resin molded product, it is difficult to maintain the effect by volatilization or elution. In addition, many organic compound antibacterial agents are toxic and their use may be restricted from the viewpoint of consumer protection, particularly in the fields of food, food processing and packaging.

  On the other hand, natural antibacterial agents represented by chili extract, chitin, chitosan, wasabi extract, mustard extract, tea extract or hinokitiol are known. The natural product system has a problem of elution and volatilization as in the case of the organic compound system, but it may be preferably used because of its high safety.

  In addition, inorganic compound-based antibacterial agents represented by silver are known, and in particular, there are many uses of resin molded products, films, fibers and the like. Inorganic compound-based antibacterial agents are advantageous in that they are difficult to elute or volatilize, have an antibacterial effect that lasts for a long time, and are highly safe. However, when trying to disperse fine particles such as silver or silver-supported zeolite in the resin, it is difficult to uniformly disperse, and the antibacterial agent located inside is difficult to work against external bacteria, In order to obtain the target antibacterial effect, it is necessary to increase the concentration of the antibacterial agent. From this, it has been pointed out that the antifungal effect is particularly inferior to the organic compound type as an antibacterial effect, and the field of use is also limited in that expensive silver is used.

  Against this background, attempts have been made to immobilize antibacterial compound groups on resins, which are disclosed in a plurality of prior art documents.

  For example, Patent Document 1 discloses a polymer-bound antibacterial agent as a polymer that suppresses elution or volatilization by binding 2,2,6,6-tetramethyl-4-piperidine to a polymer. .

  Patent Document 2 discloses an antibacterial resin film comprising a polyamide-based resin having a phosphonium sulfonate group, and the antibacterial resin film has both an antibacterial action and a sustained action.

  Both the polymer-bonded antibacterial agent described in Patent Document 1 and the antibacterial resin film described in Patent Document 2 have been successfully combined with an antibacterial compound group and immobilized on the resin.

  Patent Document 3 discloses an antibacterial property in which a polymer having a carboxyl group is formed by crosslinking a part of the carboxyl group with silver and bonding with the carboxyl group and a polyvalent metal ion. A resin is disclosed, and it is said that antibacterial properties due to silver ions are exhibited for a long period of time.

  Further, Patent Document 4 discloses an antistatic agent having a bismethide acid group.

JP 2008-214396 A JP 2001-55458 A JP-A-9-136808 JP 2010-018775 A

  For inorganic antibacterial agents, attempts have been made to uniformly disperse the antibacterial agents in the resin. For example, in the antibacterial resin of Patent Document 3, in a polymer having a carboxyl group, a part of the carboxyl group is bonded to silver and is crosslinked by bonding of the carboxyl group and a polyvalent metal ion. It is said that the antibacterial property due to ions is demonstrated for a long time. However, Patent Document 3 does not relate to an antibacterial agent containing an antibacterial organic group in the chemical structure of the resin.

  Further, the conventional antibacterial resin has a problem that it is difficult to obtain a long-lasting antibacterial effect due to elution, volatilization or the like when an organic compound type or natural product type is used.

  In addition, when using an antibacterial agent of an inorganic compound such as silver, an operation such as kneading into a resin is possible due to its high heat resistance temperature, but a sufficient antibacterial effect cannot be obtained particularly in antifungal properties. In addition, it is difficult to make the added antibacterial agent exist only in necessary places such as the surface of a material that requires antibacterial properties, and an excessive amount of the antibacterial agent is required, which is a significant cost problem.

  The present invention can be present only in a necessary place such as the surface of a material, and in addition to antibacterial properties, an antibacterial agent that continuously exhibits an excellent antifungal and antiviral effect and It is an object of the present invention to provide a surface treatment method for a base material used and an antibacterial member using the same.

  The antibacterial agent of the present invention is the antibacterial agent shown in the first aspect.

  It is an antibacterial agent containing, as an active ingredient, a resin having an organic group containing a bismethide acid group or a bismethido acid salt of the present invention, that is, an organic group represented by the general formula (1).

[Invention 1]
General formula (1):

(In the formula (1), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent which contains resin containing the organic group represented by this as an active ingredient.

When A is a hydrogen atom, the carbon of the bismethide acid group is easily dissociated as an H ⁺ ion due to the strong electron withdrawing property of perfluoromethide, and the C—H bond has both a covalent bond and an ionic bond. Thus, bismethide acid tends to become a bismethide salt by a cation. The organic group that acts as an antibacterial active ingredient contained in the antibacterial agent of the present invention may be either a bismethide acid group or an organic group containing a bismethide acid salt.

  Moreover, the antibacterial agent of this invention is an antibacterial agent shown to invention 2-9.

  Compared to the case where the antibacterial agent is simply kneaded and kneaded into the resin, the antibacterial agent containing the resin having the bismethide acid group bonded to the specific polymer chain shown in inventions 2 to 9 as an active ingredient is effective for the polymer chain. By binding an organic group containing the component bismethide acid group or bismethide acid salt, volatilization and elution of the active ingredient is suppressed, and antibacterial properties are maintained for a long period of time.

  The repeating unit having an organic group represented by the general formula (1) (an organic group containing a bismethide acid group or a bismethide acid salt) includes a repeating unit represented by the general formula (2) of the resin of the invention 2 (a ). When the repeating unit represented by the general formula (2) is exemplified, the repeating unit (a-1) represented by the general formula (3) having an ester bond of the invention 3 and a styrene chain in the main chain of the invention 4 Examples include the repeating unit (a-2) represented by the formula (4) and the repeating unit (a-3) represented by the general formula (5) having a norbornene ring in the main chain of the invention 5.

[Invention 2]
The resin is represented by the general formula (2):

(In Formula (2), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a carbon number. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond, having 1 to 12 carbon atoms. A divalent hydrocarbon group which is a linear, branched or cyclic divalent hydrocarbon group, or a combination thereof, and may have an ether bond, an ester bond, an amide bond or a urethane bond, Some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ And R ⁶ combine to form a ring And may include a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation .)
The antibacterial agent of the invention 1 which is resin which has the repeating unit (a) represented by these.

In the above general formula (1) and general formula (2), as R ¹ or R ² , CF ₃ , C ₂ F ₅ , linear or branched C ₃ F ₇ , C ₄ F ₉ are In the antibacterial agent of the present invention, CF ₃ is preferably used because of its ease of synthesis.

[Invention 3]
The repeating unit (a) is represented by the following general formula (3):

(In the formula (3), R ⁷ is a hydrogen atom, an alkyl group, a halogen atom or a trifluoromethyl group. R ⁸ is a single bond, a linear, branched or cyclic divalent group having 1 to 12 carbon atoms. Or a combination thereof, which may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of carbon atoms contained in R ⁸ is silicon. And a part or all of hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent of the invention 2 which is the repeating unit (a-1) represented by these.

[Invention 4]
The repeating unit (a) is represented by the general formula (4):

(In Formula (4), R ⁹ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond, or a urethane bond, a part of carbon atoms contained in R ⁹ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of the invention 2 which is the repeating unit (a-2) represented by these.

[Invention 5]
The repeating unit (a) is represented by the general formula (5):

(In the formula (5), R ¹⁰ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁰ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of the invention 2 which is the repeating unit (a-3) represented by these.

[Invention 6]
The resin further has the general formula (6):

(In Formula (6), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom. And an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴ is a hydrogen atom, a halogen atom, or a linear, branched or cyclic group having 1 to 35 carbon atoms, or a linear, branched or cyclic group. It is a monovalent hydrocarbon group which is a combination, and may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of the carbon atoms contained in R ¹⁴ may be substituted with silicon In addition, some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may combine to form a ring and have 3 carbon atoms. ~ 12 single It may contain cyclic, bicyclic or polycyclic structures.)
The antibacterial agent of the invention 2 which is resin containing the repeating unit (b-1) represented by these.

[Invention 7]
The resin further has the general formula (7):

(In Formula (7), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom. , An alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹¹ and R ¹² or R ¹³ may combine to form a ring, and the monocyclic, bicyclic or 3 to 12 carbon atoms R ¹⁵ may be a hydrogen atom, a halogen atom, or a monovalent group that is a linear, branched, cyclic, or linear, branched, or cyclic combination having 1 to 35 carbon atoms. Which may have an ether bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁵ may be substituted with silicon, and Part or all is fluorine atom or hydroxyl In may be substituted, R ¹⁵ is selected a hydroxyl group, a mercapto group, a carboxyl group, an amino group, an epoxy group, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, chlorosilyl group, alkoxysilyl group or a hydrosilyl group Including groups capable of reacting with other crosslinking agents.)
The antibacterial agent of the invention 2 which is resin containing the repeating unit (b-2) represented by these.

[Invention 8]
The resin is one or more groups selected from isocyanate group, hydroxyl group, mercapto group, carboxyl group, amino group, epoxy group, alkenyl group, alkynyl group, acryloyl group, methacryloyl group, chlorosilyl group, alkoxysilyl group or hydrosilyl group. A curable antibacterial agent according to invention 7, comprising a crosslinking agent, which is crosslinked with a crosslinking agent comprising

  Specifically, the group consisting of hexamethylene diisocyanate, 1,4-butanediol diglycidyl ether, paraformaldehyde, dimethyldichlorosilane, dimethyldimethoxysilane methylolated melamine and its derivatives sulfur, benzoyl peroxide or azobisisobutyronitrile. At least one crosslinking agent selected from is used.

  Next, the surface treatment method of the base material using the antibacterial agent of this invention is shown to inventions 9-14.

  An antibacterial agent containing a resin having an organic group containing a bismethide acid group or a bismethide acid salt as shown in Invention 1 as an active ingredient, particularly including a bismethide acid group or a bismethide acid salt in the specific polymer chain shown in Inventions 2 to 8 An antibacterial agent containing an organic group-bonded resin as an active ingredient can be applied in various forms.

  For example, it is possible to apply a surface treatment method of a base material that is applied after being dissolved in a solvent in a resin state and applied on a substrate to form an antibacterial film, a method of adhering to the surface after forming a sheet shape, etc. is there.

  In addition, the state of the polymerizable compound that is the precursor of the resin, or the state of the polymerizable compound that is the precursor of the repeating unit of the resin, and after adding a cross-linking agent as necessary, is applied or adhered, heated or ultraviolet rays, etc. It is possible to employ a surface treatment method in which a strong antibacterial resin film is obtained by polymerization or crosslinking by irradiation with light.

  Thus, according to the surface treatment method for a substrate of the present invention, antibacterial properties can be imparted by coating the surface of an object and efficiently applying or adhering an antibacterial agent to the substrate surface. it can.

[Invention 9]
A surface treatment method for a substrate, which comprises applying or adhering the antibacterial agent according to any one of Inventions 1 to 8 to the substrate surface to form a film.

[Invention 10]
General formula (2-1)

(In Formula (2-1), R ¹ and R ² each independently represents a fluoroalkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. Or a fluoroalkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond or 1 carbon atom. A divalent hydrocarbon group of -12 linear, branched or cyclic divalent hydrocarbon groups, or a combination thereof, having an ether bond, an ester bond, an amide bond or a urethane bond In addition, some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ Or R ⁵ and R ⁶ are And may include a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom. Or a cation.)
A surface treatment method for a base material, characterized in that a film of the antibacterial agent of inventions 1 to 8 is formed by applying or adhering a polymerizable compound which is a precursor of a repeating unit represented by

[Invention 11]
General formula (2-1):

(In Formula (2-1), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond, having 1 to 1 carbon atoms. 12 linear, branched, or cyclic divalent hydrocarbon groups, or a divalent hydrocarbon group that is a combination thereof, and having an ether bond, an ester bond, an amide bond, or a urethane bond In addition, some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ and R ⁶ are combined It may form a ring and may contain a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or It is a cation.)
In addition to the polymerizable compound represented by general formula (6-1):

(In Formula (6-1), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently, A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ¹⁴ is a hydrogen atom, a halogen atom, or a straight chain, branched, cyclic, or straight chain, branched, having 1 to 35 carbon atoms, It is a monovalent hydrocarbon group which is a cyclic combination, and may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of carbon atoms contained in R ¹⁴ is substituted with silicon. Alternatively, some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may combine to form a ring, Single ring of number 3-12 Formula, bicyclic or polycyclic structures may be included.)
Or general formula (7-1):

(In formula (7-1), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently R ¹¹ and R ¹² or R ^{13 which} are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom may be bonded to form a ring, and a monocyclic or bicyclic ring having 3 to 12 carbon atoms R ¹⁵ may be a hydrogen atom, a halogen atom, or a linear, branched, cyclic, or linear, branched, cyclic combination having 1 to 35 carbon atoms. A monovalent hydrocarbon group, which may have an ether bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁵ may be substituted with silicon, and a hydrogen atom; Part or all of fluorine atom or May be substituted with an acid group, R ¹⁵ represents a hydroxyl group, a mercapto group, a carboxyl group, an amino group, an epoxy group, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, chlorosilyl group, alkoxysilyl group or a hydrosilyl group Contains groups that can react with the chosen crosslinker.)
After the addition of the polymerizable compound represented by formula (1), the surface of the substrate according to invention 10 is formed by applying or adhering to the surface of the substrate to form a film of the antibacterial agent according to invention 6 or 7. Processing method.

In addition, the polymerizable compound represented by the general formula (2-1), the general formula (6-1), or the general formula (6-3), which is a precursor of the above repeating unit, is not limited to the monomer. The oligomer which combined the monomer may be sufficient. )
[Invention 12]
Furthermore, after adding a crosslinking agent, the film of the antimicrobial agent of the invention 8 is formed, The surface treatment method of the base material in any one of the invention 9-11 characterized by the above-mentioned.

  In the substrate surface treatment method of the present invention, the cross-linking agent includes isocyanate group, hydroxyl group, mercapto group, carboxyl group, amino group, epoxy group, alkenyl group, alkynyl group, acryloyl group, methacryloyl group, chlorosilyl group, alkoxy group. Examples of the crosslinking agent include one or more groups selected from a silyl group or a hydrosilyl group.

  Specifically, the group of hexamethylene diisocyanate, 1,4-butanediol diglycidyl ether, paraformaldehyde, dimethyldichlorosilane, dimethyldimethoxysilane methylolated melamine and its derivatives sulfur, benzoyl peroxide or azobisisobutyronitrile At least one crosslinking agent selected from is used.

[Invention 13]
The substrate surface treatment method according to invention 12, wherein the film is polymerized or crosslinked to form a cured film by heating.

  In the substrate surface treatment method of the present invention, perpivalic acid-tert-butyl is suitably used as the polymerization initiator for the polymerization.

[Invention 14]
The surface treatment method according to invention 12, wherein the film is polymerized or crosslinked to form a cured film by light irradiation.

  In the substrate surface treatment method of the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as the initiator for the photopolymerization.

  Moreover, in the surface treatment method of the base material of the present invention, not only the polymerizable compound, the initiator and the crosslinking agent, but also a solvent may be used, and 2-butanone or cyclohexanone is preferably used as the solvent.

[Invention 15]
A method for producing an antibacterial member, wherein the surface treatment is performed by the surface treatment method according to any one of Inventions 9 to 14.

An antibacterial agent having an organic group containing a bismethide acid group or a bismethide acid salt of the present invention, that is, a resin having an organic group represented by the general formula (1) as an active ingredient Even if the content of the organic group containing is low, the antibacterial activity is exhibited, and the content of the organic group (CF ₃ SO ₂ ) ₂ C— containing the bismethide acid group or bismethide acid salt in the resin is On the other hand, the antibacterial effect was seen at least 0.1% by mass or more, and the effect of high antibacterial activity was seen at 1% by mass or more.

  Further, the antibacterial agent containing a resin in which an organic group containing a bismethide acid group or a bismethide acid salt is bonded as an active ingredient to the polymer chain of the present invention is an antibacterial agent simply kneaded and kneaded into a resin. In comparison, by binding an organic group containing a bismethide acid group or bismethide acid salt, which is an active ingredient, to the polymer chain, volatilization and elution of the active ingredient is suppressed, and antibacterial properties are maintained for a long period of time.

  That is, the antibacterial agent of the present invention and the surface treatment method using the antibacterial agent can be present only in necessary places such as the surface of the material, and are excellent in antibacterial, antifungal and antiviral properties. An antibacterial agent that continuously exerts the antimicrobial properties and an antibacterial member using the same are provided.

  In addition, the antibacterial agent containing the resin having an organic group containing a bismethide acid group or bismethide acid salt as an active ingredient of the present invention exhibits antibacterial properties at a low concentration of the organic group containing a bismethide acid group or bismethide acid salt. It was.

  In addition, the antibacterial agent containing a resin having an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient as compared with a case where the antibacterial agent is simply kneaded into the resin, particularly a bismethide acid group or bismethide in a specific polymer chain. The antibacterial agent of the present invention containing a resin bonded with an organic group containing an acid salt as an active ingredient is effective by binding an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient to the polymer chain. Volatilization and elution of components are suppressed, and antibacterial properties last for a long time. In the antibacterial agent of the present invention, it is easy to make the distribution of organic groups containing bismethide acid groups or bismethido acid salts in the specific resin easy, and organic groups containing bismethide acid groups or bismethide acid salts are offset. There is no safety.

  The antibacterial agent containing, as an active ingredient, a resin having an organic group containing a bismethide acid group or a bismethide acid salt according to the present invention can be applied in various forms. For example, the antibacterial member can be efficiently imparted with antibacterial properties by coating the surface of the object by a surface treatment method such as coating. This has the effect of reducing the amount of antibacterial agent used.

  Furthermore, the antibacterial agent containing the resin having an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient of the present invention showed antibacterial activity against a wide range of bacteria. In addition to antibacterial properties, it also showed an effective inhibitory effect against mold and viruses.

  According to the present invention, in addition to excellent antibacterial properties, it has both antifungal properties and antiviral properties, has its sustainability, and can be efficiently manufactured in large quantities. An antibacterial material that can be applied and used in a wide range of fields such as industrial fields, a surface treatment method for a substrate using the same, and an antibacterial member thereof have been provided.

1. Antibacterial Agent First, the antibacterial agent of the present invention will be described.

[Invention 1]
General formula (1):

(In the formula (1), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent which contains resin containing the organic group represented by this as an active ingredient.

When A is a hydrogen atom, the carbon of the bismethide acid group is easily dissociated as an H ⁺ ion due to the strong electron withdrawing property of perfluoromethide, and the C—H bond has both a covalent bond and an ionic bond. As described above, bismethide acid is easily converted into a bismethide salt by a cation, and the organic group that acts as an antibacterial active ingredient contained in the antibacterial agent of the present invention is an organic group containing a bismethide acid group or a bismethide salt. Either of the groups may be used.

  A represents either a hydrogen atom or a cation. When the cation is a monovalent cation, A represents one-to-one by an ionic bond with the anion of the organic group (bismethide acid group) represented by the general formula (1). The bismethide salt may be formed. The polyvalent cation may form a salt with an anion corresponding to the valence.

Further, the cation bonded to C may be either a monovalent cation or a polyvalent cation. Examples of the monovalent cation include hydrogen ion (H ⁺ ), lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), silver ion (Ag ⁺ ), and copper (II) ion. (Cu ⁺ ), mercury (II) ion (Hg ⁺ ), ammonium ion (NH ⁴⁺ ), alkyl ammonium ion, anilinium ion, phenyl ammonium ion, pyridinium ion, pyrimidinium ion, pyrazolium ion, imidazolium ion , Benzimidazolium ion, triazinium ion, hexahydrotriazinium ion, triazolium ion, isoxazolium ion, thiazolium ion, isothiazolium ion, pyrolium ion, benzothiazolium ion, thiazoline-2-ion Ions, isothiazolin-3-one ion, benzisothiazolin-3-one ion, benzothiazolin-2-one ion or tetrahydrothienyl Asia-2-thione ions, and the like.

Further, as alkylammonium ions, monoalkylammonium ions (NR
H ₃ ⁺ ), dialkyl ammonium ion (NR ₂ H ₂ ⁺ ), trialkyl ammonium ion (NR ₃ H ⁺ ), tetraalkyl ammonium ion (NR ₄ ⁺ ), and the like. Furthermore, as a trialkylammonium ion, trimethylammonium ion (N (CH ₃ ) ₃ H ⁺ ), triethylammonium ion (N (C ₂ H ₅ ) ₃ H ⁺ ) or tributylammonium ion (N (C ₄ H ₉ ) ₃ H ^+), and the like.

Further, tetramethylammonium ions (N (CH ₃ ) ₄ ⁺ ), tetraethylammonium ions (N (C ₂ H ₅ ) ₄ ⁺ ), or tetrabutylammonium ions (N (C ₄ H ₉ ) _{4 are used as} tetraalkylammonium ions. ⁺ ) And the like.

Further, as the divalent cation, magnesium ion (Mg ²⁺ ), calcium ion (Ca ²⁺ ), strontium ion (Sr ²⁺ ), barium ion (Ba ²⁺ ), cadmium ion (Cd ²⁺ ), nickel (II) ion (Ni ²⁺ ), zinc ion (Zn ²⁺ ), copper (II) ion (Cu ²⁺ ), mercury (II) ion (Hg ²⁺ ), iron (II) ion (Fe ²⁺ ), cobalt (II) ion (Co ²⁺ ) ), Tin (II) ion (Sn ²⁺ ), lead (II) ion (Pb ²⁺ ) or manganese (II) ion (Mn ²⁺ ).

Furthermore, examples of the trivalent cation include aluminum ion (Al ³⁺ ), iron (III) ion (Fe ³⁺ ), and chromium (III) ion (Cr ³⁺ ).

Further, examples of the tetravalent cation include tin (IV) ion (Sn ⁴⁺ ).

A may be a complex ion, such as diammine silver ion ([Ag (NH ₃ ) ₂ ] ⁺ ), violeo ([CoCl ₂ (NH ₃ ) ₄ ] ⁺ ), tetraammine zinc (II) ion ([[ Zn (NH ₃ ) ₄ ] ²⁺ ), tetraammine copper (II) ion ([Cu (NH ₃ ) ₄ ] ²⁺ ), tetraaqua copper (II) ion ([Cu (H ₂ O) ₄ ] ²⁺ ), thiocyanoiron (III)
Ion ([Fe (SCN)] ²⁺ ), hexaammine nickel (II) ion ([Ni (NH ₃ ) ₆ ] ²⁺ ), purpleo ([CoCl (NH ₃ ) ₅ ] ²⁺ ), hexaammine cobalt (III) ion ([Co (NH ₃ ) ₆ ] ³⁺ ), hexaaquacobalt (III) ion ([Co (H ₂ O) ₆ ] ³⁺ ) or hexaammine chromium (III) ion ([Cr (NH ₃ ) ₆ ] ³⁺ ) , Roseo ([Co (NH ₃ ) ₄ (H ₂ O) ₂ ] ³⁺ ) and the like.

  Moreover, the antibacterial agent of this invention is an antibacterial agent shown to invention 2-9.

Compared to the case where the antibacterial agent is simply kneaded and kneaded into the resin, it contains a resin in which a specific polymer chain shown in inventions 2 to 9 is bonded with an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient. Since the antibacterial agent contains bismethide acid (CF ₃ SO ₂ ) ₂ C—, which is an active ingredient, in the polymer chain, volatilization and elution of the active ingredient are suppressed, and the antibacterial property lasts for a long period of time.

Further, the resin having an organic group represented by the general formula (1) exhibits antibacterial activity even when the content of the organic group containing a bismethide acid group or a bismethide acid salt is low, and the general formula in the resin The content of the organic group (CF ₃ SO ₂ ) ₂ C— containing the bismethide acid group or bismethido acid salt, which is the organic group described in (1), is at least 0.1 mol (mol)% or more with respect to the antimicrobial agent The antibacterial effect was observed, and at 1 mol% or more, an effect with high antibacterial activity was observed. Even if it adds more than 80 mol%, the effect does not change, and on the contrary, the acidity becomes too strong and is difficult to handle. Therefore, the content is preferably 0.1 mol% or more and 80 mol% or less. As described above, the antibacterial agent is preferably prepared so that the content of the organic group (CF ₃ SO ₂ ) ₂ C— containing a bismethide acid group or a bismethide acid salt is 0.1 mol% or more and 80 mol% or less. .

  The repeating unit having an organic group represented by the general formula (1) (an organic group containing a bismethide acid group or a bismethide acid salt) includes a repeating unit represented by the general formula (2) of the resin of the invention 2 (a ). When the repeating unit represented by the general formula (2) is exemplified, the repeating unit (a-1) represented by the general formula (3) having an ester bond of the invention 3 and a styrene chain in the main chain of the invention 4 Examples include the repeating unit (a-2) represented by the formula (4) and the repeating unit (a-3) represented by the general formula (5) having a norbornene ring in the main chain of the invention 5.

[Invention 2]
The resin is represented by the general formula (2):

(In Formula (2), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a carbon number. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond, having 1 to 12 carbon atoms. A divalent hydrocarbon group containing a linear, branched or cyclic divalent hydrocarbon group, or a combination thereof, and may have an ether bond, an ester bond, an amide bond or a urethane bond, Some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ And R ⁶ combine to form a ring And may include a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation .)
The antibacterial agent of the invention 1 which is resin which has the repeating unit (a) represented by these.

In the above general formula (1) and general formula (2), as R ¹ or R ² , CF ₃ , C ₂ F ₅ , linear or branched C ₃ F ₇ , C ₄ F ₉ are In the antibacterial agent of the present invention, CF ₃ is preferably used because of its ease of synthesis.

[Invention 3]
The repeating unit (a) is represented by the following general formula (3):

(In the formula (3), R ⁷ is a hydrogen atom, an alkyl group, a halogen atom or a trifluoromethyl group. R ⁸ is a single bond, a linear, branched or cyclic divalent group having 1 to 12 carbon atoms. Or a combination thereof, which may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of the carbon atoms contained in R ⁸ is silicon. And a part or all of hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent of the invention 2 which is the repeating unit (a-1) represented by these.

[Invention 4]
The repeating unit (a) is represented by the general formula (4):

(In Formula (4), R ⁹ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond, or a urethane bond, a part of carbon atoms contained in R ⁹ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of the invention 2 which is the repeating unit (a-2) represented by these.

[Invention 5]
The repeating unit (a) is represented by the general formula (5):

(In the formula (5), R ¹⁰ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁰ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of the invention 2 which is the repeating unit (a-3) represented by these.

  Further, in the antibacterial agent of the present invention, in addition to the repeating unit (a), the content of the organic group containing the bismethide acid group or bismethide acid salt which is an active ingredient of the antibacterial agent is adjusted, or the solvent solubility of the resin, coating The repeating unit (b-1) described in Invention 6 or the repeating unit (b-2) described in Invention 7 may be used in order to adjust the property and mechanical properties, or to introduce a crosslinkable functional group. . The repeating unit (b-1) is a repeating unit containing no crosslinking group, and the repeating unit (b-2) is a repeating unit containing a crosslinking group.

2. Repeating unit (a)
Next, the repeating unit (a) having a bismethide acid group, which is a constituent of the antibacterial agent of the present invention, will be described.

  Examples of the repeating unit having a bismethide acid group represented by the general formula (1) include the repeating unit (a) represented by the general formula (2) possessed by the resin of the invention 2. When the repeating unit (a) described in the general formula (2) is exemplified, the repeating unit (a-1) represented by the general formula (3) having an ester bond of the invention 3 and styrene in the main chain described in the invention 4 Examples include the repeating unit (a-2) represented by the general formula (4) having a chain, and the repeating unit (a-3) represented by the general formula (5) having a norbornene ring in the main chain described in the invention 5. . In addition, there are a resin containing a vinyl-based repeating unit (a) and a repeating unit (a) having an amide bond.

  Thus, the resin having a bismethide acid group contained in the antibacterial agent of the invention 2 includes the repeating unit (a-1) represented by the general formula (3) having an ester bond of the invention 3 and the main chain of the invention 4 There is a resin containing a repeating unit (a-2) represented by formula (4) having a styrene chain and a repeating unit (a-3) having a norbornene ring in the main chain of invention 5. Other examples include resins containing a vinyl-based repeating unit (a) and resins containing a repeating unit (a) having an amide bond.

Examples of the repeating unit (a-1) represented by the general formula (3) having an ester bond of the invention 3 include 1 to 3 of the following ester-based repeating units (a-1).

The repeating unit (a-2) represented by the general formula (4) having a styrene bond of the invention 4 includes the following styrene-based repeating unit (a-2).

  The repeating unit (a-3) represented by the general formula (5) of the invention 5 includes a repeating unit (a-3) having a norbornene chain in the main chain.

Repeating units having a norbornene chain in the main chain (a-3)

The repeating unit (a) represented by the general formula (2) of the invention 2 includes a repeating unit having a trismethide acid group, such as the following amide-based repeating units (a) 1 and 2 of the vinyl-based repeating unit (a). (A) etc. are mentioned.

3. Repeating units (b-1) and (b-2)
Next, the repeating units (b-1) and (b-2) that the resin used in the antibacterial agent of the present invention may have will be described.

  In the antibacterial agent of the present invention, in addition to the repeating unit (a), the content of the organic group described in the general formula (1), which is an active ingredient of the antibacterial agent, is adjusted, or the solvent solubility of the resin, applicability, machine The repeating unit (b-1) of the invention 6 or the repeating unit (b-2) of the invention 7 may be used for adjusting the mechanical properties or introducing a crosslinkable functional group. The repeating unit (b-1) is a repeating unit containing no crosslinking group, and the repeating unit (b-2) is a repeating unit containing a crosslinking group.

  The resin contained in the antibacterial agent of the present invention may be a polymer containing only the repeating unit (a), or the repeating unit (a) and the repeating unit (b-1) or the repeating unit (b-2). It may be a polymer containing.

  When a polyfunctional polymerizable compound such as a polyfunctional acrylate is used for the repeating unit (b-1), a resin having high mechanical strength can be obtained, which is preferably employed.

  Moreover, the resin containing a crosslinking site such as a hydroxyl group in the repeating unit (b-1) or the repeating unit (b-2) can be made into a resin having a crosslinked structure by reaction with a curing agent such as an isocyanate compound. Therefore, it becomes possible to obtain a resin having high mechanical strength, which is preferably employed.

The repeating unit (b-1) that the resin containing the antibacterial agent of the present invention may have is represented by the general formula (6).

In the formula, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R <^12> , R < ¹³ > represents a hydrogen atom, a C1-C4 alkyl group, or a halogen atom each independently. R ¹⁴ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, or a monovalent hydrocarbon group that is a combination thereof, an ether bond, an ester bond May have an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁴ may be substituted with silicon, and a part or all of hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. May be.

R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may combine to form a ring, and may contain a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms.

The repeating unit (b-2) that the resin containing the antibacterial agent of the present invention may have is represented by the general formula (7).

In the formula, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹¹ and R ¹² or R ¹³ may combine to form a ring, A monocyclic, bicyclic or polycyclic structure of 3 to 12 may be included. R ¹⁵ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, or a monovalent hydrocarbon group that is a combination thereof, an ether bond, an ester bond May have an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁵ may be substituted with silicon, and a part or all of hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. May be. R ¹⁵ is at least one capable of reacting with a crosslinking agent selected from a hydroxyl group, mercapto group, carboxyl group, amino group, epoxy group, alkenyl group, alkynyl group, acryloyl group, methacryloyl group, chlorosilyl group, alkoxysilyl group or hydrosilyl group. It is characterized by two groups.

  As repeating unit (b-2), maleic anhydride, acrylic ester, fluorine-containing acrylic ester, methacrylic ester, fluorine-containing methacrylate ester, styrene compound, fluorine-containing styrene compound, vinyl ether, fluorine-containing vinyl ether, allyl At least one compound selected from ethers, fluorine-containing allyl ethers, olefins, fluorine-containing olefins, norbornene compounds, and fluorine-containing norbornene compounds is employed.

  The acrylic ester or methacrylic ester as the repeating unit (b-2) is copolymerized with the repeating unit (a), the repeating unit (a-1), the repeating unit (a-2) or the repeating unit (a-3). If possible, the ester side chain can be used without particular limitation.

  Examples of known compounds for acrylic acid esters or methacrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, - hydroxypropyl acrylate, alkyl esters of acrylic acid or methacrylic acid such as 2-hydroxypropyl methacrylate, ethylene glycol, propylene glycol, or include acrylates or methacrylates containing tetramethylene glycol group. Furthermore, acrylamide which is unsaturated amide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, or diacetone acrylamide is mentioned. In addition, acrylonitrile, methacrylonitrile, alkoxysilane-containing vinyl silane, acrylic acid or methacrylic acid ester, tert-butyl acrylate, tert-butyl methacrylate, 3-oxocyclohexyl acrylate, 3-oxocyclohexyl methacrylate, adamantyl acrylate, adamantyl methacrylate, alkyl Examples include adamantyl acrylate, alkyl adamantyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, acrylate or methacrylate having a ring structure selected from a lactone ring or a norbornene ring, acrylic acid, or methacrylic acid. It is done. In addition, the above acrylate compounds containing a cyano group at the α-position, and similar compounds include maleic acid, fumaric acid or maleic anhydride.

  As the repeating unit (b-2), a fluorine-containing acrylic ester or a fluorine-containing methacrylate ester includes a fluorine atom or a monomer containing a fluorine atom group at the α-position of acrylic, or a fluorine atom at the ester site. An acrylic ester or methacrylic ester containing a substituent containing an atom, which includes a fluorine-containing compound containing fluorine at both the α-position and the ester moiety, and a cyano group may be introduced at the α-position. Furthermore, as a polymerizable compound having a fluorine-containing alkyl group introduced at the α-position, a trifluoromethyl group, a trifluoroethyl group, or nonafluoro-n at the α-position of the non-fluorinated acrylic acid ester or methacrylic acid ester described above. A polymerizable compound into which a fluorine-containing group selected from butyl groups is introduced is employed.

  On the other hand, the polymerizable compound containing fluorine at the ester site includes a perfluoroalkyl group at the ester site, a fluoroalkyl group that is a fluoroalkyl group, and a polymerizable compound that has a cyclic structure and a fluorine atom at the ester site. And the cyclic structure includes a fluorine-containing benzene ring, a fluorine-containing cyclopentane ring, a fluorine-containing cyclohexane ring, or a fluorine-containing cycloheptane ring substituted with a fluorine atom, a trifluoromethyl group, or a hexafluorocarbinol group. Acrylic acid ester or methacrylic acid ester having a unit to be included. Further, an ester of acrylic acid or methacrylic acid whose ester moiety is a fluorine-containing t-butyl ester group can also be used.

  As these fluorine-containing functional groups, it is also possible to use a polymerizable compound used in combination with the α-position fluorine-containing alkyl group. Such polymerizable compounds include 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, Heptafluoroisopropyl acrylate, 1,1-dihydroheptafluoro-n-butyl acrylate, 1,1,5-trihydrooctafluoro-n-pentyl acrylate, 1,1,2,2-tetrahydrotridecafluoro-n-octyl Acrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,1,1, 3,3,3-hexafluoroisopropyl methacrylate, hep Fluoroisopropyl methacrylate, 1,1-dihydroheptafluoro-n-butyl methacrylate, 1,1,5-trihydrooctafluoro-n-pentyl methacrylate, 1,1,2,2-tetrahydrotridecafluoro-n-octyl methacrylate 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- ( Trifluoromethyl) propyl] bicyclo [2.2.1] heptyl-2-yl acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2. 2.1] Heptyl-2-yl -(Trifluoromethyl) acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptyl-2-yl methacrylate, 4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl acrylate, 1,4-bis (1,1,1,3,3,3-hexafluoro-2- Hydroxyisopropyl) cyclohexyl methacrylate or 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl 2-trifluoromethyl acrylate. The fluorine-containing polymerizable compound is effective for improving the solvent solubility and surface characteristics and water repellency of the resin obtained, and contains the repeating unit (b-1) of the resin which is an active ingredient of the antibacterial agent of the present invention. It is preferably employed as the polymerizable compound to be given.

  As the repeating unit (b-1), the styrene compound and the fluorine-containing styrene compound have one functional group that protects the hexafluorocarbinol group or its hydroxyl group in addition to styrene, fluorinated styrene, or hydroxystyrene. Or the compound which couple | bonded two or more is mentioned. That is, styrene or hydroxystyrene substituted with hydrogen by a fluorine atom or a trifluoromethyl group, the above styrene having a halogen, an alkyl group or a fluorine-containing alkyl group bonded to the α-position, or a styrene containing a perfluorovinyl group. The fluorine-containing styrene-based compound is a resin that is effective in improving solvent solubility, improving the surface characteristics and water repellency of the resulting resin, and is an effective component of the antibacterial agent of the present invention, like the fluorine-containing acrylic ester. Is preferably employed as the polymerizable compound that gives the repeating unit (b-1).

  In addition, as the repeating unit (b-1), vinyl ether, fluorine-containing vinyl ether, allyl ether, fluorine-containing allyl ether is a hydroxyl group selected from a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, and a hydroxybutyl group. Alkyl vinyl ethers or alkyl allyl ethers containing groups are raised. In addition, cyclohexyl group, norbornel group, aromatic ring and cyclic vinyl having hydrogen or carbonyl bond in its cyclic structure, allyl ether, fluorine-containing vinyl ether in which part or all of hydrogen of the above functional group is substituted with fluorine atom Or fluorine-containing allyl ether.

  In addition, as the repeating unit (b-1), any vinyl ester, vinyl silane, olefin, fluorine-containing olefin, norbornene compound, fluorine-containing norbornene compound, or other compound containing a polymerizable unsaturated bond can be used without particular limitation. It is.

  The hydrocarbon olefins as the repeating unit (b-1) are ethylene, propylene, isobutene, cyclopentene, cyclohexene, and fluorinated hydrocarbon olefins are vinyl fluoride, vinylidene fluoride, trifluoroethylene, and chloroethylene. Examples include trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, or hexafluoroisobutene.

  The norbornene compound as the repeating unit (b-1) is norbornene, 1-methylnorbornene, 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 7-methylnorbornene, 5,5,6- Trimethylnorbornene, tricyclo [4.3.0.12.5] -3-decene, tricyclo [4.4.0.12.5] -3-undecene, tetracyclo [4.4.0.12.5. 17.10] -3-dodecene, 8-methyltetracyclo [4.4.0.12.5. 17.10] -3-dodecene, or 8-ethyltetracyclo [4.4.0.12.5. 17.10] -3-dodecene. The above polymerizable compounds may be used alone or in combination of two or more.

  As the repeating unit (b-2), it is particularly preferable to use the following polymerizable compound.

2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, ethyl 2- (hydroxymethyl) acrylate 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate, methacrylic acid 3- (triethoxysilyl) propyl, allyltriethoxysilane, allyltrimethoxysilane, 3- (acryloxy) propyltrimethoxysilane, [bicyclo [2.2.1] hept-5-en-2-yl] to Ethoxysilane, vinyltrimethoxysilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, N- [2- (N-vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride, allyltrichlorosilane, Trichlorovinylsilane, 3-methyl-1-penten-4-in-3-ol, 2- (furfurylthio) ethylamine, trans-aconitic acid, acrylic acid, 4-aminocinnamic acid, angelic acid, 2-acetamidoacrylic acid, 3-butene-1,2,3-tricarboxylic acid, 2-bromocinnamic acid, 4-bromocrotonic acid, 2-benzylacrylic acid, caffeic acid, 4-chlorocinnamic acid, trans-cinnamic acid, citracone Acid, trans-p-coumaric acid, trans-o-coumaric acid, t ans-m-coumaric acid, crotonic acid, α-cyanocinnamic acid, 1-cyclohexene-1-carboxylic acid, 1-cyclopentenecarboxylic acid, α-cyano-4-hydroxycinnamic acid, traumatic acid, trans-2 -Decenoic acid, 3,4-dimethoxycinnamic acid, trans-2,3-dimethoxycinnamic acid, trans-2,5-dichlorocinnamic acid, fumaric acid, monoethyl fumarate, trans-2-hexenoic acid, 2 -Heptenoic acid, monomethyl itaconic acid, monoamide maleic acid, mesaconic acid, methacrylic acid, 4-methyl-2-pentenoic acid, trans, trans-muconic acid, mucobromic acid, mucochloroic acid, 3-methylcrotonic acid, 4-methoxysilicic acid Cinnamic acid, succinic acid mono (2-acryloyloxyethyl), 3- (5-nitro-2-furyl) acrylic , 3- (3-pyridyl) acrylic acid, α-phenylcinnamic acid, shikimic acid, tiglic acid, 2-thiophene acrylic acid, 2- (trifluoromethyl) acrylic acid, 3- (trifluoromethyl) cinnamic acid 4- (trifluoromethyl) cinnamic acid, 2- (trifluoromethyl) cinnamic acid, allyl mercaptan, allyl glycidyl ether, 1,3-butadiene monoepoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, allobarbital, 1,9-decadiene, 1,11-dodecadiene, dicyclopentadiene, 2,5-dimethyl-1,5-hexadiene, diisopropylideneacetone, 2,3 -Dimethyl-1,3-butadiene, diethyl diallylmalonate, 1,3-dibenzylidene-2-cyclohexanone, 2,6-dimethyl 2, -4,6-octatriene, 1,5,9-decatriene, 9,10-epoxy-1,5-cyclododecadiene, farnesyl acetate, geranyl-linalool, geranyl nitrile, 1,5-hexadiene, 1,4-hexadiene, 1,5-hexadiene-3,4-diol, isoprene, (±) -limonene, myrcene, methylcyclopentadiene, 2,5-norbornadiene, 1,7-octadiene, monoethyl fumarate, maleic acid Ethyl hydrogen, monooctyl maleate, monomethyl maleate, monoisopropyl fumarate, mono (2-acryloyloxyethyl) succinate, 6-acrylamidohexanoic acid, acrylamide, allylamine, 1-allyl-2-thiourea, 1-allyl -3- (2-hydroxyethyl) -2-thiourine Allyl urea, methyl 3-aminocrotonate, 3-amino-5,5-dimethyl-2-cyclohexen-1-one, S-allyl-L-cysteine, 3-amino-4,4,4-trifluorocroton Contains ethyl acid, 3-amino-2-cyclohexen-1-one, 3-benzalbutyramide, crotonamide, cinnamic acid amide, 2- (1-cyclohexenyl) ethylamine, glycidyl methacrylate or polyethylene glycol diacrylate The following polyfunctional polymerizable compounds are exemplified.

  In particular, polyethylene glycol diacrylate, styrene, 2,3,4,5,6-pentafluorostyrene, 2-hydroxyethyl methacrylate, acrylonitrile, 2-norbornene and the like are preferably used.

4). Next, the crosslinking agent will be described.

  In the present invention, in order to enhance the durability of the antibacterial agent, hydroxyl group, mercapto group, carboxyl group, amino group, epoxy group, alkenyl group, alkynyl group, acryloyl group, methacryloyl group, chlorosilyl group, alkoxysilyl group or hydrosilyl group You may use the crosslinking agent which can react with a functional group.

  Examples of such a crosslinking agent include isocyanate compounds, epoxy compounds, aldehyde compounds, chlorosilanes, alkoxysilanes, melamine compounds, sulfur and sulfur compounds. Among these compounds, when a polyfunctional compound synthesizes a resin that is an active ingredient of the antibacterial agent of the present invention, it is possible to increase the crosslink density of the resin, and a resin having excellent mechanical strength can be obtained. Are preferably employed.

  Further, in the synthesis of a resin that is an active ingredient of the antibacterial agent of the present invention, a method of synthesizing a resin that is crosslinked by radical reaction using a peroxide or an azo compound as a crosslinking agent can also be adopted. Since durability is obtained, it is particularly preferably employed in the antibacterial agent of the present invention.

  The resin which is an active ingredient of the antibacterial agent of the present invention is used as a crosslinking agent in the synthesis, and as an isocyanate compound that reacts with a hydroxyl group or an amino group to form a crosslinked structure in the resin, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dichlorobiphenyl-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, And diisocyanate compounds such as tolylene-2,6-diisocyanate, trimethylhexamethylene diisocyanate, naphthalene diisocyanate, or isophorone diisocyanate. Moreover, the adduct body of polyols, such as a uretidine dione type dimerization product, biuret type trimerization product, isocyanurate type trimerization product of the diisocyanate compound, 1,3-propanediol, and trimethylolpropane, and the like. Moreover, triisocyanate, such as triphenylmethane isocyanate or tris (isocyanatophanyl) thiophosphate, etc. are mentioned.

  In the synthesis of the resin which is an active ingredient of the antibacterial agent of the present invention, hexamethylene diisocyanate is particularly preferably employed because it is stable as a compound and flexibility is obtained in the resulting resin.

  As an epoxy compound that uses a resin as an active ingredient of the antibacterial agent of the present invention as a crosslinking agent in synthesis and forms a crosslinked structure by reacting with a carboxyl group or the like, a glycidyl ether compound, a glycidyl ester compound, or a glycidyl amine compound is used. A compound, an alicyclic compound, and the like. For example, 1,4-butanediol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, diglycidyl 1,2-cyclohexanedicarboxylate, 1,7-octadiene diepoxide, 1,5-hexadienedi Examples thereof include epoxide, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,3-butadiene monoepoxide, 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene. In the synthesis of a resin that is an active ingredient of the antibacterial agent of the present invention, 1,4-butanediol diglycidyl ether having moderate reactivity is particularly preferably employed.

  Resin, which is an active ingredient of the antibacterial agent of the present invention, is used as a crosslinking agent in synthesis, and aldehyde compounds that react with phenolic hydroxyl groups to form a crosslinked structure include formaldehyde, formalin aqueous solution, paraformaldehyde, trioxane, acetaldehyde. , Polyoxymethylene or propionaldehyde. In the synthesis of a resin that is an active ingredient of the antibacterial agent of the present invention, paraformaldehyde is particularly preferably employed because it has moderate reactivity and is easy to handle.

  Resin, which is an active ingredient of the antibacterial agent of the present invention, is used as a crosslinking agent in synthesis, and chlorosilanes useful for the crosslinking reaction that forms a siloxane bond include dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, and divinyldichlorosilane. , Methyldichlorosilane, ethyldichlorosilane, phenyldichlorosilane, vinyldichlorosilane, dichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, trichlorosilane, tetrachlorosilane, 1,2-bis (trichlorosilyl) ) Ethane, bis (trichlorosilyl) acetylene, 3-chloropropyltrichlorosilane, cyclohexyltrichlorosilane, trichloro (1H, 1H, 2H, 2H-tridecafluor -n- octyl) silane, trichloro-2-cyano-ethyl silane or phenyl trichlorosilane, and the like. In the synthesis of the resin which is an active ingredient of the antibacterial agent of the present invention, dimethyldichlorosilane is particularly preferably employed because it is highly reactive, inexpensive and easily available.

  Examples of the alkoxysilanes useful for the crosslinking reaction for forming a siloxane bond used as a crosslinking agent in the synthesis of the resin which is an active ingredient of the antibacterial agent of the present invention include dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, divinyl Dimethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, phenyldimethoxysilane, vinyldimethoxysilane, dimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, trimethoxysilane, tetramethoxysilane, Dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, divinyldiethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, Nyldiethoxysilane, vinyldiethoxysilane, diethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, triethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, bis [3- (trimethoxysilyl) propyl] amine, 1,2-bis (trimethoxysilyl) ) Ethane, benzyltriethoxysilane, (3-bromopropyl) trimethoxysilane, 3-trimethoxysilylpropyl chloride, 2-cyanoethyltriethoxysilane, (chloromethyl) triethoxysilane, cyclohexyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, 1,1, Examples include 1-trifluoro-3- (trimethoxysilyl) propane, triethoxyphenylsilane, trimethoxyphenylsilane, trimethoxy (4-methoxyphenyl) silane, or trimethoxy (p-tolyl) silane. In the synthesis of the resin which is an active ingredient of the antibacterial agent of the present invention, dimethyldimethoxysilane is particularly preferably employed because it is highly reactive, inexpensive and easily available.

  Examples of the melamine compound used as a crosslinking agent in the synthesis of the resin that is an active ingredient of the antibacterial agent of the present invention and reacting with a hydroxyl group to form a crosslinked structure include melamine, methylolated melamine, and methylolated melamine derivatives. It is done. In addition, a compound obtained by reacting methylolated melamine with a lower alcohol and partially or completely etherified can be used. Further, it may be either a melamine compound monomer or a dimer or higher multimer, or a mixture thereof.

  In the synthesis of a resin which is an active ingredient of the antibacterial agent of the present invention, methylolated melamine and its derivatives are particularly preferably employed because of good reactivity and easy handling.

  Sulfur and sulfur compounds used as a crosslinking agent in the synthesis of the antibacterial agent of the present invention, which reacts with an alkenyl group, alkynyl group, acryloyl group or methacryloyl group to form a crosslinked structure, include sulfur. Tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentamethylenethiuram tetrasulfide, morpholine disulfide, or 2- (4'-morpholinodithio) benzothiazole Can be mentioned.

  In the synthesis of a resin which is an active ingredient of the antibacterial agent of the present invention, sulfur is particularly preferably employed because it is inexpensive and easy to handle.

  Peroxides useful for crosslinking by radical reaction to alkyl groups and the like used as crosslinking agents in the synthesis of resins that are active ingredients of the antibacterial agent of the present invention include benzoyl peroxide, dichlorobenzoyl peroxide, Milperoxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-trimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylper Benzoate, tert-butyl perphenyl acetate, ert- butyl perisobutyrate, tert- butyl per -sec- octoate, tert- butyl hydroperoxide peak Pareto or cumyl pin Pareto, include tert- butylperoxy diethyl acetate.

  In synthesizing a resin which is an active ingredient of the antibacterial agent of the present invention, benzoyl peroxide is particularly preferably employed because the resulting resin is excellent in mechanical properties with good reactivity.

  As an azo compound useful for crosslinking by radical reaction to an alkyl group or the like used as a crosslinking agent in the synthesis of a resin which is an active ingredient of the antibacterial agent of the present invention, azobisisobutyronitrile or dimethylazoisobutyryl Rate.

  In the synthesis of the resin which is an active ingredient of the antibacterial agent of the present invention, azobisisobutyronitrile is particularly preferably employed because it is inexpensive and easy to handle.

  These crosslinking agents can be used alone or in combination, and the curing rate, pot life, and physical properties of the resulting resin can be appropriately adjusted depending on the type and amount of the crosslinking agent.

5). Polymerization method Next, the repeating unit (a), the repeating unit (a-1), the repeating unit (a-2), or the repeating unit (a-3) is given to the resin that is the active ingredient of the antibacterial agent of the present invention. A polymerization method for obtaining a resin by homopolymerizing a polymerizable compound which is a precursor of these repeating units will be described. Moreover, the repeating unit (a), the repeating unit (a-1), the repeating unit (a-2), or the repeating unit (a-3) is given to the resin which is an active ingredient of the antibacterial agent of the present invention. The polymerization method which obtains resin by copolymerizing the polymerizable compound which is the precursor of the unit and the polymerizable compound which is the precursor of these repeating units giving the repeating unit (b-1) and the repeating unit (b-2) is explained. To do.

  Polymerization methods include radical polymerization and polymerization with transition metals.

  First, radical polymerization will be described.

  The polymerization method for obtaining the resin which is an active ingredient of the antibacterial agent of the present invention is not particularly limited as long as it is a generally used method, but radical polymerization and ionic polymerization are preferable, and coordination anion polymerization, living anion Polymerization, cationic polymerization, ring-opening metathesis polymerization, or vinylene polymerization can be employed.

  The radical polymerization is selected from batch, semi-continuous or continuous by a known polymerization method selected from bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization in the presence of a radical polymerization initiator or radical initiator. Perform by operation.

  The radical polymerization initiator is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds. To synthesize a resin that is an active ingredient of the antibacterial agent of the present invention, azobisisobutyronitrile is used. , T-butyl peroxypivalate, di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxide Oxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate is preferably used in the polymerization reaction for obtaining a resin that is an active ingredient of the antibacterial agent of the present invention.

  In the polymerization reaction for obtaining a resin which is an active ingredient of the antibacterial agent of the present invention, the reaction vessel used for the polymerization reaction is not particularly limited. In the polymerization reaction, a polymerization solvent may be used. As a polymerization solvent in the polymerization reaction for obtaining a resin that is an active ingredient of the antibacterial agent of the present invention, a solvent that does not inhibit radical polymerization is preferable, an ester system selected from ethyl acetate and n-butyl acetate, acetone, methyl isobutyl Alcohol solvents selected from ketones selected from ketones, hydrocarbons selected from toluene and cyclohexane, methanol, isopropyl alcohol, methyl isobutyl carbinol or ethylene glycol monomethyl ether can be used. It is also possible to use various solvents selected from water, ether series, cyclic ether series, chlorofluorocarbon series, and aromatic series. These solvents may be used alone or in combination of two or more. Moreover, you may use together molecular weight regulators, such as a mercaptan. In the polymerization reaction for obtaining a resin which is an active ingredient of the antibacterial agent of the present invention, the reaction temperature of the copolymerization reaction is appropriately selected depending on the radical polymerization initiator or radical polymerization initiator, and is usually 20 ° C. or higher and 200 ° C. or lower. Within the range, the range of 30 ° C. or higher and 140 ° C. or lower is particularly preferable.

  Next, polymerization with a transition metal will be described.

  In the ring-opening metathesis polymerization, a transition metal catalyst of group IV, V, VI, or VII may be used in the presence of a cocatalyst, and a known method may be used in the presence of a solvent. The transition metal catalyst is not particularly limited, and examples thereof include Ti-based, V-based, Mo-based, and W-based catalysts. In particular, in the polymerization reaction for obtaining a resin that is an active ingredient of the antibacterial agent of the present invention, Titanium (IV), vanadium chloride (IV), vanadium trisacetylacetonate, vanadium bisacetylacetonate dichloride, molybdenum (VI), or tungsten (VI) chloride is preferred. The catalyst amount is 0.001 mol% or more and 10 mol% or less, preferably 0.01 mol% or more and 1 mol% or less, based on the monomer used.

  Cocatalysts include alkylaluminum or alkyltin, especially trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum. , Tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, or trioctylaluminum Aluminums, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, or diisobutylal Dialkylaluminum halides selected from nium chloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, or isobutylaluminum dichloride, methyl Aluminum-based, tetra-n-butyltin, tetraphenyltin, or triphenylchlorotin represented by alkylaluminum sesquichlorides selected from aluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, or isobutylaluminum sesquichloride Mentioned That. The amount of the cocatalyst used is in a range of 100 equivalents or less, preferably 30 equivalents or less, in terms of molar ratio to the transition metal catalyst.

  The polymerization solvent should not inhibit the polymerization reaction, and representative examples include aromatic hydrocarbons selected from benzene, toluene, xylene, chlorobenzene, or dichlorobenzene, hydrocarbons selected from hexane, heptane, or cyclohexane. Mention may be made of halogenated hydrocarbons selected from the systems, carbon tetrachloride, chloroform, methylene chloride, or 1,2-dichloroethane. In the polymerization reaction for obtaining a resin which is an active ingredient of the antibacterial agent of the present invention, these polymerization solvents may be used alone or in combination of two or more. The reaction temperature is usually preferably from −70 ° C. to 200 ° C., particularly preferably from −30 ° C. to 60 ° C.

  Vinylene polymerization is carried out in the presence of a cocatalyst in the presence of a co-catalyst such as iron, nickel, rhodium, palladium, platinum, etc. May be used, and a known method may be used in the presence of a solvent. The polymerization catalyst is not particularly limited. In the polymerization reaction for obtaining a resin which is an active ingredient of the antibacterial agent of the present invention, in particular, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) ) Bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, bis (Allyl) nickel, bis (cyclopentadienyl) nickel, nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetate Ruacetonate tetrahydrate, rhodium (III) chloride, rhodium tris (triphenylphosphine) trichloride, palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), palladium (II) 2 -Ethylhexanoate, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitrile tris (triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis (acetonitrile) Palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (be A transition metal of group VIII selected from (zonitrile) palladium (II), palladium acetylacetonate, palladium bis (acetonitrile) dichloride, palladium bis (dimethyl sulfoxide) dichloride, or platinium bis (triethylphosphine) hydrobromide, Vanadium chloride (IV), vanadium trisacetylacetonate, vanadium bisacetylacetonate dichloride, trimethoxy (pentamethylcyclopentadienyl) titanium (IV), bis (cyclopentadienyl) titanium dichloride, or bis (cyclopentadienyl) ) It is preferable to use transition metals belonging to group IVB to VIB selected from zirconium dichloride. The catalyst amount is 0.001 mol% or more and 10 mol% or less, preferably 0.01 mol% or more and 1 mol% or less, based on the monomer used. Examples of the cocatalyst include alkylaluminoxane or alkylaluminum. In the polymerization reaction for obtaining a resin which is an active ingredient of the antibacterial agent of the present invention, in particular, methylaluminoxane (MAO), trimethylaluminum, triethylaluminum, trialuminum Propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-2-methylbutyl aluminum, tri-3-methylbutyl aluminum, tri-2-methylpentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum , Trialkylaluminums such as tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, dimethylaluminum chloride Dialkylaluminum halides selected from diethylaluminum chloride, diisopropylaluminum chloride, or diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, or isobutylaluminum dichloride And alkylaluminum sesquichlorides selected from methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, and isobutylaluminum sesquichloride. The amount of cocatalyst is 50 equivalents or more and 500 equivalents or less in terms of Al in the case of methylaluminoxane, and in the case of other alkylaluminums, it is in a range of 100 equivalents or less, preferably 30 equivalents or less, in molar ratio to the transition metal catalyst. . In addition, the polymerization solvent should not inhibit the polymerization reaction, and representative examples thereof include aromatic hydrocarbons selected from benzene, toluene, xylene, chlorobenzene, or dichlorobenzene, carbonization selected from hexane, heptane, or cyclohexane. And halogenated hydrocarbons selected from hydrogen, carbon tetrachloride, chloroform, methylene chloride, or 1,2-dichloroethane, dimethylformamide, N-methylpyrrolidone, or N-cyclohexylpyrrolidone. These polymerization solvents may be used alone or in combination of two or more. The reaction temperature is usually preferably from −70 ° C. to 200 ° C., particularly preferably from −40 ° C. to 80 ° C.

  As a method for removing the organic solvent or water as a medium from the solution or dispersion of the resin that is the active ingredient of the antibacterial agent of the present invention thus obtained, a known method can be used. For example, a method such as reprecipitation, filtration, or heating distillation under reduced pressure can be used.

6). Substrate Surface Treatment Method Next, the substrate surface treatment method will be described.

  The resin, which is an active ingredient of the antibacterial agent of the present invention, can be coated on a target base material to treat the surface of the equipment. It is possible to obtain a film by dissolving a resin obtained in advance by a polymerization reaction in a solvent, applying this to a substrate, and drying. Further, it is possible to improve the strength of the film by mixing a curing agent at the time of application, and it is preferably employed in the coating of a resin which is an active ingredient of the antibacterial agent of the present invention.

  It is also possible to cure the film by applying a polymerizable compound or a mixture of this with a curing agent to a base material, and applying heat, light or a catalyst. It can be applied without solvent and is very effective for improving the manufacturing environment.

  The solvent for dissolving the resin that is the active ingredient of the antibacterial agent of the present invention is not particularly limited as long as the resin is soluble, but ketones selected from acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, or 2-heptanone, From ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, dipropylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Selected from selected polyhydric alcohols, methanol, ethanol, isopropyl alcohol or methyl isobutyl carbinol Monohydric alcohols or derivatives thereof, cyclic ethers such as dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionic acid Esters selected from ethyl, aromatic solvents selected from xylene or toluene, fluorinated solvents selected from chlorofluorocarbons, alternative chlorofluorocarbons, perfluoro compounds, or hexafluoroisopropyl alcohol, high-boiling weak solvents for the purpose of improving coating properties A terpene-based petroleum naphtha solvent or a paraffin-based solvent can be used. These may be used alone or in combination of two or more.

  In the present invention, the antibacterial agent containing the resin having the bismethide acid group shown in the invention 1 as an active ingredient, and the resin having the bismethide acid group bonded to the specific polymer chain shown in the inventions 2 to 8 as the active ingredient An antibacterial agent is applied to the substrate surface to form a film.

  That is, the present invention is a surface treatment method for a substrate characterized in that the antibacterial agent of any one of Inventions 1 to 8 is applied to the substrate surface to form a film.

  In addition to the polymerizable compound that gives the repeating unit (a) of invention 2, the repeating unit (a-1) of invention 3, the repeating unit (a-2) of invention 4, or the repeating unit (a-3) of invention 5 The polymerizable compound which gives the repeating unit (b-1) of Invention 6 and the repeating unit (b-2) of Invention 7 may be added, or the crosslinking agent of Invention 8 may be added.

  A polyfunctional polymerizable compound having two or more polymerizable double bonds for synthesizing a resin as an active ingredient of the antibacterial agent of inventions 1 to 8 was prepared. Specifically, the polymerizable compound which gives the repeating unit (a) having a bismethide acid group shown in the inventions 2 to 5, the repeating unit (b-1) of the invention 6, and the repeating unit (b-2) of the invention 7 A polymerizable compound to be provided was prepared. After applying these compounds directly on a glass substrate without using a solvent by a bar coater, spray, spin coating or the like, or a solution containing these compounds on a glass substrate, a bar coater, spray, spin coating, etc. After coating, the film of the colorless and transparent antibacterial agent of the present invention (antibacterial film) was obtained by polymerization.

  Depending on the compound, it can be applied directly to the surface of the substrate without using a solvent. Unlike a solution using a solvent, a drying process is not required after polymerization, so a film can be obtained without using a solvent. Is preferred.

  In addition, when apply | coating with a solution, the solvent which can be used for superposition | polymerization is used suitably for a solvent. At this time, ester solvents such as ethyl acetate and n-butyl acetate, ketone solvents such as acetone, methylisobutylton or cyclohexanone, hydrocarbon solvents such as n-hexane and n-heptane, methanol, isopropyl alcohol, methyl isobutyl Alcohol solvents such as carbinol or ethylene glycol monomethyl ether, water, ether solvents, cyclic ether solvents, chlorofluorocarbon solvents, or aromatic solvents such as toluene or xylene are used. These solvents can be used alone or in combination as a polymerization solvent.

  Examples of the initiator for the radical polymerization reaction include azo compounds, peroxide compounds, and redox compounds. Particularly, azobisisobutyronitrile, tert-butyl peroxypivalate, di-tert-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, tert-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate. It is preferable to use it. Perpivalate-tert-butyl is particularly preferably used in the present invention because it is easily available and has good reactivity.

  In addition, a photopolymerization initiator can also be used for the radical polymerization reaction. In the case of alkylphenone series, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylphenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2- (dimethylamino) -2-[(4- Tilphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or oligo {2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl]} propanone, acylphosphine oxide In the system, 2,4,6-trimethylbenzoylphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is preferably used. As the photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone is particularly preferably used because it is easily available and has good reactivity.

  The polymerization reaction temperature varies depending on the type of initiator used. When a thermal polymerization initiator is used, it is usually preferably 50 ° C. or higher and 150 ° C. or lower, and particularly preferably 80 ° C. to 120 ° C. for handling.

In addition, when a photopolymerization initiator is used, radical polymerization can be performed on a relatively low heat-resistant substrate such as a PET film, and a high-pressure mercury lamp is used under a condition of about 10 mW / cm ² . Light cure by irradiation for 10 minutes. The reaction temperature for the polymerization reaction is usually preferably 0 ° C. or more and 100 ° C. or less, and particularly preferably 20 ° C. or more and 50 ° C. or less for handling.

  Examples of the base material to be applied include glass, plastic, metal, and the like, and electric parts, electronic products, building materials, craft products, clothing industrial products, medical products, and the like are exemplified.

  If necessary, the antibacterial resin can be immersed in an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution and washed with ion-exchanged water.

  In addition, the mechanical strength of the antibacterial resin is increased by impregnating the porous film with a raw material solution containing a polymerizable compound and a crosslinkable compound, and by mixing fillers such as fibers, nanosilica fine particles, and glass fibers with the raw material solution. May be.

  Although there is no restriction | limiting in particular in the thickness of an antibacterial resin, 20 nm or more and 1 mm or less are preferable. It is difficult to apply thinner than 20 nm, and it is not necessary to make it thicker than 1 mm. The film thickness is adjusted by the coating thickness on the substrate, that is, the coating amount per unit volume.

  Hereinafter, specific examples of the present invention will be described. The present invention is not limited to the following examples.

  In the Example of this invention, the example using MA-ABMD as a polymeric compound for making a resin contain the acryl-type repeating unit (a-1) containing the bismethide acid group of the invention 3 is the synthesis example 1 of resin. 11 and Examples 1-11.

  Next, as an example of using BTSB-DMSS as a polymerizable compound for causing the resin to contain the styrenic repeating unit (a-2) containing a bismethide acid group of Invention 4, Synthesis Examples 12, 13 and Example 12 were used. , 13.

  Next, as an example of using BTSB-NB-OH as a polymerizable compound for causing the resin to contain the norbornene-based repeating unit (a-3) containing a bismethide acid group of Invention 5, Synthesis Examples 14, 15 and Examples 14 and 15 are shown.

  Furthermore, what was obtained in Resin Synthesis Examples 1 to 15 was converted into a resin film in Examples 1 to 19, and the obtained resin film was used as a test piece, and Example JIS Z2801: 2006 "Antimicrobial Test Method" According to the method, an antibacterial test was conducted using Escherichia coli NBRC 3972 to evaluate the antibacterial property.

A resin obtained by reacting polyethylene glycol diacrylate with MA-EATf having a structure having a monomethide acid group in Comparative Example 1, and in Comparative Example 2, a polyethylene glycol diacrylate and a hexafluorocarbinol group (— (CF ₃ ) ₂ OH ), A resin obtained by reacting MA-3,5-HFA-CHOH, a resin obtained by reacting only polyethylene glycol diacrylate with Comparative Example 3, and a polyethylene film as Comparative Example 4, and performing an antibacterial activity test. The antibacterial properties were compared with the resin (Examples 1 to 13) containing a bismethide acid group of the present invention.

  Since the resin containing bismethide acid groups used in Resin Synthesis Examples 1 to 15 is easy to synthesize and easy to handle, it can be particularly suitably used for the antibacterial agent of the present invention.

  Specifically, it is a resin containing a repeating unit (a) having a bismethide acid group obtained by polymerizing MA-ABMD, BTSB-DMSS, and BTSB-NB-OH.

The structural formulas of MA-ABMD, BTSB-DMSS, BTSB-NB-OH, MA-EATf, MA-3,5-HFA-CHOH, BTSB-CDMS, NBOG and A-200 are shown below.

  Hereinafter, the synthesis example of the polymerizable monomer which gives the repeating unit contained in the resin as the active ingredient of the antibacterial agent of the present invention is shown.

[Synthesis example of BTSB-DMSS]
Under a nitrogen atmosphere, 2.08 g of magnesium and 22 ml of tetrahydrofuran were added to a 100 ml three-necked flask equipped with a reflux condenser and stirred at 23 ° C. Subsequently, a mixture of p-bromostyrene (14.50 g), dibromoethylene (0.31 g) and tetrahydrofuran (62 ml) was gradually added dropwise into the three-necked flask over 1 hour at this temperature under a nitrogen atmosphere. After dropping, stirring was continued for 2 hours, and 9.81 g of BTSB-CDMS was gradually added dropwise at 23 ° C. over 30 minutes. After the dropping, stirring was continued for 30 minutes, and then a washing operation of adding a 1N aqueous hydrochloric acid solution and toluene and stirring and mixing was performed twice. After the washing operation, the content was azeotroped with toluene, and after dehydration operation, 0.25 g of the above non-flex MBP was added, vacuum distillation was performed at 138 to 142 ° C. under a reduced pressure of 150 Pa, and 4- ( 4,4-bis (trifluoromethanesulfonyl) butyldimethylsilyl) styrene (hereinafter abbreviated as BTSB-DMSS) was distilled to obtain 11.42 g. At this time, the yield was 53.9%. The reaction formula of this synthesis example is as shown in Reaction Formula (1) below.

[Spectral data of BTSB-DMSS]
1H-NMR (solvent: deuterated chloroform); σ = 6.15-5.97 (m, 2H), 5.72-5.67 (m, 1H), 4.78 (t, J = 8.0 Hz, 1H), 2.49-2.47 (m, 2H), 1.76-1.69 (m, 2H), 0.63 (t, J = 8.0 Hz, 2H), 0.10 (s, 6H) ppm
19F-NMR (solvent: deuterated chloroform); σ = −73.30 ppm

[Synthesis Example of BTSB-NB-OH]
Under a nitrogen atmosphere, 10.06 g (0.0359 mol) of bismethide acid and 17 ml of tetrahydrofuran were added to a 100 ml three-necked flask equipped with a reflux condenser and stirred at 0 ° C. Subsequently, 24 ml of methylmagnesium chloride (3M) was gradually added dropwise into the three-necked flask over 30 minutes at this temperature under a nitrogen atmosphere. After the dropping, stirring was continued for 30 minutes at 23 ° C., and a solution prepared by dissolving 6.46 g (0.0359 mol) of NBOG having the above structure in 24 ml of tetrahydrofuran was gradually added dropwise over 10 minutes at that temperature. After dropping, stirring was continued for 3 hours, and then a washing operation of adding 1N hydrochloric acid aqueous solution and toluene and stirring and mixing was performed twice. After the washing operation, the content was azeotroped with toluene, and after dehydration operation, 0.25 g of the above non-flex MBP was added, and vacuum distillation was performed at 149 to 152 ° C. under a reduced pressure of 130 Pa. (Hereinafter abbreviated as BTSB-NB-OH) was distilled to obtain 11.4 g. At this time, the yield was 68.9%. The reaction formula of this synthesis example is as shown in Reaction Formula (2) below.

[Spectral data of BTSB-NB-OH]
1H-NMR (solvent: deuterated chloroform); σ = 6.15 (m, 1H), 5.92 (m, 1H), 5.57 (m, 1H), 4.04 (m, 1H), 3. 63-3.59 (m, 2H), 3.27-3.23 (m, 2H), 2.58-2.52 (m, 2H), 2.36 (m, 1H), 1.82 ( m, 1H), 1.58 (m, 1H), 1.50 (m, 1H), 1.27 (m, 1H), 1.14 (m, 1H), 0.51 (m, 1H) ppm19F -NMR (solvent: deuterated chloroform); σ = -72.80 (s, 3F), -73.80 (s, 3F) ppm

  Below, the polymerization method of resin used for the antibacterial agent of this invention is demonstrated.

[Resin Synthesis Example 1]
In a glass flask, 3-methacryloxy-1,1-bis (trifluoromethanesulfonyl) butanoic acid (hereinafter abbreviated as MA-ABMD), 1.51 g (0.0037 mol) and polyethylene glycol diacrylate (Shin Nakamura Chemical) 2.68 g (0.0088 mol) manufactured by Kogyo Co., Ltd., product name: A-200), and tert-butyl perpivalate as a polymerization initiator (product name: Perbutyl PV manufactured by Nippon Oil & Fats Co., Ltd.) 0.10 g The mixture was degassed with sufficient stirring, and nitrogen gas was introduced.

  5 ml of the solution was placed on a glass plate and applied using a bar coater. The mixture was placed in an inert oven equipped with a nitrogen introducing device that had been adjusted to 80 ° C. in advance, and heated at 80 ° C. for 30 minutes. Next, the temperature was raised at 1 ° C. per minute, and further cured by holding at 120 ° C. for 60 minutes to form a cured coating film on the glass substrate.

  In addition, two glass plates were prepared in advance, and a small piece of 0.2 mm thick glass serving as a spacer was sandwiched between the peripheral portions so that a gap was formed, and the solution was injected into the gap using the capillary phenomenon. . After maintaining in an oven heated to 80 ° C. for 30 minutes in a nitrogen atmosphere, the temperature was increased at 1 ° C. per minute, and further maintained at 120 ° C. for 60 minutes for curing. After removing from the oven and cooling to room temperature, it was immersed in a vat with water. After 1 hour, the resin film was peeled off from the glass plate, wiped with a waste cloth, and then allowed to dry at room temperature to obtain a cured self-supporting film.

[Resin Synthesis Example 2]
In a glass flask, MA-ABMD, 4.06 g (0.0100 mol), polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 0.76 g (0.0025 mol), and polymerization 0.10 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) as an initiator was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Resin Synthesis Example 1.

[Resin Synthesis Example 3]
In a glass flask, MA-ABMD, 0.528 g (0.0013 mol) and polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 3.435 g (0.0113 mol), and polymerization 0.10 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) as an initiator was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Resin Synthesis Example 1.

[Resin Synthesis Example 4]
In a glass flask, MA-ABMD, 0.053 g (0.00013 mol) and polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 3.760 g (0.01237 mol), and polymerization 0.10 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) as an initiator was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Resin Synthesis Example 1.

[Resin Synthesis Example 5]
In a glass flask, MA-ABMD, 0.053 g (0.00013 mol), polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 7.864 g (0.02587 mol), and polymerization 0.10 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) as an initiator was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Resin Synthesis Example 1.

[Resin Synthesis Example 6]
In a glass flask, MA-ABMD, 0.0053 g (0.000013 mol), polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 3.7960 g (0.012487 mol), and polymerization 0.10 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) as an initiator was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Resin Synthesis Example 1.

[Resin Synthesis Example 7]
In a glass flask, 5.00 g (0.0123 mol) of MA-ABMD was dissolved in 10.4 g of 2-butanone and mixed. To this solution was added 0.057 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 240 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 4.08 g of a white solid.

GPC measurement results; Mw = 80,100, Mw / Mn = 2.77
DSC measurement result; Tg = 160 ° C.
[Resin Synthesis Example 8]
In a glass flask, 3.90 g (0.0096 mol) of MA-ABMD and 1.00 g (0.0096 mol) of styrene (Tokyo Chemical Industry Co., Ltd.) were dissolved and mixed with 9.8 g of 2-butanone. . To this solution was added 0.094 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 100 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 1.59 g of a white solid.

GPC measurement result; Mw = 31,200, Mw / Mn = 1.98
DSC measurement result; Tg = 116 ° C.
[Resin Synthesis Example 9]
In a glass flask, 2-butanone 9.8 g, MA-ABMD 2.03 g (0.0050 mol), 2,3,4,5,6-pentafluorostyrene (Tokyo Chemical Industry Co., Ltd.) 0 .97 g (0.0050 mol) was dissolved and mixed. To this solution was added 0.049 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 200 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 2.31 g of a white solid.

GPC measurement results; Mw = 74,500, Mw / Mn = 2.02
DSC measurement result; Tg = 132 ° C.
[Resin Synthesis Example 10]
In a glass flask, 1.80 g (0.0044 mol) of MA-ABMD and 0.07 g (0.0005 mol) of 2-hydroxyethyl methacrylate were dissolved and mixed with 1.4 g of 2-butanone. To this solution was added 0.024 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 100 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 1.77 g of a white solid.

GPC measurement results; Mw = 429,400, Mw / Mn = 4.87
DSC measurement result; Tg = 148 ° C.
[Resin Synthesis Example 11]
In a glass flask, 0.20 g (0.0005 mol) of MA-ABMD and 4.96 g (0.0495 mol) of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.3 g of 2-butanone. Mixed. To this solution was added 0.123 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 105 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 4.13 g of a white solid.

GPC measurement result; Mw = 36,400, Mw / Mn = 1.71
DSC measurement result; Tg = 148 ° C.
[Resin Synthesis Example 12]
In a glass flask, 5.08 g (0.0105 mol) of BTSB-DMSS was added to 2.8 g of butyl acetate and dissolved and mixed. To this solution, 0.55 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) was added as a polymerization initiator, degassed with sufficient stirring, and after introducing nitrogen gas, 70 ° C. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 28 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 4.65 g of a white solid.

GPC measurement result; Mw = 33,300, Mw / Mn = 1.44
[Resin Synthesis Example 13]
In a glass flask, 7.54 g (0.0156 mol) of BTSB-DMSS and 8.01 g (0.1511 mol) of acrylonitrile were added to 7.7 g of butyl acetate and dissolved and mixed. To this solution, 0.41 g of perpivalic acid-tert-butyl (manufactured by Nippon Oil & Fats Co., Ltd., product name: perbutyl PV) was added as a polymerization initiator, degassed with sufficient stirring, and nitrogen gas was introduced. The reaction was carried out for 16 hours. The solution after completion of the reaction was added dropwise to 120 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 14.90 g of a white solid.

GPC measurement result: Mw 500,000 or more [Resin synthesis example 14]
In a glass flask, 9.24 g (0.0201 mol) of BTSB-NB-OH was added to 4.4 g of toluene, dissolved and mixed. To this solution, 0.141 g of dichlorobis (benzonitrile) palladium (II) and 2.15 g of boron trifluoride ethyl ether were added, degassed with sufficient stirring, and nitrogen gas was introduced, followed by reaction at 23 ° C. for 4 hours. Was done. The solution after completion of the reaction was added dropwise to 82 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 5.09 g of a white solid.

GPC measurement results; Mw = 9,000, Mw / Mn = 1.48
[Resin Synthesis Example 15]
In a glass flask, 2.47 g (0.0054 mol) of BTSB-NB-OH and 4.59 g (0.0488 mol) of 2-norbornene were added to 4.4 g of toluene and dissolved and mixed. To this solution, 0.200 g of dichlorobis (benzonitrile) palladium (II) and 2.05 g of boron trifluoride ethyl ether were added, degassed with sufficient stirring, and nitrogen gas was introduced, followed by reaction at 23 ° C. for 4 hours. Was done. The solution after completion of the reaction was added dropwise to 80 g of n-heptane to obtain a white precipitate. This precipitate was separated by filtration and dried under reduced pressure at 75 ° C. to obtain 6.31 g of a white solid.

GPC measurement result: Mw 500,000 or more A test piece for evaluating the antibacterial property of the synthesized resin was prepared. Using the prepared test piece, an antibacterial test was performed using Escherichia coli NBRC 3972 according to the method of JIS Z2801: 2006 “Antimicrobial test method”. A polyethylene film was used as the unprocessed test piece. About an Example, the process of obtaining an antibacterial resin from the hardened | cured material of the synthesis examples 1-6 of the said resin, the hardened | cured material of the synthesis examples 1-6, and the white solid of the synthesis examples 7-15 is demonstrated.

[Example 1]
The cured product obtained in Resin Synthesis Example 1 was cooled to room temperature and then immersed in water to obtain a resin film of 50 mm × 50 mm × 0.05 mm.

[Example 2]
A resin film was obtained from the cured product obtained in Resin Synthesis Example 2 in the same procedure as in Example 1.

[Example 3]
From the cured product obtained in Resin Synthesis Example 3, a resin film was obtained in the same procedure as in Example 1.

[Example 4]
From the cured product obtained in Resin Synthesis Example 4, a resin film was obtained in the same procedure as in Example 1.

[Example 5]
A resin film was obtained from the cured product obtained in Resin Synthesis Example 5 in the same procedure as in Example 1.

[Example 6]
From the cured product obtained in Resin Synthesis Example 6, a resin film was obtained in the same procedure as in Example 1.

[Example 7]
0.2 g of the white solid obtained in Resin Synthesis Example 7 was dissolved and mixed in 3.8 g of N, N-dimethylformamide (hereinafter abbreviated as DMF). The solution is applied on a glass plate, held in an oven heated to 120 ° C. for 30 minutes, then heated at 1 ° C. per minute, and further held at 160 ° C. for 60 minutes to cure, thereby forming a resin film Got.

[Example 8]
0.2 g of the white solid obtained in Resin Synthesis Example 8 was dissolved in 3.8 g of DMF and mixed. A resin film was obtained in the same procedure as in Example 7.

[Example 9]
0.2 g of the white solid obtained in Resin Synthesis Example 9 was dissolved and mixed in 3.8 g of DMF. A resin film was obtained in the same procedure as in Example 7.

[Example 10]
1.50 g of the white solid obtained in Resin Synthesis Example 10 was dissolved in 10.0 g of cyclohexanone, and 0.33 g of pyridine and 0.10 g of hexamethylene diisocyanate were added and stirred to obtain a uniform solution. The solution was applied on a glass plate, temporarily dried at room temperature for 1 hour, held in an oven heated to 80 ° C. for 30 minutes, then heated at 1 ° C. per minute, and further increased to 130 ° C. The cured film was obtained by holding for 60 minutes. This was immersed in a beaker containing 1 L of 1N hydrochloric acid aqueous solution at 80 ° C. for 1 hour, washed with ion-exchanged water, and dried under reduced pressure at 75 ° C. to obtain a resin film.

[Example 11]
0.2 g of the white solid obtained in Resin Synthesis Example 11 was dissolved and mixed in 3.8 g of DMF. A resin film was obtained in the same procedure as in Example 7.

[Example 12]
0.2 g of the white solid obtained in Resin Synthesis Example 12 was dissolved in 3.8 g of DMF and mixed. A resin film was obtained in the same procedure as in Example 7.

[Example 13]
0.2 g of the white solid obtained in Resin Synthesis Example 13 was dissolved in 3.8 g of DMF and mixed. A resin film was obtained in the same procedure as in Example 7.

[Example 14]
0.2 g of the white solid obtained in Resin Synthesis Example 14 was dissolved in 3.8 g of DMF and mixed. A resin film was obtained in the same procedure as in Example 7.

[Example 15]
0.1 g of the white solid obtained in Resin Synthesis Example 11 was dissolved in 9.9 g of methyl isobutyl carbinol. The solution was applied onto a 4-inch silicon wafer substrate by a spin coater and dried at 90 ° C. for 3 minutes to obtain a cured film having a thickness of 20 nm.

[Example 16]
A test piece having a size of 50 mm × 50 mm was cut out from the resin film obtained in the same procedure as in Example 1, and immersed in 200 mL of 0.05N aqueous sodium hydroxide solution. After leaving at room temperature for 12 hours, the membrane was taken out from the mixed solution, and the membrane surface was washed with distilled water. Due to the sodium ions in the liquid, the bismethide acid group in the resin film becomes an organic group containing a sodium salt (bismethide acid salt).

[Example 17]
A test piece having a size of 50 mm × 50 mm was cut out from the resin film obtained in the same procedure as in Example 2, and immersed in 200 mL of 0.05N aqueous sodium hydroxide solution. After leaving at room temperature for 12 hours, the membrane was taken out from the mixed solution, and the membrane surface was washed with distilled water. By the sodium ions in the liquid, the bismethide acid group in the resin film becomes an organic group including a sodium salt (bismethide acid salt).

[Example 18]
A test piece having a size of 50 mm × 50 mm was cut out from the resin film obtained in the same procedure as in Example 5, and immersed in 500 mL of a 0.5% by mass silver acetate aqueous solution. After leaving at room temperature for 12 hours, the membrane was taken out from the mixed solution, and the membrane surface was washed with distilled water. Due to the silver ions in the liquid, the bismethide acid group in the resin film becomes an organic group containing a silver salt (bismethide acid salt).

[Example 19]
A test piece having a size of 50 mm × 50 mm was cut out from a resin film obtained in the same procedure as in Example 5, and immersed in 500 mL of a 0.5 mass% imidazole aqueous solution. After leaving at room temperature for 12 hours, the membrane was taken out from the mixed solution, and the membrane surface was washed with distilled water. . The bismethide acid group in the resin film becomes an organic group containing an imidazolium salt (bismethide salt).

[Comparative Example 1]
MA-EATf, 0.97 g (0.0037 mol) and polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 3 containing a monomethide acid group having the above structure in a glass flask. .40 g (0.0088 mol) and 0.10 g of perpivalic acid-tert-butyl (manufactured by NOF Corporation, product name: perbutyl PV) as a polymerization initiator were added, and the mixture was deaerated while being sufficiently stirred, and nitrogen Gas was introduced. Thereafter, the solution was cured by the same procedure as in Example 1 to obtain a resin film.

[Comparative Example 2]
In a glass flask, MA-3,5-HFA-CHOH containing a hexafluorocarbinol group (-(CF ₃ ) ₂ OH) having the above structure, 1.85 g (0.0037 mol) and polyethylene glycol diacrylate (new) 2.68 g (0.0088 mol) manufactured by Nakamura Chemical Co., Ltd., product name: A-200, and tert-butyl perpivalate as a polymerization initiator (manufactured by NOF Corporation, product name: perbutyl PV) 0 .10 g was added, degassed with sufficient stirring, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Example 1 to obtain a resin film.

[Comparative Example 3]
In a glass flask, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-200) 3.80 g (0.0125 mol) and perpivalic acid-tert-butyl as a polymerization initiator (Japan) 0.10 g (manufactured by Yushi Co., Ltd., product name: perbutyl PV) was added, deaerated while being sufficiently stirred, and nitrogen gas was introduced. Thereafter, the solution was cured by the same procedure as in Example 1 to obtain a resin film.

[Comparative Example 4]
Polyethylene film as an unprocessed test piece.

[Comparative Example 5]
Nafion 117 film as a test specimen for comparison.

[Evaluation of antibacterial properties]
In order to evaluate the antibacterial properties of the synthesized resin films, resin films containing resins having bismethide acid groups (Examples 1 to 18), resin films not containing bismethide acid groups (Comparative Examples 1 to 3 and 5), unprocessed A test piece having a size of 50 mm × 50 mm was cut out from a resin film having a thickness of 0.2 mm of a polyethylene film (Comparative Example 4) as a test piece, and Escherichia coli NBRC 3972 according to the method of JIS Z2801: 2006 “Antimicrobial Test Method”. ) Was used to conduct an antibacterial test. The results are shown in Table 1.

The amount of methide in Table 1 is the ratio of the number of moles of monomer 1 in the sum of the polymerizable compound containing bismethide acid group (monomer 1) and the polymerizable compound not containing bismethide acid group (monomer 2). is there. The sterilization rate is calculated by the following formula. The antibacterial activity value is a logarithmic value of the number obtained by dividing the number of bacteria after incubation for 24 hours of unprocessed product (B) by the number of bacteria after culture for 24 hours of processed antibacterial product (C). Sterilization rate, 99% or higher) is defined as effective.

  As shown in Table 1, it was found that the antibacterial member obtained by coating the surface with the antibacterial agent having bismethide acid groups obtained in Examples 1 to 19 of the present invention showed excellent antibacterial activity. In comparison, the antibacterial member having no bismethide acid group did not exhibit antibacterial activity.

[Evaluation of mold resistance]
In order to evaluate the mold resistance of the synthesized resin film, a resin film containing a resin having a bismethide acid group (Examples 1, 3, 4, 6), a polyethylene film as a non-processed test piece (Comparative Example 4), and Nafion A test piece having a size of 40 mm × 40 mm was cut out from the resin film of 117 film (Comparative Example 5).

The test method was compliant with JIS Z 2911: 2000 “mold resistance test method (Appendix 1 plastic product test)”, and the strains were used by mixing the five designated types shown in Table 2.

Test criteria are as shown in Table 3.

The results of the test are as shown in Table 4. Mold resistance was observed in the films of Examples 1, 3, 4, and 6, and mold resistance was not observed in the films of Comparative Examples 4 and 5.

[Evaluation of antiviral properties]
In order to evaluate the antiviral properties of the synthesized resin film, the thickness of a resin film containing a resin having a bismethide acid group (Examples 3 and 4) and a polyethylene film (Comparative Example 4) as an unprocessed test piece is about 0.2 mm. A test piece having a size of 50 mm × 50 mm was cut out from the resin film.

  As an evaluation virus, an influenza A virus having an envelope and a feline calicivirus having no envelope were used.

  The test was carried out by placing a polypropylene film having a size of 40 mm × 40 mm in order to increase the contact efficiency between the test piece and the virus after 200 ml of the virus solution was dropped on the test piece.

  Two hours later, the virus is recovered from the solution obtained by bringing the test piece into contact with the virus solution, and the solution for which the reaction has been stopped is diluted 10-fold, and the reaction stop solution stock solution or the diluted solution is infected to the virus infectivity titration cell. The cytopathic effect due to virus growth was observed.

  As a result, the resin membranes of Examples 3 and 4 showed high antiviral properties against influenza A virus and feline calicivirus, and no cytopathic effect was observed not only in the diluted solution but also in the reaction stop solution stock solution.

Furthermore, a polyethylene film was tested in a similar way, the reaction stop solution undiluted for influenza A virus to 10 ⁵ fold dilutions was observed cytopathic effects, and do not show a cytopathic effect in 10 ⁶ dilution or It was. For up to 10 ⁴ fold dilution from reaction stopper undiluted feline calicivirus virus observed cytopathic effect, no longer show a cytopathic effect in 10 ⁵ fold dilution or dilution.

  Furthermore, Nafion 117 film (Comparative Example 5) was tested in the same manner. As a result, the viability of the eluate stock solution against influenza A virus was 80% or less, and cytotoxicity was observed. When diluted 10 times or more, no cytotoxicity was observed and antiviral properties were exhibited. No cytotoxicity against feline calicivirus was observed, and the eluate stock solution showed antiviral properties.

Claims (15)

General formula (1):

(In the formula (1), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent which contains resin containing the organic group represented by this as an active ingredient. The resin is represented by the general formula (2):

(In Formula (2), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a carbon number. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond, having 1 to 12 carbon atoms. A divalent hydrocarbon group which is a linear, branched or cyclic divalent hydrocarbon group, or a combination thereof, and may have an ether bond, an ester bond, an amide bond or a urethane bond, Some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ And R ⁶ combine to form a ring And may include a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation .)
The antibacterial agent of Claim 1 which is resin which has the repeating unit (a) represented by these. The repeating unit (a) is represented by the following general formula (3):

(In the formula (3), R ⁷ is a hydrogen atom, an alkyl group, a halogen atom or a trifluoromethyl group. R ⁸ is a single bond, a linear, branched or cyclic divalent group having 1 to 12 carbon atoms. Or a combination thereof, which may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of carbon atoms contained in R ⁸ is silicon. And a part or all of hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation. .)
The antibacterial agent of Claim 2 which is a repeating unit (a-1) represented by these. The repeating unit (a) is represented by the general formula (4):

(In Formula (4), R ⁹ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond, or a urethane bond, a part of carbon atoms contained in R ⁹ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of Claim 2 which is a repeating unit (a-2) represented by these. The repeating unit (a) is represented by the general formula (5):

(In the formula (5), R ¹⁰ is a single bond, a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group that is a combination thereof, and an ether. May have a bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁰ may be substituted with silicon, and a part or all of hydrogen atoms may be fluorine atoms or hydroxyl groups C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The antibacterial agent of Claim 2 which is a repeating unit (a-3) represented by these. The resin further has the general formula (6):

(In Formula (6), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom. And an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴ is a hydrogen atom, a halogen atom, or a linear, branched or cyclic group having 1 to 35 carbon atoms, or a linear, branched or cyclic group. It is a monovalent hydrocarbon group which is a combination, and may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of the carbon atoms contained in R ¹⁴ may be substituted with silicon In addition, some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may combine to form a ring and have 3 carbon atoms. ~ 12 single It may contain cyclic, bicyclic or polycyclic structures.)
The antibacterial agent of Claim 2 which is resin containing the repeating unit (b-1) represented by these. The resin further has the general formula (7):

(In Formula (7), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom. , An alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹¹ and R ¹² or R ¹³ may combine to form a ring, and the monocyclic, bicyclic or 3 to 12 carbon atoms R ¹⁵ may be a hydrogen atom, a halogen atom, or a monovalent group that is a linear, branched, cyclic, or linear, branched, or cyclic combination having 1 to 35 carbon atoms. Which may have an ether bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁵ may be substituted with silicon, and Part or all is fluorine atom or hydroxyl In may be substituted, R ¹⁵ is selected a hydroxyl group, a mercapto group, a carboxyl group, an amino group, an epoxy group, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, chlorosilyl group, alkoxysilyl group or a hydrosilyl group Including groups capable of reacting with other crosslinking agents.)
The antibacterial agent of Claim 2 which is resin containing the repeating unit (b-2) represented by these. The resin is one or more groups selected from isocyanate group, hydroxyl group, mercapto group, carboxyl group, amino group, epoxy group, alkenyl group, alkynyl group, acryloyl group, methacryloyl group, chlorosilyl group, alkoxysilyl group or hydrosilyl group. The curable antibacterial agent according to claim 7, comprising a cross-linking agent that is cross-linked by a cross-linking agent containing A surface treatment method for a base material, wherein the antibacterial agent according to any one of claims 1 to 8 is applied or adhered to the surface of the base material to form a film. General formula (2-1)

(In Formula (2-1), R ¹ and R ² each independently represents a fluoroalkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. Or a fluoroalkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond or 1 carbon atom. A divalent hydrocarbon group of -12 linear, branched or cyclic divalent hydrocarbon groups, or a combination thereof, having an ether bond, an ester bond, an amide bond or a urethane bond In addition, some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ Or R ⁵ and R ⁶ are And may include a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom. Or a cation.)
A coating of an antibacterial agent according to any one of claims 1 to 8 is formed by applying or adhering a polymerizable compound, which is a precursor of a repeating unit represented by Substrate surface treatment method. General formula (2-1):

(In Formula (2-1), R ¹ and R ² are each independently a fluoroalkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ⁶ is a single bond, having 1 to 1 carbon atoms. 12 linear, branched, or cyclic divalent hydrocarbon groups, or a divalent hydrocarbon group that is a combination thereof, and having an ether bond, an ester bond, an amide bond, or a urethane bond In addition, some of the carbon atoms contained in R ⁶ may be substituted with silicon, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ and R ⁶ are combined It may form a ring and may contain a monocyclic, bicyclic or polycyclic structure having 3 to 12 carbon atoms, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or It is a cation.)
In addition to the polymerizable compound represented by general formula (6-1):

(In Formula (6-1), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently, A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R ¹⁴ is a hydrogen atom, a halogen atom, or a straight chain, branched, cyclic, or straight chain, branched, having 1 to 35 carbon atoms, It is a monovalent hydrocarbon group which is a cyclic combination, and may have an ether bond, an ester bond, an amide bond or a urethane bond, and a part of carbon atoms contained in R ¹⁴ is substituted with silicon. Alternatively, some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ¹¹ and R ¹² or R ¹³ and R ¹⁴ may combine to form a ring, Single ring of number 3-12 Formula, bicyclic or polycyclic structures may be included.)
Or general formula (7-1):

(In formula (7-1), R ¹¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a fluoroalkyl group having 1 to 4 carbon atoms. R ¹² and R ¹³ are each independently R ¹¹ and R ¹² or R ^{13 which} are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom may be bonded to form a ring, and a monocyclic or bicyclic ring having 3 to 12 carbon atoms R ¹⁵ may be a hydrogen atom, a halogen atom, or a linear, branched, cyclic, or linear, branched, cyclic combination having 1 to 35 carbon atoms. A monovalent hydrocarbon group, which may have an ether bond, an ester bond, an amide bond or a urethane bond, a part of carbon atoms contained in R ¹⁵ may be substituted with silicon, and a hydrogen atom; Part or all of fluorine atom or May be substituted with an acid group, R ¹⁵ represents a hydroxyl group, a mercapto group, a carboxyl group, an amino group, an epoxy group, an alkenyl group, an alkynyl group, an acryloyl group, a methacryloyl group, chlorosilyl group, alkoxysilyl group or a hydrosilyl group Contains groups that can react with the chosen crosslinker.)
The base according to claim 10, wherein the antibacterial agent film according to claim 6 is formed by adding or adhering to the surface of the substrate after adding the polymerizable compound represented by formula (10). Material surface treatment method. Furthermore, after adding a crosslinking agent, the membrane | film | coat of the antibacterial agent of Claim 8 is formed, The surface treatment method of the base material of any one of Claim 9 thru | or 11 characterized by the above-mentioned. 13. The substrate surface treatment method according to claim 12, wherein the film is polymerized or crosslinked to form a cured film by heating. 13. The substrate surface treatment method according to claim 12, wherein the film is polymerized or crosslinked to form a cured film by light irradiation. A method for producing an antibacterial member, wherein the surface treatment is performed by the surface treatment method according to any one of claims 9 to 14.