JP5315549B2 - Antifouling antibacterial and antifungal coating, method for producing the same, and product using the same - Google Patents

Description

The present invention relates to an antifouling antibacterial and antifungal film, a method for producing the same, and a product using the same, and more specifically, has high durability, can be produced at low cost, and is highly safe for human bodies and the environment. The present invention relates to a transparent antifouling antibacterial and antifungal film, a method for producing the same, and a product using the same.

The demand for antibacterial and antibacterial products has been increasing in response to the recent improvement in public health awareness associated with changes in the living environment and the aging of society. Condensation and mold generation associated with improved airtightness in houses, mass infections due to frequent pathogenic Escherichia coli and Legionella bacteria, etc., have spurred this trend.

In developing antibacterial and antifungal products, it is necessary to consider the safety and toxicity of antibacterial and antifungal ingredients, as well as the activity of controlling bacteria and mold. From this point of view, organic compounds having antibacterial and antifungal activity such as natural products, or metal atoms or ions such as Ag (silver) and Cu (copper) as active antibacterial and antifungal agents that have no risk of toxicity and environmental pollution Is attracting attention.

For example, Patent Document 1 includes a branch of leaves of the genus Euphoridae, a rhododendron plant curcuma rhizome, an allergic plant of the Labiatae family Mankihiki Koshi plant, a rhododendron Koganeyanagi plant rhizome, a scorpionaceae Nagasaruogase plant, a urushiaceae lanshinboku. Disclosed is an antimicrobial composition for application containing at least one or more types of water extract of plant bark and / or branches and leaves of the Asteraceae plant, and a coating resin and / or an application solvent. ing.

Patent Document 2 discloses a decorative board in which a metallic inorganic antibacterial agent in which an antibacterial metal ion such as silver ion is chemically bonded to an apatite ceramic is contained in at least a decorative layer laminated on a core layer. .

Patent Document 3 discloses a rubber article that includes at least one non-silicone rubber component such as NBR, and further includes at least one silver-based inorganic antibacterial agent and exhibits a surface-available silver amount of at least 0.075 μg / dm ^2. Has been.

Patent Document 4 discloses a solution in which silver ultrafine particles having a particle size of 0.01 μm or less and ceramic fine particles having a particle size of 0.1 μm or less are mixed in ammonia water, and the silver ultrafine particles are adhered and held on the surface of the ceramic fine particles. A and a solution B in which isopropyl alcohol and a water-soluble urethane resin are mixed in water are mixed, and then immediately applied to the mold, and then melted in the mold at a temperature of 380 degrees Celsius or higher. An antibacterial film is formed by injecting a molding material and forming an antibacterial thin film layer that holds ceramic fine particles containing silver ultrafine particles on the surface of the plastic molded product at the part where the plastic molding material is contacted by the molding heat. A plastic molded article having an action and a method for producing the same are disclosed.

JP 2006-022075 A JP 2008-1000041 A JP 2008-031485 A Japanese Patent Laid-Open No. 2005-007836

However, antibacterial and antifungal products coated with an organic agent such as the antimicrobial composition for application described in Patent Document 1 have a low durability because the effects gradually fade with repeated use. Further, in the decorative plate described in Patent Document 2, the rubber article described in Patent Document 3, and the plastic molded product described in Patent Document 4, a metal ion-based antibacterial and antifungal component is bonded and fixed to the surface or inside of the substrate. The antibacterial and antifungal effect lasts for a longer period of time, but it requires kneading into the substrate and heating at a high temperature in the production stage. Therefore, there are problems such as high manufacturing cost and narrow application range.
In any of Patent Documents 1 to 4, there is no description of means and methods for combining antibacterial and antifungal effects and antifouling properties.

The present invention has been made in view of such circumstances, and is a highly durable, inexpensive and transparent antifouling antibacterial and antifouling coating that is highly safe for the human body and the environment, and a method for producing the same, and those The purpose is to provide products using

According to a first aspect of the present invention, there is provided a first film substance having a fluorocarbon group chemically bonded to the surface of a substrate, and a first bonding substance having a coordination bond group that forms a coordination bond with a metal atom or metal ion. 2 on the surface of the mixed coating film via a coordination bond formed between the mixed monomolecular film formed on the surface of the substrate in a state of being mixed at the molecular level and the coordination bond group. The object is achieved by providing an antifouling antibacterial and antifouling film characterized by containing a fixed antibacterial and antibacterial metal atom or metal ion.
The term “antibacterial / antifungal metal atom or metal ion” refers to a thiol group, hydroxyl group, carboxyl group present on the surface or active center of membrane proteins and enzymes of microorganisms such as bacteria and fungi. Proliferation or survival of these microorganisms by binding to polar groups such as amino groups and amino groups, causing denaturation and inactivation, inhibiting their function, and reaching the inside of cells to inactivate enzymes. Refers to any metal atom or ion capable of preventing

The antibacterial and antifungal metal atom or metal ion bonded to the coordination bond group of the second membrane substance can suppress the growth of bacteria and fungi that may adversely affect the human body. Further, since the surface energy of the antifouling antibacterial and antifungal film is reduced by the first film substance having a fluorocarbon group, the surface of the film is kept clean, and the nutrient source for bacteria and fungi The adhesion of the organic film to the coating surface is also suppressed, and the antibacterial and antifungal effect can be further enhanced.

Since the mixed film formed by the first and second film substances chemically bonded to the surface of the base material is a thin film on the order of nm, the antifouling antibacterial and antifouling film is various without affecting the color tone and texture of the base material. It can be applied to various base materials. Further, the antifouling antibacterial and antifungal coating is extremely excellent in durability because it is covalently bonded to the base material. Furthermore, since the film forming process is very simple, the antifouling antibacterial and antifouling coating can be produced at low cost, and does not depend on the shape of the base substrate, and has a large surface area. It can also be easily manufactured.

In the first aspect of the present invention, the first and second film substances are reacted by a reaction between any of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group and the surface of the substrate. It may be fixed to the surface of the substrate through a formed bond.
The alkoxysilyl group and the halosilyl group can form a covalent bond by a condensation reaction with the surface of various substrates made of metals, ceramics, resins, fibers, etc. having an active hydrogen group such as a hydroxyl group. Moreover, the thiol group and sulfide group can form a covalent bond on the surface of a base material made of a noble metal such as gold or a transition metal.

According to a second aspect of the present invention, a first film compound having a first surface binding group that forms a bond with the surface of a substrate at one end of the molecule and a fluorocarbon group at the other end, and one end of the molecule A second surface binding group that forms a bond with the surface of the base material and a third film compound having a first reactive group at the other end is mixed with the surface of the base material and reacted, Forming a mixed monomolecular film of the first and third film substances chemically bonded to the surface of the substrate; a second reactive group and a metal atom forming a bond with the first reactive group; Alternatively, each molecule having a coordination bond group that forms a coordinate bond with a metal ion is bonded to the third film substance via a bond formed by the reaction of the first and second reactive groups. consists of a step D for converting the mixed monomolecular film of said first and second film materials, fluoride to one end of the molecule carbonitride Forming a first film material, and mixtures monomolecular film of the second film material having a coordinating group of the one end of the molecule to form a metal atom or metal ion coordinate bonds with groups on the surface of the substrate Fixing the metal atom or metal ion to the surface of the mixed monolayer through the coordination bond formed between the antibacterial and antifungal metal atom or metal ion and the coordination bond group in Step A The above-described problems are solved by providing a method for producing an antifouling antibacterial and antifungal film characterized by comprising the step B.

Since the mixed film of the first and second film substances chemically bonded to the surface of the base material is a thin film having a film thickness of the order of nm, the method for producing an antifouling antibacterial / antifungal film according to this aspect (hereinafter “book” The antifouling antibacterial and antifungal coating obtained by the “method” can be applied to various substrates without impairing the color tone or texture of the substrate. In addition, the antifouling antibacterial and antifouling coating produced by this method is very excellent in durability because it is covalently bonded to the substrate. Furthermore, since the film forming process is very simple, the present method can be carried out at a low cost and can easily produce an antifouling antibacterial and antifungal film on the surface of a large-area substrate. it can.

In the second aspect of the present invention, the step A includes a first surface-bonding group that forms a bond with the surface of the substrate at one end of the molecule, and a fluorocarbon group at the other end. A membrane compound and a second surface binding group (which may be the same as or different from the first surface binding group) that forms a bond with the surface of the substrate at one end of the molecule and a first surface at the other end A step C of reacting a third film compound each having a reactive group with the surface of the substrate to form a mixed film of the first and third film substances chemically bonded to the surface of the substrate; A molecule having a second reactive group that forms a bond with the first reactive group and a coordination bond group that forms a coordinate bond with a metal atom or metal ion, respectively, Binding to the third membrane material via a bond formed by a group reaction, the first and second That consisted of Step D of converting to a mixed coating material. By doing so, an antifouling antibacterial and antifungal film can be produced using a raw material that is easier to obtain and cheaper than a film compound having a surface binding group and a coordination binding group at both ends of the molecule. At the same time, adverse effects such as a decrease in yield due to the reaction between the surface bonding group and the coordination bonding group can be avoided.

In the second aspect of the present invention, the surface binding group may be any of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group.
The alkoxysilyl group and the halosilyl group can form a covalent bond by a condensation reaction with the surface of various substrates made of metals, ceramics, resins, fibers, etc. having an active hydrogen group such as a hydroxyl group. Moreover, the thiol group and sulfide group can form a covalent bond on the surface of a base material made of a noble metal such as gold or a transition metal.

In the first and second aspects of the present invention, the metal atom or metal ion is preferably an Ag, Cu, Zn atom, or an ion of these metals.
Since these metal atoms or metal ions have high antibacterial and antifungal properties and do not have a harmful effect on the human body and the environment, they can be used as highly safe antibacterial and antifungal agents.

A third aspect of the present invention solves the above-mentioned problems by providing a product characterized in that the antifouling antibacterial and antifungal film according to the first aspect of the present invention is formed on the surface. is there.

1st-3rd aspect of this invention WHEREIN: The said base material or articles | goods is either a building, a motor vehicle, a ship, an aircraft, a train, apparel products, jewelry, and a decoration, or the material used for them. It may be.
All of these materials are used for articles that often come into contact with the human body. Especially for buildings, automobiles, ships, aircraft, and trains, there are many opportunities for many people to touch in public places. . Accordingly, there is a strong demand for compatibility between antifouling properties, antibacterial and antifungal properties, and safety, and the present invention can be suitably applied.

According to the method for producing an antifouling antibacterial and antifouling coating and an antifouling antibacterial and antifouling coating according to the present invention, an antifouling antibacterial and antifouling coating can be formed on the surface of various substrates at a low cost. Provided are an antifouling antibacterial and antifouling coating film having antifouling properties, antibacterial and antifungal properties, durability, safety to human bodies and the environment, and a method for producing the same. In addition, even after metal atoms or ions having antibacterial and antifungal properties are released from the surface of the antifouling antibacterial and antifouling coating, the coordination bonding groups remain without being lost, so the metal atoms or ions are recombined. Thus, the antibacterial and antifungal properties can be restored any number of times, and the antibacterial and antifungal properties can be exhibited semipermanently as long as the film of the film compound remains.

The product on which the antifouling antibacterial and antifouling film according to the present invention is formed has high antifouling property, antibacterial and antibacterial properties, durability, safety for human body and environment, and antibacterial and antifungal properties from the surface. Even after the metal atoms or ions are released, the antibacterial and antifungal properties can be restored any number of times by recombining the metal atoms or ions, and as long as the coating of the film substance remains semi-permanent Can exhibit antibacterial and antifungal properties.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention. In the present specification, the terms “film compound” and “film substance” respectively refer to a compound used as a starting material for forming a water- and oil-repellent mixed coating, and the formed water- and oil-repellent properties. Used to refer to the components of the mixed coating.
Here, FIG. 1 is an explanatory view schematically showing the cross-sectional structure of the antifouling antibacterial and antifungal film according to the first embodiment of the present invention expanded to the molecular level, and FIG. 2 is the second embodiment of the present invention. In the manufacturing method of the antifouling antibacterial and antifungal film according to the embodiment of the present invention, a conceptual diagram enlarged to the molecular level in order to explain the process of forming a mixed monomolecular film having a fluorocarbon group and an epoxy group, FIG. It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the monomolecular film which has a fluorocarbon group and an imidazolyl group in the manufacturing method of the antifouling antibacterial and antifungal film.

As shown in FIG. 1, the antifouling antibacterial and antifouling coating 10 is a fluorocarbon group chemically bonded to the surface of the substrate 11 (in FIG. 1, a pentadecafluorodecyl group is shown as an example. 2 and 3) and a mixed monomolecular film 13 having an imidazolyl group (a first film substance having a pentadecafluorodecyl group and a second film having an imidazolyl group (an example of a coordination bond group)) An example of a mixed film formed on the surface of the substrate 11 in a state where the substance is mixed at the molecular level ) and the surface of the mixed monomolecular film 13 through the coordinate bond formed between the coordinate bond groups. And fixed copper ions (an example of antibacterial and antifungal metal atoms or metal ions). Note that FIG. 1 shows only two imidazolyl groups coordinated to a copper ion, but actually four imidazolyl groups are coordinated to the copper ion in a planar square shape.

The antifouling antibacterial and antifouling coating 10 is formed by a step A in which a mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group is formed on the surface of the substrate 11 and a copper ion and an imidazolyl group. It can be produced by a method for producing an antifouling antibacterial and antifouling coating comprising the step B of fixing copper ions to the surface of the mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group via a coordinate bond.

Step A includes an alkoxysilane compound (an example of a first film compound) having a first surface binding group that forms a bond with the surface of the substrate 11 at one end of the molecule and a fluorocarbon group at the other end, and An alkoxysilane compound having an alkoxysilyl group (an example of a second surface reactive group) that forms a bond with the surface of the substrate 11 at one end of the molecule, and an epoxy group (an example of a first reactive group) at the other end A mixed monomolecular film 12 having a fluorocarbon group and an epoxy group chemically bonded to the surface of the base material 11 (an example of the third film compound) is mixed with the surface of the base material 11 and reacted. Step C (FIG. 2) for forming a mixed film of the third film substance), forming a covalent bond with an amino group (an example of the second reactive group) that forms a bond with the epoxy group and a copper ion Each having an imino group (an example of a coordination bond group) 2-Methylimidazole (an example of a molecule) is reacted with a mixed monomolecular film 12 having a fluorocarbon group and an epoxy group, and has an epoxy group via a bond formed by the reaction between the epoxy group and the amino group. Step D (FIG. 3), in which 2-methylimidazole is bonded to the film substance, and the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group is converted into a mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group. Consists of.

As the base material 11 that can be used, an arbitrary material having an active hydrogen group on the surface that can undergo a condensation reaction with an alkoxysilyl group to form a covalent bond can be used. Note that FIG. 2 illustrates a case where a hydroxyl group is included as an example of an active hydrogen group, but an amino group, a thiol group (mercapto group), a sulfide group, a carboxyl group, or the like may be used. Examples of the material of the substrate 11 include inorganic oxides such as glass, ceramics and enamel, metals such as aluminum, nickel and stainless steel, and organic materials such as resins, fibers and fabrics. When an organic material is used, cellulose having a hydroxyl group can be used as it is, but an active hydrogen group may be formed on the surface by acid treatment with concentrated nitric acid or the like and corona discharge treatment, or by plasma treatment or the like. A molecule having an active hydrogen group may be grafted.

Examples of the alkoxysilane compound containing a fluorocarbon group include alkoxysilane compounds represented by the following general formula (Formula 1).

In the above formula, m represents an integer of 0 to 20, n represents an integer of 0 to 9, and R represents an alkyl group having 1 to 4 carbon atoms.
Y represents either (CH ₂ ) _k (k represents an integer of 1 to 3) or a single bond, and Z represents O (ether oxygen), COO, Si (CH ₃ ) ₂ , and single Represents one of the bonds.

Examples of the halosilane compound containing a fluorocarbon group that can be used in Step C include the compounds shown in the following (1) to (12).

(1) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
(2) CF 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{(3) CF 3 (CF 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
(4) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(5) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(6) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(7) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) _{3
(8) CF 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(9) CF 3 (CF 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
_{(10) CF 3 (CF 2} ) 7 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(11) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(12) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

The alkoxysilane compound having an epoxy group has a functional group containing an epoxy group (oxirane ring) and an alkoxysilyl group at both ends of the linear alkylene group, and is represented by the following general formula (Formula 2). An alkoxysilane compound is preferable.

In the above formula, E represents a functional group having an epoxy group, j represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.

As an example of the alkoxysilane compound which has an epoxy group which can be used in process C, the compound shown to following (21)-(34) is mentioned.

_{(21) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OCH 3) 3
_{(22) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
(23) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) _{3
(24) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(25) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(26) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(27) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OC 2 H 5) 3
_{(28) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
_{(29) (CH 2 OCH)} CH 2 O (CH 2) 11 Si (OC 2 H 5) 3
_{(30) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(31) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(32) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3
_{(33) (CH 2 OCH)} (CH 2) 10 Si (OCH 3) 3
(34) (CH ₂ OCH) (CH ₂ ) ₁₀ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) CH ₂ O— group represents a functional group (glycidyloxy group) represented by Chemical Formula 3, and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group represented by Chemical Formula 4 Represents a functional group (3,4-epoxycyclohexyl group), and a (CH ₂ OCH)-group represents a functional group (epoxy group, oxirane group) represented by Formula 5.

When a solution containing an alkoxysilane compound is applied to the surface of the base material 11 and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group on the surface of the base material 11 undergo a condensation reaction. A monomolecular film 12 having an epoxy group having a structure as shown in FIG. The three single bonds extending from the oxygen atoms are bonded to the surface of the substrate 11 or the silicon (Si) atoms of the adjacent silane compound, and at least one of them is bonded to the oxygen atoms on the surface of the substrate 11. doing.

In the formula, R ¹ represents a linear alkylene group E— containing a fluorocarbon group CF ₃ (CF ₂ ) _n —Y—Z— (CH ₂ ) _m — (see Chemical Formula 1) and a functional group having an epoxy group. It represents one of (CH ₂ ) _j — (see Chemical Formula ₂ ).
Three single bonds extending from the oxygen atom are bonded to the surface of the substrate 11 or the silicon (Si) atom of the adjacent silane compound, and at least one of them is bonded to the oxygen atom on the surface of the substrate 11. doing.

The total concentration of the alkoxysilane compound having a fluorocarbon group and the alkoxysilane compound having an epoxy group is preferably 0.5 to 3% by mass.
The molar ratio of the alkoxysilane compound having a fluorocarbon group and the alkoxysilane compound having an epoxy group is not particularly limited, and the type and use of the base material 11, a balance between the required antifouling properties and antibacterial and antifungal properties, In addition, it can be appropriately selected according to the type of membrane compound used.

Further, the solution may contain a condensation catalyst for promoting the condensation reaction between the alkoxysilyl group and the hydroxyl group on the surface of the substrate 11. As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelate include bis (acetylacetonyl) di-propyl titanate.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the base material 11, so it is preferable to remove these impurities in advance by thoroughly washing and drying the base material 11.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction at room temperature is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when H3 of Japan Epoxy Resin Co., which is a ketimine compound, is used in place of dibutyltin diacetate as the condensation catalyst and the reaction is performed under the same conditions, the reaction time can be shortened to about 1 hour.

Furthermore, when a mixture of H3 and dibutyltin diacetate (mixing ratio is 1: 1) by Japan Epoxy Resin Co., Ltd. is used as the condensation catalyst, and the other conditions are the same, the monomolecular film 12 having an epoxy group is produced. The reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

For the preparation of the solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

After completion of the reaction, the mixture is washed with a solvent to remove excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances. As shown schematically in FIG. 2, a mixed unit having a fluorocarbon group and an epoxy group is obtained. A molecular film 12 is formed on the surface of the substrate 11.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. . In order to increase the cleaning efficiency, ultrasonic treatment or the like may be performed together.

As the surface binding group, a halosilane compound having a halosilyl group in place of the alkoxysilyl group in the compounds shown in the above (1) to (12) and (21) to (34) may be used. In this case, a condensation catalyst and a cocatalyst are not required, an alcohol solvent cannot be used, and it is more susceptible to hydrolysis than an alkoxysilane compound, so use a dry solvent in dry air (relative humidity of 30% or less). The reaction is different from the case of the alkoxysilane compound, but other reaction conditions (concentration of halosilane compound, reaction time, etc.) are the same as in the case of the alkoxysilane compound.

The surface bonding groups of the film compound having a fluorocarbon group and the film compound having an epoxy group may be the same as each other. For example, one may be different such that one is an alkoxysilyl group and the other is a halosilyl group. In this case, since the reactivity of the both with respect to the surface functional group of the substrate 11 is different, the mixing ratio of both in the solution and the existing ratio of both in the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group Note that are not necessarily the same. Therefore, it is preferable to examine in advance the relationship between the mixing ratio of both in the solution and the existing ratio of both in the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group.

In this embodiment, the case where the substrate 11 has an active hydrogen group on the surface has been described. However, the substrate has no active hydrogen group on the surface (Au) or the surface is plated with Au. In this case, a film compound having any one of a thiol group, an alkyl sulfide group, and a triazine thiol group can be used as the surface binding group.

In Step D, 2-methylimidazole is reacted with the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group, and the 2-methylimidazole is bonded via a bond formed by a reaction between the epoxy group and the 1-position amino group. Methylimidazole is bonded to form a mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group.
2-Methylimidazole has an amino group that reacts with an epoxy group at the 1-position, and forms a bond by a crosslinking reaction as shown in Chemical Formula 7 below.

Reaction of epoxy group and 2-methylimidazole on mixed monomolecular film 12 having fluorocarbon group and epoxy group is a mixed monomolecular film having fluorocarbon group and epoxy group in a solution in which 2-methylimidazole is dissolved. By immersing the base material 11 on which 12 is fixed, or by applying a solution of 2-methylimidazole on the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group, 2-methylimidazole and fluoride It can be performed by bringing the mixed monomolecular film 12 having a carbon group and an epoxy group into contact with each other and heating.

For the preparation of the solution, any solvent that can dissolve 2-methylimidazole and does not dissolve or swell the mixed monomolecular film 12 having the base material 11 and the fluorocarbon group and the epoxy group. Can be used. Considering price, volatility at room temperature, toxicity, etc., preferred solvents include alcohols such as methanol, ethanol, propanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and mixed solvents of these solvents and water. Can be mentioned. The concentration of 2-methylimidazole is preferably 0.005 mol / L to 0.1 mol / L.

Although heating temperature and time are suitably adjusted according to the kind of base material, the density | concentration of 2-methylimidazole solution, etc., they are 80-100 degreeC and 30 minutes-24 hours, respectively, for example. As needed, you may heat for several hours-dozens of hours at higher temperature (for example, 150 degreeC).

After the completion of the reaction, washing with a solvent to remove excess 2-methylimidazole remaining on the surface as an unreacted product, a monomolecular film 13 having an imidazolyl group is obtained as schematically shown in FIG.

As the washing solvent, any solvent that can dissolve 2-methylimidazole can be used, but there are dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying. preferable. In order to increase the cleaning efficiency, ultrasonic treatment or the like may be performed together.

In the present embodiment, 2-methylimidazole is used as the molecule having the second reactive group and the coordinate bond group, but any imidazole derivative represented by the following chemical formula 8 can be used. Alternatively, an imidazole-metal complex may be used. Furthermore, in addition to the imidazole derivative, for example, any molecule having a functional group capable of forming a complex with a metal atom or metal ion, such as a pyrrolyl group or a thienyl group, and a functional group having reactivity with an epoxy group Can be used.

Specific examples of the imidazole derivative represented by Chemical Formula 8 include those shown in the following (41) to (48).
(41) 2-methylimidazole (R ₂ = Me, R ₄ = R ₅ = H)
(42) 2-undecyl imidazole _{(R 2 = C 11 H 23} , R 4 = R 5 = H)
(43) 2-pentadecyl-imidazole _{(R 2 = C 15 H 31} , R 4 = R 5 = H)
(44) 2-methyl-4-ethylimidazole _{(R 2 = Me, R 4} = Et, R 5 = H)
(45) 2-Phenylimidazole (R ₂ = Ph, R ₄ = R ₅ = H)
(46) 2-phenyl-4-ethylimidazole _{(R 2 = Ph, R 4} = Et, R 5 = H)
(47) 2-phenyl-4-methyl-5-hydroxymethylimidazole _{(R 2 = Ph, R 4} = Me, R 5 = CH 2 OH)
(48) 2-Phenyl-4,5-bis (hydroxymethyl) imidazole (R ₂ = Ph, R ₄ = R ₅ = CH ₂ OH)
Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.

In the step B, antifouling is achieved by fixing copper ions on the surface of the mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group via a coordination bond formed between the copper ion and the imidazolyl group. The antibacterial and antifungal coating 10 is obtained (see FIG. 1).
Coordination bonds are formed by immersing the base material 11 on which a mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group is fixed in a solution in which a copper salt is dissolved, or mixing having a fluorocarbon group and an imidazolyl group By applying a solution in which a copper salt is dissolved on the monomolecular film 13, the copper salt can be brought into contact with the mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group. Coordination bonds can be formed at room temperature, and the time required for the reaction is several tens of minutes to several hours.

For the preparation of the solution, an arbitrary solvent that can dissolve the copper salt and does not dissolve or swell the mixed monomolecular film 13 having the base material 11 and the fluorocarbon group and the imidazolyl group is used. Water is most preferred. As the copper salt, any salt soluble in a solvent can be used. Specific examples of the copper salt in the case of using water as a solvent include copper chloride (II), copper bromide (II), copper nitrate ( II), copper sulfate (II) and the like. Although the density | concentration of a copper salt can be suitably adjusted according to the base material 11, the kind of salt used, etc., it is 0.01 mol / L-0.1 mol / L, for example.
In order to adjust pH, a base such as alkali hydroxide may be appropriately added to the solution.

In this embodiment, copper (II) ions are used as metal atoms or ions having antibacterial and antifungal activity. However, thiol groups, hydroxyl groups, carboxyl groups, amino acids present on the surface or active center of membrane proteins and enzymes, etc. Any metal atom or ion that binds to a polar group such as a group to inhibit its function by causing denaturation or deactivation or reaches the inside of a cell to deactivate the enzyme can be used. Other metal atoms or ions that can be used include silver and zinc metal atoms and ions thereof.

In the present embodiment, first, the monomolecular film 12 having an epoxy group is formed in the step C, and then the coordination bond group is introduced by the reaction with 2-methylimidazole in the step D. A mixed film of a film compound having a coordination bond group directly on the surface of the substrate 11 can be formed using an alkoxysilane compound having a functional group capable of forming a complex with a metal atom or metal ion. In this case, examples of the membrane compound that can be used include an alkoxysilane compound having an amino group at one end of a linear alkylene group and represented by the following general formula (Formula 9).

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms. The epoxy group may be protected with a protecting group in order to avoid side reactions with the alkoxysilyl group. The protecting group is preferably one that can be easily removed by hydrolysis or the like. Specific examples include a ketimine derivative produced by the reaction between a ketone and an amino group, a t-butoxycarbonyl (t-Boc) group, and a benzyloxycarbonyl (Z). And carbamate derivatives such as groups, phthalimide derivatives and the like.
The amino group may be a secondary amine other than the primary amine as shown in Chemical Formula 7, and an alkoxysilane compound containing a functional group having an imino group such as a pyrrole group or an imidazolyl group may be used instead of the amino group. Can do.
In this case, examples of the alkoxysilane compound having an amino group that can be used include the compounds shown in the following (51) to (58).

(51) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) _{3
(52) H 2 N (CH} 2) 5 Si (OCH 3) 3
_{(53) H 2 N (CH} 2) 7 Si (OCH 3) 3
_{(54) H 2 N (CH} 2) 9 Si (OCH 3) 3
_{(55) H 2 N (CH} 2) 5 Si (OC 2 H 5) 3
_{(56) H 2 N (CH} 2) 5 Si (OC 2 H 5) 3
_{(57) H 2 N (CH} 2) 7 Si (OC 2 H 5) 3
_{(58) H 2 N (CH} 2) 9 Si (OC 2 H 5) 3

Among condensation catalysts, a compound containing a tin (Sn) salt reacts with an amino group contained in an alkoxysilane derivative to generate a precipitate, and thus cannot be used as a condensation catalyst.
Therefore, when an alkoxysilane compound having an amino group is used, a compound similar to the above is used alone except for a carboxylic acid tin salt, a carboxylic acid ester tin salt, a carboxylic acid tin salt polymer, and a carboxylic acid tin salt chelate. Or 2 or more types can be mixed and used as a condensation catalyst.
The types of cocatalysts that can be used and combinations thereof, the type of solvent, the alkoxysilane compound, the condensation catalyst, and the concentration of the cocatalyst, the reaction conditions, and the reaction time are the same as when using an alkoxysilane compound having an epoxy group. Since there is, description is abbreviate | omitted.

As a product on which the antifouling antibacterial and antifungal coating 10 according to the present invention is formed, a metal capable of forming a bond with an active hydrogen group such as a hydroxyl group, a thiol group, a triazine thiol group or the like on the surface. Any article or part of the article, member, or part of the article is included. Specific examples of products include the following. These are merely examples, and are not limited to these.
(A) Examples of blades:
Kitchen knife, scissors, knife, cutter, carving sword, razor, clipper, saw, canna, chisel, cone, awl, bite, drill blade, mixer blade, juicer blade, flour mill blade, lawn mower blade, Punch, press cut, staple blade, can open blade, surgical knife, etc.

(B) Examples of needles:
Acupuncture needles, sewing needles, sewing needles, tatami needles, injection needles, surgical needles, safety pins, etc.

(C) Examples of ceramic products:
Products made of ceramic, glass, ceramics or enamel. For example, sanitary ceramics (for example, toilet bowls, washbasins, baths, etc.), tableware (for example, tea bowls, dishes, bowls, cups, cups, bottles, coffee-boiled containers, pots, mortars, cups, etc.) Etc.), aquarium (aquaculture tank, appreciation aquarium, etc.), chemical laboratory equipment (beaker, reaction vessel, test tube, flask, petri dish, cooling tube, stir bar, stirrer, mortar, vat, syringe), tile, tile, Enamel tableware, enamel basin, enamel pan, various concrete products.

(D) Example of mirror:
Hand mirrors, sight mirrors, bathroom mirrors, bathroom mirrors, automotive mirrors (back mirrors, side mirrors), half mirrors, show window mirrors, department store product mirrors, etc.

(E) Examples of molding members:
Press mold, cast mold, injection mold, transfer mold, vacuum mold, blow mold, extrusion mold, inflation mold, fiber spinning Base, calendar processing roll, etc.

(F) Examples of ornaments and jewelry:
Jewelry such as watches, glasses frames and pearls, pearls, pearls, rubies, emeralds, garnets, cat's eyes, diamonds, topaz, bloodstone, aquamarine, sardonyx, turquoise, jade, marble, amethyst, cameo, opal, crystal, glass, etc. Furthermore, platinum, gold, silver, copper, aluminum, titanium, tin or their alloys and stainless steel rings, bracelets, brooches, tie pins, earrings, necklaces and other precious metal decoration products.

(G) Examples of food molds:
Cake baking mold, cookie baking mold, bread baking mold, chocolate molding mold, jelly molding mold, ice cream molding mold, oven dish, ice tray, etc.

(H) Examples of cooking utensils and kitchen equipment:
Pots, kettles, kettles, pots, frying pans, hot plates, grilled nets, oil drainers, octopus grilled plates, sinks, etc.

(I) Examples of paper: gravure paper, water / oil repellent paper, poster paper, high-grade brochure paper

(J) Examples of resins:
Polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyethersulfone, polyphenylene sulfide, phenol resin, furan resin, urea resin, epoxy resin, polyurethane , Silicon resin, ABS resin, methacrylic resin, acrylate resin, polyacetal, polyphenylene oxide, etc.

(K) Examples of home appliances and information communication equipment:
Television, radio, tape recorder, audio, CD, refrigeration equipment refrigerator, freezer, air conditioner, juicer, mixer, fan blade, lighting equipment, dial, hair dryer, telephone, facsimile, mobile phone, personal computer and peripherals Equipment (eg keyboard, mouse) etc.

(L) Examples of sports equipment:
Skis, fishing rods, pole vaulting poles, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fishnets, fishing floats, etc.

(M) Examples applied to vehicle parts:
(1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector, (2) Cellulose plastic: car mark, handle (3) FRP (fiber reinforced resin): outer plate bumper, engine cover, (4 ) Phenolic resin: Brake (5) Polyacetal: Wiper gear, gas valve, carburetor parts (6) Polyamide: Radiator fan (7) Polyarylate: Direction indicator lens, instrument panel lens, relay housing (8) Polybutylene terephthalate (PBT): Rear end, front fender (9) Polyamino bismaleimide: engine parts, gear box, wheel, suspension drive system (10) Methacrylic resin: lamp cover lens, instrument panel and cover, center mark (11) Polyprop Down: bumper (12) polyphenylene oxide: radiator grill, wheel cap (13) polyurethane: a bumper, fender, instrument panel, a fan (14) Unsaturated polyester resin: body, fuel tank, heater housing, instrument panel

(N) Examples of office supplies:
Fountain pens, ballpoint pens, sharp pencils, brush holders, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, drafting tools, etc.

(O) Examples of building materials:
Roofing materials, outer wall materials, interior materials. Roof tiles such as kiln tiles, slate tiles, and tin (galvanized iron plate). Outer wall materials include wood (including processed wood), mortar, concrete, calcium slab, ceramic sizing, metal sizing, brick, stone, plastic material, aluminum and other metal materials. Interior materials include wood (including processed wood), metal materials such as aluminum, plastic materials, paper, and fibers.

(P) Examples of stone:
Flower kite, marble, granite, etc. For example, buildings, building materials, art, figurines, baths, tombstones, monuments, gate pillars, stone walls, paving stones, etc.

(Q) Examples of musical instruments and audio equipment:
Percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and other acoustic instruments such as microphones and speakers. Specifically, percussion instruments such as drums and cymbals, stringed instruments such as violins, cellos, guitars and kotos, keyboard instruments such as pianos, woodwind instruments such as flutes, clarinet, shakuhachi, brass instruments such as horns and trumpets, and microphones , Audio equipment such as speakers and earphones.

(R) Examples of textile products:
It is a so-called apparel product and includes general natural fiber products, chemical fibers, synthetic fiber products, fur products, leather products, and paper products. Specifically, clothing, hats, ties, shoes, bags, umbrellas, raincoats, sports clothing, wall cloths, curtains, jutans, furniture, vehicle interiors, sheets, sanitary products, paper diapers, bedding, sheets, Fishing net etc.

Examples carried out for confirming the features and effects of the present invention will be described below.
Example 1 Formation of Antifouling Antibacterial Antifungal Film (1) Formation of Mixed Monomolecular Film Having Fluorocarbon Group and Epoxy Group A quartz substrate used as a base material is sequentially ultrasonicated in chloroform, acetone and ethanol. Washed. Next, an excimer cleaning process was performed on the quartz substrate cleaned with an organic solvent. The quartz substrate washed in this manner is added to a toluene solution (each 0.01 mol / L) of pentadecafluorodecyltrimethoxysilane (Chemical Formula 10) and 11,12-epoxydodecyltrimethoxysilane (Chemical Formula 11) (EDDS). Soaked for 2 hours. Thereafter, the quartz substrate was pulled up, rinsed with toluene, and left in the atmosphere for 24 hours.

(2) Formation of mixed monomolecular film having fluorocarbon group and imidazolyl group The quartz substrate on which the mixed monomolecular film having fluorocarbon group and epoxy group is formed in the above (1) is used as a methanol solution of 2-methylimidazole. It was immersed in a solution prepared by diluting 5 mL of (0.1 mol / L) with 50 mL of pure water and allowed to stand for 1 hour while heating at 80 ° C. After pulling up the substrate, the substrate was heated in a muffle furnace at 150 ° C. for 24 hours. After removing from the furnace, ultrasonic cleaning was sequentially performed in chloroform, acetone, and ethanol. In this way, an epoxy group and an amino group of 2-methylimidazole were reacted to form a mixed monomolecular film having a fluorocarbon group and an imidazolyl group.

(3) Formation of antifouling antibacterial and antifouling coating The quartz substrate on which the mixed monomolecular film having a fluorocarbon group and an imidazolyl group in (2) above was formed, and 10 mL of a 0.1 mol / L aqueous solution of copper (II) chloride, It was immersed in a solution prepared by mixing 50 mL of pure water and 3 mL of a 0.1 mol / L aqueous solution of sodium hydroxide and left at room temperature for 2 hours. The substrate was pulled up and dried to obtain an antifouling antibacterial and antifungal coating in which copper (II) ions were coordinated to the imidazolyl group.

Comparative Example: Formation of Monomolecular Film Having Alkyl Group According to the same procedure as in Example 1 (1) except that octadecyltrimethoxysilane CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ was used as a film compound, A monomolecular film having an alkyl group was formed on the surface of the substrate.

Example 2: Evaluation of antifouling antibacterial and antifungal coating (1) Measurement of water drop contact angle The water contact angle was evaluated by an automatic contact angle meter CA-VP (Kyowa Interface Science Co., Ltd.). The amount of water droplets was fixed at 3 μL, 5 points were measured for each sample, and the average value and standard deviation were evaluated. A quartz substrate after excimer laser cleaning treatment, a quartz substrate with a monomolecular film having an epoxy group, a quartz substrate with a monomolecular film having an imidazolyl group, and a copper (II) ion (Cu ^The contact angle was measured for each quartz substrate on which an antifouling antibacterial and antifungal film was formed by coordination of ( ²⁺ ).

Table 1 shows a quartz substrate after excimer laser cleaning treatment, a quartz substrate on which a monomolecular film having an epoxy group is formed, a quartz substrate on which a monomolecular film having an imidazolyl group is formed, and Cu ²⁺ on a monomolecular film having an imidazolyl group. The measurement result of the water droplet contact angle of the quartz substrate on which the antifouling antibacterial and antifungal coating is formed by coordination is shown.

The quartz substrate after the excimer laser cleaning treatment showed a low value of 4.1 degrees. This is because the soiling due to organic matter was removed and the hydrophilicity was increased by exposing the hydroxyl group to the surface. After the formation of the monomolecular film having an epoxy group, the water droplet contact angle increased. This is due to the increase in hydrophobicity due to the formation of a monomolecular film having an epoxy group on a quartz substrate. Further, after the formation of the monomolecular film having an imidazolyl group, the contact angle of the water droplet was further increased. This is considered to be because the imidazolyl group having higher hydrophobicity was bonded. When Cu ²⁺ was coordinated, a slight decrease in the water droplet contact angle was observed. This is thought to be due to the increased polarity of the surface of the antifouling antibacterial and antifouling coating due to the coordination of Cu ²⁺ .

(2) Measurement of infrared absorption spectrum Red quartz substrate on which a monomolecular film having a fluorocarbon group and an epoxy group, a monomolecular film having a fluorocarbon group and an imidazolyl group, and a monomolecular film having an alkyl group are formed FT-IR Nicolet 8700 was used for measurement of the external absorption spectrum. The substrate to be measured was placed in the sample chamber of the FT-IR apparatus, and nitrogen substitution was performed at a flow rate of 10 L / min for 5 hours. First, a quartz substrate on which no monomolecular film was formed was measured as a reference, and then the substrate on which the monomolecular film was formed was measured to obtain a difference spectrum between the two. Further, the orientation of the monomolecular film was evaluated by measuring the polarizing plate attached to the spectrometer while rotating it by 0 to 90 degrees.

The confirmation of the reaction between 2-methylimidazole and the epoxy-terminated monolayer was confirmed by the absorption peak of the methyl group on the imidazole ring. The orientation of the monomolecular film on the substrate was confirmed from the relationship between the angle of the deflecting plate and the absorption intensity. Specifically, when the absorption spectrum at the angle of the polarizing plate is 0 degree, the absorption spectrum shows strong absorption, which means that the molecules forming the monomolecular film are “sleeping” on the substrate, and the absorption at 90 degrees. A strong spectrum indicates that the molecule is upright.

In the quartz substrate on which the monomolecular film having the fluorocarbon group and the epoxy group produced in Example 1 (1) and the monomolecular film having the alkyl group produced in the comparative example were formed, 2925 cm ⁻¹ (reverse CH ₂₎ The absorbance ratio of the absorption peak of symmetric stretching vibration) and 2850 cm ⁻¹ (absorption peak of symmetric stretching vibration) was about 1.0: 2.0 for the former and about 1.0: 1.7 for the latter. This is almost equal to the ratio of the number of methylene carbons (10:21 and 10:17, respectively) in the film compounds forming the former and the latter monomolecular film, and in the former, the reaction between the epoxy group and the alkoxysilyl group occurs. It was confirmed that both formed a monomolecular film.

In addition, when comparing the infrared absorption spectra of a quartz substrate on which a monomolecular film having a fluorocarbon group and an epoxy group and a monomolecular film having a fluorocarbon group and an imidazolyl group are respectively formed, the latter is 2925 cm ^−1. In addition, the absorbance at 2850 cm ⁻¹ increased in comparison with the former, and a new peak was observed at 2960 cm ⁻¹ (CH reverse symmetrical stretching vibration peak). This is believed to be due to the methyl group in 2-methylimidazole.
From this, it was confirmed that the imidazolyl group was bonded and fixed to the surface of the monomolecular film by the reaction between the epoxy group-terminated monomolecular film and 2-methylimidazole.

(3) Measurement of ultraviolet-visible (UV-VIS) absorption spectrum In order to confirm the coordination of Cu ²⁺ to the imidazolyl group, an anti-fouling antibacterial anti-fouling coating using an ultraviolet-visible spectrophotometer (V-530) The UV-VIS spectrum of the quartz substrate on which was formed was measured. A difference spectrum was obtained using a substrate on which a monomolecular film having an imidazolyl group was formed as a reference. In order to measure minute changes in absorbance in a monomolecular film, the monomolecular film having an imidazolyl group and an antifouling antibacterial and antifouling coating were divided into four quartz substrates, which were laminated with a jig. The measurement was performed in the state.

An absorption peak derived from a complex of Cu ²⁺ and 2-methylimidazole was observed at 250 nm to 260 nm, and it was confirmed that the monomolecular film having an imidazolyl group and Cu ²⁺ formed a complex. Moreover, when the density ^| concentration of Cu < ²⁺ > couple | bonded and fixed to the antifouling antibacterial antifungal film was calculated | required with the analytical curve method, the value of 0.8 * 10 < ^-6 > M / cm < ² > was obtained.

(4) Antibacterial test First, an agar medium (standard agar medium, Nissui Pharmaceutical Co., Ltd.) and a petri dish to be used are wrapped in aluminum foil and then heated at 121 ° C. for 15 minutes in a high-temperature steam sterilizer (SANYO Electric Medica MLS-3750). Sterilization was performed. Next, E. coli (NBRC3301 Escherichia coli) was inoculated on the petri dish on which the agar medium was prepared, and cultured at 37 ° C. for 30 minutes in an incubator (SANYO Electric Medica MCO-17ALC). Next, a quartz substrate on which an antifouling antibacterial and antifungal coating is formed as an antibacterial and antifungal treatment group and an untreated quartz substrate as a control group are placed on an agar medium on which E. coli has propagated, and again in the incubator. Culture was performed. Cultivation was carried out for 9 days, and during the period (2 days, 8 days, and 9 days after the start of culture), the growth condition of E. coli on the surface of the medium was visually confirmed for the antibacterial / antifungal treatment group and the control group. The antibacterial effect was measured from the change over time. Visual confirmation was performed with the quartz substrate removed.

Escherichia coli breeding was confirmed in both the antibacterial and antifungal treatment group and the control group, while the control group had colonies of E. coli on the agar medium, whereas the antibacterial and antifungal treatment group had agar. The culture medium was generally white and cloudy, and there was a difference in the breeding state. In addition, in the antibacterial and antifungal treatment group, only the portion on which the quartz substrate was placed was transparent. Therefore, in the antibacterial / antifungal treatment group, the growth of Escherichia coli was suppressed in the part that was in contact with the antifouling antibacterial / antifungal coating, and such antibacterial / antifungal effect was sustained for at least 9 days. Confirmed to do.

It is explanatory drawing which expanded the cross-sectional structure of the antifouling antibacterial antifungal film which concerns on the 1st Embodiment of this invention to the molecular level, and was represented typically. It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the monomolecular film which has an epoxy group in the manufacturing method of the antifouling antibacterial antifungal film which concerns on the 2nd Embodiment of this invention. It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the monomolecular film | membrane which has an imidazolyl group in the manufacturing method of the antifouling antibacterial and antifungal film.

Explanation of symbols

10: Antifouling antibacterial antifouling coating 11: Base material 12: Mixed monomolecular film having fluorocarbon group and epoxy group 13: Mixed monomolecular film having fluorocarbon group and imidazolyl group

Claims (10)

A first film substance having a fluorocarbon group chemically bonded to the surface of the substrate and a second film substance having a coordination bond group that forms a coordinate bond with a metal atom or metal ion are mixed at a molecular level. Antibacterial and antifungal metal fixed to the surface of the mixed coating through a coordination bond formed between the mixed monomolecular film formed on the surface of the base material in a state of being bonded and the coordination bond group An antifouling antibacterial and antifouling coating comprising an atom or a metal ion. The first and second film materials are bonded to each other through a bond formed by a reaction between any of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group and the surface of the substrate. 2. The antifouling antibacterial and antifungal film according to claim 1, wherein the antifouling antibacterial and antifungal film is fixed to the surface of the material. The antifouling antibacterial and antifungal coating according to any one of claims 1 and 2, wherein the metal atom or metal ion is an Ag, Cu, Zn atom or an ion of these metals. The said base material is a material used for any of a building, a motor vehicle, a ship, an aircraft, a train, an apparel product, jewelry, and a decoration, The any one of Claims 1-3 characterized by the above-mentioned. Antifouling antibacterial and antifouling coating as described. A first film-binding group that forms a bond with the surface of the substrate at one end of the molecule, a first film compound having a fluorocarbon group at the other end, and a bond with the surface of the substrate at one end of the molecule The second surface binding group is chemically bonded to the surface of the base material by reacting the third film compound having the first reactive group at the other end with the surface of the base material. Forming a mixed monomolecular film of the first and third film substances, and forming a coordinate bond with the second reactive group and metal atom or metal ion that form a bond with the first reactive group; Molecules each having a coordinating bond group to be bonded to the third film substance via a bond formed by the reaction of the first and second reactive groups, and the first and second film substances mixing consists of a step D for converting the monolayer, the first film having a fluorocarbon group at one end of the molecule And a step A of mixing monomolecular film of the second film material is formed on the surface of the substrate having a coordinating group of the one end of the molecule to form a metal atom or metal ion and a coordination bond,
A step B of fixing the metal atom or metal ion to the surface of the mixed monolayer through a coordination bond formed between the antibacterial and antifungal metal atom or metal ion and the coordination bond group; A method for producing an antifouling antibacterial and antifungal film, comprising: 6. The method for producing an antifouling antibacterial / antifungal film according to claim 5 , wherein the surface binding group is any one of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group. The method for producing an antifouling antibacterial and antifungal film according to claim 5 or 6, wherein the metal atom or metal ion is any one of Ag, Cu, Zn atom and ions of these metals. The said base material is a material used for either a building, a motor vehicle, a ship, an aircraft, a train, an apparel product, jewelry, and an ornament, Any one of Claims 5-7 characterized by the above-mentioned. A method for producing the antifouling antibacterial and antifungal coating described An antifouling antibacterial and antifungal film according to any one of claims 1 to 4 is formed on the surface. The product according to claim 9 , wherein the product is any one of a building, an automobile, a ship, an aircraft, a train, an apparel product, a jewelry, and a decoration.

Images