JP5422857B2 - Antifouling, antibacterial and antifungal radiating fin, method for producing the same, and air conditioner using the same - Google Patents

Description

The present invention relates to an antifouling antibacterial and antifungal radiating fin, a method for producing the same, and an air conditioner using the same. More specifically, the present invention relates to an antifouling, antibacterial and antifungal heat dissipating fin that has high durability and can be manufactured at low cost and has high safety to the human body and the environment, a manufacturing method thereof, and an air conditioner using them.

The demand for antibacterial and antibacterial air conditioners has been increasing in response to the improvement of public hygiene awareness accompanying changes in the living environment and the aging of society in recent years. 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 the development of antibacterial and anti-air conditioners, 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 Ag (silver), Cu (copper), zinc (Zn), as antibacterial and antifungal agents having high toxicity and low risk of environmental pollution Metal atoms or ions such as tin (Sn) have attracted 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 inefficiency and 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 since the antibacterial substance can be immobilized at a high concentration only through the covalent bond on the outermost surface, the efficiency is high, the durability is high, and the human body can be manufactured at low cost. An object of the present invention is to provide an antifouling antibacterial and antifungal radiation fin having high safety to the environment, a manufacturing method thereof, and an air conditioner using them.

The first aspect of the present invention is the first film substance having a fluorocarbon group chemically bonded to the surface of the fin and the second film having a coordination bond group that forms a coordinate bond with a metal atom or metal ion. A mixed film formed by a film substance, and an antibacterial and antifungal metal atom or metal ion fixed to the surface of the mixed film through a coordination bond formed between the coordination bond groups. By providing an antifouling antibacterial and antifungal heat dissipating fin characterized by the above, the above-mentioned problems are solved.
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 metal atoms or ions such as Ag, Cu, Zn, Sn, etc.

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. Furthermore, since the surface energy of the antifouling antibacterial and antifungal radiation fins is reduced by the first film material having a fluorocarbon group, the surface of the coating is kept clean, and the nutrition of bacteria and fungi Adhesion of the organic film as a source to the coating surface is also suppressed, and the antibacterial and antifungal effect can be further enhanced.
Here, the first film substance is for enhancing the antifouling property, and is not necessarily included when the antifouling property is not required.

The mixed film formed by the first and second film substances chemically bonded to the fin surface is a thin film of the order of nm, so even if it is formed on the surface of the fin, it does not hinder heat conduction, and various thermal equipment It can be applied to. In addition, the antifouling antibacterial and antifungal coating is extremely excellent in durability because it is covalently bonded to the fin. Furthermore, since the film forming process is very simple, it is possible to manufacture antifouling antibacterial and antifungal heat dissipating fins at low cost, and without depending on the shape of the base fins, and on the surface of the fins with a large area. Can also be easily manufactured.

In the first aspect of the present invention, the first and second film substances are 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 fin. It may be fixed to the surface of the fin through the formed connection.
The alkoxysilyl group and the halosilyl group can form a covalent bond by a condensation reaction with the fin surface of aluminum or an alloy thereof having an active hydrogen group such as a hydroxyl group. Moreover, thiol groups and sulfide groups can also form thiolate bonds on the surface of fins made of noble metals such as gold or transition metals.

According to a second aspect of the present invention, there is provided a first film substance having a fluorocarbon group at one end of a molecule, and a second film having a coordination bond group forming a coordinate bond with a metal atom or metal ion at one end of the molecule. Forming the mixed film of the film substance on the surface of the fin, the metal atom or through the coordination bond formed between the antibacterial and antifungal metal atom or metal ion and the coordination bond group The present invention solves the above problems by providing a method for producing an antifouling, antibacterial and antifungal heat dissipating fin, comprising the step B of fixing metal ions to the surface of the mixed coating.

Since the mixed film of the first and second film substances chemically bonded to the surface of the fin is a thin film having a film thickness of the order of nm, the method for producing the antifouling antibacterial and antifungal heat dissipating fin according to this aspect (hereinafter “book” The antifouling antibacterial and antifungal heat dissipating fin obtained by “method” has a nano-level film thickness and can be applied to various fins without impairing the heat conduction characteristics of the fin. In addition, the antifouling antibacterial and heat radiating fin manufactured by this method has an antibacterial and antifungal substance fixed to the fin through a covalent bond or a coordinate bond. It is much stronger than the other, and it is extremely durable. Furthermore, since the film forming process is very simple, the present method can be carried out at a low cost, and an antifouling antibacterial and antifungal heat dissipating fin and the same are used on the surface of a large area fin. Air conditioners can be made.

Furthermore, in the second aspect of the present invention, the step A includes a first surface binding group that forms a bond with the surface of the fin 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 fin at one end of the molecule, and a first reaction at the other end A step C of reacting a third film compound each having a functional group with the surface of the fin to form a mixed film of the first and third film substances chemically bonded to the surface of the fin; A molecule having a second reactive group that forms a bond with a reactive group and a coordination bond group that forms a coordinate bond with a metal atom or metal ion, respectively, is reacted with the first and second reactive groups. Bound to the third membrane material through a bond formed by 1 and may be made and a step D of converting the mixture coating film of the second film material. By doing so, it is possible to produce antifouling antibacterial and antifungal heat dissipating fins using raw materials that are easier to obtain and cheaper than film compounds each having a surface binding group and a coordination bond group at both ends of the molecule. In addition, 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.

Here, when only antibacterial and antifungal properties are required, the first film substance containing a fluorocarbon group may not necessarily be included.

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 fins made of metal, ceramics, resin, fiber, etc. having an active hydrogen group such as a hydroxyl group. In addition, the thiol group and sulfide group can form a covalent bond on the surface of a fin 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, Sn 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.

According to a third aspect of the present invention, there is provided an air conditioner characterized in that the antifouling, antibacterial and antifungal heat dissipating fins according to the first aspect of the present invention are formed on the surface. It is.

According to a fourth aspect of the present invention, there is provided a first film substance having a fluorocarbon group and a second film substance having a linking group that forms a thiolate bond with a metal atom or metal fine particle, chemically bonded to the surface of the fin. An antifouling antibacterial and antifungal property comprising: a mixed film to be formed; and antibacterial and antifungal metal fine particles fixed to the surface of the mixed film through a bond formed between the binding groups. The problem is solved by providing a heat dissipating fin.

Here, the metal fine particles are nano-sized fine particles, preferably the wavelength of visible light (400 nm) or less, more preferably 200 to 10 nm, which does not impair the color tone, gloss, texture, and heat dissipation characteristics of the fin. So it is convenient. In addition, the linking group that forms a thiolate bond includes a thiol group or a triazine thiol group that is easy to handle.
Furthermore, “antibacterial and antifungal metal atom or metal fine particle” means a thiol group, a hydroxyl group, a surface protein such as bacteria and fungi (mold), and a membrane protein and enzyme, such as surfaces and active centers. It binds to polar groups such as carboxyl groups and amino groups to cause denaturation and inactivation, inhibits their functions, or reaches the inside of cells to inactivate enzymes, etc. It refers to metal atoms or fine particles such as Ag, Cu, Zn, and Sn that can prevent survival.

The antibacterial and antifungal metal fine particles bonded to the binding group of the second membrane substance can suppress the growth of bacteria and fungi that may adversely affect the human body. Furthermore, since the surface energy of the antifouling antibacterial and antifungal radiation fin is reduced by the first film substance having a fluorocarbon group, the adhesion of dirt to the surface of the coating is reduced, and in addition to being kept clean, Adhesion of the organic material serving as a nutrient source for bacteria and fungi to the coating surface is also suppressed, and the antibacterial and antifungal effect can be further enhanced.
Also in this embodiment, since the antibacterial substance can be immobilized at a high concentration only on the outermost surface through a covalent bond, it is highly efficient, durable, inexpensive and can be manufactured at a low cost, and is highly safe for the human body and the environment. The antibacterial and antifouling heat dissipating fins, the manufacturing method thereof, and the air conditioner using them can be provided.
Here, when only antibacterial and antifungal properties are required, the first film substance containing a fluorocarbon group may not necessarily be included.

Since the mixed film formed by the first and second film substances chemically bonded to the surface of the fin is a thin film of the order of nm, the antifouling antibacterial and antifungal heat dissipating fin does not impair the heat conduction characteristics of the fin, Applicable to radiating fins. Further, the antifouling antibacterial and antifungal heat dissipating fins are extremely excellent in durability because they are covalently bonded to the fins. Furthermore, since the film forming process is very simple, the antifouling antibacterial and antifungal heat dissipating fins can be manufactured at a low cost, and do not depend on the shape of the base fins, and on the surface of the fins with a large area. Can also be formed easily.

In the fourth aspect of the present invention, the first and second film substances are 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 fin. It may be fixed to the surface of the fin through the formed connection.
The alkoxysilyl group and the halosilyl group can form a covalent bond by a condensation reaction with the surface of various fins made of metal, ceramics, resin, fiber, etc. having an active hydrogen group such as a hydroxyl group.
Further, the thiol group and sulfide group can form a thiolate bond with antibacterial and antifungal particles such as Ag, Cu, Zn and Sn.

According to a fifth aspect of the present invention, there is provided a first film material having a fluorocarbon group at one end of a molecule and a second film material having a bonding group that forms a thiolate bond with a metal atom or metal fine particle at one end of the molecule. Step A for forming a mixed film on the surface of the fin, and Step B for fixing the metal fine particles to the surface of the mixed film through a bond formed between the antibacterial and antifungal metal fine particles and the binding group. The above-mentioned problems are solved by providing a method for producing an antifouling antibacterial and antifungal heat dissipating fin.

Since the mixed film of the first and second film substances chemically bonded to the surface of the fin is a thin film having a film thickness of the order of nm, the method for producing the antifouling antibacterial and antifungal heat dissipating fin according to this aspect (hereinafter “book” The antifouling antibacterial and antifungal heat dissipating fins obtained by the “method” can be applied to various heat dissipating fins without impairing the heat conduction characteristics of the fins. Moreover, since the antifouling antibacterial and heat radiating fins manufactured by this method are covalently bonded to the fins, they are extremely excellent in durability. Furthermore, since the film forming process is very simple, this method can be carried out at a low cost, and an antifouling antibacterial and antifungal heat dissipating fin can be easily formed on the surface of a large area fin. it can.

In the fifth aspect of the present invention, the step A includes a first film having a first surface binding group that forms a bond with the surface of the fin at one end of the molecule and a fluorocarbon group at the other end. A 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 fin at one end of the molecule and a first reactivity at the other end Reacting the surface of the fin with a third film compound each having a group to form a mixed film of the first and third film materials chemically bonded to the surface of the fin; Molecules each having a second reactive group that forms a bond with a reactive group and a metal atom or a bonding group that forms a thiolate bond with a metal fine particle are formed by the reaction of the first and second reactive groups. Binding to the third membrane material through a bond, and Beauty may be made and a step D of converting the mixture coating film of the second film material. In this way, an antifouling, antibacterial and antifungal heat dissipating fin 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 binding group at both ends of the molecule. In addition, adverse effects such as a decrease in yield due to the reaction between the surface binding group and the binding group can be avoided.

In the fifth 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 fins made of metal, ceramics, resin, fiber, etc. having an active hydrogen group such as a hydroxyl group. In addition, the thiol group and the sulfide group can form a covalent bond on the surface of the fin made of light metal.

In the fourth and fifth aspects of the present invention, the metal fine particles are preferably any one of Ag, Cu, Zn, and Sn.
These metal fine particles have high antibacterial and antifungal properties and are firmly bonded to the fin surface, so they have little harmful effect on the human body and the environment. It is possible to use.

According to a sixth aspect of the present invention, there is provided an air conditioner characterized in that the antifouling, antibacterial and antifungal heat dissipating fins according to the third aspect of the present invention are formed on the surface. It is.

1st-6th aspect of this invention WHEREIN: The said fin may be used for the air conditioner used for either a building, a motor vehicle, a ship, an aircraft, and a train.
Furthermore, if the fin is aluminum or an aluminum alloy and the surface is oxidized, the durability can be further improved.

According to the manufacturing method of the antifouling antibacterial antifouling heat radiation fin and the antifouling antibacterial antifouling heat dissipation fin according to the present invention, the antifouling antibacterial antifouling film can be efficiently formed on the surface of various fins at a low cost. An antifouling antibacterial antifouling heat radiation fin having both antifouling properties, antibacterial and antibacterial properties, durability, and safety for the human body and the environment, a manufacturing method thereof, and an air conditioner using the same can be provided.
In addition, since metal atoms or ions having antibacterial and antifungal properties are fixed to the surface of the first antifouling and antibacterial and heat radiating fin according to the present invention via covalent bonds or coordinate bonds, most of them Although it is not released, even if released, the coordinating group remains without being lost, so that antibacterial and antifungal properties can be restored any number of times by recombining metal part fine particles or ions. As long as the film of the film compound remains, the antibacterial and antifungal properties can be exhibited semipermanently.

Furthermore, since the metal fine particles having antibacterial and antifungal properties are fixed to the surface of the second antifouling and antibacterial and heat radiating fin according to the present invention through thiolate bonds, they are almost released. However, even if released, the thiol-bonding group remains without being lost, so it is possible to restore antibacterial and antifungal properties any number of times by recombining the metal part fine particles. As long as the coating remains, antibacterial and antifungal properties can be exhibited semipermanently.

It is explanatory drawing which expanded the cross-sectional structure of the antifouling antibacterial antifungal radiation fin 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 radiation fin 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 said antifouling antibacterial antifungal radiation fin.

It is explanatory drawing which expanded the cross-sectional structure of the antifouling antibacterial antifungal radiation fin which concerns on the 1st Embodiment of this invention to the molecular level, and was represented typically. In the method for producing an antifouling antibacterial and antifungal heat dissipating fin according to the second embodiment of the present invention, it has been expanded to the molecular level to explain the process of forming a mixed monomolecular film having a fluorocarbon group and a thiol group. It is a conceptual diagram. It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of fixing Cu microparticles | fine-particles in the manufacturing method of the antifouling antibacterial and antifungal radiation fin.

(Embodiment 1)
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 explanation schematically showing the cross-sectional structure of the antifouling antibacterial and heat radiating fin, in which the antibacterial substance according to the first embodiment of the present invention is fixed as a complex ion, expanded to the molecular level. FIG. 2 shows a mixed monomolecular film having a fluorocarbon group and an epoxy group in a method for producing an antifouling antibacterial and antifungal radiation fin in which an antibacterial substance according to a second embodiment of the present invention is fixed as a complex ion. FIG. 3 is a conceptual diagram enlarged to the molecular level to explain the process of forming the antifouling antibacterial / antifungal radiation fin, and forms a monomolecular film having a fluorocarbon group and an imidazolyl group. It is the conceptual diagram expanded to the molecular level in order to demonstrate a process.

As shown in FIG. 1, the antifouling antibacterial and antifungal radiating fin 10 is a fluorocarbon group chemically bonded to the surface of the fin (in FIG. 1, a pentadecafluorodecyl group is shown as an example. The same applies to FIGS. 2 and 3) and a mixed monomolecular film 13 having an imidazolyl group (a first film material having a pentadecafluorodecyl group and a second film material having an imidazolyl group (an example of a coordination bond group)) Copper ions (antibacterial and antifungal metal atoms or metal ions) fixed to the surface of the mixed film through a coordinate bond formed between the coordinate bond group formed between the film and the coordination bond group. Example). 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.

Antifouling, antibacterial and antifungal heat dissipating fins 10 are formed between 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 fin 11, and a copper ion and an imidazolyl group. It can be produced by a method for producing an antifouling antibacterial and antifungal heat dissipating fin having a step B for fixing copper ions to the surface of a 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 fin 11 at one end of the molecule and a fluorocarbon group at the other end, and the molecule An alkoxysilane compound (first example of a second reactive group) having an alkoxysilyl group (an example of a second surface reactive group) that forms a bond with the surface of the fin 11 at one end of 3) is mixed with the surface of the fin 11 to react, and the mixed monomolecular film 12 (first and third films) having a fluorocarbon group and an epoxy group chemically bonded to the surface of the fin 11. Step C (FIG. 2) for forming a mixed film of materials), an amino group that forms a bond with an epoxy group (an example of a second reactive group), and an imino group that forms a coordinate bond with a copper ion ( 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 an epoxy group is formed through a bond formed by a reaction between the epoxy group and an amino group. Step D for bonding 2-methylimidazole to a film material having fluorinated carbon and converting the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group into a mixed monomolecular film 13 having a fluorocarbon group and an imidazolyl group (FIG. 3). ).

As the fin 11 that can be used, any 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. Or an aluminum alloy is convenient.
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 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 alkoxysilane compound containing a fluorocarbon group that can be used in Step D 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 fin 11 and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group on the surface of the fin 11 cause a condensation reaction. A monomolecular film 12 having an epoxy group having a structure as shown is formed. The three single bonds extending from the oxygen atom are bonded to the surface of the fin 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 fin 11. Yes.

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 fin 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 fin 11. Yes.

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 fin 11, a balance between antifouling properties and antibacterial and antifungal properties required, and It can select suitably according to the kind etc. of film | 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 fin 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 fin 11, so it is preferable to remove these impurities beforehand by thoroughly washing and drying the fin 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 fin 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 fin 11 with respect to the surface functional group is different, the mixing ratio of both in the solution and the ratio of both in the mixed monomolecular film 12 having a fluorocarbon group and an epoxy group are obtained. Note that they 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 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. 2-methylimidazole and fluorinated carbon can be obtained by immersing the fin 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. It can be performed by bringing the mixed monomolecular film 12 having a group and an epoxy group into contact with each other and heating to about 100 ° C.

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 fin 11 and the fluorocarbon group and the epoxy group is used. be able to. 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 fin, 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 completion of the reaction, the mixture is washed with a solvent to remove excess 2-methylimidazole remaining on the surface as an unreacted product, whereby a mixed 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. An antibacterial / antifungal radiation fin 10 is obtained (see FIG. 1).
Coordination bonds are formed by immersing the fin 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 by mixing a single unit having a fluorocarbon group and an imidazolyl group. By applying a solution in which a copper salt is dissolved on the molecular 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 fin 11 and the fluorocarbon group and the imidazolyl group is used. Although it is possible, 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 fin 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, zinc, tin metal atoms and their ions.

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 fin 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 chemical 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.

(Embodiment 2)
Here, FIG. 4 is an enlarged view of the cross-sectional structure of the antifouling antibacterial and antifouling heat dissipating fin in which metal (for example, Cu) fine particles having antibacterial action are fixed on the surface according to the first embodiment of the present invention to the molecular level. FIG. 5 is a schematic diagram schematically showing the antifouling antibacterial and heat radiating fins according to the second embodiment of the present invention, in which a mixed monomolecular film having a fluorocarbon group and a thiol group is formed. FIG. 6 is a conceptual diagram enlarged to the molecular level to explain the process of performing the process, and FIG. 6 illustrates the process of forming a monomolecular film having a fluorocarbon group and Cu fine particles in the method of manufacturing the antifouling antibacterial and antifungal radiation fin. It is the conceptual diagram expanded to the molecular level in order to do.

As shown in FIG. 4, the antifouling antibacterial and antifungal heat dissipating fin 20 has a fluorocarbon group 22 chemically bonded to the surface of the fin 21 (in FIG. 1, a pentadecafluorodecyl group is illustrated as an example. The same applies to FIGS. 5 and 6.) Mixed monomolecular film 23 in which Cu fine particles are fixed via S (first film substance having pentadecafluorodecyl group and Cu fine particles are fixed via thiolate bonds) An example of a mixed coating formed by mixing the second film substances.

Here, as shown in FIG. 5, the antifouling antibacterial and antifungal heat dissipating fins 20 are prepared by mixing antifouling substances each having a fluorocarbon group and a thiol group (for example, 1: 1 in molecular composition). Forming the formed mixed monomolecular film 22 on the surface of the fin 21; and
As shown in FIG. 6, Cu fine particles having antibacterial action are formed on the surface of the mixed monomolecular film 22 through a thiolate bond formed between the thiol group and metal (for example, Cu) fine particles having antibacterial action. Fixing process B
It can manufacture by the manufacturing method of the antifouling antibacterial and antifungal heat dissipating fin.

More specifically, in step A, an alkoxysilane compound (an example of a first film compound) having a surface binding group that forms a bond with the surface of the fin 21 at one end of the molecule and a fluorocarbon group at the other end. And an alkoxysilane compound (second film) having an alkoxysilyl group (an example of a surface reactive group) that forms a bond with the surface of the fin 21 at one end of the molecule and a thiol group (an example of a reactive group) at the other end. An example of a compound is mixed with the surface of the fin 21 and reacted to form a mixed monomolecular film 22 having a fluorocarbon group and a thiol group chemically bonded to the surface of the fin 21 (mixing of the first and second film materials). An example of a film) (FIG. 5), and step B includes from step B (FIG. 6) of fixing metal (for example, Cu) fine particles having antibacterial action via the thiol group by thiolate bonds. Become.

The fin 21 can be made of any material having an active hydrogen group on the surface capable of forming a covalent bond by condensation reaction with an alkoxysilyl group.

Examples of the alkoxysilane compound containing a fluorocarbon group include an alkoxysilane compound represented by the following general formula (Formula 10).

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 alkoxysilane compound containing a fluorocarbon group that can be used in Step D include compounds shown in the following (61) to (72).

(61) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
(62) CF 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{(63) CF 3 (CF 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
(64) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(65) CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
(66) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
(67) CF 3 CH 2 O} (CH 2) 15 Si (OC 2 H 5) 3
_{(68) CF 3 (CH 2} ) 3 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{(69) CF 3 (CF 2} ) 5 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
_{(70) CF 3 (CF 2} ) 7 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
(71) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
(72) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃

The alkoxysilane compound having a thiol group has a functional group containing a thiol group (oxirane ring) and an alkoxysilyl group at both ends of the linear alkylene group, and is represented by the following general formula (Formula 11). An alkoxysilane compound is preferable.

In the above formula, E represents a functional group having a thiol group or a triazine thiol 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 a thiol group which can be used in process C, the compound shown to following (81)-(94) is mentioned.

(81) HSCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(82) HSCH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(83) HSCH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(84) TrCH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(85) TrCH (CH ₂ ) ₄ Si (OCH ₃ ) ₃
(86) TrCH (CH ₂ ) ₆ Si (OCH ₃ ) ₃
(87) HSCH ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃
(88) HSCH ₂ O (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(89) HSCH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) ₃
(80) TrCH (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
(91) TrCH (CH ₂ ) ₄ Si (OC ₂ H ₅ ) ₃
(92) TrCH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(93) HS (CH ₂ ) ₁₀ Si (OCH ₃ ) ₃
(54) HS (CH ₂ ) ₁₀ Si (OC ₂ H ₅ ) ₃

Here, Tr group represents the functional group (triazine thiol group) represented by Chemical formula 12, and represents:

When the solution containing the two alkoxysilane compounds is applied to the surface of the fin 21 and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group on the surface of the fin 21 cause a condensation reaction. A monomolecular film 22 having a thiol group having a structure as shown in Chemical Formula 13 is formed. The three single bonds extending from the oxygen atom are bonded to the surface of the fin 21 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 fin 21. Yes.

In the formula, R ¹ represents a linear alkylene group E— containing a fluorocarbon group CF ₃ (CF ₂ ) _n —YZ— (CH ₂ ) _m — (see Chemical Formula 1) and a functional group having a thiol group. It represents one of (CH ₂ ) _j- (see Chemical _Formula 11).
The three single bonds extending from the oxygen atoms are bonded to the surface of the fin 21 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 fin 21. Yes.

The total concentration of the alkoxysilane compound having a fluorocarbon group and the alkoxysilane compound having a thiol 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 a thiol group is not particularly limited, and the type and use of the fin 21, the balance between antifouling properties and antibacterial and antifungal properties required, and It can select suitably according to the kind etc. of film | membrane compound used. In addition, if the addition amount of the chemical | medical agent containing a fluorocarbon group becomes close to 0, naturally antifouling property will be lost.

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 fin 21. 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 fin 21. Therefore, it is preferable to remove these impurities in advance by thoroughly washing and drying the fin 21.
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 metal salts described above, the reaction 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 from Japan Thiol Resin, which is a ketimine compound, is used instead 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) from Japan Thiol Resin is used as the condensation catalyst, and the other conditions are the same, the monomolecular film 12 having a thiol 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 the reaction is completed, 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. 5, a mixed unit having a fluorocarbon group and a thiol group is obtained. A molecular film 22 is formed on the surface of the fin 21.

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.

The same surface binding groups of the membrane compound having a fluorocarbon group and the membrane compound having a thiol group can be used to form the same composition as the chemical solution composition because the reaction rate can be the same. .

The reaction between the thiol group on the mixed monomolecular film 12 having a fluorocarbon group and a thiol group and the metal fine particles can be performed by bringing the metal fine particles dispersed in an organic solvent (for example, alcohol) into contact with each other and heating.

Although heating temperature and time are suitably adjusted according to the kind of metal (Ag, Cu, Zn, Sn, etc.), they are room temperature-70 degreeC and 30 minutes-24 hours, respectively, for example. If necessary, a solvent having a higher boiling point may be used and heated at a high temperature (for example, 150 ° C.) for several hours to several tens of hours.

After the completion of the reaction, washing with a solvent and washing and removing fine particles remaining on the surface as unreacted materials can yield a monomolecular film 23 having Cu (metal) fine particles.

As the cleaning solvent, any solvent that can disperse the metal fine particles can be used. Further, in order to increase the cleaning efficiency, ultrasonic treatment or the like may be performed together.

In the present embodiment, a substance having a thiol group as a reactive group is used. However, any molecule can be used as long as it is a functional group capable of fixing metal fine particles by reacting with metal fine particles such as triazine thiol groups. .

In this embodiment, Cu fine particles are used as the metal fine particles having antibacterial and antifungal activity, but silver, zinc, and tin fine particles may be mentioned as other antibacterial metal fine particles that can be used.

In the case of forming a transparent antifouling antibacterial and antifungal heat dissipating fin, the monomolecular film has a thickness of about 1 nanometer, so that the heat dissipating characteristics of the base are not impaired at all. The size of the fine particles is preferably metal fine particles having a particle diameter of 500 microns to 10 nm.

Examples of the air conditioner on which the antifouling antibacterial and antifungal heat dissipating fin 20 according to the present invention is formed include indoor and vehicle air conditioners.

Examples carried out for confirming the features and effects of the present invention will be described below.
Example 1 Preparation of Antifouling Antibacterial Antifungal Heat Dissipation Fin 1 (1) Formation of Mixed Monomolecular Film Having Fluorocarbon Group and Epoxy Group Aluminum Fin Used as Fins in Succession in Chloroform, Acetone, and Ethanol Sonicated. Next, excimer cleaning treatment was performed on the aluminum fins cleaned with an organic solvent. The aluminum fins washed in this manner are added to a toluene solution (each 0.01 mol / L) of pentadecafluorodecyltrimethoxysilane (Chemical Formula 14) and 11,12-epoxydodecyltrimethoxysilane (Chemical Formula 15) (EDDS). Soaked for 2 hours. Thereafter, the aluminum fins were pulled up, rinsed with toluene, and left in the atmosphere for 24 hours.

(2) Formation of a mixed monomolecular film having a fluorocarbon group and an imidazolyl group The aluminum fin formed with the mixed monomolecular film having a fluorocarbon group and an epoxy group in the above (1) is converted into 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 heating 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) Preparation of Antifouling Antibacterial Antifungal Heat Dissipating Fin 1 The aluminum fin formed with the mixed monomolecular film having the fluorocarbon group and the imidazolyl group in the above (2) is used as a copper (II) chloride 0.1 mol / L aqueous solution. It was immersed in a solution prepared by mixing 10 mL, pure water 50 mL, and sodium hydroxide 0.1 mol / L aqueous solution 3 mL and left at room temperature for 2 hours. The substrate was pulled up and dried to obtain an antifouling antibacterial and antifungal heat dissipating fin 10 in which copper (II) ions were coordinated to the imidazolyl group.

Comparative Example: Formation of a monomolecular film having an alkyl group Aluminum was prepared in the same manner as in Example 1 (1) except that octadecyltrimethoxysilane CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ was used as the film compound. A monomolecular film having an alkyl group was formed on the surface of the fin.

Example 2: Evaluation of antifouling antibacterial and antifungal radiation fin 1 (1) Measurement of water droplet contact angle The water droplet 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. Aluminum fin after excimer laser cleaning treatment, aluminum fin with a monomolecular film having an epoxy group, aluminum fin with a monomolecular film having an imidazolyl group, copper (II) ion (Cu) on a monomolecular film having an imidazolyl group ²⁺ ) was coordinated and the contact angle was measured for each of the aluminum fins that formed antifouling, antibacterial and antifungal radiation fins.

Table 1 shows aluminum fins after excimer laser cleaning treatment, aluminum fins having a monomolecular film having an epoxy group, aluminum fins having a monomolecular film having an imidazolyl group, and Cu ²⁺ on a monomolecular film having an imidazolyl group. The measurement result of the water droplet contact angle of the aluminum fin which coordinated and formed the antifouling antibacterial and antifungal radiation fin is shown.

The aluminum fin 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 the monomolecular film having an epoxy group on the aluminum fin. 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 antifungal heat dissipating fin due to the coordination of Cu ^2+. .

(2) Measurement of infrared absorption spectrum Red of aluminum fin formed with monomolecular film having fluorocarbon group and epoxy group, monomolecular film having fluorocarbon group and imidazolyl group, and monomolecular film having alkyl group 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, after measuring with an aluminum fin not forming a monomolecular film as a reference, the substrate on which the monomolecular film was formed was measured, and a difference spectrum between the two was obtained. 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 aluminum fin formed with 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, 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 aluminum fins each formed with a monomolecular film having a fluorocarbon group and an epoxy group, and a monomolecular film having a fluorocarbon group and an imidazolyl group, in the latter case, 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 Antifouling antibacterial and antifungal heat dissipation using an ultraviolet-visible spectrophotometer (V-530) to confirm the coordination of Cu ²⁺ to the imidazolyl group The UV-VIS spectrum of the aluminum fin on which the fin 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 the monomolecular film, the monomolecular film having an imidazolyl group and the aluminum fins each having antifouling, antibacterial and antifungal heat dissipating fins were divided and sandwiched between jigs. Measurements were performed in a laminated 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 radiation fin was calculated | required by 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, on the agar medium on which E. coli was propagated, place anti-fouling anti-bacterial and anti-heat radiation fins as antibacterial and anti-bacterial treatment groups, and untreated aluminum fins as control groups, and again in the incubator. Incubation was carried out. 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 aluminum fins 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 the antibacterial and antifungal treatment group, only the portion on which the aluminum fins were placed was transparent. From this fact, in the antibacterial and antifungal treatment group, the growth of E. coli was suppressed in the portion that was in contact with the antifouling antibacterial and antifungal heat dissipating fins, and such antibacterial and antifungal effects were maintained for at least 9 days. It was confirmed to last.

Example 3 Preparation of Antifouling Antibacterial Antifungal Heat Dissipation Fin 2 (1) Formation of Mixed Monomolecular Film Having Fluorocarbon Group and Thiol Group Al Alloy Fin Used in Chloroform, Acetone, and Ethanol in Succession Ultrasonic washed. Next, excimer light was applied to the Al alloy fin that had been cleaned with an organic solvent to perform a photocleaning treatment. The Al alloy fins washed in this way were converted into toluene solutions of pentadecafluorodecyltrimethoxysilane (Chemical Formula 16) and ω-thioldecyltrimethoxysilane (Chemical Formula 17) (TDTS) (molecular composition ratio 1: 1) (respectively). Was immersed in 0.01 mol / L) for 2 hours. Thereafter, the Al alloy fin was pulled up, rinsed with toluene, and left in the atmosphere for 24 hours.

(3) Immobilization of antibacterial and antifungal Cu nanoparticles 1 g of the above-mentioned AL alloy fin formed with a mixed monomolecular film containing a mixture of fluorocarbon groups and thiol groups, with a size of about 10 nm of Cu nanoparticles. The thiol group and Cu nanoparticles were reacted and fixed by immersing in an ethanol solution dispersed at about / L at 50 ° C. for about 1 hour.
Thereafter, the substrate was pulled up, washed with water and dried to obtain an antifouling antibacterial and antifungal heat dissipating fin in which Cu nanoparticles were bonded to the surface of the AL alloy fin in a single layer form through a thiolate bond.

Example 4 Evaluation of Antifouling Antibacterial Antifungal Heat Dissipating Fin 2 (1) Measurement of Water Drop Contact Angle Water droplet contact angle, which is a measure of antifouling property, was measured using an automatic contact angle meter CA-VP (Kyowa Interface Science Co., Ltd.) Company). 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. The contact angle was measured for each of the AL alloy fin after the excimer light cleaning treatment and the AL alloy fin formed with a monomolecular film in which Cu fine particles were fixed.

The AL alloy fin after the excimer light 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. Furthermore, after the formation of a monomolecular film having a fluorocarbon group and metal fine particles, it becomes a measure of antifouling properties (the larger the water droplet contact angle, the smaller the surface energy of the coating and the higher the antifouling effect). The water droplet contact angle was 99 degrees.
On the other hand, in the coating film except for pentadecafluorodecyltrimethoxysilane in Example 1, the water droplet contact angle, which is a measure of antifouling property, was 15 degrees or less. This is thought to be because the hydrophilicity increased due to the unevenness of Cu having oxidized surfaces.
That is, it was confirmed that the antibacterial film containing no fluorocarbon group has no antifouling property.

(2) Antibacterial test First, wrap the used agar medium (standard agar medium, Nissui Pharmaceutical Co., Ltd.) and petri dish with aluminum foil, and heat 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, on the agar medium on which Escherichia coli was propagated, an AL alloy fin formed with antifouling antibacterial and antifungal heat dissipating fins as an antibacterial and antifungal treatment group and an untreated AL alloy fin as a control group were placed respectively. Culture was performed in an incubator. 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 AL alloy fins 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 turbid, and there was a difference in the breeding state. In addition, in the antibacterial and antifungal treatment group, only the portion on which the AL alloy fin was placed was transparent. From this fact, in the antibacterial and antifungal treatment group, the growth of E. coli was suppressed in the part that was in contact with the antifouling antibacterial and antifungal heat dissipating fins, and such an antibacterial and antifungal effect was maintained for at least 14 days. It was confirmed to last.
Even after this test, the water contact angle did not change at all.

10 : Antifouling antibacterial and antifungal radiation fin 1
11: Fin 12: Mixed monomolecular film having fluorocarbon group and epoxy group 13: Mixed monomolecular film having fluorocarbon group and imidazolyl group
20 : Antifouling antibacterial and antifungal radiation fin 2
21: Fin 22: Mixed monomolecular film having a fluorocarbon group and a thiol group 23: Mixed monomolecular film in which Cu fine particles are fixed via a thiolate bond

Claims (15)

A first film substance having a fluorocarbon group chemically bonded to the surface of the fin, and a second film substance having a coordination bond group that forms a coordination 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 Antifouling antibacterial and antifungal heat dissipating fins containing atoms or metal ions. The first and second film materials are bonded to the fin through a bond formed by a reaction between one of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group and the surface of the fin. The antifouling antibacterial and antifungal heat dissipating fin according to claim 1, which is fixed to a surface. The antifouling antibacterial and antifungal heat dissipating fin according to claim 1 or 2, wherein the metal atom or metal ion is an Ag, Cu, Zn, Sn atom or an ion of these metals. An air conditioner comprising the antifouling antibacterial and antifungal radiation fins according to any one of claims 1 to 3. A mixed monolayer of a first film material having a fluorocarbon group at one end of a molecule and a second film material having a coordination bond group that forms a coordinate bond with a metal atom or metal ion at one end of the molecule Forming on the surface of the fin A;
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; I have a,
Step A is
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 Ltd. antifouling antibacterial antifungal radiating fins, characterized in Rukoto a and a step D of mixing into a monolayer of Method. 6. The method for producing an antifouling antibacterial and antifungal heat dissipating fin 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 heat dissipating fin according to claim 5 or 6, wherein the metal atom or metal ion is an Ag, Cu, Zn, Sn atom or an ion of these metals. . The first film substance having a fluorocarbon group chemically bonded to the surface of the fin and the second film substance having a bond group that forms a thiolate bond with a metal atom or metal fine particle are mixed in a molecular level. A mixed monomolecular film formed on the surface of the substrate, and antibacterial and antifungal metal fine particles fixed on the surface of the mixed film through a bond formed between the binding groups. Antifouling, antibacterial and heat radiating fins. The first and second film materials are bonded to the fin through a bond formed by a reaction between one of an alkoxysilyl group, a halosilyl group, a thiol group, a sulfide group, and a carboxyl group and the surface of the fin. The antifouling antibacterial and antifungal heat dissipating fin according to claim 8, which is fixed to a surface. Wherein the metal fine particles, Ag, Cu, Zn, antifouling antibacterial antifungal radiating fin according to any one of claims 8 and 9, characterized in that a Sn. An air conditioner comprising the antifouling, antibacterial and antifungal radiation fins according to any one of claims 8 to 10 . A mixed film of a first film material having a fluorocarbon group at one end of a molecule and a second film material having a bond group that forms a thiolate bond with a metal atom or metal fine particle at one end of the molecule is formed on the surface of the fin. a step a of, via a bond formed between the antimicrobial antifungal of metal fine particles and the bonding group, have a step B of fixing the metal atom or metal particles on the surface of the mixture film,
Step A is
A first surface binding 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 first film compound each having a second surface that forms a bond with the surface of the substrate at one end of the molecule
A third film compound having a bonding group and the first reactive group at the other end is mixed with the surface of the substrate.
And reacting to form a mixed single molecule of the first and third film substances chemically bonded to the surface of the substrate
Step C of forming a film, a second reactive group that forms a bond with the first reactive group, and a metal source
Molecules each having a coordination bond group that forms a coordination bond with a child or a metal ion,
And bonded to the third membrane material through a bond formed by the reaction of the second reactive group,
Serial first and second film manufacturing method of antifouling antibacterial antifungal radiating fins, characterized in Rukoto a and a step D of mixing into a monolayer of a substance. The method for producing an antifouling antibacterial and antifungal heat dissipating fin according to claim 12 , 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 heat dissipating fin according to claim 12 or 13, wherein the metal atom or metal fine particle is any one of Ag, Cu, Zn and Sn. The antifouling antibacterial and antifungal heat dissipating fin and air conditioner according to any one of claims 1 to 14 , wherein the fin is made of aluminum or an aluminum alloy and the surface thereof is oxidized.