Laminate

Abstract

The present invention provides a laminate capable of suppressing the growth of bacteria or viruses on the outer surface of a container. [Solution] The laminate (10) comprises a base material (101) and a surface resin layer (102) on the base material (101). The base material (101) includes a plastic film. The surface resin layer (102) comprises a resin (102a) and zirconium phosphate particles (102b) supported with zinc and silver, which have antibacterial properties, antiviral properties, or both antibacterial and antiviral properties. A portion of the zinc and silver supported zirconium phosphate particles (102b) is exposed to the outside of the resin (102a) in a convex shape.

Description

Technical Field

[0001] The present disclosure relates to a laminate.

Background Art

[0002] Commodities such as soft drinks, seasonings, cosmetics, and detergents are sold in the form of labeled containers with plastic labels such as shrink films attached to the outer surfaces of various containers.

[0003] For example, Patent Document 1 describes an antiviral shrink film. The antiviral shrink film described in Patent Document 1 is composed of a shrink base material and a functional layer that is on one side of the shrink base material and is the outermost layer of the antiviral shrink film. The functional layer is composed of an inorganic antiviral agent powder and a hard coat agent, and the antiviral shrink film contains 0.01 g or more and 0.03 g or less of the inorganic antiviral agent powder per 1 m , , ,

[0005] , ,<000**********30>,<000**********29>,<000**********27>,<000**********25>,<000**********23>,<000**********21>,<000**********33>,<000**********31>When the area where a part of the surface of the particles of the inorganic antiviral agent powder is exposed on the exposed surface is defined as the single exposed area, the sum of the single exposed areas of the exposed effective powder particles present in a certain section of the exposed surface is defined as the total exposed area, and the percentage of the total exposed area to the area of the certain section is defined as the occupancy percentage of the exposed effective powder, the occupancy percentage of the exposed effective powder is set to 50% or more and 80% or less.

Prior Art Documents

Patent Documents

[0004] [[ID=************]] [[ID=************]]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, it is rare for the contents of labeled containers, such as seasonings or detergents, to be used up in a single sitting.

[0006] For example, soy sauce bottles are always available in restaurants and are picked up every time a customer uses soy sauce on their food. Similarly, detergent bottles are available in every home and are picked up every time the user uses detergent. Furthermore, large refill pouches are typically not used up in one go, and users usually pick them up and use them multiple times.

[0007] Thus, labeled containers or pouches, which are designed to contain contents that are used multiple times, are typically handled by the user multiple times.

[0008] However, if a container fitted with the antiviral shrink film described in Reference 1 is handled multiple times by an unspecified number of people, there is a possibility that bacteria or viruses may adhere to and multiply on the outer surface of the container, and therefore, improvements are requested.

[0009] In particular, given the recent COVID-19 pandemic and heightened awareness of hygiene, there is a strong need to suppress the growth of bacteria or viruses on the outer surface of containers. [Means for solving the problem]

[0010] According to the embodiments disclosed herein, the invention comprises a substrate and a surface resin layer on the substrate, wherein the substrate includes a plastic film, and the surface resin layer comprises a resin and zinc and silver supporting the resin, which have antibacterial properties, antiviral properties, or both antibacterial and antiviral properties. A laminate can be provided comprising zirconium phosphate particles, wherein a portion of the zinc and silver-supported zirconium phosphate particles are convexly exposed to the outside from the resin. [Effects of the Invention]

[0011] According to the embodiments disclosed herein, it is possible to provide a laminate capable of suppressing the growth of bacteria or viruses on the outer surface of a container.

Brief Description of the Drawings

[0012] [Figure 1] It is a schematic cross-sectional view of an example of the laminate of the embodiment. [Figure 2] It is a schematic cross-sectional view of another example of the laminate of the embodiment. [Figure 3] It is a schematic cross-sectional view of still another example of the laminate of the embodiment. [Figure 4] It is a photograph of the cross-section of the laminate of Experimental Example 8 magnified 2000 times. [Figure 5] (a) is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 1 before heat shrinkage is binarized, and (b) is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 1 after 50% heat shrinkage is binarized. [Figure 6] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example '1 before heat shrinkage is binarized. [Figure 7] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example '1 after 50% heat shrinkage is binarized. [[ID=X]] [Figure 8] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 6 before heat shrinkage is binarized. [Figure 9] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 6 after 50% heat shrinkage is binarized. <X000079> [Figure 10] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 7 before heat shrinkage is binarized. [Figure 11] It is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 7 after 50% heat shrinkage is binarized. [Figure 12] (a) is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 8 before heat shrinkage is binarized, and (b) is a diagram in which the surface of the surface resin layer of the laminate of Experimental Example 8 after 50% heat shrinkage is binarized.

Modes for Carrying Out the Invention

[0013] Note: There seems to be an error in the original text where the tag [Figure 8] and are not properly labeled in the context. I have translated them as <X000079> and <X000079> respectively for the purpose of maintaining the integrity of the translation. You may want to check the original text for accuracy.<Laminate> FIG. 1 shows a schematic cross-sectional view of an example of the laminate 10 of an embodiment. As shown in FIG. 1, the laminate 10 includes a base material 101, a surface resin layer 102 on the base material 101, and an ink layer 103 provided on the side opposite to the side where the surface resin layer 102 of the base material 101 is provided.

[0014] <Base material> The base material 101 is a substrate containing a resin capable of supporting at least the surface resin layer 102.

[0015] As the resin contained in the base material 101, for example, polyester resins (such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, etc.), polystyrene resins (such as polystyrene, styrene-butadiene copolymer, etc.), polyolefin resins (such as polyethylene, polypropylene, etc.), polyvinyl chloride resins, polyamide resins (such as nylon, etc.), aramid resins, polyimide resins, polyphenylene sulfide resins, or acrylic resins can be used. The base material 101 may contain one of these resins or two or more of them.

[0016] The base material 101 may be, for example, a heat-shrinkable plastic film (shrink film). When the base material 101 is a shrink film, for example, the laminate 10 can be used as a shrink label or an overlap package that can be attached to the outer surface of a container. When the base material 101 is a shrink film, the base material 101 is heated to 90°C When immersed in hot water for 10 seconds, the heat shrinkage rate in the main shrinkage direction of the base material 101 is preferably 30% or more and 90% or less, and more preferably 40% or more and 85% or less. Also, when the base material 101 is a shrink film, the heat shrinkage rate in the direction perpendicular to the main shrinkage direction of the base material 101 when immersed in hot water at 90°C for 10 seconds is preferably -3% or more and 15% or less, and more preferably -1% or more and 10% or less. <00001x04> The base material 101 may be, for example, a non-heat-shrinkable plastic film. If the base material 101 is a non-heat-shrinkable plastic film, the laminate 10 can be used, for example, as a wrap-around label that can be wrapped around the outer surface of a container, a tack label that can be attached to the outer surface of a container, or as a flexible packaging bag such as a flat bag, gusset bag, pillow bag, or pouch. If the base material 101 is a non-heat-shrinkable plastic film, the heat shrinkage rate of the base material 101 in the main shrinkage direction when the base material 101 is immersed in 90°C hot water for 10 seconds is preferably less than 3%, and more preferably less than 1%.

[0018] The substrate 101 may be a single-layer film consisting of one layer, or a multilayer film consisting of two or more layers. The thickness of the substrate 101 can be, for example, 5 μm to 150 μm, preferably 5 μm to 120 μm, and more preferably 5 μm to 100 μm.

[0019] <Surface resin layer> As shown in Figure 1, the surface resin layer 102 comprises a resin 102a and zinc and silver-supported zirconium phosphate particles 102b (hereinafter sometimes simply referred to as "particles 102b") which have antibacterial properties, antiviral properties, or both antibacterial and antiviral properties. In the surface resin layer 102, a portion of at least one particle 102b is exposed convexly to the outside from the resin 102a. The surface resin layer 102 may also contain particles 102b that are completely embedded in the resin 102a, as long as it contains particles 102b that are partially exposed convexly to the outside from the resin 102a.

[0020] <Resin> The resin 102a only needs to be able to support the particles 102b such that a portion of at least one particle 102b is convexly exposed to the outside from the resin 102a.

[0021] Resin 102a may contain, for example, an acrylic resin as a resin component. As the acrylic resin included as a resin component of resin 102a, for example, a polymer composed of at least an acrylic monomer as a monomer component can be used. The monomer components constituting the above acrylic resin may include monomer components other than acrylic monomers. The main component of the resin component of resin 102a preferably contains a thermoplastic resin, and more preferably contains a thermoplastic acrylic resin. The acid value of the resin component of resin 102a may be, for example, 2 mg KOH / g or more and 500 mg KOH / g or less, preferably 10 mg KOH / g or more and 200 mg KOH / g or less, more preferably 15 mg KOH / g or more and 100 mg KOH / g or less, and even more preferably 20 mg KOH / g or more and 80 mg KOH / g or less. The acid value of the resin component of resin 102a is calculated based on JIS K 5601-2-1:1999.

[0022] Examples of acrylic monomers include linear or branched alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. (meth)acrylate alkyl ester [preferably (meth)acrylate C] 1-12Alkyl esters, etc.; (meth)acrylic acid; carboxyl group-containing (meth)acrylic acid esters such as carboxyethyl acrylate; hydroxyl group-containing (meth)acrylic acid esters such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate [preferably hydroxy C (meth)acrylate] 1-8 [Alkyl esters, etc.]; (meth)acrylate cyclohexyl Examples include monomers having a (meth)acryloyl group (monomers having at least an acryloyl group or a methacryloyl group), such as cycloalkyl (meth)acrylate esters like syl and isobornyl (meth)acrylate; (meth)acrylamide derivatives such as N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide; and dialkylaminoalkyl (meth)acrylate esters such as dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dipropylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylate, and dipropylaminopropyl(meth)acrylate. The acrylic monomer may be used alone or in combination of two or more.

[0023] Examples of monomer components constituting acrylic resins other than acrylic monomers include carboxyl group-containing polymerizable unsaturated compounds or their anhydrides such as crotonic acid, itaconic acid, fumaric acid, and maleic acid; styrene compounds such as styrene, vinyltoluene, and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride; vinyl ethers such as methyl vinyl ether; cyano group-containing vinyl compounds such as (meth)acrylonitrile; ethylene or propylene, etc.

[0024] <Other ingredients> The surface resin layer 102 may further contain nitrated cotton in addition to the resin component in the resin 102a. When the surface resin layer 102 further contains nitrated cotton in addition to the resin component, the stickiness of the surface of the surface resin layer 102 tends to be reduced. When nitrated cotton is added to the resin 102a, the handling properties of the resin solution when coating the resin 102a can be improved. Furthermore, when the surface resin layer 102 contains, together with or in place of nitrated cotton, for example, cellulose acetate butyrate (CAB resin) or cellulose acetate propionate (CAP resin) in the resin 102a, the stickiness of the surface of the surface resin layer 102 can be reduced and the handling performance can be improved. In addition, when the substrate 101 is PET, the adhesion between the substrate 101 and the surface resin layer 102 can be improved by including nitrated cotton in the resin 102a of the surface resin layer 102.

[0025] The surface resin layer 102 may further contain, in addition to the resin component, a lubricant, an anti-blocking agent, an anti-settling agent, or a matting agent in the resin 102a. Examples of matting agents include acrylic beads, silica, or barium sulfate. When the surface resin layer 102 further contains acrylic beads, silica, or barium sulfate in addition to the resin component in the resin 102a, the surface resin layer 102 tends to be able to function as a matte varnish. The lubricant may be present in an amount of, for example, 2% to 30% by weight, and preferably 5% to 25% by weight, when the total weight of the surface resin layer 102 is considered as 100%. The lubricant may contain particles larger than, for example, the zinc and silver-supported zirconium phosphate particles described later. The lubricant may also be exposed in a convex manner from the resin 102a of the surface resin layer 102.

[0026] <Zirconium phosphate particles supported with zinc and silver> The zinc and silver-supported zirconium phosphate particles 102b only need to possess antibacterial properties, antiviral properties, or both antibacterial and antiviral properties.

[0027] Particle 102b tends to exhibit antibacterial or antiviral properties over a wide range of bacterial or viral species. Furthermore, particle 102b has high heat resistance, exhibits antibacterial or antiviral properties over a long period of time, and tends to have little adverse effect on the human body.

[0028] A portion of the particles 102b are exposed outward in a convex manner from the resin 102a of the surface resin layer 102. In this embodiment, "exposed outward in a convex manner" means that a portion of the particles 102b protrudes outward more than the particles exposed from the exposed surface of the functional layer described in Patent Document 1. That is, the point on the surface of the particles 102b exposed to the outside from the resin 102a that is furthest outward from the resin 102a in this embodiment should be located further away from the resin 102a than the surface of the particles exposed from the exposed surface of the functional layer described in Patent Document 1. The extent to which the surface of the particles described in Patent Document 1 is exposed from the exposed surface of the functional layer is clear to those skilled in the art from, for example, Figures 1 to 4 of Patent Document 1 and the description in Patent Document 1 related to these figures.

[0029] The median diameter D50 of particle 102b is preferably greater than the thickness of the surface resin layer 102. When the median diameter D50 of particle 102b is greater than the thickness of the surface resin layer 102, there is a tendency for a portion of the particle 102b to be suitably exposed to the outside in a convex shape from the surface resin layer 102. The median diameter D50 is determined by counting the individual particle sizes of particle 102b from smallest to largest and taking the diameter of the particle exactly in the middle.

[0030] The median diameter D50 of particle 102b can be, for example, 1 μm or more and 5 μm or less. When the median diameter D50 of particle 102b is 1 μm or more and 5 μm or less, when the thickness of the surface resin layer 102 is, for example, 0.3 μm or more and 2 μm or less, a portion of particle 102b tends to be suitably exposed to the outside in a convex shape from the surface resin layer 102. The thickness of the surface resin layer 102 is preferably 0.5 μm or more and 1 μm or less.

[0031] The median diameter D50 of particle 102b was measured using a particle size distribution analyzer employing laser diffraction and scattering under the following measurement conditions. Specifically, the Microtrack 3300EX II from Microtrack-Bell was used as the particle size distribution analyzer.

[0032] (Measurement conditions) Particle name: glass Particle permeability: transparent Particle refractive index: 1.51 Particle shape: true spherical Solvent: Methanol 35% by weight, Isopropyl alcohol (IPA) 25% by weight, Ethyl acetate 40% by weight Solvent refractive index: 1.333~1.377

[0033] <Ink layer> The ink layer 103 is a layer containing an ink resin composition. The ink resin composition contained in the ink layer 103 may include, for example, pigments, resins, and additives. The ink layer 103 can be, for example, a design printing layer. The design printing layer is a layer containing pigments that displays a visible pattern or characters.

[0034] In the laminate 10 of the embodiment shown in Figure 1, the ink layer 103 is provided on the side opposite to the side of the substrate 101 where the surface resin layer 102 is provided. However, the ink layer 103 may also be provided on the side of the substrate 101 where the surface resin layer 102 is provided.

[0035] Figure 2 shows a schematic cross-sectional view of another example of the laminate 10 of the embodiment. As shown in Figure 2, when the ink layer 103 is provided on the side of the substrate 101 where the surface resin layer 102 is provided, the ink layer 103 may be provided between the substrate 101 and the surface resin layer 102.

[0036] Figure 3 shows a schematic cross-sectional view of yet another example of the laminate 10 of the embodiment. As shown in Figure 3, the ink layer 103 may be provided on both the side of the substrate 101 on which the surface resin layer 102 is provided and the side of the substrate 101 on which the surface resin layer 102 is provided.

[0037] <Other layers> When the laminate 10 is used as a tack label, the laminate 10 may, for example, have an adhesive layer and a release layer in this order from the base material 101 side, on the side opposite to the side where the surface resin layer 102 of the base material 101 is provided. Also, when the laminate 10 is used as a pouch, for example, a sealant layer may be provided on the side opposite to the side where the surface resin layer 102 of the base material 101 is provided.

[0038] <Method for manufacturing laminates> The laminate 10 shown in Figure 1 can be manufactured, for example, as follows. First, a base material 101 is prepared. The base material 101 can be prepared by forming a film using methods such as the inflation method, tubular method, extrusion method, or calendering method, and if necessary, by further stretching the film.

[0039] Next, an ink layer 103 is formed on one surface of the substrate 101. The ink layer 103 can be formed, for example, by applying an ink resin composition for forming the ink layer 103 to one surface of the substrate 101 and then drying or curing it.

[0040] Subsequently, a surface resin layer 102 is formed on the side of the substrate 101 opposite to the side where the ink layer 103 is provided. The surface resin layer 102 can be formed, for example, as follows. First, a resin composition for forming the surface resin layer 102 is prepared by mixing resin 102a diluted with a solvent with particles 102b. Next, the solvent is removed by applying the resin composition to the side of the substrate 101 opposite to the side where the ink layer 103 is provided and then drying it. This makes it possible to form a surface resin layer 102 in which a portion of the particles 102b are exposed convexly from the resin 102a. The resin composition for forming the surface resin layer 102 is preferably applied by an intaglio printing method such as gravure printing.

[0041] <Application> If the base material 101 is a heat-shrinkable plastic film, the laminate 10 of the embodiment can be used, for example, as a shrink label. A shrink label is a plastic label that can be attached to the outer surface of a container such as a PET bottle, a metal container, or a glass container by heat shrinking.

[0042] If the base material 101 is a non-heat-shrinkable plastic film, the laminate 10 of the embodiment can be used, for example, as a wrap-around label, a tack label, or a pouch.

[0043] Wrap-around labels are attached to the outer surface of containers such as PET bottles, with the ends being bonded together. This plastic label can be attached to the outer surface of a container without heat shrinkage. For example, by adhering one end of the plastic label to the outer surface of the container, wrapping the plastic label around the outer surface of the container, and finally adhering the ends of the plastic label together, the label can be attached to the outer surface of the container.

[0044] Tack labels are plastic labels that can be attached to the outer surface of containers such as PET bottles by adhering them to the outer surface with an adhesive layer or the like.

[0045] A pouch is a bag-shaped container formed by heat-sealing a sealant layer of plastic film.

[0046] Regardless of the application for which the laminate 10 of the embodiment is used, the laminate is attached to the container or the container is configured such that the surface resin layer 102 is located on the outer surface of the container.

[0047] In the laminate 10 of the embodiment, a portion of the particles 102b having antibacterial properties, antiviral properties, or both antibacterial and antiviral properties are exposed outward in a convex manner from the resin 102a of the surface resin layer 102 on the substrate 101.

[0048] Therefore, when the laminate 10 of the embodiment is attached to the outer surface of a container, for example, as a shrink label, wrap-around label, or tack label, or when it is molded into the container itself, such as a pouch, bacteria or viruses that arrive at the surface resin layer 102 from outside the laminate 10 will have their growth suppressed by the action of particles 102b that are exposed outward in a convex shape from the resin 102a. It can be inferred that this makes it possible to reduce the total number of bacteria or viruses on the outer surface of the container.

[0049] For the reasons stated above, the laminate 10 of the embodiment can suppress the growth of bacteria or viruses on the outer surface of the container. When the base material 101 of the laminate 10 of the embodiment is a heat-shrinkable plastic film, the abrasion resistance of the surface resin layer 102 of the laminate 10 after heat shrinkage (the difficulty of particles 102b physically detaching from the surface resin layer 102) tends to improve compared to before heat shrinkage, which is particularly preferable.

[0050] Furthermore, if the substrate 101 of the laminate 10 is a heat-shrinkable plastic film, the number of particles 102b per unit area on the surface of the substrate 101 after heat shrinkage increases compared to before heat shrinkage. This makes it possible to achieve both manufacturability and antibacterial and / or antiviral properties. This is for the following reasons.

[0051] In other words, when a resin composition for forming a surface resin layer 102 containing resin 102a and particles 102b is applied to the surface of a substrate 101, the content ratio of particles 102b on the surface of the substrate 101 (particles / m²) 2 As the amount increases, in the manufacturing process, for forming the surface resin layer 102 There is a tendency for particles 102b in the resin composition to easily transfer to rollers or the like (causing powdering).

[0052] Such powdering can degrade the quality of the manufactured laminate. However, if the base material 101 is a heat-shrinkable plastic film and the laminate 10 is attached to the outer surface of a container by heat shrinking, the content of particles 102b at the manufacturing stage (i.e., before heat shrinking) can be adjusted to suppress powdering, while the content of particles 102b in the heat-shrinked laminate 10 attached to the container can be adjusted to exhibit sufficient antibacterial and / or antiviral properties. Furthermore, since the content of particles 102b in the heat-shrinked laminate 10 is higher than that of the laminate 10 before heat shrinking, the antibacterial and / or antiviral properties of the heat-shrinked laminate 10 can be improved compared to the laminate before heat shrinking.

[0053] Furthermore, in the laminate 10 of the embodiment, a portion of the particles 102b are exposed outward in a convex manner from the resin 102a of the surface resin layer 102. Compared to the particles described in Patent Document 1, which are not exposed outward in a convex manner from the functional layer, the antibacterial performance, antiviral performance, or both antibacterial and antiviral performance can be further improved.

[0054] As shown in the experimental examples described later, the laminate 10 of the embodiment has particularly excellent water resistance. Therefore, even when the laminate 10 of the embodiment is attached to a container that is expected to come into contact with water, such as a beverage bottle or a household item used in a bathroom, it can exhibit sufficient antibacterial and / or antiviral properties. Furthermore, when the base material 101 is a heat-shrinkable plastic film, the laminate 10 of the embodiment may be heat-shrinked by blowing steam onto it in a steam tunnel and then attached to the container. In this case as well, the laminate 10 of the embodiment will come into contact with water, but it will still be possible to exhibit the antibacterial and / or antiviral properties of the laminate 10 of the embodiment. [Examples]

[0055] <First consideration> (Fabrication of the laminate in Experimental Example 1) First, an unoriented polystyrene film (a non-heat-shrinkable plastic film, so-called CPS film) or a 30 μm thick HOP film (a uniaxially oriented, heat-shrinkable plastic film in which polyester (PET) film, polystyrene film, and PET film are laminated in that order) was prepared as the plastic film constituting the base material. Next, a resin composition for forming the surface resin layer was applied to the entire surface of one side of the plastic film by gravure printing and then dried to form the surface resin layer. The laminate of Experimental Example 1 was thus prepared.

[0056] In Experimental Example 1, the resin composition for forming the surface resin layer was prepared by diluting 18.2 parts by weight of solids containing acrylic resin as the resin component and 3 parts by weight of zinc and silver-supported zirconium phosphate particles (hereinafter referred to as "functional particles") having antibacterial properties, antiviral properties, or both antibacterial and antiviral properties, with 103.8 parts by weight of an organic solvent. The thickness of the acrylic resin in the surface resin layer of the laminate in Experimental Example 1 was about 0.5 to 1 μm, and the median diameter D50 of the functional particles was about 3 μm.

[0057] (Fabrication of the laminate in Experimental Example 1') First, an unoriented polystyrene film (non-heat-shrinkable plastic film, so-called CPS film (20 μm thick)) or a 35 μm thick HOP film was prepared as the plastic film constituting the base material. Next, a resin composition for forming the surface resin layer was applied to the entire surface of one side of the plastic film by gravure printing and then dried to form the surface resin layer. The laminate of Experimental Example 1' was thus prepared. In the evaluation of the laminates of Experimental Example 1', Experimental Examples 1-9, and the Reference Example described later, the plastic film used as the base material for antibacterial and antiviral evaluation was a 20 μm thick CPS film, while the plastic film used as the base material for other evaluations (evaluation of component shedding, abrasion resistance evaluation, haze value, binarization) was a 35 μm thick HOP film.

[0058] In Experimental Example 1', the resin composition for forming the surface resin layer was prepared by diluting 20 parts by weight of solids containing acrylic resin as the resin component and 1 part by weight of zinc and silver-supported zirconium phosphate particles (hereinafter referred to as "functional particles") having antibacterial properties, antiviral properties, or both antibacterial and antiviral properties, with 104 parts by weight of an organic solvent. The thickness of the acrylic resin in the surface resin layer of the laminate in Experimental Example 1' is 0.5 The particle size was approximately 1 μm, and the median diameter D50 of the functional particles was approximately 3 μm.

[0059] (Fabrication of a laminated structure as an example) The reference example laminate was fabricated using the same method and conditions as in Experimental Example 1', except that silver-supported glass nanoparticles, which have a structure in which silver ions are contained in water-soluble glass as the main component, were used instead of functional particles.

[0060] (Antibacterial activity evaluation) First, the laminates of Experimental Example 1 and Reference Example, prepared as described above, were subjected to either water-resistant or light-resistant treatment. Water-resistant treatment was performed by immersing each laminate of Experimental Example 1 and Reference Example in room temperature water for 16 to 18 hours. Light-resistant treatment was performed by irradiating each laminate of Experimental Example 1 and Reference Example with a sunshine lamp for 8 ± 0.4 hours.

[0061] For each laminate of Experimental Example 1 and Reference Example after water-resistant or light-resistant treatment, the number of viable bacteria was measured after contacting the surface resin layer of each laminate of Experimental Example 1 and Reference Example with the following bacterial species for 24 hours under the following antibacterial evaluation conditions, and the antibacterial activity value was calculated. The results are shown in Table 1.

[0062] (Antibacterial activity evaluation conditions) Test method: JIS Z 2801:2010 "Antibacterial treated products - Test method for antibacterial properties and antibacterial effect" (Film adhesion method) Bacterial species: Escherichia coli NBRC 3972, Staphylococcus aureus NBRC 12732

[0063] [Table 1]

[0064] The values ​​in Table 1 represent the antibacterial activity values ​​of the laminates in Experimental Example 1 and Reference Example after water-resistant treatment or light-resistant treatment. A higher antibacterial activity value in Table 1 indicates superior antibacterial properties. The antibacterial activity value is the difference in the logarithmic number of viable bacteria after 24 hours of contact between the laminates in Experimental Example 1 and Reference Example (after water-resistant treatment or light-resistant treatment) and the blank laminate. The blank laminate was prepared using the same method and under the same conditions as Experimental Example 1, except that it did not contain zirconium phosphate particles supported with zinc and silver in the acrylic resin solution.

[0065] (Antibacterial activity evaluation results) As shown in Table 1, the laminate of Experimental Example 1 after water-resistant treatment was confirmed to have antibacterial properties against both Escherichia coli and Staphylococcus aureus, compared to the laminate of Reference Example after water-resistant treatment.

[0066] Furthermore, as shown in Table 1, the laminate of Experimental Example 1 after light-resistant treatment was confirmed to have antibacterial activity against E. coli compared to the laminate of Reference Example after light-resistant treatment. The antibacterial activity value of the laminate of Experimental Example 1 after light-resistant treatment against Staphylococcus aureus was lower than that of the laminate of Reference Example after light-resistant treatment. However, since the antibacterial activity value of the laminate of Experimental Example 1 after light-resistant treatment against Staphylococcus aureus is 2.0 or higher, its antibacterial activity against Staphylococcus aureus has been demonstrated. Yes, they are.

[0067] (Antiviral evaluation) For each laminate of Experimental Example 1 and Reference Example after the above-described water-resistant or light-resistant treatment, the viral infectivity titer was measured after contacting the surface resin layer of each laminate of Experimental Example 1 and Reference Example with the following virus species for 24 hours under the following antiviral evaluation conditions, and the antiviral activity value was calculated. The results are shown in Table 2.

[0068] (Antiviral evaluation conditions) Test method: ISO 21702:2019 "Measurement of antiviral activity of plastics and other non-porous surfaces" Virus species: Influenza A, Feline Calicivirus

[0069] [Table 2]

[0070] The values ​​in Table 2 represent the antiviral activity values ​​of the laminates in Experimental Example 1 and Reference Example after water-resistant treatment or light-resistant treatment. A higher antiviral activity value in Table 2 indicates superior antiviral performance. The antiviral activity values ​​in Table 2 were calculated using the following formula (1).

[0071]

number

[0072] (Antiviral activity evaluation results) As shown in Table 2, the laminate of Experimental Example 1 after water-resistant treatment and the laminate of Experimental Example 1 after light-resistant treatment were confirmed to have antiviral properties against both influenza A and feline calicivirus, respectively, compared to the laminate of Reference Example after water-resistant treatment and the laminate of Reference Example after light-resistant treatment.

[0073] (Evaluation of component loss of functional particles before and after water-resistant treatment) Using a 35 μm thick HOP film as the base material, elemental analysis was performed on the surface of the surface resin layer of each laminate in Experimental Example 1' and Reference Example before and after water-resistant treatment, using SEM (Scanning Electron Microscope) observation (×1000), to confirm the detachment of constituent components of functional particles before and after water-resistant treatment. The results are shown in Table 3.

[0074] [Table 3]

[0075] In Table 3, "A" indicates that the element in the left column was detected, and "B" indicates that the element in the left column was not detected. "-" in Table 3 means that the element in the left column is not present. Element detection is defined as a detection peak of 5 cps / eV or higher.

[0076] As shown in Table 3, in the reference example laminate, the detachment of zinc, silver, and phosphorus was observed after water-resistant treatment compared to before water-resistant treatment. On the other hand, in the experimental example 1' laminate, no elemental detachment was observed before or after water-resistant treatment. From these results, it is concluded that the reference example laminate has inferior water resistance compared to the experimental example 1' laminate, and therefore, improvement in functionality (especially antiviral properties) cannot be achieved.

[0077] (Abrasion resistance evaluation) The abrasion resistance of the surface resin layer (the retention capacity of the functional particles of the acrylic resin in the surface resin layer) of the laminate in Experimental Example 1', which used a 35 μm thick HOP film as the plastic film constituting the base material, after thermal shrinkage was evaluated based on the following abrasion resistance test.

[0078] First, referring to JIS L 0849:2013 8.1.2 "Friction Tester Type II (JSPS Type)", a K-liner (corrugated cardboard) surface was used as the friction element of a dye friction fastness tester (DAIEI KAGAKU SEIKI MFG CO. LTD), and the laminate of Experimental Example 1' was attached and fixed as a test specimen so that the surface resin layer faced the K-liner side. Next, a load of 500g was applied to the friction element, and the laminate of Experimental Example 1' was moved back and forth horizontally 500 times with the K-liner surface in contact with the surface resin layer. After that, the surface condition of the surface resin layer of the laminate of Experimental Example 1' was evaluated. The results are shown in Table 4.

[0079] The above abrasion resistance evaluation was performed on both the laminate of Experimental Example 1' before heat shrinkage (Experimental Example 1'-1) and the laminate after heat shrinkage by 30% (Experimental Example 1'-2), according to the following abrasion resistance evaluation criteria.

[0080] (Abrasion resistance evaluation criteria) A... No functional particles were observed to have detached after horizontal reciprocating motion. B...Functional particles that had detached after horizontal reciprocating motion were observed. C...A significant number of functional particles that had detached after horizontal reciprocating motion were observed. D...A significant number of functional particles that had detached after horizontal reciprocating motion were observed, and surface wear was also pronounced.

[0081] [Table 4]

[0082] As is clear from the results shown in Table 4, the laminate of Experimental Example 1' after heat shrinkage showed less detachment of functional particles from the surface of the surface resin layer compared to the laminate of Experimental Example 1' before heat shrinkage, confirming improved abrasion resistance.

[0083] <Second Consideration> (Fabrication of laminates for experimental examples 2-5) Laminates for Experimental Examples 2-5, shown in Table 5 below, were fabricated using the same method and under the same conditions as Experimental Example 1', except that the coverage rate of the surface resin layer on the surface of a substrate made of a 20 μm thick CPS film was changed from 100% (surface resin layer covering the entire surface of the substrate). In addition, a laminate of Experimental Example 1', which has a substrate made of a 20 μm thick CPS film, was also prepared. In other words, the first study focused on the so-called solid-coverage surface resin layer, and the second study investigated varying the degree of coverage based on gradation, etc.

[0084] [Table 5]

[0085] In Table 5, the percentage values ​​for coverage in Experimental Examples 1' and 2-5 represent the proportion of the substrate surface occupied by the surface resin layer as a percentage (=100 × (area of ​​surface resin layer installation) / (total surface area of ​​the substrate where the surface resin layer is installed)). In addition, "0.08mm stripe" in Experimental Example 4 of Table 5 indicates a configuration in which a 0.08mm wide line of surface resin layer is alternately installed on the substrate surface, with one area of ​​installation and one area of ​​non-installation (coverage rate considered to be 50%). In addition, "0.15mm stripe" in Experimental Example 5 of Table 5 indicates a configuration in which a 0.15mm wide line of surface resin layer is alternately installed and one area of ​​non-installation (coverage rate considered to be 50%).

[0086] (Antibacterial activity evaluation) For the laminates of Experimental Examples 1' and 2-5 prepared as described above, the number of viable bacteria [cells / cm³] after contacting the surface resin layer of each laminate with the following bacterial species for 24 hours under the following antibacterial evaluation conditions, without performing the above-mentioned water-resistant and light-resistant treatments. 2 ]oh The antibacterial activity levels were measured. The results are shown in Table 6.

[0087] (Antibacterial activity evaluation conditions) Test method: JIS Z 2801:2010 "Antibacterial treated products - Test method for antibacterial properties and antibacterial effect" Bacterial species: Escherichia coli NBRC 3972, Staphylococcus aureus NBRC 12732 Bacterial suspension conditions: Escherichia coli 1 / 500 NB 0.4 mL, Staphylococcus aureus 1 / 500 NB 0.4 mL Operating conditions: 35°C, 24 hours Size: 4cm x 4cm (covering film)

[0088] [Table 6]

[0089] (Antibacterial activity evaluation results) As shown in Table 6, the laminates of Experimental Example 1' and Experimental Examples 2-5 demonstrated antibacterial activity against Escherichia coli and Staphylococcus aureus even under conditions without the water-resistant and light-resistant treatments described above. Furthermore, the results shown in Table 6 also confirmed that a coverage rate of 50% or more of the surface resin layer on the substrate surface is preferable to improve antibacterial activity against Escherichia coli and Staphylococcus aureus.

[0090] <Third consideration> (Fabrication of laminates for experimental examples 6-7) The laminate in Experimental Example 6 was prepared using the same method and conditions as in Experimental Example 1', except that the functional particle content of the resin composition for forming the surface resin layer was 2 parts by weight and the organic solvent content was 128 parts by weight. The laminate in Experimental Example 7 was prepared using the same method and conditions as in Experimental Example 1', except that the functional particle content of the resin composition for forming the surface resin layer was 2 parts by weight and the organic solvent content was 118 parts by weight.

[0091] Figure 4 shows a 2000x magnified photograph of the cross-section of the laminate in Experimental Example 7. In Figure 4, the convex protrusions in the black areas correspond to the functional particles. Therefore, it can be confirmed that in the laminate of Experimental Example 7, some of the functional particles are exposed convexly from the surface resin layer.

[0092] (Haze value) For each of the laminates in Experimental Example 1' and Experimental Examples 6-7, the haze value before thermal shrinkage was determined. Furthermore, for the laminates in Experimental Example 1' and Experimental Examples 6-7, the haze value after 50% thermal shrinkage was determined. The results are shown in Table 7 below.

[0093] The haze value was measured using a haze meter (NDH-7000) and conforms to JIS standards. This value was calculated based on K 7136, "Method for Determining Haze in Transparent Plastic Materials."

[0094] (Binarization) Figure 6 shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 1' before thermal shrinkage. In Figure 6, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0095] As shown in Figure 6, the total number of pixels in the image of the laminate in Experimental Example 1' before thermal shrinkage was 306,560 pixels, while the number of pixels in the white areas corresponding to the functional particles was 6,546 pixels.

[0096] Therefore, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 1' before thermal shrinkage (percentage of functional particle exposure) was 2.14% (= 100 × 6546 / 306560). The results are shown in Table 7.

[0097] Figure 7 shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 1' after 50% thermal shrinkage. In Figure 7, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0098] As shown in Figure 7, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 1' after thermal shrinkage (percentage of exposed functional particles) was 4.47%. The results are shown in Table 7.

[0099] Figure 8 shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 6 before thermal shrinkage. In Figure 6, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0100] As shown in Figure 8, the total number of pixels in the image of the laminate in Experimental Example 6 before thermal shrinkage was 306,560 pixels, while the number of pixels in the white areas corresponding to the functional particles was 9,065 pixels.

[0101] Therefore, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 6 before thermal shrinkage (percentage of exposed functional particles) was 2.96% (=100 × 9065 / 306560). The results are shown in Table 7.

[0102] Figure 9 shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 6 after 50% thermal shrinkage. In Figure 9, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0103] As shown in Figure 9, the total number of pixels in the image of the laminate in Experimental Example 6 after 50% thermal shrinkage was 306,560 pixels, while the number of pixels in the white areas corresponding to functional particles was 22,126 pixels.

[0104] Therefore, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 6 after 50% thermal shrinkage (percentage of exposed functional particles) was 7.22% (= 100 × 22126 / 306560). The results are shown in Table 7.

[0105] Figure 10 shows a binarized image of the surface resin layer of the laminate in Experimental Example 7 before thermal shrinkage. In Figure 10, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0106] As shown in Figure 10, the total number of pixels in the image of the laminate in Experimental Example 7 before thermal shrinkage is 306. While the number of pixels in the white areas corresponding to functional particles was 560, the number of pixels in the white areas was 18,323.

[0107] Therefore, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 7 before thermal shrinkage (percentage of exposed functional particles) was 5.98% (= 100 × 18323 / 306560). The results are shown in Table 7.

[0108] Figure 11 shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 7 after 50% thermal shrinkage. In Figure 11, the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0109] As shown in Figure 11, the total number of pixels in the image of the laminate in Experimental Example 7 after 50% thermal shrinkage was 306,560 pixels, while the number of pixels in the white areas corresponding to functional particles was 24,918 pixels.

[0110] Therefore, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 7 after 50% thermal shrinkage (percentage of exposed functional particles) was 8.13% (= 100 × 24918 / 306560). The results are shown in Table 7.

[0111] Binarization was performed by magnifying the images 1000 times using SEM under the following loading conditions, and reading images of the surface resin layer of the laminates in Experimental Examples 1', 6-7 before thermal shrinkage or after 50% thermal shrinkage. The read images were then imported into a computer and binarized using the image analysis software "Image J". The threshold was determined using Otsu's method (discriminant analysis method).

[0112] (Loading conditions) Equipment used: Electron microscope "Miniscope(R)TM3030Plus" Backscattered electron observation Acceleration voltage: 15.0kV

[0113] [Table 7]

[0114] As shown in Table 7, the haze values ​​of the laminates in Experimental Examples 1' and 6-7 before thermal shrinkage were 12-21, and the haze values ​​after 50% thermal shrinkage were 23-39. From these results, it can be considered that even when the laminate of this embodiment undergoes 50% thermal shrinkage, if the haze value is 80 or less, and especially if it is 50 or less, the surface appearance of the laminate of this embodiment will not be abnormal. Note that "50% thermal shrinkage" means that the length of the surface of the laminate of this embodiment in the lateral direction (CD direction) before thermal shrinkage is 50% shorter than before thermal shrinkage.

[0115] Furthermore, as shown in Table 7, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer before heat shrinkage of the laminates in Experimental Examples 1' and 6-7 was 2.14% to 5.98%, and the ratio after 50% heat shrinkage was 4.47% to 8.13%. From these results, it is considered that in order to keep the haze value of the laminate of this embodiment below 80, and especially below 50, when the laminate of this embodiment is heat-shrunk by 50%, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer after 50% heat shrinkage of the laminate of this embodiment should be less than 17%, and especially less than 10%. In addition, the lower limit of the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer after 50% heat shrinkage of the laminate of this embodiment is preferably 1.5% or more, more preferably 2% or more, and even more preferably 5% or more.

[0116] <Fourth consideration> (Fabrication of laminates in experimental examples 8-9) The laminate in Experimental Example 8 was prepared using the same method and under the same conditions as in Experimental Example 1, except that the functional particle content of the resin composition for forming the surface resin layer was 4 parts by weight. The laminate in Experimental Example 9 was prepared using the same method and under the same conditions as in Experimental Example 1, except that the functional particle content of the resin composition for forming the surface resin layer was 6 parts by weight.

[0117] (Antibacterial activity evaluation) Each of the laminates in Experimental Examples 6-9, prepared as described above, was subjected to a water-resistant treatment or Lightfastness treatment was performed. Waterfastness treatment was performed by immersing each laminate from Experimental Examples 6-9 in room temperature water for 16-18 hours. Lightfastness treatment was performed by irradiating each laminate from Experimental Examples 6-9 with a sunshine lamp for 8 ± 0.4 hours.

[0118] For each laminate from Experimental Examples 6-9 after water-resistant or light-resistant treatment, the number of viable bacteria was measured after 24 hours of contact with the surface resin layer of each laminate from Experimental Examples 6-9 under the following antibacterial evaluation conditions, and the antibacterial activity value was calculated. The results are shown in Table 8.

[0119] (Antibacterial activity evaluation conditions) Test method: JIS Z 2801:2010 "Antibacterial treated products - Test method for antibacterial properties and antibacterial effect" (Film adhesion method) Bacterial species: Escherichia coli NBRC 3972, Staphylococcus aureus NBRC 12732

[0120] [Table 8]

[0121] The values ​​in Table 8 represent the antibacterial activity values ​​of each laminate from Experimental Examples 6-9 after water-resistant or light-resistant treatment. A higher antibacterial activity value in Table 8 indicates superior antibacterial properties. The antibacterial activity value is the difference in the logarithmic number of viable bacteria after 24 hours of contact between the laminates from Experimental Examples 6-9 (after water-resistant or light-resistant treatment) and the blank laminate. The blank laminate was prepared using the same method and under the same conditions as Experimental Examples 6-9, except that it did not contain zirconium phosphate particles supported with zinc and silver in the acrylic resin solution.

[0122] (Antibacterial activity evaluation results) As shown in Table 8, the laminates of Experimental Examples 6-9, after water-resistant and light-resistant treatments, were confirmed to have antibacterial properties against both Escherichia coli and Staphylococcus aureus.

[0123] (Antiviral evaluation) For each laminate in Experimental Examples 8-9 after the water-resistant or light-resistant treatment described above, the viral infectivity titer was measured after contacting the surface resin layer of each laminate in Experimental Examples 8-9 with the following virus species for 24 hours under the following antiviral evaluation conditions, and the antiviral activity value was calculated. The results are shown in Table 9.

[0124] (Antiviral evaluation conditions) Test method: ISO 21702:2019 "Measurement of antiviral activity of plastics and other non-porous surfaces" Virus species: Influenza A, Feline Calicivirus

[0125] [Table 9]

[0126] The values ​​in Table 9 represent the antiviral activity values ​​of each laminate in Experimental Examples 8-9 after water-resistant treatment or light-resistant treatment. A higher antiviral activity value in Table 9 indicates superior antiviral performance. The antiviral activity values ​​in Table 9 were calculated using the formula (1) above.

[0127] (Antiviral activity evaluation results) As shown in Table 9, the laminates of Experimental Examples 8-9, after water-resistant treatment and light-resistant treatment, were confirmed to have antiviral properties against both influenza A and feline calicivirus, respectively.

[0128] (Haze value) For each of the laminates in Experimental Example 1 and Experimental Examples 8-9, the haze value before thermal shrinkage and the haze value after 50% thermal shrinkage were determined. The results are shown in Table 10 below.

[0129] The haze value was measured using a haze meter (NDH-7000) and conforms to JIS standards. This value was calculated based on K 7136, "Method for Determining Haze in Transparent Plastic Materials."

[0130] (Binarization) Figure 5(a) shows a binarized view of the surface of the surface resin layer of the laminate in Experimental Example 1 before thermal shrinkage. In Figure 5(a), the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0131] As shown in Figure 5(a), the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 1 before thermal shrinkage (percentage of functional particle exposure) was 6.73%. The results are shown in Table 10.

[0132] Figure 5(b) shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 1 after 50% thermal shrinkage. In Figure 5(b), the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0133] As shown in Figure 5(b), the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 1 before thermal shrinkage (percentage of functional particle exposure) was 12.51%. The results are shown in Table 10.

[0134] Figure 12(a) shows a binarized view of the surface of the surface resin layer of the laminate in Experimental Example 8 before thermal shrinkage. In Figure 12(a), the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0135] As shown in Figure 12(a), the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 8 before thermal shrinkage (percentage of functional particle exposure) was 8.21%. The results are shown in Table 10.

[0136] Figure 12(b) shows a binarized image of the surface of the surface resin layer of the laminate in Experimental Example 8 after 50% thermal shrinkage. In Figure 12(b), the areas shown in black correspond to the surface resin layer, and the areas shown in white correspond to the functional particles.

[0137] As shown in Figure 12(b), the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of the laminate in Experimental Example 8 after 50% heat shrinkage (percentage of exposed functional particles) was 14.43%. The results are shown in Table 10.

[0138] Using the same method and conditions as in Experimental Examples 1 and 8, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of Experimental Example 9 was determined before and after thermal shrinkage. The results are shown in Table 10. As shown in Table 10, the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of Experimental Example 9 before thermal shrinkage was 11.30%, and the ratio of the area of ​​functional particles to the total surface area of ​​the surface resin layer of Experimental Example 9 after thermal shrinkage was 18.10%.

[0139] [Table 10]

[0140] (Abrasion resistance evaluation) The abrasion resistance of the surface resin layer (the retention capacity of the functional particles of the acrylic resin in the surface resin layer) of the laminates in Experimental Examples 8-9, which used a 35 μm thick HOP film as the plastic film constituting the base material, was evaluated before thermal shrinkage based on the following abrasion resistance test.

[0141] First, referring to JIS L 0849:2013 8.1.2 "Friction Tester Type II (JSPS Type)", the surface resin layer of each laminate from Experimental Examples 8-9 was used as the friction element of the dye friction fastness tester (DAIEI KAGAKU SEIKI MFG CO. LTD). The test specimens were attached and fixed so that the surface resin layer of each laminate from Experimental Examples 8-9 faced the surface resin layer side of each laminate from Experimental Examples 8-9. Next, a load of 500g was applied to the friction element, and the surface resin layer of each laminate from Experimental Examples 8-9 was brought into contact with the surface resin layer of each laminate from Experimental Examples 8-9 and performed a horizontal reciprocating motion 200 times. After that, the surface condition of the surface resin layer of the laminates from Experimental Examples 8-9 was evaluated. The results are shown in Table 11.

[0142] (Abrasion resistance evaluation criteria) A... No functional particles were observed to have detached after horizontal reciprocating motion. B...Functional particles that had detached after horizontal reciprocating motion were observed. C...A significant number of functional particles that had detached after horizontal reciprocating motion were observed. D...A significant number of functional particles that had detached after horizontal reciprocating motion were observed, and surface wear was also pronounced.

[0143] [Table 11]

[0144] As is clear from the results shown in Table 11, the laminate in Experimental Example 8 before heat shrinkage showed less detachment of functional particles from the surface of the surface resin layer compared to the laminate in Experimental Example 9 before heat shrinkage, confirming improved abrasion resistance.

[0145] <Fifth consideration> (Fabrication of the laminate in Experimental Example 10) The laminate in Experimental Example 10 was prepared using the same method and under the same conditions as in Experimental Example 8, except that a resin component with an acid value of 13.4 mgKOH / g was used as the resin component constituting the resin of the surface resin layer. The acid value of the resin component constituting the resin of the surface resin layer of the laminates in Experimental Examples 1' and 1-9 was 30.6 mgKOH / g. The acid value of the resin component constituting the resin of the surface resin layer of the laminates in Experimental Examples 1' and 1-10 was calculated based on JIS K 5601-2-1:1999.

[0146] (Antibacterial activity evaluation) The laminated material of Experimental Example 10, prepared as described above, was subjected to either water-resistant or light-resistant treatment. Water-resistant treatment was performed by immersing the laminated material of Experimental Example 10 in water at room temperature for 16 to 18 hours. Light-resistant treatment was performed by irradiating the laminated material of Experimental Example 10 with a sunshine lamp for 8 ± 0.4 hours.

[0147] The laminates of Experimental Example 10, after water-resistant or light-resistant treatment, were evaluated by measuring the number of viable bacteria after 24 hours of contact with the surface resin layer of the laminates of Experimental Example 10 under the following antibacterial evaluation conditions, and calculating the antibacterial activity value. The results are shown in Table 12.

[0148] (Antibacterial activity evaluation conditions) Test method: JIS Z 2801:2010 "Antibacterial treated products - Test method for antibacterial properties and antibacterial effect" (Film adhesion method) Bacterial species: Escherichia coli NBRC 3972, Staphylococcus aureus NBRC 12732

[0149] [Table 12]

[0150] The values ​​in Table 12 indicate the antibacterial activity values ​​of the laminates in Experimental Example 10 after water-resistant or light-resistant treatment. A higher antibacterial activity value in Table 12 indicates superior antibacterial properties. The antibacterial activity value is the difference in the logarithmic number of viable bacteria after 24 hours of contact between the laminate of Experimental Example 10 (after water-resistant or light-resistant treatment) and the blank laminate. The blank laminate was prepared using the same method and under the same conditions as Experimental Example 10, except that it did not contain zirconium phosphate particles supported with zinc and silver in the acrylic resin solution.

[0151] (Antibacterial activity evaluation results) As shown in Table 12, the laminates of Experimental Example 10, after water-resistant treatment and light-resistant treatment, were confirmed to have antibacterial properties against both Escherichia coli and Staphylococcus aureus.

[0152] (Antiviral evaluation) The laminates of Experimental Example 10, after the above-described water-resistant or light-resistant treatments, were evaluated by measuring the viral infectivity titer after exposing the surface resin layer of the laminate of Experimental Example 10 to the following virus species for 24 hours under the following antiviral evaluation conditions, and calculating the antiviral activity value. The results are shown in Table 13.

[0153] (Antiviral evaluation conditions) Test method: ISO 21702:2019 "Measurement of antiviral activity of plastics and other non-porous surfaces" Virus type: Influenza A

[0154] [Table 13]

[0155] The values ​​in Table 13 represent the antiviral activity values ​​of the laminates from Experimental Example 10 after water-resistant or light-resistant treatment. A higher antiviral activity value in Table 13 indicates superior antiviral performance. The antiviral activity values ​​in Table 13 were calculated using the formula (1) described above.

[0156] (Antiviral activity evaluation results) As shown in Table 13, the laminates of Experimental Example 10, after water-resistant and light-resistant treatments, were confirmed to have antiviral properties against influenza A.

[0157] (others) The haze values ​​and the percentage of functional particles exposed in the laminate of Experimental Example 10, both before and after 50% thermal shrinkage, were similar to those of the laminate in Experimental Example 8.

[0158] As described above, the embodiments and experimental examples have been explained, but it was also planned from the outset that the various configurations of the embodiments and experimental examples described above could be combined as appropriate.

[0159] The embodiments and experimental examples disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than the foregoing description, and all modifications within the meaning and scope equivalent to the claims are intended. [Explanation of Symbols]

[0160] 10 Laminate, 101 Substrate, 102 Surface resin layer, 102a Resin, 102b Zirconium phosphate particles supported with zinc and silver, 103 Ink layer.

Claims

1. Substrate and The substrate comprises a surface resin layer, The aforementioned substrate includes a plastic film, The surface resin layer comprises a resin and zirconium phosphate particles supported with zinc and silver having antibacterial properties, antiviral properties, or both antibacterial and antiviral properties within the resin. A laminate in which some of the zinc and silver-supported zirconium phosphate particles are exposed outward from the resin in a convex manner.

2. The laminate according to claim 1, wherein the substrate is a heat-shrinkable plastic film.

3. The laminate according to claim 2, wherein the haze value of the laminate after thermal shrinkage is 80 or less.

4. The laminate according to claim 2 or claim 3, wherein the ratio of the area of ​​the zinc and silver-supported zirconium phosphate particles to the total surface area of ​​the surface resin layer of the laminate after heat shrinkage is less than 17%.

5. The laminate according to any one of claims 1 to 4, further comprising an ink layer on at least one side of the substrate where the surface resin layer is provided and on the side of the substrate opposite to the side where the surface resin layer is provided.

6. The laminate according to any one of claims 1 to 5, wherein the acid value of the resin component of the resin in the surface resin layer is 10 mg KOH / g or more and 200 mg KOH / g or less.

Images