Antibacterial film, method for producing antibacterial film, and decorative material

Abstract

An object of the present disclosure is to provide an antibacterial film which exhibits antibacterial activity in a short time and has excellent appearance (particularly, transparency), a method for producing the antibacterial film, and a decorative material including the antibacterial film.SOLUTION: The antibacterial film 10 of the present embodiment includes an antibacterial layer 2, the antibacterial layer 2 contains a resin component and silver nanoparticles 3, the antibacterial layer 2 contains a cationic functional group-containing polymer as the resin component, and the amount of the silver nanoparticles 3 added to the total mass of the antibacterial layer 2 is in a range of 3% by mass to 10% by mass.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to an antimicrobial film, a method for manufacturing an antimicrobial film, and a cosmetic material. [Background technology]

[0002] Some antibacterial films contain metal particles such as silver, copper, and zinc as an antibacterial component. An antibacterial layer containing these metal particles may be formed, for example, by applying a coating liquid containing metal particles and a resin component to a substrate. This manufacturing method can impart antibacterial functionality to a desired substrate. Therefore, antibacterial films comprising a substrate and an antibacterial layer formed by coating are widely used as antibacterial products. The antibacterial layer in antibacterial films is often composed mainly of an antibacterial agent and a binder resin. Furthermore, due to the stability of antibacterial activity, antibacterial agents containing silver as an antibacterial component are often used. From the viewpoint of achieving both stable antibacterial activity and good appearance, the use of small particle silver-based antibacterial agents is effective.

[0003] It has been reported that silver nanoparticles, which are small particles containing silver, exhibit antibacterial activity. For example, Patent Document 1 describes spraying a dispersion of silver nanoparticles onto an article to impart antibacterial properties. Patent Document 2 also discloses an antibacterial resin material in which a resin material is brought into contact with an aqueous solution containing silver ions or a silver complex, and then irradiated with ionizing radiation to support and fix silver nanoparticles on the surface. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6867640 [Patent Document 2] Japanese Patent Publication No. 2022-170335 Summary of the Invention [Problem to be solved by the invention]

[0005] Antibacterial films using silver nanoparticles are sometimes used in applications such as cards, food packaging, building materials such as wallpaper and flooring, touch panels and displays, etc. Due to their small particle size, silver nanoparticles are more effective than conventional antibacterial agents in that they can impart antibacterial properties without affecting the appearance of the product. In producing an antibacterial film, the technology disclosed in Patent Document 1 uses silver nanoparticles in the form of an aqueous suspension, and therefore is thought to be inapplicable to a wet coating process using an organic solvent.

[0006] Furthermore, the technology disclosed in Patent Document 2 involves a special process of irradiating with ionizing radiation, and therefore, when applied to coating on films, there is a possibility that the production costs will increase and it will be more difficult to achieve large area coating than with conventional wet coating such as gravure coating. Therefore, there is a need to prepare antibacterial films using silver nanoparticles using a common wet coating process, in which silver nanoparticles are dispersed in a coating liquid and then coated onto a substrate.

[0007] The release of silver ions is necessary for the antibacterial activity to be realized, and it is believed that exposure of the silver-based antibacterial agent to the coating surface is important for the release of silver ions. However, when silver nanoparticles are used as an antibacterial agent, their small particle size can prevent the silver nanoparticles from being exposed on the coating film, and the amount of silver ions required to exhibit antibacterial activity cannot be obtained. In particular, in the aforementioned applications of cards, food packaging, building materials, touch panels, displays, etc., where antibacterial activity is required to be exhibited in a short period of contact with a bacterial solution, it is necessary to produce a coated film that can obtain the amount of eluted Ag required to exhibit antibacterial activity in a short period of time. As described above, it has been difficult for conventional antibacterial films to achieve both rapid development of antibacterial activity and excellent appearance (particularly transparency).

[0008] The present disclosure has been made in consideration of the above circumstances, and aims to provide an antibacterial film that exhibits antibacterial activity in a short period of time and has excellent appearance (particularly transparency), a method for manufacturing such an antibacterial film, and a cosmetic material that includes such an antibacterial film. [Means for solving the problem]

[0009] An antibacterial film according to one embodiment for solving the above problem is an antibacterial film having an antibacterial layer, the antibacterial layer containing a resin component and silver nanoparticles, the resin component containing a cationic functional group-containing polymer, and the amount of the silver nanoparticles added relative to the total mass of the antibacterial layer is in the range of 3% by mass or more and 10% by mass or less.

[0010] In addition, one embodiment of a method for manufacturing an antibacterial film for solving the above problem includes a step of forming an antibacterial layer by applying a coating liquid containing silver nanoparticles and a cationic functional group-containing polymer to a film-like substrate, and the amount of silver nanoparticles added to the antibacterial layer is within the range of 3 mass% to 10 mass%.

[0011] A decorative material according to one aspect for solving the above-mentioned problems has the above-mentioned antibacterial film on an adherend. [Effects of the Invention]

[0012] The antibacterial film and decorative material according to one embodiment of the present disclosure exhibit antibacterial activity in a short period of time and can also provide excellent appearance (particularly transparency). In other words, the antibacterial film and decorative material according to one embodiment of the present disclosure can achieve both the exhibiting of antibacterial activity in a short period of time and excellent appearance (particularly transparency). [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic cross-sectional view showing the layer structure of an antibacterial film according to an embodiment of the present disclosure. [Figure 2] 1 is a schematic cross-sectional view showing the layer structure of a decorative material according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following describes an antibacterial film, a manufacturing method for an antibacterial film, and a decorative material according to embodiments of the present disclosure, with reference to the drawings. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, and the like differ from reality. Layers not shown in the drawings may also be added. The embodiments shown below exemplify configurations for embodying the technical concept of the present disclosure, and the technical concept of the present disclosure is not limited to the materials, shapes, structures, and the like of the components described below. Various modifications can be made to the technical concept of the present disclosure within the technical scope defined by the claims.

[0015] Furthermore, the directions of "left and right" and "up and down" in the following explanation are merely definitions for the convenience of explanation and do not limit the technical idea of ​​the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left."

[0016] The present inventors have newly discovered that by adding silver nanoparticles as an antibacterial agent and hydrophilizing a coating film containing silver nanoparticles, antibacterial activity is exerted in a short time and excellent appearance (particularly transparency) can be obtained. Specifically, the inventors have newly discovered that in an antibacterial layer prepared by applying a coating liquid in which silver nanoparticles are dispersed in a resin to a substrate, the antibacterial layer contains a cationic functional group-containing polymer as a resin component (binder component) constituting the antibacterial layer, and the amount of silver nanoparticles added is within the range of 3% by mass to 10% by mass relative to the total mass of the antibacterial layer, antibacterial activity is exerted in a short time and excellent appearance (particularly transparency) can be obtained. In this embodiment, the term "short period" means approximately one to three hours.

[0017] Hereinafter, an embodiment of the present disclosure (hereinafter referred to as "the present embodiment") will be described with reference to the drawings. The antibacterial film in the present embodiment is used for various purposes such as food packaging, daily necessities, building materials, electronic devices, and vehicle components.

[0018] [Layer structure of antibacterial film 10] The antibacterial film 10 according to this embodiment includes a substrate 1 and an antibacterial layer 2 supported on the substrate 1. Specifically, the antibacterial film 10 includes, for example, the substrate 1 and the antibacterial layer 2, as shown in FIG. The substrate 1 supports the antibacterial layer 2. The lower surface of the antibacterial layer 2 is in contact with the substrate 1. The antibacterial layer 2 only needs to cover at least a part of the substrate 1.

[0019] The upper surface of the antibacterial layer 2 opposite to the lower surface in contact with the substrate 1 is the surface of the antibacterial film 10. The upper surface of the antibacterial layer 2 is the active surface of the antibacterial film 10 that exhibits antibacterial activity. The antibacterial layer 2 contains an antibacterial component and a resin component. The antibacterial component contained in the antibacterial layer 2 is silver nanoparticles 3. The antibacterial layer 2 is, for example, a coating film formed by coating and curing a coating liquid. The antibacterial film according to this embodiment may not include the substrate 1 and may be composed of only the antibacterial layer 2.

[0020] <Base material 1> The material of the substrate 1 may be any material that can be coated with the antibacterial layer 2. The substrate 1 may have a single layer structure or a multilayer structure. The material of the substrate 1 is, for example, a resin film. Examples of materials for the resin film include at least one selected from the group consisting of polyester, polypropylene, polystyrene, nylon, polycarbonate, polyacrylonitrile, and polyimide.

[0021] The thickness of the substrate 1 may be any thickness that allows the antibacterial layer 2 to be formed by coating on the substrate 1. From the viewpoint of improving the transportability of the substrate 1 and the coatability for forming the antibacterial layer 2, the thickness of the substrate 1 is preferably 4 μm or more, and more preferably 12 μm or more. The upper limit of the thickness of the substrate 1 is not particularly limited, but from the viewpoint of increasing the flexibility of the substrate 1, it is preferably 100 μm or less, and more preferably 50 μm or less. The thickness of the substrate 1 is the average value of the sample thickness values ​​on the cross section of the object to be measured. The sample thickness value is the thickness of the sample obtained by measuring the thickness at 10 measurement points spaced 1 mm apart on the cross section of the object to be measured, excluding measurement points whose difference from the average value is 50% or more.

[0022] <Antibacterial layer 2> The antibacterial layer 2 contains a polymer having a cationic functional group on the side chain (hereinafter, for convenience, also referred to as a "cationic functional group-containing polymer") as a resin component (binder component). Here, the cationic functional group-containing polymer described above functions as a hydrophilic additive that imparts hydrophilicity to the antibacterial layer 2 . In this embodiment, among the above-mentioned cationic functional group-containing polymers, polymers containing a nitrogen atom in the cationic functional group are preferred.

[0023] Furthermore, among the polymers containing the above-mentioned nitrogen atom in the cationic functional group, polymers having primary to quaternary ammonium salts are preferred, and among them, polymers having quaternary ammonium salts (hereinafter, for convenience, also referred to as "quaternary ammonium salt-based polymers") are particularly preferred. The number of classes in the above "polymers having primary to quaternary ammonium salts" indicates the number of atoms other than hydrogen (H) atoms bonded to nitrogen (N) atoms, that is, the number of substituents.

[0024] The above-mentioned "ammonium salt" refers to a salt containing a cationic N atom (i.e., the number of single bonds of the N atom is "4"), such as R-NH2(CH3). + X - corresponds to a secondary ammonium salt, where R is, for example, an alkyl group and X is, for example, chlorine. Furthermore, as the quaternary ammonium salt-based polymer in this embodiment, for example, a polymer described in Japanese Patent No. 6408096 can be used, but the quaternary ammonium salt-based polymer in this embodiment is not limited to the polymer described in this publication.

[0025] The antibacterial layer 2 can be made hydrophilic by using a polymer containing a cationic functional group as the resin component constituting the antibacterial layer 2. As a result, the antibacterial activity is exhibited in a short period of time. The mechanism by which the antibacterial activity is exhibited due to the hydrophilization of the antibacterial layer 2 will be described later. The antibacterial layer 2 preferably contains the cationic functional group-containing polymer in a range of 5% by mass to 30% by mass of the total mass of the resin components of the antibacterial layer 2, more preferably in a range of 8% by mass to 20% by mass, and even more preferably in a range of 8% by mass to 15% by mass. With the above-described configuration, the antibacterial layer 2 can be made hydrophilic, and antibacterial activity is exhibited in a short period of time.

[0026] The antibacterial layer 2 may contain two or more types of cationic functional group-containing polymers. For example, the cationic functional group-containing polymer may include an ammonium salt-based polymer and a polymer other than the ammonium salt-based polymer. When the antibacterial layer 2 contains an ammonium salt-based polymer and a polymer other than the ammonium salt-based polymer, the content of the ammonium salt-based polymer may be greater than the content of the polymer other than the ammonium salt-based polymer. Even with the above-mentioned configuration, the antibacterial layer 2 can be made hydrophilic, and antibacterial activity is exhibited in a short period of time.

[0027] The cationic functional group-containing polymer may also contain a quaternary ammonium salt polymer and an ammonium salt polymer other than the quaternary ammonium salt polymer (for example, a primary ammonium salt polymer or a secondary ammonium salt polymer). When a quaternary ammonium salt polymer and an ammonium salt polymer other than the quaternary ammonium salt polymer are contained, the content of the quaternary ammonium salt polymer may be higher than the content of the ammonium salt polymer other than the quaternary ammonium salt polymer. Even with the above-mentioned configuration, the antibacterial layer 2 can be made hydrophilic, and antibacterial activity is exhibited in a short period of time.

[0028] The amount of silver nanoparticles 3 added to the antibacterial layer 2 may be in the range of 3% by mass or more and 10% by mass or less, preferably in the range of 3% by mass or more and 7% by mass or less, and more preferably in the range of 5% by mass or more and 7% by mass or less, relative to the total mass of the antibacterial layer 2. With the above-mentioned configuration, as will be described later, a sufficient amount of silver ions can be eluted, and antibacterial activity is exhibited in a short period of time. The antibacterial layer 2 contains a resin component (resin base) in addition to the above-mentioned cationic functional group-containing polymer. The resin component (resin base) constituting the antibacterial layer 2 may be a thermosetting resin or an ultraviolet curable resin.

[0029] The resin component (resin base) constituting the antibacterial layer 2 is preferably a thermosetting resin, from the viewpoint of easily achieving uniform curing while containing the silver nanoparticles 3. Examples of thermosetting resins include acrylic resins, urethane resins, and epoxy resins. Among the above-mentioned thermosetting resins, acrylic resins are preferred when improved transparency and adhesion to the substrate 1 are required. In this embodiment, the term "resin base" refers to a resin that accounts for 50% by mass or more of the total mass of the resin components that make up the antibacterial layer 2.

[0030] The antibacterial layer 2 is formed by applying an antibacterial layer coating liquid, which is a coating liquid for forming the antibacterial layer 2, to the upper surface of the substrate 1 and curing the film thus formed. The antibacterial layer coating liquid contains a base agent and a curing agent for forming the resin component of the antibacterial layer 2, a cationic functional group-containing polymer which is a hydrophilic additive, silver nanoparticles 3, and auxiliary agents such as a dispersing agent and a stabilizer as required. That is, the antibacterial layer coating liquid in this embodiment contains at least the above-mentioned resin components (main resin, curing agent, and hydrophilic additive) and silver nanoparticles 3.

[0031] The amount of silver nanoparticles 3 added to the antibacterial layer coating liquid may be in the range of 3% by mass to 10% by mass, preferably in the range of 3% by mass to 7% by mass, and more preferably in the range of 5% by mass to 7% by mass, relative to the total mass of the antibacterial layer coating liquid. The antibacterial layer coating liquid can be applied by any known method, such as bar coating, spin coating, offset coating, gravure coating, roll coating, die coating, etc. The method for curing the film made of the coating liquid is a method that depends on the curing type of the resin component of the antibacterial layer 2, and may be heat drying or ultraviolet irradiation.

[0032] The antibacterial layer coating liquid may be a two-component curing type or a one-component curing type. The components of the two-component curing coating liquid may contain a polyol component as a main component and an isocyanate component as a curing agent. The polyol component may be an acrylic polyol, a polyester polyol, a polyether polyol, or an epoxy polyol. The isocyanate component may be tolylene diisocyanate, hexamethylene diisocyanate, or metaxylene diisocyanate. The amount of antibacterial coating liquid applied was 0.2 g / m 2 More than 12.9g / m 2 It is preferable that the content is within the range of 0.7 g / m 2 More than 10.3g / m 2 More preferably, it is within the range of 1.3 g / m 2 More than 6.5g / m 2It is more preferable that the content is within the following range.

[0033] In this embodiment, "silver nanoparticles" refers to silver particles having an average particle diameter (volume-based median diameter: D50) of 100 nm or less. That is, in this embodiment, the average particle diameter of the silver nanoparticles 3 may be 100 nm or less, preferably 80 nm or less, and more preferably 50 nm or less. If the average particle diameter of the silver nanoparticles 3 is 100 nm or less, the frequency of contact between the silver nanoparticles 3 and water molecules diffused in the resin constituting the antibacterial layer 2 increases, increasing the amount of eluted silver ions and improving the stability of antibacterial activity. Furthermore, although there is no particular lower limit to the average particle size of the silver nanoparticles 3, it is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more. If the average particle size of the silver nanoparticles 3 is 1 nm or more, the silver nanoparticles 3 are easy to manufacture and therefore readily available.

[0034] Furthermore, it is preferable that the average particle diameter of the silver nanoparticles 3 is smaller than the thickness of the antibacterial layer 2. Regarding the average particle diameter of the silver nanoparticles 3, the ratio of the average particle diameter of the silver nanoparticles 3 to the thickness of the antibacterial layer 2 (average particle diameter of silver nanoparticles 3 / thickness of antibacterial layer 2) is preferably within a range of 0.1 or more and less than 1, more preferably within a range of 0.5 or more and less than 1, and even more preferably within a range of 0.8 or more and less than 1. If the ratio of the average particle diameter of the silver nanoparticles 3 to the thickness of the antibacterial layer 2 is within the above numerical range, the antibacterial activity and dispersibility are improved. Furthermore, the silver nanoparticles 3 may have a protective layer formed from a dispersant so as to cover the surface of the silver nanoparticles 3. When the silver nanoparticles 3 have a protective layer, it is possible to effectively prevent secondary aggregation of the silver nanoparticles 3. Furthermore, it is possible to suppress the occurrence of haze caused by secondary aggregation of the silver nanoparticles 3, i.e., it is possible to impart excellent transparency.

[0035] Dispersants that form the protective layer can be broadly classified into anionic, cationic, and nonionic types, and can be appropriately selected depending on the surface potential and dispersion medium of the silver nanoparticles 3. Among the above dispersants, nonionic dispersants are particularly preferred. Nonionic dispersants can be broadly classified into, for example, alkylene oxide adduct types and carbocation amide types, and in this embodiment, polyvinylpyrrolidone (PVP), a nonionic polymer, is particularly preferred. Representative anionic types include sulfate esters, phosphate esters, carboxylic acids, and sulfonic acids, and many of them have an ethylene oxide (EO) adduct molecular structure.Cationic types include quaternary ammonium salts, which can be classified into Cl salts, non-Cl salts, and EO adducts.

[0036] The dispersant forming the protective layer according to this embodiment may be anionic. Preferred anionic dispersants include polyoxyethylene alkyl ether phosphates (salts), polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether acetates, and polyoxyethylene alkyl ether succinates, with polyoxyethylene alkyl ether phosphates (salts) being particularly preferred. Specific examples include, but are not limited to, Phosphanol RB-40, RD-510Y, RD720N, RL-210, RS-410 (Toho Chemical Industry Co., Ltd.), NIKKOL DDP-8NV, DDP-2, DDP-4, DDP-6, DDP-8, DDP-10 (Nikko Chemicals Co., Ltd.), Plysurf A212C, A215C, A208F, M208F, A208A, A208B, A210B, A219B, DB-01, AL, DBS (Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like.

[0037] The thickness of the antibacterial layer 2 is preferably 0.5 μm or more, and more preferably 1 μm or more, when improvements in the uniformity of the thickness of the antibacterial layer 2, the coatability of the antibacterial layer 2, the mechanical durability of the antibacterial layer 2, and the antibacterial activity of the antibacterial layer 2 are required. The thickness of the antibacterial layer 2 is preferably 10 μm or less, and more preferably 5 μm or less, when improvements in the adhesion of the antibacterial layer 2 to the substrate 1 and a reduction in the load required for curing the antibacterial layer 2 are required. The thickness of the antibacterial layer 2 is the average value of the sample thickness values ​​on the cross section of the measurement object. The sample thickness value is the thickness of the sample obtained by measuring the thickness at 10 measurement points spaced 1 mm apart on the cross section of the measurement object, excluding measurement points whose measured values ​​differ from the average value by 50% or more.

[0038] The surface roughness (Sa) of the upper surface of the antibacterial layer 2, which is the active surface of the antibacterial film 10 that exhibits antibacterial activity, is preferably in the range of 0.0005 μm to 0.1 μm, and more preferably in the range of 0.001 μm to 0.01 μm. If the surface roughness (Sa) of the upper surface of the antibacterial layer 2 is within the above numerical range, a sufficient amount of silver ions will be eluted from the upper surface of the antibacterial layer 2. As a result, the antibacterial performance can be improved.

[0039] As described above, the antibacterial layer 2 of the antibacterial film 10 of this embodiment contains at least a resin component (a resin base, a curing agent, and a hydrophilic additive) and silver nanoparticles 3. Furthermore, when forming the antibacterial layer 2 of the antibacterial film 10 of this embodiment, silver nanoparticles 3 encapsulated in a protective layer formed from a dispersant may be added to the resin component (a resin base, a curing agent, and a hydrophilic additive) and cured. Adding the silver nanoparticles 3 encapsulated in the protective layer to the resin component can dramatically improve the dispersibility of the silver nanoparticles 3 in the resin component, i.e., in the antibacterial layer 2. However, it may be difficult or impractical to directly identify the silver nanoparticles 3 encapsulated in the protective layer based on the structure and properties of the completed antibacterial film 10 depending on the circumstances. The reasons for this are explained below. The silver nanoparticles 3 added while encapsulated in the protective layer are dispersed with high dispersibility, and even in the state of the produced antibacterial film 10, the silver nanoparticles 3 are highly dispersed in the antibacterial layer 2.

[0040] However, in the process of producing the antibacterial layer 2, various processes such as curing treatment are usually performed, and these processes may cause the protective layer encapsulating the silver nanoparticles 3 to be crushed or a chemical reaction to occur. Therefore, depending on the treatment process of the antibacterial film 10, the state in which the protective layer of the silver nanoparticles 3 is crushed and the state in which a chemical reaction occurs in the completed antibacterial film 10 may vary, and there is a high possibility that the silver nanoparticles 3 are not encapsulated (encased) by the protective layer. If the silver nanoparticles 3 are not encapsulated by the protective layer, it is difficult to specify the physical properties of the silver nanoparticles 3 within a numerical range. It is also expected that it may be difficult to determine whether the constituent material of the crushed protective layer is the protective layer of the silver nanoparticles 3 or a material added separately from the silver nanoparticles 3.

[0041] As described above, the present disclosure differs from conventional techniques in that silver nanoparticles 3 are highly dispersed in the antibacterial film 10. However, it is conceivable that there may be cases where it is impractical to specify the structure and characteristics of the antibacterial film 10 within a numerical range analyzed based on measurements, whether this is because the silver nanoparticles 3 are added in an encapsulated state.

[0042] [Effect] In the antibacterial test of this embodiment, the antibacterial film 10 is brought into contact with a test bacterial solution containing water for 24 hours. During this time, water molecules diffuse through the free volume of the polymer chains of the resin component that forms the antibacterial layer 2, causing the resin, which is a constituent component, to swell. Therefore, it is thought that not only the silver nanoparticles 3 present on the outermost surface of the coating film (i.e., near the outermost surface of the antibacterial layer 2), but also the silver nanoparticles 3 present in the resin of the coating film (i.e., inside the antibacterial layer 2) come into contact with water molecules. Silver ions are eluted from the silver nanoparticles 3 that come into contact with water molecules, and the eluted silver ions migrate into the test bacterial solution, where they act on the bacteria in the test bacterial solution, thereby exhibiting antibacterial activity.

[0043] The inventors of the present application have newly discovered that in order to increase the contact efficiency between the silver nanoparticles 3 present in the resin of the coating film (i.e., inside the antibacterial layer 2) and the water molecules contained in the test bacterial solution, it is necessary to make it easier for the water molecules to diffuse through the resin of the coating film, and therefore that ``hydrophilizing the coating film'' is effective. Here, "hydrophilizing a coating film" means increasing the affinity for water and enabling the formation of hydrogen bonds between the constituent molecules (constituent resins) of the coating film and water molecules. Specifically, "hydrophilizing a coating film" refers to, for example, using a hydrophilic resin that is a polymer of a monomer having a polar group as a constituent material of the coating film, or adding a hydrophilic resin that is a polymer of a monomer having a polar group to the constituent material of the coating film.

[0044] The cationic functional group-containing polymer used in this embodiment has cationic functional groups in its side chains, which can increase the hydrophilicity of the coating film. Furthermore, when an ammonium salt-based polymer, particularly a quaternary ammonium salt-based polymer, is used as the cationic functional group-containing polymer, ammonium salts such as quaternary ammonium salts themselves have antibacterial activity. Therefore, it is believed that an antibacterial film with antibacterial activity can be obtained by contacting the bacterial solution for a short period of time due to the additive effect of the elution of silver ions and the ammonium salt such as quaternary ammonium salt.

[0045] Furthermore, because the silver nanoparticles 3 have a relatively small particle diameter, they can suppress an increase in haze in both cases: external haze caused by the surface irregularities of the antibacterial layer 2, and internal haze caused by scattering by the silver nanoparticles 3 themselves. In other words, by using the silver nanoparticles 3, the transparency of the antibacterial layer 2 can be increased. Furthermore, since the particle diameter of the silver nanoparticles 3 is smaller than the thickness of the antibacterial layer 2, it is possible to prevent the silver nanoparticles 3 from falling off from the antibacterial layer 2 (coating film). Furthermore, by using an acrylic resin as the main resin component (resin component) constituting the antibacterial layer 2, good adhesion to the substrate 1 can be achieved and high transparency can be imparted.

[0046] As described above, the antibacterial film 10 having the configuration according to this embodiment exhibits an antibacterial activity of 2.0 or more after 3 hours of contact with a bacterial solution in an antibacterial test based on JIS Z2801. When the surface of the antibacterial layer 2 is kept in close contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area on the surface of the antibacterial layer 2, is 14 ng / cm. 2 As a result, the haze of the antibacterial film 10 becomes 2.0 or less. Furthermore, in the case of the antibacterial film 10 having the configuration according to this embodiment, when the contact time with a bacterial solution in an antibacterial test based on JIS Z2801 is set to 1 hour, the antibacterial activity after 1 hour is 2.0 or more, and when the surface of the antibacterial layer 2 is kept in close contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area on the surface of the antibacterial layer 2, is 27 ng / cm 2 As a result, the haze of the antibacterial film 10 becomes 2.0 or less.

[0047] [Layer structure of decorative material 20] The decorative material 20 according to this embodiment includes an adherend 5 and an antibacterial film 10 adhered to the adherend 5. Specifically, as shown in FIG. 2, the decorative material 20 has, for example, the antibacterial film 10 on the adherend 5.

[0048] <Adherent material 5> The material of the adherend 5 may be any material that can adhere the antibacterial film 10 to the adherend 5. The adherend 5 may be a single-layer structure or a multi-layer structure. The material of the adherend 5 is, for example, a resin film. Examples of materials for the resin film include at least one selected from the group consisting of polyester, polypropylene, polystyrene, nylon, polycarbonate, polyacrylonitrile, and polyimide.

[0049] The thickness of the adherend 5 may be any thickness that allows the antibacterial film 10 to be adhered to the adherend 5. From the viewpoint of improving the transportability of the adherend 5 and the adhesiveness of the antibacterial film 10, the thickness of the adherend 5 is preferably 4 μm or more, and more preferably 12 μm or more. The upper limit of the thickness of the adherend 5 is not particularly limited, but from the viewpoint of increasing the flexibility of the adherend 5, it is preferably 100 μm or less, and more preferably 50 μm or less. The thickness of the adherend 5 is the average value of the sample thickness values ​​on the cross section of the object to be measured. The sample thickness value is the thickness of the sample obtained by measuring the thickness at 10 measurement points spaced 1 mm apart on the cross section of the object to be measured, excluding measurement points whose difference from the average value is 50% or more.

[0050] (Effects of the embodiment) The antibacterial film, the method for manufacturing the antibacterial film, and the decorative material according to the present embodiment have the following effects. (1) The antibacterial film 10 according to this embodiment includes an antibacterial layer 2, which contains a resin component and silver nanoparticles. The resin component contains a polymer containing a cationic functional group, and the amount of silver nanoparticles 3 added relative to the total mass of the antibacterial layer 2 is within the range of 3% by mass or more and 10% by mass or less. According to this configuration, it is possible to provide an antibacterial film that exhibits antibacterial activity in a short time of about 1 to 3 hours and that also has excellent appearance (particularly transparency).

[0051] (2) The cationic functional group-containing polymer contained in the antibacterial film 10 according to this embodiment may be a quaternary ammonium salt-based polymer. This configuration makes it possible to provide an antibacterial film with even more enhanced antibacterial activity.

[0052] (3) The average particle size of the silver nanoparticles 3 contained in the antibacterial film 10 according to this embodiment may be smaller than the film thickness of the antibacterial layer 2 . This configuration can prevent the silver nanoparticles 3 from falling off from the antibacterial layer 2.

[0053] (4) In the antibacterial film 10 according to the present embodiment, when the contact time with a bacterial solution is 3 hours in an antibacterial test based on JIS Z2801, the antibacterial activity after 3 hours is 2.0 or more, and when the surface of the antibacterial layer 2 is kept in close contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area on the surface of the antibacterial layer 2, is 14 ng / cm 2 That is the above, and it is preferable that the haze of the antibacterial film 10 is 2.0 or less. According to this configuration, it is possible to provide an antibacterial film that exhibits antibacterial activity in a short time of about 1 to 3 hours and that also has excellent appearance (particularly transparency).

[0054] (5) In the antibacterial film 10 according to the present embodiment, when the contact time with a bacterial solution is 1 hour in an antibacterial test based on JIS Z2801, the antibacterial activity after 1 hour is 2.0 or more, and when the surface of the antibacterial layer 2 is kept in close contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area on the surface of the antibacterial layer 2, is 27 ng / cm 2 That is the above, and it is preferable that the haze of the antibacterial film 10 is 2.0 or less. According to this configuration, it is possible to provide an antibacterial film that exhibits antibacterial activity in a short time of about 1 to 3 hours and that also has excellent appearance (particularly transparency).

[0055] (6) The resin component contained in the antibacterial film 10 according to this embodiment may contain an acrylic resin in addition to the cationic functional group-containing polymer. According to this configuration, when the antibacterial film 10 includes the substrate 1, the antibacterial film has good adhesion to the substrate 1 and can be given high transparency. Furthermore, with this configuration, even if the antibacterial film 10 is composed only of the antibacterial layer 2, i.e., does not have a substrate 1, the antibacterial film can have sufficient mechanical strength for use and high transparency.

[0056] (7) The antibacterial film 10 according to this embodiment may include a substrate 1 and an antibacterial layer 2 supported on the substrate 1 . This configuration provides the antibacterial film with sufficient mechanical strength for use.

[0057] (8) The method for manufacturing the antibacterial film 10 according to this embodiment includes a step of applying a coating liquid containing silver nanoparticles 3 and a cationic functional group-containing polymer to a film-like substrate 1 to form an antibacterial layer 2, and the amount of silver nanoparticles 3 added relative to the total mass of the antibacterial layer 2 is within the range of 3% by mass or more and 10% by mass or less. According to this configuration, it is possible to provide an antibacterial film that exhibits antibacterial activity in a short time of about 1 to 3 hours and that also has excellent appearance (particularly transparency).

[0058] (9) In the method for producing the antibacterial film 10 according to this embodiment, the cationic functional group-containing polymer may be a quaternary ammonium salt-based polymer. This configuration makes it possible to provide an antibacterial film with even more enhanced antibacterial activity.

[0059] (10) The coating liquid used in the method for producing the antibacterial film 10 according to this embodiment may contain an acrylic resin in addition to the cationic functional group-containing polymer. According to this configuration, when the antibacterial film 10 includes the substrate 1, it has good adhesion to the substrate 1 and can be given high transparency. Furthermore, with this configuration, even when the antibacterial film 10 is composed of only the antibacterial layer 2, i.e., does not have a substrate 1, it is possible to provide an antibacterial film that has sufficient mechanical strength for use and high transparency.

[0060] (11) The decorative material 20 according to this embodiment has the antibacterial film 10 described above on the adherend 5 . According to this configuration, it is possible to provide an antibacterial film that exhibits antibacterial activity in a short time of about 1 to 3 hours and that also has excellent appearance (particularly transparency).

[0061] (Example) The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples. Antibacterial films of Examples 1 to 4 and Comparative Examples 1 to 3 were produced and analyzed for their antibacterial activity.

[0062] <How to make antibacterial film> [Example 1] Preparation of antibacterial coating solution The antibacterial layer coating liquid contained 69.7 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical), 12.7 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei), 14.6 mass percent of a quaternary ammonium salt polymer (Acrit 1WX-1020, manufactured by Taisei Fine Chemical), and 3.00 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich) with an average particle size of 25 nm (volume-based median diameter), based on the total mass of the antibacterial layer coating liquid. In this case, ethyl acetate (Kanto Chemical, Shika Grade 1) was used as the solvent, and the solvent was added so that the solid content concentration in the coating liquid was 20 mass %, and the mixture was thoroughly mixed using a magnetic stirrer to prepare the antibacterial layer coating liquid of Example 1.

[0063] - Formation of antibacterial layer As the substrate, a biaxially stretched polyethylene terephthalate film (Cosmoshine A4260: manufactured by Toyobo Co., Ltd., thickness: 50 μm) cut into an A4 size was used. 1 mL to 2 mL of the antibacterial layer coating liquid of Example 1 was dropped onto the substrate using a dropper, and the antibacterial layer coating liquid of Example 1 was coated onto the substrate using the #30 bar of a wireless bar coater (A-Bar: manufactured by Mitsui Electric Seiki Co., Ltd.). The coated film was dried for 1 minute in an atmospheric oven heated to 80°C, thereby forming the antibacterial layer of Example 1.

[0064] [Example 2] The antibacterial film of Example 2 was produced in the same manner as Example 1, except that the antibacterial layer coating liquid contained 73.0 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical), 12.5 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei), 9.5 mass percent of a quaternary ammonium salt polymer (Acrit 1WX-1020, manufactured by Taisei Fine Chemical), and 5.00 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich) with an average particle size of 25 nm (volume-based median diameter), relative to the total mass of the antibacterial layer coating liquid.

[0065] [Example 3] The antibacterial film of Example 3 was produced in the same manner as Example 1, except that the antibacterial layer coating liquid contained 69.1 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical), 11.9 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei), 9.0 mass percent of a quaternary ammonium salt polymer (Acrit 1WX-1020, manufactured by Taisei Fine Chemical), and 10.0 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich) with an average particle size of 25 nm (volume-based median diameter), relative to the total mass of the antibacterial layer coating liquid.

[0066] [Example 4] The antibacterial film of Example 4 was produced in the same manner as in Example 1, except that the antibacterial layer coating liquid was mixed with 66.9 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical Co., Ltd.), 12.2 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd.), 14.0 mass percent of a quaternary ammonium salt polymer (Acrit 1WX-1020, manufactured by Taisei Fine Chemical Co., Ltd.), and 7.00 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich Co., Ltd.) with an average particle size of 25 nm (volume-based median diameter).

[0067] [Comparative Example 1] The antibacterial film of Comparative Example 1 was produced in the same manner as Example 1, except that the antibacterial layer coating liquid contained 83.9 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical Co., Ltd.), 13.1 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd.), and 3.00 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich Co., Ltd.) with an average particle diameter of 25 nm (volume-based median diameter), based on the total mass of the antibacterial layer coating liquid.

[0068] Comparative Example 2 The antibacterial film of Comparative Example 2 was produced in the same manner as Example 1, except that the antibacterial layer coating liquid contained 75.7 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical), 13.4 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei), 9.9 mass percent of a quaternary ammonium salt polymer (Acrit 1WX-1020, manufactured by Taisei Fine Chemical), and 1.00 mass percent of silver nanoparticles (NCXSEPD25, manufactured by Sigma-Aldrich) with an average particle diameter of 25 nm (volume-based median diameter), relative to the total mass of the antibacterial layer coating liquid.

[0069] Comparative Example 3 The antibacterial film of Comparative Example 3 was produced in the same manner as in Example 1, except that 85.2 mass percent of a base agent containing an acrylic compound (Acrit 6AN-6000, manufactured by Taisei Fine Chemical Co., Ltd.), 13.3 mass percent of a curing agent containing an isocyanate (Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd.), and 1.5 mass percent of a silver-based antibacterial agent (PTC-NT ANV Additive (ST), manufactured by Dainichiseika Chemicals Co., Ltd.) with an average particle size of 3 μm (volume-based median diameter) were mixed relative to the total mass of the antibacterial layer coating liquid, and the #10 bar of a wireless bar coater (A-Bar, manufactured by Mitsui Electric Seiki Co., Ltd.) was used.

[0070] Table 1 shows the components of the antibacterial films (antibacterial layers) of Examples 1 to 4 and Comparative Examples 1 to 3 described above. The "hydrophilizing additive" in Table 1 refers to the added quaternary ammonium salt polymer.

[0071] [Table 1]

[0072] <Particle size measurement> The particle size of the silver nanoparticles was measured using a transmission electron microscope (TEM) and was measured as the Feret diameter using ImageJ.

[0073] <Film thickness measurement> The thickness of the antibacterial layer was obtained by observing the cross section of the antibacterial film obtained by block cutting using a microtome (Ultramicrotome UC7: manufactured by Leica Microsystems) under an optical microscope (BX51: manufactured by Olympus). Thickness measurements were performed in two visual fields at five measurement points per visual field, and the average value of the thickness of a total of 10 measurement points was taken as the thickness of the layer being measured.

[0074] <Elution amount Ev> The amount of Ag ions dissolved per unit area Ev was measured by the following steps (a) to (d). Step (a): A test piece is prepared by molding the antibacterial film 10 into a square shape with a side length of 5 cm. 0.4 mL of pure water is dropped onto the surface of the test piece. Then, a polyethylene film with a side length of 4 cm is attached to the surface of the test piece after the pure water has been dropped. This allows the area of ​​the test piece surface covered by the polyethylene film to be uniformly wetted with pure water. Therefore, the area to be measured for Ag ion elution is 16 cm. 2 is. Step (b): After the treatment in step (a) above, the test piece is placed in a petri dish, and the petri dish is placed in an environment of a temperature of 35±1°C and a humidity of 90% RH or higher for 24 hours. Step (c): After the treatment in step (b), the surface of the test piece is washed with pure water, and the pure water used for washing is collected in a centrifuge tube. The collected liquid is then diluted with dilute nitric acid to prepare an extract for measuring the amount of eluted Ag ions, Ev. Step (d): The amount of Ag ions (ng / mL) is measured using atomic absorption spectrometry for the extract (mL) obtained by the treatment in step (c). Based on the measurement results, the amount of Ag ions eluted per unit area, Ev (ng / cm), is calculated using the following formula (1): 2 ) is calculated.

[0075] Elution amount of Ag ions Ev (ng / cm 2 ) = Ag ion amount measurement result (ng / mL) × volume of extract (mL) × dilution ratio of extract / measurement area (cm 2 )...(Formula 1)

[0076] When the surface is placed in pure water for 24 hours, the amount of Ag elution Ev, which is the amount of Ag ions eluted per unit area of ​​the surface, is 14 ng / cm 2 In this case, the antibacterial activity was exhibited when the bacterial solution was in contact for 3 hours. When the surface is placed in pure water for 24 hours, the amount of Ag elution Ev, which is the amount of Ag ions eluted per unit area of ​​the surface, is 27 ng / cm 2 In this case, the antibacterial activity was exhibited when the bacterial solution was in contact for 1 hour. When the surface is placed in contact with pure water for 24 hours, the amount of Ag elution Ev, which is the amount of Ag ions eluted per unit area of ​​the surface, is 0.14 ng / cm 2 In this case, the antibacterial activity was exhibited after 24 hours of contact with the bacterial solution.

[0077] <Evaluation method> [Evaluation 1. Antibacterial activity] The antibacterial test was conducted in accordance with JIS Z2801:2010 (Antibacterial processed products - Antibacterial test method, antibacterial effect). The test conditions are as follows. ·Bacterial species: Escherichia coli (E.coli), strain number NBRC 3972 ·Bacterial liquid inoculation amount: 0.4mL Contact time between bacterial solution and film: 1 hour, 3 hours, 24 hours Unprocessed test piece: A film from the examples and comparative examples in which the antibacterial agent silver nanoparticles had been omitted (i.e., a film containing no silver nanoparticles) was used. The size was 5cm x 5cm. Cover film: additive-free polyethylene film Calculation of antibacterial activity value R: The antibacterial activity value R was calculated using the following formula (2). In the following formula (2), the viable cell count Ut is the average of the logarithmic values ​​of the viable cell counts of the untreated test specimen after 1 hour, 3 hours, and 24 hours, and the viable cell count At is the average of the logarithmic values ​​of the viable cell counts of the antibacterial treated test specimens (antibacterial films 10 of the Examples and Comparative Examples) after 1 hour, 3 hours, and 24 hours.

[0078] Antibacterial activity value R = viable bacteria count Ut - viable bacteria count At Equation (2) The evaluation results of the antibacterial activity of the antibacterial films 10 of the Examples and Comparative Examples are shown in Tables 2 and 3. In this evaluation, the threshold value for whether or not antibacterial activity is exhibited was set to 2.0. In other words, if the antibacterial activity value R is 2.0 or higher, it was evaluated that antibacterial activity is exhibited. Therefore, in Tables 2 and 3, if the antibacterial activity was 2.0 or higher, it was marked as "〇 (pass)", and if it was less than 2.0, it was marked as "× (fail)".

[0079] [Rating 2. Haze] The haze was measured using a haze meter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136. The evaluation results of the haze for the antibacterial films 10 of the Examples and Comparative Examples are shown in Tables 2 and 3. In this evaluation, the threshold value for whether haze occurs (i.e., whether excellent transparency is provided) was set to 2.0. In other words, if the measured haze value is less than 2.0, it was evaluated as having excellent transparency, with no haze or only a very small amount of haze. Therefore, in Tables 2 and 3, if the measured haze value is less than 2.0, it is marked as "Good (pass)", and if it is 2.0 or more, it is marked as "Poor (fail)".

[0080] [Table 2]

[0081] [Table 3]

[0082] <Evaluation results> As shown in Table 2, if the antibacterial layer 2 contains a resin component and silver nanoparticles 3, and the resin component contains a quaternary ammonium salt-based polymer that is a cationic functional group-containing polymer, and the amount of silver nanoparticles 3 added to the total mass of the antibacterial layer 2 is within the range of 3 mass% to 10 mass%, the antibacterial film 10 will exhibit antibacterial activity in a short period of time and will have excellent appearance (particularly transparency).

[0083] Furthermore, for example, this embodiment can have the following configuration. (1) An antibacterial film comprising an antibacterial layer, the antibacterial layer contains a resin component and silver nanoparticles, The resin component contains a cationic functional group-containing polymer, An antibacterial film, wherein the amount of the silver nanoparticles added to the antibacterial layer is within a range of 3% by mass to 10% by mass. (2) The antibacterial film according to (1) above, wherein the cationic functional group-containing polymer is a quaternary ammonium salt-based polymer. (3) The antibacterial film according to (1) or (2) above, wherein the average particle size of the silver nanoparticles is smaller than the thickness of the antibacterial layer. (4) When the contact time with the bacterial solution in the antibacterial test based on JIS Z2801 is 3 hours, the antibacterial activity after 3 hours is 2.0 or more. When the surface of the antibacterial layer is in contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area of ​​the surface, is 14 ng / cm 2 That's all, The antibacterial film according to any one of (1) to (3) above, which has a haze of 2.0 or less. (5) When the contact time with the bacterial solution in the antibacterial test based on JIS Z2801 is 1 hour, the antibacterial activity after 1 hour is 2.0 or more. When the surface of the antibacterial layer is in contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area of ​​the surface, is 27 ng / cm 2 That's all, The antibacterial film according to any one of (1) to (3) above, which has a haze of 2.0 or less. (6) The antibacterial film according to any one of (1) to (5) above, wherein the resin component contains an acrylic resin in addition to the cationic functional group-containing polymer. (7) A substrate; The antibacterial film according to any one of (1) to (6) above, comprising the antibacterial layer supported on the substrate. (8) a step of applying a coating liquid containing silver nanoparticles and a cationic functional group-containing polymer to a film-like substrate to form an antibacterial layer; A method for producing an antibacterial film, wherein the amount of silver nanoparticles added to the antibacterial layer is in the range of 3% by mass to 10% by mass. (9) The method for producing an antibacterial film according to (8) above, wherein the cationic functional group-containing polymer is a quaternary ammonium salt-based polymer. (10) The method for producing an antibacterial film according to (8) or (9), wherein the coating liquid contains an acrylic resin in addition to the cationic functional group-containing polymer. (11) A decorative material having the antibacterial film according to any one of (1) to (7) above on an adherend. [Explanation of symbols]

[0084] 1 Base material 2 Antibacterial layer 3. Silver nanoparticles 5 Adherent material 10 Antibacterial film 20 Cosmetic materials

Claims

1. An antibacterial film comprising an antibacterial layer, the antibacterial layer contains a resin component and silver nanoparticles, The resin component contains a cationic functional group-containing polymer, An antibacterial film, wherein the amount of silver nanoparticles added relative to the total mass of the antibacterial layer is in the range of 3 mass % to 10 mass %.

2. The antibacterial film according to claim 1 , wherein the cationic functional group-containing polymer is a quaternary ammonium salt-based polymer.

3. The antibacterial film according to claim 1 or 2, wherein the average particle size of the silver nanoparticles is smaller than the thickness of the antibacterial layer.

4. When the contact time with the bacterial solution in the antibacterial test based on JIS Z2801 is 3 hours, the antibacterial activity after 3 hours is 2.0 or more, When the surface of the antibacterial layer is in contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area of ​​the surface, is 14 ng / cm ２ That's all, 3. The antibacterial film according to claim 1, wherein the haze is 2.0 or less.

5. When the contact time with the bacterial solution in the antibacterial test based on JIS Z2801 is 1 hour, the antibacterial activity after 1 hour is 2.0 or more, When the surface of the antibacterial layer is in contact with pure water for 24 hours, the amount of Ag elution, which is the amount of Ag ions eluted per unit area of ​​the surface, is 27 ng / cm ２ That's all, 3. The antibacterial film according to claim 1, wherein the haze is 2.0 or less.

6. 3. The antibacterial film according to claim 1, wherein the resin component contains an acrylic resin in addition to the cationic functional group-containing polymer.

7. A substrate; The antimicrobial film of claim 6 , comprising: the antimicrobial layer supported on the substrate.

8. a step of applying a coating liquid containing silver nanoparticles and a cationic functional group-containing polymer to a film-like substrate to form an antibacterial layer; The method for manufacturing an antibacterial film, wherein the amount of silver nanoparticles added relative to the total mass of the antibacterial layer is in the range of 3 mass% to 10 mass%.

9. The method for producing an antibacterial film according to claim 8 , wherein the cationic functional group-containing polymer is a quaternary ammonium salt-based polymer.

10. The method for producing an antibacterial film according to claim 8 or 9, wherein the coating liquid contains an acrylic resin in addition to the cationic functional group-containing polymer.

11. A decorative material having the antibacterial film according to claim 1 or 2 on an adherend.

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