JP2012092088A - Antibacterial agent composition, and substrate surface treatment method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial agent composition applied to the surface of a material.SOLUTION: The antibacterial agent composition contains a fluorine-containing polymerizable compound represented by general formula (1); wherein, Rand Rare fluoroalkyl groups; Rand Rare a hydrogen atom or the like; and Ris a single bond or a bivalent organic group.

Description

  The present invention relates to a composition for an antibacterial agent and a surface treatment method for a substrate using the same.

  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. Unlike temporary sterilization, antibacterial means that microorganisms are targeted at a level below sterilization and above bacteriostasis for a long period of time to suppress the growth of microorganisms. Sterilization is a level at which microorganisms are killed or disappeared, and bacteriostasis is a level at which the growth of microorganisms is suppressed.

  Bacteria whose antibacterial agents exhibit antibacterial activity include gram positive bacteria and 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, and viruses without an outer membrane are Strong resistance. The main viruses having no outer membrane are enteroviruses such as polio and reovirus 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 system as an antibacterial effect, and there is a problem that the field of use is 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 made of 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-bound 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.

  Incidentally, 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 include 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 is a composition for an antibacterial agent that can be present only in a necessary place such as the surface of a material, and that continuously exhibits an excellent antifungal and antiviral effect in addition to antibacterial properties Another object is to provide a surface treatment method using the same.

  The fluorinated polymerizable compound of the general formula (1) having an organic group composed of a bismethide acid group or a bismethide acid salt of the present invention, and the inclusion of the general formulas (2) to (4) included in the general formula (1) A composition for an antibacterial agent containing a fluorine-polymerizable compound is prepared by adding a cross-linking or a solvent as necessary, and then polymerizing fluorine-containing polymerizable compounds with each other or a fluorine-containing polymerizable compound and another polymerizable compound. It becomes resin.

  In the general formula (1), C (carbon) and A are bonded by a covalent bond or an ionic bond, and A represents a hydrogen atom or a cation.

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 is likely to become a bismethide salt due to a cation, and the organic group that acts as an antibacterial active ingredient contained in the composition for an antibacterial agent of the present invention is a bismethide acid group or a bismethide acid salt. Either of organic groups consisting of

[Invention 1]
General formula (1):

(In Formula (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 a carbon number. 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 represents a single bond and has 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 are linked to form a ring It may be 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. is there.)
The composition for antibacterial agents containing the fluorine-containing polymeric compound 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 composition for an antibacterial agent of the present invention, CF ₃ is preferably used because of ease of synthesis.

  Moreover, when the fluorine-containing polymerizable compound (a) represented by the general formula (1) is exemplified, the fluorine-containing polymerizable compound (a-1) represented by the general formula (2) having an ester bond of the invention 2, The fluorine-containing polymerizable compound (a-2) represented by the general formula (3) having a styrene chain in the main chain of the invention 3 and the compound represented by the general formula (4) having a norbornene ring in the main chain of the invention 4 A fluorine-polymerizable compound (a-3) is mentioned.

[Invention 2]
General formula (2):

(In the formula (2), 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 divalent having 1 to 12 carbon atoms. A divalent hydrocarbon group which is a hydrocarbon group or a combination thereof, 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 ⁸ is silicon. It may be substituted, 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 composition for antibacterial agents of the invention 1 containing the fluorine-containing polymeric compound represented by these.

[Invention 3]
General formula (3):

(In Formula (3), 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 composition for antibacterial agents of the invention 1 containing the fluorine-containing polymeric compound represented by these.

[Invention 4]
General formula (4):

(In the formula (4), 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 formed by combining these, and 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 composition of the invention 1 containing the fluorine-containing polymeric compound represented by these.

  Furthermore, in the composition for an antibacterial agent of the present invention, in addition to the fluorine-containing polymerizable compound (a), the content of an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient of the antibacterial agent is adjusted, or a resin The polymerizable compound (b-1) represented by the general formula (5) of the invention 5 or the invention 6 in order to adjust the solvent solubility, coating property, mechanical properties, or introduce a crosslinkable functional group The polymerizable compound (b-2) represented by the general formula (6) may be used. The polymerizable compound (b-1) is a polymerizable compound containing no crosslinking group, and the polymerizable compound (b-2) is a polymerizable compound containing a crosslinking group.

[Invention 5]
Furthermore, the general formula (5):

(In Formula (5), 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. C ¹⁴ is 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, cyclic, or straight, branched, or cyclic group having 1 to 35 carbon atoms. 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 monocyclic, Bicyclic or polycyclic structures may be included, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The composition for antibacterial agents of the invention 1-4 containing the polymeric compound represented by these.

[Invention 6]
Furthermore, 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. , 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 at least one functional group.)
The composition for antibacterial agents of the invention 1-5 containing the polymeric compound represented by these.

  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 thereof include a crosslinking agent containing at least one group selected from a silyl group or a hydrosilyl group.

  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.

[Invention 7]
Further, at least one group selected from an isocyanate group, 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, a chlorosilyl group, an alkoxysilyl group or a hydrosilyl group. The composition for antibacterial agents of the invention 5 or the invention 6 containing the crosslinking agent to contain.

[Invention 8]
The antibacterial resin obtained by carrying out the polymerization reaction or the crosslinking reaction of the antibacterial agent composition of invention 1-7.

  Subsequently, the surface treatment method of the base material using the composition for antibacterial agents of this invention is shown to invention 9-13.

  The composition for an antibacterial agent containing the fluorine-containing polymerizable compound shown in the invention 1 to the invention 7 can be applied in various forms.

  For example, the antibacterial agent composition can be polymerized to form a resin, then dissolved in a solvent, and then applied to a substrate to form an antibacterial film.

  In addition, a composition for an antibacterial agent obtained by adding another polymerizable compound or a cross-linking agent to a fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt, if necessary, is applied to or adhered to a substrate. It is possible to employ a surface treatment method in which a strong antibacterial resin film is obtained by polymerization or crosslinking by heating or irradiation with light such as ultraviolet rays.

  Thus, according to the substrate surface treatment method of the present invention, the antibacterial member is coated on the surface of the object, and the antibacterial composition is efficiently applied or adhered to the substrate surface. It is possible to impart antibacterial properties.

[Invention 9]
A method for treating the surface of a substrate, comprising applying or adhering the antibacterial composition according to any one of inventions 1 to 7 to the substrate surface.

[Invention 10]
General formula (5):

(In Formula (5), 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. C ¹⁴ is 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, cyclic, or straight, branched, or cyclic group having 1 to 35 carbon atoms. 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 monocyclic, Bicyclic or polycyclic structures may be included.)
Or 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. , 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 processing method of the invention 9 characterized by forming the film | membrane by apply | coating or adhering to the base-material surface the composition for antibacterial agents which added further the polymeric compound represented by these.

[Invention 11]
Furthermore, after adding a crosslinking agent, the said film | membrane is formed, The method of the invention 9 or the invention 10 characterized by the above-mentioned.

[Invention 12]
The method according to inventions 9 to 11, 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 13]
The method of inventions 9 to 11, 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 14]
A method for producing an antibacterial member, wherein the surface treatment is performed by the method of inventions 9 to 13.

[Invention 15]
General formula (7):

(In the formula (7), R ¹⁶ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms or a combination thereof, and part or all of the carbon atoms are substituted with silicon. R ¹⁶ may have an ether bond, an ester bond, an amide bond or a urethane bond, and part or all of the hydrogen atoms contained in R ¹⁶ are a fluorine atom or a hydroxyl group. May be substituted, C and A are bonded by a covalent bond or an ionic bond, A is a hydrogen atom or a cation, B is

Any one of the groups. ]
A fluorine-containing polymerizable compound represented by the formula:

The composition for antibacterial agents containing the fluorine-containing polymerizable compound represented by the general formula (1) having an organic group containing a bismethide acid group or a bismethido acid salt of the present invention, specifically, included in the general formula (1) The composition for an antibacterial agent containing the fluorine-containing polymerizable compound represented by the general formulas (2) to (4) is excellent even if the content of the organic group containing a bismethide acid group or a bismethide acid salt is low. For example, the content of an organic group (CF ₃ SO ₂ ) ₂ C— containing a bismethide acid group or a bismethide acid salt in the resin after polymerization is at least 0 with respect to the antibacterial composition. The antibacterial effect was observed at 1 mol (mol)% or more, and a high antibacterial effect was observed at 1 mol% or more.

Further, in comparison with the conventional antibacterial agent simply kneaded and kneaded the antibacterial agent into the resin, the composition for antibacterial agent of the present invention is used, and the fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt. If a compound is applied to a substrate and polymerized to form a resin, a resin film in which an organic group containing a bismethide group or bismethide acid salt as an active ingredient is bonded to the polymer chain is formed, and volatilization and elution of the active ingredient is suppressed, and antibacterial properties are obtained. Sex lasts for a long time.

  In other words, the antibacterial agent composition and the surface treatment method using the same allow the presence of a methide group only in a necessary place such as the surface of the material, and thus antibacterial, antifungal and antifungal properties can be present. Provided are an antibacterial composition and an antibacterial member using the same, which continuously exert an excellent effect on viral properties. It is easy to make the distribution of bismethido acid groups or organic groups containing bismethido acid salts uniform in the film, and the organic groups containing bismethide acid groups or bismethide acid salts are not displaced and the safety is high.

  Thus, the composition for antibacterial agents containing a fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt of 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 composition for an antibacterial agent containing a fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt 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. There are provided a composition for an antibacterial agent 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.

1. Antibacterial composition First, the composition for an antibacterial agent of the present invention will be described.

[Invention 1]
General formula (1):

(In Formula (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 a carbon number. 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 represents a single bond and has 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 are linked to form a ring It may be 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. is there.)
The composition for antibacterial agents containing the fluorine-containing polymeric compound represented by these.

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 the alkylammonium ion, a monoalkylammonium ion (NRH ₃ ⁺ ), a dialkylammonium ion (NR ₂ H ₂ ⁺ ), a trialkylammonium ion (NR ₃ H ⁺ ), a tetraalkylammonium ion (NR ₄ ⁺ ), etc. Can be mentioned. 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) ions ([Fe (SCN)] ²⁺ ), hexaammine nickel (II) ions ([Ni (NH ₃ ) ₆ ] ²⁺ ), purpleo ([CoCl (NH ₃ ) ₅ ] ²⁺ ), hexaammine cobalt ( III) ions ^{_{([Co (NH 3) 6}} ] 3+), hexa aqua cobalt (III) ions _{([Co (H 2 O)} 6] 3+) or hexamine chromium (III) ions ([Cr ( H _{3) 6]} ^3+), Rozeo _{([Co (NH 3) 4} (H 2 O) 2] 3+) , and the like.

In addition, the composition for an antibacterial agent containing the fluorine-containing polymerizable compound represented by the general formula (1) exhibits antibacterial activity even when the content of an organic group containing a bismethide acid group or a bismethide acid salt is low, and the resin The content of the organic group (CF ₃ SO ₂ ) ₂ C— containing the bismethide acid group or bismethide acid salt, which is the organic group described in the general formula (1), is at least 0.1 mol with respect to the antibacterial agent composition. The antibacterial effect was observed at (mol)% or more, and the effect of high antibacterial activity was observed at 1 mol% or more. 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. Thus, the composition for an antibacterial agent is prepared so that the content of an 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. It is preferable.

[Invention 2]
General formula (2):

(In the formula (2), 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 divalent having 1 to 12 carbon atoms. A divalent hydrocarbon group which is a hydrocarbon group or a combination thereof, 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 ⁸ is silicon. It may be substituted, 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 composition for antibacterial agents of the invention 1 containing the fluorine-containing polymeric compound (a-1) represented by these.

[Invention 3]
General formula (3):

(In Formula (3), 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 composition for antibacterial agents of the invention 1 containing the fluorine-containing polymeric compound (a-2) represented by these.

[Invention 4]
General formula (4):

(In the formula (4), 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 composition of the invention 1 containing the fluorine-containing polymeric compound (a-3) represented by these.

[Invention 5]
Furthermore, the general formula (5):

(In Formula (5), 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. C ¹⁴ is 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, cyclic, or straight, branched, or cyclic group having 1 to 35 carbon atoms. 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 monocyclic, Bicyclic or polycyclic structures may be included, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The composition for antibacterial agents of the invention 1-4 containing the polymeric compound (b-1) represented by these.

[Invention 6]
Furthermore, 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. , 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 at least one functional group.)
The composition for antibacterial agents of the invention 1-5 containing the polymeric compound (b-2) represented by these.

[Invention 7]
Further, it contains 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 composition for antibacterial agents of the invention 5 or the invention 6 containing a crosslinking agent.

[Invention 8]
The antibacterial resin obtained by carrying out the polymerization reaction or the crosslinking reaction of the antibacterial agent composition of invention 1-7.

2. Fluorine-containing polymerizable compound (a)
Next, the fluorine-containing polymerizable compound (a) having an organic group containing a bismethide acid group or a bismethide acid salt contained in the composition for an antibacterial agent of the present invention will be described.

  When the fluorine-containing polymerizable compound (a) represented by the general formula (1) is exemplified, the fluorine-containing polymerizable compound (a-1) represented by the general formula (2) having an ester bond of the invention 2 and the invention 3 The fluorine-containing polymerizable compound (a-2) represented by the general formula (3) having a styrene chain in the main chain thereof, and the fluorine-containing polymerization represented by the general formula (4) having a norbornene ring in the main chain of the invention 4 Compound (a-3). Other examples include a vinyl-based fluorine-containing polymerizable compound (a) and a fluorine-containing polymerizable compound (a) having an amide bond.

  As described above, the fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt represented by the general formula (1) of the invention 1 has the general formula (2) having an ester bond of the invention 2. The fluorinated polymerizable compound (a-1) represented, the fluorinated polymerizable compound (a-2) represented by the general formula (3) having a styrene chain in the main chain of the invention 3, or the main chain of the invention 4 Some of them contain a fluorine-containing polymerizable compound (a-3) represented by the general formula (4) having a norbornene ring. In addition, examples of the fluorine-containing polymerizable compound having an organic group containing a bismethide acid group or a bismethide acid salt include a vinyl-based fluorine-containing polymerizable compound and a fluorine-containing polymerizable compound having an amide bond.

Examples of the fluorine-containing polymerizable compound (a-1) represented by the general formula (3) having an ester bond according to the invention include 1 to 3 of the following ester-based fluorine-containing polymerizable compound (a-1).

Examples of the fluorine-containing polymerizable compound (a-2) represented by the general formula (3) having a styrene bond of the invention 3 include the following styrene-based fluorine-containing polymerizable compounds (a-2).

The fluorine-containing polymerizable compound (a-3) represented by the general formula (4) of the invention 4 includes a fluorine-containing polymerizable compound (a-3) having a norbornene chain in the main chain.

The fluorine-containing polymerizable compound (a) represented by the general formula (1) of the invention 1 includes the following amide-type fluorine-containing polymerizable compounds (a) 1 and 2 of the vinyl-type fluorine-containing polymerizable compound (a). And the like, and a fluorine-containing polymerizable compound (a) having a trismethide acid group.

3. Polymerizable compounds (b-1) and (b-2)
Next, the polymerizable compounds (b-1) and (b-2) that the resin used in the antibacterial composition of the present invention may have will be described.

  In the composition for an antibacterial agent of the present invention, in addition to the fluorine-containing polymerizable compound (a), the content of an organic group containing a bismethide acid group or a bismethide acid salt as an active ingredient of the antibacterial agent is adjusted, or a resin solvent Polymerization compound (b-1) represented by general formula (5) or polymerization represented by general formula 6 in order to adjust solubility, coatability, mechanical properties, or to introduce a crosslinkable functional group A functional compound (b-2) may be used. The polymerizable compound (b-1) is a polymerizable compound containing no crosslinking group, and the polymerizable compound (b-2) is a polymerizable compound containing a crosslinking group.

  The polymerizable compound contained in the composition for an antibacterial agent of the present invention may include only the fluorine-containing polymerizable compound (a), or the fluorine-containing polymerizable compound (a) and the polymerizable compound (b-1) or A polymerizable compound (b-2) may be included.

  When a polyfunctional polymerizable compound such as a polyfunctional acrylate is used for the polymerizable compound (b-1), it becomes possible to obtain a resin having high mechanical strength, which is preferably employed.

  Furthermore, by adding a polymerizable compound (b-1) or a polymerizable compound (b-2) containing a crosslinking site such as a hydroxyl group, a resin having a crosslinked structure by reaction with a curing agent such as an isocyanate compound It is also possible to obtain a resin with high mechanical strength, which is preferably employed.

The polymerizable compound (b-1) that may be contained in the antibacterial agent composition of the present invention is represented by the general formula (5).

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

The polymerizable compound (b-2) which may contain the antibacterial agent composition of the present invention 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 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 the polymerizable compound (b-2), maleic anhydride, acrylic ester, fluorine-containing acrylic ester, methacrylic ester, fluorine-containing methacrylate, styrene compound, fluorine-containing styrene compound, vinyl ether, fluorine-containing vinyl ether, At least one compound selected from allyl ether, fluorine-containing allyl ether, olefins, fluorine-containing olefins, norbornene compounds, and fluorine-containing norbornene compounds is employed.

  The acrylic ester or methacrylic ester as the polymerizable compound (b-2) is a fluorine-containing polymerizable compound (a), a fluorine-containing polymerizable compound (a-1), a fluorine-containing polymerizable compound (a-2) or If it can be copolymerized with the fluorine-containing polymerizable compound (a-3), 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.

  In addition, as the polymerizable compound (b-2), the fluorine-containing acrylic ester and the fluorine-containing methacrylate ester have a fluorine atom or a monomer having a fluorine atom contained in the α-position of the acrylic, or an ester site. An acrylic ester or methacrylic ester containing a substituent containing a fluorine 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 resulting resin, and is preferably used as the polymerizable compound (b-1) contained in the antibacterial agent composition of the present invention. Adopted.

  Further, as the polymerizable compound (b-1), the styrene compound and the fluorine-containing styrene compound have one functional group protecting the hexafluorocarbinol group or its hydroxyl group in addition to styrene, fluorinated styrene, or hydroxystyrene. One or a plurality of bonded compounds may be 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 styrenic compound is effective in improving the solvent solubility and the surface properties and water repellency of the resulting resin, similarly to the fluorine-containing acrylic ester, and is contained in the composition for an antibacterial agent of the present invention. It is preferably employed as the polymerizable compound (b-1).

  As the polymerizable compound (b-1), vinyl ether, fluorine-containing vinyl ether, allyl ether, and fluorine-containing allyl ether were selected from methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, and hydroxybutyl group. Alkyl vinyl ethers or alkyl allyl ethers containing hydroxyl 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.

  Moreover, as a polymeric compound (b-1), if it is a compound containing a vinyl ester, vinyl silane, an olefin, a fluorine-containing olefin, a norbornene compound, a fluorine-containing norbornene compound, or another polymerizable unsaturated bond, it will be used without a restriction | limiting. Is possible.

  The hydrocarbon olefin as the polymerizable compound (b-1) is ethylene, propylene, isobutene, cyclopentene, cyclohexene, and fluorinated hydrocarbon olefins are vinyl fluoride, vinylidene fluoride, trifluoroethylene, Examples include chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, or hexafluoroisobutene.

  The norbornene compound as the polymerizable compound (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 polymerizable compound (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, citraconic acid, trans-p -Coumaric acid, trans-o-coumaric acid, trans-m-coumaric acid, crotonic acid, α-cyanocinnamic acid, 1-cyclohexene-1-carboxylic acid, 1-cyclopentenecarboxylic acid, α-cyano-4-hydroxy Cinnamic acid, traumatic acid, trans-2-decenoic acid, 3,4-dimethoxycinnamic acid, trans-2,3-dimethoxycinnamic acid, trans-2,5-dichlorocinnamic acid, fumaric acid, fumaric Acid monoethyl, trans-2-hexenoic acid, 2-heptenoic acid, monomethyl itaconate, maleic acid monoamide, mesaconic acid, methacrylic acid, 4 Methyl-2-pentenoic acid, trans, trans-muconic acid, mucobromic acid, mucochloroic acid, 3-methylcrotonic acid, 4-methoxycinnamic acid, succinic acid mono (2-acryloyloxyethyl), 3- (5-nitro 2-furyl) acrylic acid, 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-dodecadie 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, fumaric acid Monoethyl, ethyl hydrogen maleate, monooctyl maleate, mono maleate Cyl, monoisopropyl fumarate, succinic acid mono (2-acryloyloxyethyl), 6-acrylamidohexanoic acid, acrylamide, allylamine, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl)- 2-thiourea, allylurea, methyl 3-aminocrotonate, 3-amino-5,5-dimethyl-2-cyclohexen-1-one, S-allyl-L-cysteine, 3-amino-4,4,4 -Ethyl trifluorocrotonate, 3-amino-2-cyclohexen-1-one, 3-benzalbutyramide, crotonamide, cinnamic amide, 2- (1-cyclohexenyl) ethylamine, glycidyl methacrylate or polyethylene glycol The following polyfunctional polymerizable compounds containing diacrylate 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 obtain a resin having excellent mechanical strength. Are preferably employed.

  In addition, in the synthesis of a resin using the composition for an antibacterial agent of the present invention, a resin synthesis method in which a peroxide or an azo compound is used as a cross-linking agent and cross-linked by a radical reaction can be employed. It is particularly preferably employed for the antibacterial agent of the present invention because of its durability.

  In the synthesis of the resin using the antibacterial agent composition of the present invention, 1,4-phenylene diisocyanate is used as an isocyanate compound that is used as a crosslinking agent and reacts with a hydroxyl group or an amino group to form a crosslinked structure in the resin. Narate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichlorobiphenyl-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate And diisocyanate compounds such as narate, 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 a resin using the composition for an 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.

  In the synthesis of the resin using the composition for an antibacterial agent of the present invention, the epoxy compound used as a crosslinking agent and reacting with a carboxyl group to form a crosslinked structure includes a glycidyl ether compound, a glycidyl ester compound, and glycidyl. Examples include amine compounds and alicyclic compounds. For example, 1,4-butanediol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, diglycidyl 1,2-cyclohexanedicarboxylate, 1,7-octadiene diepoxide, 1,5-hexadiene diene 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 using the antibacterial agent composition of the present invention, 1,4-butanediol diglycidyl ether having an appropriate reactivity is particularly preferably employed.

As an aldehyde compound used as a crosslinking agent in the synthesis of a resin using the composition for an antibacterial agent of the present invention and reacting with a phenolic hydroxyl group to form a crosslinked structure, formaldehyde, formalin aqueous solution, paraformaldehyde, trioxane, Acetaldehyde, polyoxymethylene or propionaldehyde may be mentioned. In the synthesis of a resin using the composition for an antibacterial agent of the present invention, paraformaldehyde is particularly preferably employed because it has moderate reactivity and is easy to handle.

  In the synthesis of the resin using the composition for antibacterial agent of the present invention, chlorosilanes used as a crosslinking agent and useful for a crosslinking reaction for forming a siloxane bond include dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, divinyl. Dichlorosilane, 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-tridecaful) B -n- octyl) silane, trichloro-2-cyano-ethyl silane or phenyl trichlorosilane and the like, can be mentioned. In the synthesis of a resin using the composition for an antibacterial agent of the present invention, dimethyldichlorosilane is particularly preferably employed because it is highly reactive, inexpensive and easily available.

  In the synthesis of the resin using the composition for an antibacterial agent of the present invention, alkoxysilanes useful as a crosslinking agent for forming a siloxane bond used as a crosslinking agent include dimethyldimethoxysilane, diethyldimethoxysilane, and diphenyldimethoxysilane. , Divinyldimethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, phenyldimethoxysilane, vinyldimethoxysilane, dimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, trimethoxysilane, tetramethoxy Silane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, divinyldiethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, Phenyldiethoxysilane, 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, cyclohexyltrimethoxy Lan, 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 a resin using the composition for an antibacterial agent of the present invention, dimethyldimethoxysilane is particularly preferably employed because it is highly reactive, inexpensive and easily available.

  In the synthesis of the resin using the composition for an antibacterial agent of the present invention, the melamine compound used as a crosslinking agent to react with a hydroxyl group to form a crosslinked structure includes melamine, methylolated melamine, methylolated melamine derivatives. Is mentioned. 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 using the composition for an antibacterial agent of the present invention, methylolated melamine and its derivatives are particularly preferably employed because they are highly reactive and easy to handle.

  In the synthesis of the resin using the antibacterial agent composition of the present invention, as a sulfur and sulfur compound used as a crosslinking agent, which reacts with an alkenyl group, alkynyl group, acryloyl group or methacryloyl group to form a crosslinked structure. , Sulfur, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentamethylenethiuram tetrasulfide, morpholine disulfide, or 2- (4′-morpholinodithio) benzothiazole Etc.

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

  In the synthesis of the resin using the composition for an antibacterial agent of the present invention, as a peroxide useful for crosslinking by radical reaction to an alkyl group or the like used as a crosslinking agent, benzoyl peroxide, dichlorobenzoyl peroxide can be used. , Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide Oxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-trimethyl-2,5-di (tert-butylperoxy) hexane, tert- Butyl perbenzoate, tert-butyl perphenyl acetate tert- butyl perisobutyrate, tert- butyl per -sec- octoate, tert- butyl hydroperoxide peak Pareto or cumyl pin Pareto, include tert- butylperoxy diethyl acetate.

  In the synthesis of a resin using the composition for an antibacterial agent of the present invention, benzoyl peroxide is particularly preferably employed because the resulting resin is excellent in mechanical properties with good reactivity.

  In the synthesis of the resin using the composition for an antibacterial agent of the present invention, an azo compound useful as a crosslinking agent for crosslinking by radical reaction to an alkyl group or the like is azobisisobutyronitrile or dimethylazoiso. A butyrate is mentioned.

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). Next, as the composition for an antibacterial agent of the present invention, the fluorine-containing polymerizable compound (a), the fluorine-containing polymerizable compound (a-1), the fluorine-containing polymerizable compound (a-2), or the fluorine-containing polymerizable compound. A polymerization method for obtaining a resin by homopolymerizing these fluorine-containing polymerizable compounds using the compound (a-3) will be described. Moreover, as a composition for antibacterial agents of the present invention, a fluorine-containing polymerizable compound (a), a fluorine-containing polymerizable compound (a-1), a fluorine-containing polymerizable compound (a-2), or a fluorine-containing polymerizable compound ( A polymerization method for obtaining a resin by copolymerizing the fluorine-containing polymerizable compound, the polymerizable compound (b-1), and the polymerizable compound (b-2) using a-3) will be described.

  Polymerization methods include radical polymerization and polymerization with transition metals.

  First, radical polymerization will be described.

  The polymerization method for obtaining the resin from the antibacterial agent composition of the present invention is not particularly limited as long as it is a commonly used method, but radical polymerization and ionic polymerization are preferable, and coordination anion polymerization and living anion polymerization are preferred. 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 using the composition for an 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 An alcohol solvent selected from ketones selected from ketones, hydrocarbons selected from toluene and cyclohexane, methanol, isopropyl alcohol, methyl isobutyl carbinol, and 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.

In the presence of a cocatalyst, vinylene polymerization is performed in the presence of a co-catalyst, such as a group VIII transition metal catalyst such as iron, nickel, rhodium, palladium, or platinum, or a metal catalyst of group IVB to VIB selected from zirconium, titanium, vanadium, chromium, molybdenum, or tungsten. 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. . 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, a substrate surface treatment method will be described.

  The antibacterial agent composition of the present invention can be coated on a target base material and surface-treated on the equipment. The composition for antibacterial agent of the present invention can be dissolved in a solvent, applied to a substrate and dried to obtain a film. It is also possible to improve the strength of the film by mixing a curing agent at the time of coating and polymerizing the fluorine-containing polymerizable compound or polymerizable compound contained in the antibacterial agent composition to form a resin. In the invention, it is preferably adopted.

  In addition, the composition for antibacterial agent of the present invention, in which a curing agent is mixed with a fluorine-containing polymerizable compound or a polymerizable compound, is applied to a base material, and the resin is cured by applying heat, light or a catalyst, and the film is cured. It is also possible to make it. It can be applied without solvent and is very effective for improving the manufacturing environment.

  The solvent used in the antibacterial agent composition of the present invention is not particularly limited as long as the antibacterial agent composition is soluble without reacting with the antibacterial agent composition, but acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl are not limited. Ketones selected from ketones or 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, dipropylene glycol monoacetate, monomethyl ether, monoethyl ether , Polyhydric alcohols selected from monopropyl ether, monobutyl ether or monophenyl ether and methanol, ethanol, isopropyl alcohol, methyl Monohydric alcohols selected from isobutyl carbinol, or derivatives thereof, cyclic ethers such as dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid Aromatic solvents selected from methyl, ethyl ethoxypropionate, xylene, or toluene, fluorinated solvents selected from chlorofluorocarbons, alternative chlorofluorocarbons, perfluoro compounds, or hexafluoroisopropyl alcohol. In addition, terpene-based petroleum naphtha solvents and paraffin-based solvents, which are high-boiling weak solvents, can be used. These may be used alone or in combination of two or more.

  In the present invention, the antibacterial agent composition shown in inventions 1 to 7 is applied to the substrate surface to form a film.

  That is, this invention is a surface treatment method of a base material characterized in that the antibacterial agent composition of any one of the inventions 1 to 7 is applied to the base material surface to form a film.

  The fluorine-containing polymerizable compound (a) of the invention 2, the fluorine-containing polymerizable compound (a-1) of the invention 3, the fluorine-containing polymerizable compound (a-2) of the invention 4, or the fluorine-containing polymerizable compound of the invention 5 ( In addition to the polymerizable compound giving a-3), the polymerizable compound (b-1) of the general formula (5) and the polymerizable compound giving the polymerizable compound (b-2) of the general formula (6) The cross-linking agent of Invention 7 may be added.

  A polyfunctional polymerizable compound having two or more polymerizable double bonds for synthesizing a resin using the composition for antibacterial agents of Inventions 1 to 7 was prepared. Specifically, the fluorine-containing polymerizable compound (a) having a bismethide acid group shown in Inventions 1 to 4, the polymerizable compound (b-1) of the general formula (5), and the polymerizable compound of the general formula (6) A polymerizable compound giving (b-2) 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 polymer was polymerized to obtain a colorless and transparent film (antibacterial film) using the composition for an antibacterial agent of the present invention.

  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 reaction temperature during polymerization 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.

  The antibacterial resin using the composition for antibacterial agents of the present invention can be immersed in an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution and washed with ion-exchanged water as necessary.

  Further, by impregnating a porous film with a raw material solution containing a fluorine-containing polymerizable compound, a polymerizable compound or a crosslinkable compound, by mixing fillers such as fibers, nano silica fine particles and glass fibers into the raw material solution, etc. You may raise the mechanical strength of the antimicrobial resin using the composition for antimicrobial agents.

  Although there is no restriction | limiting in particular in the thickness of the antibacterial resin using the composition for antibacterial agents of this invention, 20 nm or more and 1 mm or less are preferable. If it is thinner than 20 nm, coating becomes difficult, 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 Examples of the present invention, examples in which MA-ABMD is used as the acrylic fluorine-containing polymerizable compound (a-1) containing a bismethide acid group of Invention 2 are resin synthesis examples 1 to 11 and examples 1 to 1. 11 shows.

  Next, examples using BTSB-DMSS as the styrene-based fluorine-containing polymerizable compound (a-2) containing a bismethide acid group of Invention 3 are shown in Synthesis Examples 12 and 13 and Examples 12 and 13.

  Next, examples in which BTSB-NB-OH was used as the norbornene-based fluorine-containing polymerizable compound (a-3) containing a bismethide acid group of the invention 4 were shown in Synthesis Examples 14 and 15 and Examples 14 and 15. .

  Furthermore, what was obtained in the synthesis examples 1 to 15 of the resin was converted into a resin film in Examples 1 to 19, and the obtained resin film was used as a test piece. Example JIS Z2801: 2006 “Antimicrobial test method” The antibacterial property test was performed using Escherichia coli NBRC 3972 according to the method of "."

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 resins containing bismethide acid groups of the present invention (Examples 1 to 19).

  Since the resin containing bismethide acid groups used in Resin Synthesis Examples 1 to 13 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 fluorine-containing polymerizable compound (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, synthesis examples of the fluorine-containing polymerizable compound to be contained in the composition for an antibacterial agent of the present invention will be 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 is as shown below in Reaction Formula (1).

[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 is as shown below in Reaction Formula (2).

[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) ppm
19F-NMR (solvent: deuterated chloroform); σ = −72.80 (s, 3F), −73.80 (s, 3F) ppm

  Below, the polymerization method of resin using the composition for antibacterial agents 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 = 123 ° 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 a resin synthesized using the composition for an antibacterial agent of the present invention 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 and the white solid of the synthesis examples 7-15 is demonstrated.

[Example 1]
By cooling the cured product obtained in Resin Synthesis Example 1 to room temperature and then immersing it in water, 50 mm × 50
A resin film of mm × 0.05 mm was obtained.

[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 added to N, N-dimethylformamide (hereinafter DMF).
It was dissolved in 3.8 g and mixed. 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 6.

[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 6.

[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 a mixed solution with 200 mL of 0.05N sodium hydroxide 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 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 18]
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 wt% aqueous silver acetate 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 the resin film obtained in the same procedure as in Example 5, and immersed in 500 mL of a 0.5 wt% 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.

[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 based on JIS Z 2911: 2000 “fungal resistance test method (Appendix 1 Plastic product test)”, and the strains were used by mixing the five designated strains shown in Table 2.

Test criteria are as shown in Table 3.

As a result of the test, 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. R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or a carbon atom. 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 represents a single bond or 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 , R ⁶ may be partially substituted with silicon, and some or all of hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups, and R ³ and R ⁴ or R ⁵ and ^{R 6,} the ring bond to 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 composition for antibacterial agents containing the fluorine-containing polymeric compound represented by these. General formula (2):

(In the formula (2), 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 divalent having 1 to 12 carbon atoms. A divalent hydrocarbon group which is a hydrocarbon group or a combination thereof, 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 ⁸ is silicon. It may be substituted, 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 composition for antibacterial agents of Claim 1 containing the fluorine-containing polymeric compound represented by these. General formula (3):

(In Formula (3), 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 composition for antibacterial agents of Claim 1 containing the fluorine-containing polymeric compound represented by these. General formula (4):

(In the formula (4), 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 composition of Claim 1 containing the fluorine-containing polymeric compound represented by these. Furthermore, the general formula (5):

(In Formula (5), 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. C ¹⁴ is 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, cyclic, or straight, branched, or cyclic group having 1 to 35 carbon atoms. 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 monocyclic, Bicyclic or polycyclic structures may be included, C and A are bonded by a covalent bond or an ionic bond, and A is a hydrogen atom or a cation.)
The composition for antibacterial agents of any one of Claims 1 thru | or 4 containing the polymeric compound represented by these. Furthermore, 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. , 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 at least one functional group.)
The composition for antibacterial agents of any one of Claims 1 thru | or 5 containing the polymeric compound represented by these. Furthermore, one or more groups selected from an isocyanate group, 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, a chlorosilyl group, an alkoxysilyl group or a hydrosilyl group The composition for antibacterial agents according to claim 5 or 6, comprising a crosslinking agent. An antibacterial resin obtained by polymerizing or crosslinking the antibacterial agent composition according to any one of claims 1 to 7. A method for treating the surface of a substrate, comprising applying or adhering the antibacterial composition according to any one of claims 1 to 7 to the surface of the substrate. General formula (5):

(In Formula (5), 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. C ¹⁴ is 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, cyclic, or straight, branched, or cyclic group having 1 to 35 carbon atoms. 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 monocyclic, Bicyclic or polycyclic structures may be included.)
Or 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. , 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 treatment method according to claim 9, wherein a film is formed by applying or adhering a composition for an antibacterial agent further added with a polymerizable compound represented by the formula: The method according to claim 9, further comprising forming the film after adding a crosslinking agent. The method according to any one of claims 9 to 11, wherein the film is polymerized or crosslinked to form a cured film by heating. The method according to claim 9 or 11, 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 13. General formula (7):

(In the formula (7), R ¹⁶ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 12 carbon atoms or a combination thereof, and part or all of the carbon atoms are substituted with silicon. R ¹⁶ may have an ether bond, an ester bond, an amide bond or a urethane bond, and part or all of the hydrogen atoms contained in R ¹⁶ are a fluorine atom or a hydroxyl group. May be substituted, C and A are bonded by a covalent bond or an ionic bond, A is a hydrogen atom or a cation, B is

Any one of the groups. ]
A fluorine-containing polymerizable compound represented by the formula: