Laminate

Abstract

To provide a laminate excellent in antibacterial and antiviral properties.SOLUTION: A laminate 1 comprises a substrate 2 and a resin layer 3 that is disposed on one surface of the substrate and contains a resin and at least one of an antibacterial agent and an antiviral agent, in which the arithmetic average height Sa of a surface of the resin layer that is opposite to the substrate is 0.3 μm or more and 2.0 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a laminate having antibacterial and antiviral properties.

Background Art

[0002] Conventionally, from the perspective of hygiene, antibacterial and antiviral products have been developed in various technical fields. These days, the infectious disease (COVID-19) caused by the novel coronavirus (SARS-CoV-2) is spreading worldwide, and there is a strong demand for antibacterial and antiviral products.

[0003] As antibacterial and antiviral products, various forms are known. For example, Patent Document 1 proposes an antiviral decorative board.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in antibacterial and antiviral products, there is room for improvement in antibacterial effects, antiviral effects, and their persistence.

[0006] The present disclosure has been made in view of the above circumstances, and the main object thereof is to provide a laminate excellent in antibacterial and antiviral properties.

Means for Solving the Problems

[0007] One embodiment of the present disclosure is a laminate having a base material and a resin layer disposed on one surface of the base material and containing a resin and at least one of an antibacterial agent and an antiviral agent, wherein the arithmetic mean height Sa of the surface of the resin layer opposite to the base material is 0.3 μm or more and 2.0 μm or less.

Advantages of the Invention

[0008] In the present disclosure, there is an effect that a laminate excellent in antibacterial properties and antiviral properties can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and is not to be construed as limited to the description of the embodiments exemplified below. Also, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the actual form for the sake of clearer explanation, but this is merely an example and does not limit the interpretation of the present disclosure. Further, in this specification and each drawing, the same reference numerals may be assigned to the same elements as those described above with respect to the already shown drawings, and detailed description may be appropriately omitted.

[0011] In this specification, when expressing the manner of disposing one member on another member, if simply denoted as "on" or "under", unless otherwise specified, it shall include both the case where another member is disposed directly above or directly below so as to be in contact with a certain member, and the case where another member is disposed above or below a certain member with yet another member in between. Further, in this specification, when expressing the manner of disposing one member on the surface of another member, if simply denoted as "on the surface", unless otherwise specified, it shall include both the case where another member is disposed directly above or directly below so as to be in contact with a certain member, and the case where another member is disposed above or below a certain member with yet another member in between.

[0012] Hereinafter, the laminate in the present disclosure will be described in detail.

[0013] The laminate in the present disclosure is a laminate having a base material and a resin layer disposed on one surface of the base material and containing at least one of a resin, an antibacterial agent, and an antiviral agent, wherein the arithmetic mean height Sa of the surface of the resin layer opposite to the base material is 0.3 μm or more and 2.0 μm or less.

[0014] FIG. 1 is a schematic cross-sectional view showing an example of the laminate of the present disclosure. As shown in FIG. 1, the laminate 1 of the present disclosure has a base material 2 and a resin layer 3 disposed on one surface of the base material 2 and containing at least one of a resin, an antibacterial agent, and an antiviral agent. Further, the arithmetic mean height Sa of the surface of the resin layer 3 opposite to the base material 2 is within a predetermined range.

[0015] In the present disclosure, the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is within a predetermined range, and since the antibacterial agent and the antiviral agent protrude on the surface on the side opposite to the base material of the resin layer, it becomes easier for the antibacterial agent and the antiviral agent to come into contact with bacteria and viruses adhering to the surface of the resin layer, so that the antibacterial property and the antiviral property can be improved. Further, since the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is within a predetermined range, a decrease in resistance to rubbing can be suppressed, and the detachment of the antibacterial agent and the antiviral agent from the resin layer can be suppressed. Therefore, the antibacterial effect and the antiviral effect can be sustained.

[0016] Hereinafter, each component of the laminate of the present disclosure will be described.

[0017] 1. Resin layer The resin layer in the present disclosure is disposed on one surface of the base material and contains resin and at least one of an antibacterial agent and an antiviral agent. Further, the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is within a predetermined range.

[0018] (1) Characteristics of the resin layer In the present disclosure, the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is 0.3 μm or more, may be 0.5 μm or more, and may be 0.8 μm or more. Further, the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is 2.0 μm or less, may be 1.5 μm or less, may be 1.2 μm or less, and may be 1.0 μm or less. By the arithmetic mean height Sa being within the above range, antibacterial properties and antiviral properties can be improved. On the other hand, if the arithmetic mean height Sa is too small, the desired antibacterial properties and antiviral properties may not be obtained. Further, if the arithmetic mean height Sa is too large, the degree of protrusion of the antibacterial agent or antiviral agent on the surface opposite to the base material of the resin layer increases, the resistance to abrasion decreases, and the antibacterial agent or antiviral agent is likely to fall off from the resin layer, so the antibacterial properties and antiviral properties may decrease. Further, depending on the use of the laminate, etc., there may be cases where a long laminate is wound in a roll shape or a plurality of sheet-like laminates are laminated. In such cases, if the arithmetic mean height Sa is too large, the surface on the base material side of the laminate may be damaged by contact with the surface on the resin layer side of the laminate.

[0019] Here, the arithmetic mean height Sa is a value measured in accordance with ISO 25178. The arithmetic mean height Sa can be measured using a non-contact surface shape measuring device of the optical interference method. As the non-contact surface shape measuring device of the optical interference method, for example, the non-contact surface / layer cross-sectional shape measuring system VertScan2.0 R5500GML-A150-AC manufactured by Rhombus Systems can be used. The details of the measurement method of the arithmetic mean height Sa will be described in the section of the examples described later.

[0020] Also, the arithmetic mean roughness Ra of the surface on the side opposite to the base material of the resin layer is, for example, 0.3 μm or more, may be 0.5 μm or more, and may be 0.8 μm or more. Also, the arithmetic mean roughness Ra of the surface on the side opposite to the base material of the resin layer is, for example, 2.0 μm or less, may be 1.5 μm or less, and may be 1.2 μm or less. By the arithmetic mean roughness Ra being within the above range, antibacterial properties and antiviral properties can be improved. On the other hand, if the arithmetic mean roughness Ra is too small, there is a possibility that desired antibacterial properties and antiviral properties cannot be obtained. Also, if the arithmetic mean roughness Ra is too large, the degree of protrusion of the antibacterial agent or antiviral agent on the surface on the side opposite to the base material of the resin layer becomes large, the resistance to abrasion decreases, and the antibacterial agent or antiviral agent is likely to fall off from the resin layer, so the antibacterial properties and antiviral properties may decrease. Also, depending on the use of the laminate, etc., there may be cases where a long laminate is wound in a roll shape or a plurality of sheet-like laminates are laminated. In such cases, if the arithmetic mean roughness Ra is too large, the surface on the base material side of the laminate may be damaged by contact with the surface on the resin layer side of the laminate.

[0021] Here, the arithmetic mean roughness Ra is a value measured in accordance with JIS B0601. The arithmetic mean roughness Ra can be measured using a non-contact surface shape measuring device of the optical interference method. As the non-contact surface shape measuring device of the optical interference method, for example, the non-contact surface / layer cross-section shape measuring system VertScan2.0 R5500GML-A150-AC manufactured by Rhombus Systems can be used. The details of the measurement method of the arithmetic mean roughness Ra will be described in the section of Examples described later.

[0022] In addition, the contact angle of the surface of the resin layer opposite to the base material with respect to water is, for example, 70° or more, and may be 75° or more. Further, the contact angle of the surface of the resin layer opposite to the base material with respect to water is, for example, 100° or less, and may be 95° or less. When the contact angle is within the above range, adhesion of water to the surface of the resin layer opposite to the base material can be suppressed, and antibacterial and antiviral properties can be further improved. When the contact angle is within the above range, it becomes difficult for water to adhere to the surface opposite to the base material of the resin layer, so it dries easily. In this case, compared with the case where the contact angle of water on the surface opposite to the base material of the resin layer is relatively small, since the drying speed is fast, bacteria and viruses are subject to a sudden change in the surrounding environment. Due to this influence, it is considered that the proteins of bacteria are likely to denature, and the growth of bacteria can be suppressed. In addition, it is considered that the proteins of viruses are also likely to denature, and the viruses can be inactivated. Therefore, it is considered that the antibacterial and antiviral properties can be further improved. In the present disclosure, the arithmetic mean height Sa of the surface of the resin layer opposite to the base material is within a predetermined range, and since the surface of the resin layer opposite to the base material has irregularities, it is estimated that the contact angle of the surface of the resin layer opposite to the base material with respect to water becomes relatively large.

[0023] Here, the contact angle with respect to water is a value measured by the θ / 2 method. Details of the method for measuring the contact angle of water will be described in the section of Examples below.

[0024] (2) Material of the resin layer The resin layer in the present disclosure contains a resin and at least one of an antibacterial agent and an antiviral agent. Hereinafter, each component of the resin layer will be described.

[0025] (1) Antibacterial agent and antiviral agent In the present disclosure, the resin layer contains at least one of an antibacterial agent and an antiviral agent. Note that "at least one of an antibacterial agent and an antiviral agent" includes an antibacterial agent, an antiviral agent, and an antibacterial and antiviral agent. An "antibacterial and antiviral agent" is a substance having both antibacterial activity and antiviral activity.

[0026] The resin layer may contain, for example, an antibacterial agent, an antiviral agent, both an antibacterial agent and an antiviral agent, or an antibacterial and antiviral agent.

[0027] The antibacterial agent used in the present disclosure is not particularly limited as long as it is a substance capable of suppressing the growth of bacteria, and general antibacterial agents can be used. For example, organic antibacterial agents, inorganic antibacterial agents, photocatalyst antibacterial agents, etc. can be mentioned. Also, these antibacterial agents may be used in combination.

[0028] The antiviral agent used in the present disclosure is not particularly limited as long as it is a substance capable of reducing the number of viruses, and general antiviral agents can be used. For example, organic antiviral agents, inorganic antiviral agents, photocatalyst antiviral agents, etc. can be mentioned. Also, these antiviral agents may be used in combination.

[0029] The antibacterial and antiviral agent used in the present disclosure is not particularly limited as long as it is a substance capable of suppressing the growth of bacteria and reducing the number of viruses, and general antibacterial and antiviral agents can be used. For example, organic antibacterial and antiviral agents, inorganic antibacterial and antiviral agents, photocatalyst antibacterial and antiviral agents, etc. can be mentioned. Also, these antibacterial and antiviral agents may be used in combination.

[0030] Examples of organic antibacterial agents, organic antiviral agents, and organic antibacterial and antiviral agents include organic synthetic types and organic natural types. Examples of organic synthetic types include alcohol-based, phenol-based, aldehyde-based, carboxylic acid-based, ester-based, ether-based, nitrile-based, peroxide-based, halogen-based, pyridine - quinoline-based, triazine-based, isothiazolone-based, imidazole - thiazole-based, anilide-based, biguanide-based, disulfide-based, thiocarbamate-based, guanidine-based, hydrogen peroxide water-based, surfactant-based, organometallic-based, etc. Examples of organic natural types include terpene-based, carbohydrate-based, tropolone-based, ester-based, chitosan, propolis, polylysine, tea catechin, extracts of mustard and wasabi (allyl isothiocyanate), etc.

[0031] Examples of inorganic antibacterial agents, inorganic antiviral agents, and inorganic antibacterial and antiviral agents include silver-based, zinc-based, copper-based, etc.

[0032] Examples of photocatalyst-based antibacterial agents, photocatalyst-based antiviral agents, and photocatalyst-based antibacterial and antiviral agents include titanium oxide, zinc oxide, etc.

[0033] The antibacterial agent, antiviral agent, and antibacterial and antiviral agent may be used alone or in combination of two or more.

[0034] When the antibacterial agent, antiviral agent, and antibacterial and antiviral agent are inorganic, such as silver-based, zinc-based, copper-based, etc., for example, antibacterial agents, antiviral agents, and antibacterial and antiviral agents obtained by supporting or containing metal ions such as silver ions, zinc ions, or copper ions on a carrier can be used.

[0035] Note that "containing metal ions in a carrier" means holding metal ions or substances capable of generating metal ions in the carrier in some form. Also, "substances capable of generating metal ions" means substances that generate metal ions due to external factors or time-dependent factors, such as substances that generate metal ions when dissolved in water or the like.

[0036] As the carrier, for example, inorganic compounds such as zeolite, silica gel, apatite, glass, zirconium phosphate, and titanium phosphate are preferable, and among them, porous inorganic compounds are more preferable.

[0037] The antibacterial agent, antiviral agent, and antibacterial and antiviral agent preferably have a particulate shape. In the case of particles, a resin layer satisfying the above-mentioned arithmetic mean height Sa is easily obtained.

[0038] Examples of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent having a particulate shape include, among the above, inorganic-based, photocatalytic-based, or organic particulate-based among the above-mentioned organic systems.

[0039] The shape of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is not particularly limited, and can be, for example, any shape such as spherical, ellipsoidal, polyhedral, or scaly.

[0040] Also, the average particle diameter of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is, for example, 3 μm or more, may be 5 μm or more, and may be 7 μm or more. If the average particle diameter is within the above range, a resin layer satisfying the above-described arithmetic mean height Sa is likely to be obtained. Further, when the average particle diameter is within the above range, when forming a resin layer by applying a resin composition containing at least one of a resin and an antibacterial agent and an antiviral agent, the stability of the resin composition is likely to be obtained. On the other hand, the average particle diameter of the particles is, for example, 15 μm or less, may be 12 μm or less, and may be 10 μm or less. If the average particle diameter is within the above range, a resin layer satisfying the above-described arithmetic mean height Sa is likely to be obtained. Also, if the average particle diameter is too large, the degree of protrusion of the antibacterial agent or antiviral agent on the surface of the resin layer opposite to the base material increases, the resistance to rubbing decreases, and the antibacterial agent and antiviral agent are likely to fall off from the resin layer, so the antibacterial property and antiviral property may decrease. Further, depending on the use of the laminate, etc., there may be cases where a long laminate is wound into a roll shape or a plurality of sheet-like laminates are laminated. In such cases, if the average particle diameter is too large, the surface on the base material side of the laminate may be damaged by contact with the surface on the resin layer side of the laminate.

[0041] Also, the average particle diameter of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is preferably larger than the thickness of the resin layer. Thereby, a resin layer satisfying the above-described arithmetic mean height Sa is likely to be obtained.

[0042] Specifically, the ratio (D / T) of the average particle diameter D of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent to the thickness T of the resin layer is preferably more than 1.0, more preferably 1.5 or more, may be 3.5 or more, and may be 5.0 or more. If the above ratio is within the above range, a resin layer satisfying the above arithmetic mean height Sa is likely to be obtained. On the other hand, the ratio (D / T) of the average particle diameter D of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent to the thickness T of the resin layer may be, for example, 12.0 or less, and may be 6.0 or less. If the above ratio is within the above range, a resin layer satisfying the above arithmetic mean height Sa is likely to be obtained. Also, if the above ratio is too large, the degree of protrusion of the antibacterial agent or antiviral agent on the surface of the resin layer opposite to the base material increases, the resistance to abrasion decreases, and the antibacterial agent or antiviral agent is likely to fall off from the resin layer, so the antibacterial property and antiviral property may decrease.

[0043] Here, the average particle diameter of the particles of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent can be the average value of the particle diameters of any 10 particles obtained by measuring from the cross-section in the thickness direction of the laminate observed by a scanning electron microscope (SEM). In addition, when the particle shape is not spherical, the major axis of the particle is taken as the particle diameter.

[0044] Also, the thickness of the resin layer can be the average value of the thicknesses of any 10 locations obtained by measuring from the cross-section in the thickness direction of the laminate observed by a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a scanning transmission electron microscope (STEM).

[0045] The content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent in the resin layer is not particularly limited as long as the desired antibacterial and antiviral properties can be obtained, and can be appropriately set according to the types of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent, the configuration and use of the laminate, etc. Specifically, the total content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent in the resin layer is 0.5% by mass or more, and may be 1.0% by mass or more, or may be 2.0% by mass or more. If the content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is too small, the desired antibacterial and antiviral properties may not be obtained. On the other hand, the total content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent in the resin layer is, for example, 10.0% by mass or less, and may be 8.0% by mass or less, or may be 6.0% by mass or less. If the content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is too large, although the antibacterial and antiviral properties can be sufficiently obtained, the strength, scratch resistance, etc. of the resin layer may decrease. Also, if the content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is too large, there is a possibility that the transparency decreases, and depending on the types of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent, the resin layer may become cloudy. If the transparency of the resin layer decreases, it may be difficult to visually recognize the underlying layer of the resin layer, such as a base material or a decorative layer described later. Furthermore, if the content of the antibacterial agent, antiviral agent, and antibacterial and antiviral agent is too large, the cost may increase.

[0046] (2) Resin The resin contained in the resin layer in the present disclosure is not particularly limited as long as it is a resin capable of dispersing an antibacterial agent or an antiviral agent, and examples thereof include a thermoplastic resin and a cured resin.

[0047] Here, the cured resin refers to a cured product of a curable resin.

[0048] Examples of the thermoplastic resin include polyolefin resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetate, polyacrylonitrile, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), polyamide, polyimide, polyetherimide, acrylic resin, polycarbonate, polyacetal, polyarylate, etc. The thermoplastic resin may be used alone or in combination of two or more kinds.

[0049] Examples of the curable resin used for the cured resin include thermosetting resins and radiation-curable resins.

[0050] Here, the ionizing radiation means those having energy quanta capable of polymerizing or crosslinking molecules among electromagnetic waves or charged particle beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

[0051] The thermosetting resin is a resin that cures by heating. Examples of the thermosetting resin include acrylic resins, urethane resins, phenol resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc.

[0052] When using a thermosetting resin, for example, a thermosetting resin composition containing a thermosetting resin and, if necessary, a curing agent or a curing catalyst can be used.

[0053] Examples of the radiation-curable resin include electron beam-curable resins and ultraviolet ray-curable resins. The radiation-curable resin is a compound having a radiation-curable functional group (hereinafter, "electro..." It is also referred to as a "radiation-curable compound".) A radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation. Examples of radiation-curable functional groups include functional groups having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group, and an epoxy group, an oxetanyl group, and the like.

[0054] In the present specification, the (meth)acryloyl group means an acryloyl group or a methacryloyl group. Also, in the present specification, (meth)acrylate means acrylate or methacrylate.

[0055] Specifically, the radiation-curable compound can be appropriately selected and used from among conventionally used polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") as radiation-curable resins.

[0056] Examples of the radiation-curable compound include compounds having two or more ethylenically unsaturated bond groups. Specifically, polyfunctional (meth)acrylate-based compounds having two or more ethylenically unsaturated bond groups can be mentioned. As the polyfunctional (meth)acrylate-based compound, either a monomer or an oligomer can be used.

[0057] The radiation-curable resin may be used alone or in combination of two or more.

[0058] When the radiation-curable compound is an ultraviolet-curable compound, for example, an ultraviolet-curable resin composition containing an ultraviolet-curable compound, a photopolymerization initiator, a photopolymerization accelerator, and the like can be used.

[0059] (3) Other components In the present disclosure, the resin layer may contain various additives in addition to the above-mentioned resin, antibacterial agent, and antiviral agent, as long as the antibacterial and antiviral properties are not impaired. Examples of the additives include antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, abrasion resistant agents, antistatic agents, slip agents, mold release agents, pigments, surface modifiers (leveling agents), and antifouling agents.

[0060] (a) Antioxidant The resin layer can contain an antioxidant. Among them, when the antibacterial agent and antiviral agent are silver-based antibacterial agents and antiviral agents, the resin layer preferably contains a phosphorus-based antioxidant as the antioxidant. Thereby, it is possible to suppress the discoloration of the silver-based antibacterial agent and antiviral agent to brown by light such as ultraviolet rays and visible light. The principle by which the phosphorus-based antioxidant can suppress discoloration is unknown, but it is considered that the alteration of silver ions is suppressed by some action.

[0061] (i) Phosphorus-based antioxidant Examples of the phosphorus-based antioxidant include a compound having a phosphorous acid structure represented by the following formula (1), a compound having a phosphonic acid structure represented by the following formula (2), a compound having a phosphinic acid structure represented by the following formula (3), and a compound having a phosphine oxide structure represented by the following formula (4). Among these, the compound having a phosphorous acid structure represented by the following formula (1) is preferable. One or more phosphorus-based antioxidants can be used.

[0062]

Chemical formula

[0063] Examples of the compound having a phosphorous acid structure represented by the above formula (1) include compounds represented by the following general formulas (1-1) to (1-3). Among the general formulas (1-1) to (1-3), those of the general formulas (1-1) and (1-2) are preferable in that they tend to have good solubility in the resin composition used for forming the resin layer. By improving the solubility of the phosphorus-based antioxidant in the resin composition, the phosphorus-based antioxidant can be diffused throughout the resin layer, making it easier to further suppress discoloration.

[0064]

Chemical formula

[0065] In the general formula (1-1), R 11 , R 12 and R 13 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hydrocarbon group which may contain a hetero atom, and these may have substituents. Further, two selected from R 11 , R 12 and R 13 may be bonded to form a ring.

[0066] From the viewpoint of further suppressing discoloration, at least one of R 11 , R 12 and R 13 is preferably a linear alkyl group. The number of carbon atoms of the linear alkyl group is preferably 6 or more and 18 or less, more preferably 8 or more and 15 or less, and even more preferably 8 or more and 10 or less. When at least one of R 11 , R 12 and R 13 is a linear alkyl group, the remaining R 11 , R 12 and R 13 are preferably phenyl groups. Further, from the viewpoints of enhancing solubility and further suppressing discoloration, it is preferable that R 11 , R 12 and R 13 do not bond to each other (R 11 , R 12and R 13 It is preferable that two selected from the following do not combine to form a ring).

[0067] Specific examples of the phosphorus-based antioxidant of the general formula (1-1) are shown in the following formulas (1-1-1) to (1-1-3).

[0068]

Chemical formula

[0069] In the general formula (1-2), R 23 is a hydrocarbon group which may contain a hetero atom and may further have a substituent. Also, R 21 , R 22 , R 24 and R 25 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hydrocarbon group which may contain a hetero atom and may further have a substituent. Also, R 21 and R 22 may combine to form a ring. Also, R 24 and R 25 may combine to form a ring.

[0070] From the viewpoint of further suppressing discoloration, at least one of R 21 , R 22 , R 24 and R 25 is preferably a linear alkyl group, and more preferably all are linear alkyl groups. The number of carbon atoms of the linear alkyl group is preferably 6 or more and 18 or less, and more preferably 12 or more and 15 or less. Also, from the viewpoints of enhancing solubility and further suppressing discoloration, R 21 , R 22 , R 24 and R 25 preferably do not bond to each other (it is preferable that R 21 , R 22 , R 24 and R 25 do not combine to form a ring).

[0071] Specific examples of the phosphorus-based antioxidant of the general formula (1-2) are shown below. In the following general formula (1-2-1), each R independently represents a linear alkyl group having 12 to 15 carbon atoms.

[0072]

Chemical formula

[0073] In the general formula (1-3), R 32 is a hydrocarbon group which may contain a hetero atom and may further have a substituent. R 31 and R 33 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hydrocarbon group which may contain a hetero atom and may further have a substituent.

[0074] The phosphorus-based antioxidant may or may not have an ethylenic double bond polymerizable with the curable resin. Among them, it is preferably not present. Since the phosphorus-based antioxidant does not have an ethylenic double bond polymerizable with the curable resin, the degree of freedom of movement of the phosphorus-based antioxidant in the resin layer increases, and the phosphorus-based antioxidant can be easily diffused throughout the resin layer, making it easier to suppress discoloration.

[0075] From the viewpoint of facilitating good solubility in the resin composition, the molecular weight of the phosphorus-based antioxidant is preferably, for example, 1500 or less, more preferably 1300 or less, and even more preferably 1200 or less. The lower limit of the molecular weight of the phosphorus-based antioxidant is not particularly limited, but is usually 270 or more, preferably 300 or more, and more preferably 330 or more.

[0076] The content of the phosphorus-based antioxidant is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, based on 100 parts by mass in total of, for example, the antibacterial agent, the antiviral agent, and the antibacterial and antiviral agent. When the content of the phosphorus-based antioxidant is within the above range, discoloration can be easily suppressed. On the other hand, the content of the phosphorus-based antioxidant is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 70 parts by mass or less, based on 100 parts by mass in total of, for example, the antibacterial agent, the antiviral agent, and the antibacterial and antiviral agent. If the content of the phosphorus-based antioxidant is too high, the strength of the resin layer may decrease.

[0077] (ii) Other antioxidants The resin layer may contain other antioxidants as long as the effects of the present disclosure are not inhibited. Examples of other antioxidants include phenolic antioxidants, sulfur-based antioxidants, and amine-based antioxidants.

[0078] Note that antioxidants other than the phosphorus-based antioxidant are less likely to suppress discoloration. Therefore, when a phosphoric acid-based antioxidant is added to suppress discoloration, it is preferable that the resin layer substantially does not contain antioxidants other than the phosphorus-based antioxidant. Here, that the resin layer substantially does not contain antioxidants other than the phosphorus-based antioxidant means that the content of antioxidants other than the phosphorus-based antioxidant in the resin layer is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less.

[0079] (b) Light stabilizer The resin layer can contain a light stabilizer. Among them, when the antibacterial agent or the antiviral agent is a silver-based antibacterial agent or antiviral agent, it is preferable that the resin layer contains a light stabilizer. Thereby, discoloration can be more suppressed. The light stabilizer is superior to the state of the resin composition in suppressing discoloration in the state of the resin layer.

[0080] Examples of the light stabilizer include hindered amine compounds. The hindered amine compound has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

[0081] Examples of the hindered amine compound include NH-type hindered amine compounds, NR-type hindered amine compounds, and NOR-type hindered amine compounds. Among these, from the viewpoint of more easily suppressing discoloration, NH-type hindered amine compounds and NR-type hindered amine compounds are preferable, and NR-type hindered amine compounds are more preferable. That is, the resin layer preferably contains one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds, and more preferably contains one or more hindered amine compounds selected from NR-type hindered amine compounds.

[0082] The NH-type hindered amine compound means that the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton remains as a hydrogen atom. Specific examples of the NH-type hindered amine compound include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

[0083] The NR-type hindered amine compound means that the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is substituted with an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 or more and 12 or less, and more preferably 1 (the alkyl group is a methyl group). Specific examples of the NR-type hindered amine compound include 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioic acid bis[1,2,2,6,6-pentamethyl-4-piperidinyl], sebacic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl), sebacic acid 1-methyl 10-(1,2,2,6,6-pentamethyl-4-piperidyl), 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, and the like.

[0084] The NOR-type hindered amine compound refers to a compound in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is replaced by OR 1 or OCOR 2 Here, R 1 and R 2 are an alkyl group and / or a cycloalkyl group, preferably an alkyl group and / or a cycloalkyl group having 5 to 12 carbon atoms.

[0085] The base dissociation constant (pkb) of the hindered amine compound is preferably, for example, 8.5 or less, more preferably 7.0 or less, and even more preferably 6.0 or less. When the pkb of the hindered amine compound is 8.5 or less, discoloration can be more easily suppressed. The lower limit of the pkb of the hindered amine compound is not particularly limited, but is preferably, for example, 4.0 or more, and more preferably 4.5 or more.

[0086] The hindered amine compound may or may not have an ethylenic double bond polymerizable with the curable resin.

[0087] From the viewpoint of facilitating good solubility in the resin composition, the molecular weight of the hindered amine compound is preferably, for example, 1000 or less, more preferably 800 or less, and even more preferably 700 or less. The lower limit of the molecular weight of the hindered amine compound is not particularly limited, but is usually 200 or more, preferably 215 or more, and more preferably 230 or more.

[0088] The content of the light stabilizer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 50 parts by mass or more, based on 100 parts by mass in total of the antibacterial agent, antiviral agent and antibacterial and antiviral agent. When the content of the light stabilizer is within the above range, discoloration can be easily suppressed. On the other hand, the content of the light stabilizer is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 200 parts by mass or less, based on 100 parts by mass in total of the antibacterial agent, antiviral agent and antibacterial and antiviral agent. If the content of the light stabilizer is too high, the strength of the resin layer may decrease. The resin layer preferably contains a hindered amine compound as the light stabilizer within the above range.

[0089] (c) Ultraviolet absorber From the viewpoint of weather resistance, the resin layer preferably contains an ultraviolet absorber.

[0090] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, etc. Among them, triazine-based ultraviolet absorbers are preferred. One or more kinds of ultraviolet absorbers can be used.

[0091] Among the triazine-based ultraviolet absorbers, a hydroxyphenyltriazine-based ultraviolet absorber in which at least one organic group selected from a hydroxyphenyl group, an alkoxyphenyl group, and an organic group containing these groups is linked to three positions of the triazine ring is more preferred, and a hydroxyphenyltriazine-based ultraviolet absorber represented by the following general formula (A) is even more preferred. Since the hydroxyphenyltriazine-based ultraviolet absorber has a branched structure, it is expected to be less likely to bleed out from the resin layer, and excellent weather resistance can be obtained for a longer period. Also, ultraviolet absorbers having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group are preferred in that they are likely to suppress bleeding out.

[0092]

Chemical formula

[0093] In the general formula (A), R 11 is a divalent organic group, and R 12 is an ester group represented by -C(=O)OR 15 , and R 13 , R 14 and R 15 are each independently a monovalent organic group, and n 11 and n 12 are each independently an integer of 1 or more and 5 or less.

[0094] Examples of the divalent organic group of R 11 include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group. Among them, from the viewpoint of weather resistance, an alkylene group is preferable, and the number of carbon atoms thereof is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, still more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 4 or less. The alkylene group and the alkenylene group may be linear, branched, or cyclic, but linear and branched are preferable. Examples of the alkylene group having 1 or more and 20 or less carbon atoms include a methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,3-propylene, 1,2-propylene, 2,2-propylene and other various propylene groups (hereinafter, "various" means those including linear, branched, and isomers thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups, and various icosylene groups.

[0095] Examples of the monovalent organic groups of R 13 and R 14 include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. Among them, aromatic hydrocarbon groups such as an aryl group and an arylalkyl group are preferable, and an aryl group is more preferable. In particular, R 13 and R14 As the monovalent organic group of , a phenyl group is preferred.

[0096] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. For example, a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, etc. can be mentioned.

[0097] The arylalkyl group is preferably an arylalkyl group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 7 to 10 carbon atoms. For example, a benzyl group, a phenethyl group, various phenylpropyl groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, various hexylbenzyl groups, etc. can be mentioned.

[0098] R 15 Examples of the monovalent organic group of include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. Among them, aliphatic hydrocarbon groups such as an alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred. That is, R 12 is preferably an alkyl ester group or an alkenyl ester group, and more preferably an alkyl ester group.

[0099] The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, various icosyl groups can be mentioned.

[0100] The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms. For example, vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, various icosenyl groups can be mentioned.

[0101] As the hydroxyphenyltriazine compound represented by the general formula (A), more specifically, R 11 is an alkylene group having 1 to 20 carbon atoms, R 12 and R 15 is an alkyl ester group in which R 13 and R 14 are alkyl groups having 1 to 20 carbon atoms, R 11 and n 12 is preferably a hydroxyphenyltriazine compound where n 11 is an alkylene group having 1 to 12 carbon atoms, R 12 and R 15 is an alkyl ester group in which R 13 and R 14 are alkyl groups having 2 to 16 carbon atoms, R 11 and n 12 is more preferably a hydroxyphenyltriazine compound where n 11 is an alkylene group having 1 to 8 carbon atoms, R 12 is R 15 and an alkyl ester group which is an alkyl group having 6 to 12 carbon atoms, R 13 and R 14 are aryl groups having 6 to 10 carbon atoms, n 11 and n 12 is still more preferably a hydroxyphenyltriazine compound where n 11 is an alkylene group having 1 to 4 carbon atoms, R12 and R 15 is an ester group in which R is an alkyl group having 8 carbon atoms, and R 13 and R 14 is a phenyl group, and n 11 and n 12 is a hydroxyphenyltriazine compound where n is 1 is particularly preferred.

[0102] The content of the ultraviolet absorber is preferably, for example, 0.2 parts by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and even more preferably 1.0 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the resin.

[0103] (d) Extender pigment The resin layer may contain an extender pigment. The extender pigment is used, for example, to adjust the design property of the laminate.

[0104] Examples of the extender pigment include inorganic particles such as silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and organic particles such as polyethylene, urethane resin, polycarbonate, and polyamide (nylon).

[0105] The shape of the extender pigment is not particularly limited, but polyhedral, spherical, scaly, etc. are preferred. Also, the average particle diameter of the extender pigment is usually 1 μm or more and 10 μm or less, preferably 3 μm or more and 8 μm or less.

[0106] (e) Colorant The resin layer may contain a colored layer as needed. Thereby, the resin layer can be colored to a desired hue, lightness, and chroma.

[0107] As the colorant, it may be appropriately selected from the same ones as those used in the colorant layers and the pattern layers described later. By coloring the resin layer with an appropriate color (hue, lightness, and chroma) using the colorant, the design appearance can be improved, or the discoloration caused by light or the like of the resin layer can be made less noticeable. In combination with the discoloration reduction effect by adding an antioxidant, the discoloration reduction effect of the resin layer can be further enhanced.

[0108] (4) Resin layer The thickness of the resin layer in the present disclosure is not particularly limited. However, as described above, it is preferably smaller than the average particle diameter of the particles of the antibacterial agent or the antiviral agent. Specifically, the thickness of the resin layer is 0.5 μm or more, and may be 1.0 μm or more, or may be 2.0 μm or more. If the thickness of the resin layer is within the above range, it is easy to obtain a resin layer that satisfies the above-described arithmetic mean height Sa. On the other hand, if the thickness of the resin layer is too thin, the degree of protrusion of the antibacterial agent or the antiviral agent on the surface opposite to the base material side of the resin layer becomes large, the resistance to rubbing decreases, and the antibacterial agent or the antiviral agent easily falls off from the resin layer, so the antibacterial property and the antiviral property may decrease. Also, depending on the use of the laminate, etc., there may be cases where a long laminate is wound in a roll shape or a plurality of sheet-like laminates are laminated. In such cases, if the thickness of the resin layer is too thin, the surface on the base material side of the laminate may be damaged by contact with the surface on the resin layer side of the laminate. On the other hand, the thickness of the resin layer is, for example, 5.0 μm or less, and may be 4.0 μm or less, or may be 3.0 μm or less. If the thickness of the resin layer is within the above range, it is easy to obtain a resin layer that satisfies the above-described arithmetic mean height Sa.

[0109] As a method for forming the resin layer, for example, a method of directly applying a resin composition onto a base material, drying it, and curing it as necessary to form the resin layer is preferable. By such a method, it is easy to obtain a resin layer that satisfies the desired arithmetic mean height Sa.

[0110] The resin composition contains, for example, a resin, at least one of an antibacterial agent and an antiviral agent, and optionally an additive and a solvent. The coating method of the resin composition is not particularly limited, and known coating methods can be used.

[0111] When curing the resin composition, the curing method is appropriately selected according to the type of the curable resin, and examples thereof include heating and irradiation with ionizing radiation such as ultraviolet rays and electron beams.

[0112] In the present disclosure, for example, as shown in FIG. 1, a resin layer 3 may be disposed on one side of the substrate 2, or as shown in FIG. 2, resin layers 3 may be disposed on both sides of the substrate 2, respectively. Further, for example, as shown in FIGS. 1 and 2, the resin layer 3 may be disposed over the entire surface on the substrate 2, or as shown in FIGS. 3(a) and (b), the resin layer 3 may be disposed on a part of the substrate 2.

[0113] 2. Substrate The substrate in the present disclosure is a member that supports the resin layer. Since the laminate having the substrate does not require the resin layer to be thick for self-supporting properties, it is easy to obtain a resin layer that satisfies the desired arithmetic mean height Sa, and the amount of the antibacterial agent and the antiviral agent used can be reduced, and the manufacturing cost can be reduced.

[0114] The form of the substrate is not particularly limited, and examples thereof include flat shapes such as films, sheets, and plates; three-dimensional shapes such as polyhedrons, prisms, cylinders, spherical surfaces, and ellipsoidal surfaces of revolution.

[0115] The material of the substrate is not particularly limited, and examples thereof include resin materials, metal materials, glass, ceramics, non-woven fabrics, cloth, paper, and woody materials.

[0116] The substrate may be a single layer or multiple layers. Further, when the substrate is multiple layers, an adhesive layer may be disposed between the layers.

[0117] Examples of the resin used for the base material include, for example, thermoplastic resins and curable resins. The thermoplastic resin is not particularly limited, and examples thereof include the thermoplastic resins used for the above resin layer. Further, the curable resin is not particularly limited, and examples thereof include the curable resins used for the above resin layer.

[0118] Further, the base material may be surface-treated in order to improve adhesion.

[0119] The thickness of the base material is not particularly limited and is appropriately set according to the type of the base material, the configuration and use of the laminate, etc.

[0120] 3. Other configurations The laminate of the present disclosure may have layers other than the base material and the resin layer. Examples of the other layers include, for example, a decorative layer, a protective layer, a primer layer, an adhesive layer, a heat-seal layer, etc. Further, the laminate of the present disclosure may further have a functional layer according to the use. Examples of the functional layer include, for example, a magnetic layer for magnetic recording applications; a conductor layer that functions as a circuit, a copper wire for current, or an electromagnetic wave shielding layer; a gas barrier layer for suppressing the permeation of gases such as water vapor and oxygen; a light reflection layer that reflects visible light with a high reflectance; an antireflection layer for suppressing the reflection of visible light, etc.

[0121] (1) Decorative layer From the viewpoint of improving the design property, the laminate of the present disclosure can have a decorative layer between the base material and the resin layer. The position of the decorative layer is preferably on the side closer to the base material from the viewpoint of enhancing the weather resistance of the decorative layer. For example, when the laminate has a primer layer described later, the decorative layer is preferably disposed between the base material and the primer layer.

[0122] The decorative layer may be disposed over the entire surface of the base material or may be partially disposed on the base material.

[0123] Examples of the decorative layer include, for example, a colored layer, a pattern layer, a metal layer, etc.

[0124] The coloring layer is disposed on the entire surface of the substrate and can be formed by applying the coloring layer composition in a solid coating manner.

[0125] The pattern layer is partially disposed on the substrate and can be formed by printing the pattern layer composition in a pattern such as a design.

[0126] The pattern (design) expressed by the decorative layer is not particularly limited, and known patterns (designs) can be applied.

[0127] The coloring layer and the pattern layer contain a resin. Further, the coloring layer and the pattern layer may contain additives such as colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, and light stabilizers.

[0128] The thickness of the coloring layer and the pattern layer is appropriately selected according to the desired pattern. From the viewpoint of improving the design property, for example, it is 0.5 μm or more and 20 μm or less, and may be 1 μm or more and 10 μm or less, or may be 2 μm or more and 5 μm or less.

[0129] The thickness of the metal layer can be, for example, 0.1 μm or more and 1 μm or less.

[0130] The coloring layer and the pattern layer can be formed, for example, by applying the coloring layer composition or the pattern layer composition and drying and curing as necessary. As the coating method, for example, known coating methods such as the gravure printing method, the bar coating method, the roll coating method, the reverse roll coating method, and the comma coating method can be used.

[0131] (2) Primer layer The laminate of the present disclosure may have a primer layer between the substrate and the resin layer. The primer layer can improve the adhesion between the substrate and the resin layer, and further can ensure the long-term interlayer adhesion when exposed to ultraviolet rays.

[0132] The material of the primer layer is not particularly limited as long as it can enhance the adhesion between the base material and the resin layer, and known materials for the primer layer can be applied. The primer layer may contain an ultraviolet absorber or a light stabilizer in order to improve weather resistance.

[0133] The thickness of the primer layer is, for example, 0.01 μm or more and 10 μm or less, and may be 0.7 μm or more and 8 μm or less, or may be 1.0 μm or more and 6 μm or less.

[0134] (3) Protective layer From the viewpoint of protecting the decorative layer and the like, the laminate of the present disclosure may have a protective layer between the decorative layer and the resin layer.

[0135] The protective layer may be a single layer or a multilayer.

[0136] The resin contained in the protective layer is not particularly limited as long as it is a resin having transparency. Examples thereof include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (ABS resins), acrylic resins, vinyl chloride resins, and the like. Among these, polyolefin resins are preferred from the viewpoint of processability.

[0137] The protective layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant.

[0138] The thickness of the protective layer is, for example, 20 μm or more and 150 μm or less, and may be 40 μm or more and 120 μm or less, or may be 60 μm or more and 100 μm or less.

[0139] The protective layer can be formed, for example, by applying a composition for the protective layer and drying and curing it as necessary. As the coating method, for example, known coating methods such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, and a comma coating method can be used.

[0140] (4) First adhesive layer The laminate in the present disclosure may have a first adhesive layer between each layer.

[0141] For the first adhesive layer, for example, adhesives such as urethane adhesives, acrylic adhesives, epoxy adhesives, and rubber adhesives can be used.

[0142] The thickness of the first adhesive layer is, for example, 0.1 μm or more and 30 μm or less, may be 1 μm or more and 15 μm or less, and may be 2 μm or more and 10 μm or less.

[0143] The first adhesive layer can be formed, for example, by applying a composition for the first adhesive layer and drying and curing it as necessary. As the coating method, for example, known coating methods such as the gravure printing method, bar coating method, roll coating method, reverse roll coating method, and comma coating method can be used.

[0144] (5) Second Adhesive Layer The laminate of the present disclosure may have a second adhesive layer on the surface opposite to the resin layer of the base material. The second adhesive layer is a layer for attaching the laminate to an object.

[0145] The adhesive contained in the second adhesive layer is not particularly limited, and for example, a pressure-sensitive adhesive can be used. As the pressure-sensitive adhesive, a general pressure-sensitive adhesive can be used, and examples include rubber-based, acrylic-based, silicone-based, and urethane-based ones.

[0146] The thickness of the second adhesive layer is not particularly limited as long as desired adhesiveness can be obtained, and for example, it can be 0.5 μm or more and 100 μm or less.

[0147] As a method for forming the second adhesive layer, for example, a method of applying a composition for the second adhesive layer on a base material and drying it can be mentioned.

[0148] A separator may be disposed on the surface of the second adhesive layer opposite to the base material.

[0149] (6) Heat-sealing layer The laminate of the present disclosure may have a heat-sealing layer on the surface opposite to the resin layer of the base material. The heat-sealing layer is a layer for, for example, bonding laminates together or bonding a laminate and a container when the laminate is used as a packaging material.

[0150] The heat-sealing layer is not particularly limited, and a general heat-sealing layer can be applied.

[0151] The thickness of the heat-sealing layer is not particularly limited as long as the desired heat-sealing property can be obtained.

[0152] In addition, as a method for forming the heat-sealing layer, for example, the base material and the heat-sealing layer may be bonded through an adhesive layer, the base material and the heat-sealing layer may be laminated and formed into a film by a co-extrusion method, the heat-sealing layer may be extrusion-laminated on the base material by a T-die method or the like, or the heat-sealing layer may be formed into a film on the base material by coating.

[0153] 4. Laminate The laminate of the present disclosure may have transparency depending on the application and the like.

[0154] Examples of the uses of the laminate of the present disclosure include, for example, surface materials for interior parts such as walls, floors, and ceilings of buildings; surface materials for exterior parts such as exterior walls, roofs, eaves, and door pockets of buildings; surface materials for fittings such as windows, window frames, doors, and door frames (interior or exterior parts); surface materials for accessories (such as handles) of fittings; surface materials for jigs of fittings; surface materials for handrails, waist walls, moldings, thresholds, duck wells, and eaves of buildings; surface materials for outdoor (exterior) parts such as fences, gates, columns of drying racks, and handrails; surface materials for furniture such as wardrobes, desks, chairs, cupboards, and kitchen sinks; surface materials for accessories (such as handles) of furniture; surface materials for jigs of furniture; surface materials for housings of household electrical appliances, etc.; surface materials for accessories (such as handles, switches, and touch panels) of household electrical appliances; surface materials for jigs of household electrical appliances; surface materials for OA equipment; surface materials for accessories (such as keyboards and touch panels) of OA equipment; surface materials for jigs of OA equipment; surface materials for interior or exterior parts of vehicles (such as walls, floors, ceilings, handrails, columns, operation panels, levers, handles, and steering wheels); partitions of buildings; shielding plates or shielding curtains for preventing droplet infection of bacteria and viruses; face protectors such as face guards and goggles; surface materials for face protectors; business forms such as invoices; cards; surface materials for business forms and cards; packaging materials; surface materials for packaging materials, etc.

[0155] Among these, the uses of the laminate of the present disclosure are preferably surface materials for housings of household electrical appliances, etc.; surface materials for accessories (such as handles, switches, and touch panels) of household electrical appliances; surface materials for jigs of household electrical appliances; surface materials for OA equipment; surface materials for accessories of OA equipment; surface materials for jigs of OA equipment; shielding plates or shielding curtains for preventing droplet infection of bacteria and viruses; face protectors; surface materials for face protectors; business forms; cards; surface materials for business forms and cards; packaging materials; surface materials for packaging materials, etc.

[0156] Note that the present disclosure is not limited to the above embodiments. The above embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits the same operational effects is included in the technical scope of the present disclosure.

Examples

[0157] Hereinafter, examples are shown to further explain the present disclosure.

[0158] [Comparative Example 1] The following materials were mixed and stirred to prepare a resin composition. [Composition of Resin Composition] · Acrylic resin composition (Hakurinith) (Hakurinith 45-3 Revised 3 UV, manufactured by Showa Ink Industry Co., Ltd.): 66.5 parts by mass · Silver-based antiviral agent (Neosintol AV-18F, particle size 3.0 μm, manufactured by Sumika Environmental Science Co., Ltd.): 0.1 part by mass · Toluene: 16.75 parts by mass · Methyl ethyl ketone: 16.75 parts by mass

[0159] On a polyester film (Lumirror 150T60, manufactured by Toray Industries, Inc.), the above resin composition was applied using a bar coater, and further, silver ink (VAHS No.2 Silver, manufactured by Showa Ink Industry Co., Ltd.) was printed using a tabletop silk printing machine to produce a transfer film having a polyester film, a resin composition film, and a silver printed layer. As the base material, a card sheet (Diafix PG-MCT, manufactured by Mitsubishi Chemical Corporation) was used. The surface of the silver printed layer of the above transfer film and the card sheet were bonded together, sandwiched between stainless steel plates, and heat-pressed using a small heat press machine. Then, the polyester film was peeled off to obtain a laminate.

[0160] [Example 1] The following materials were mixed and stirred to prepare a resin composition. [Composition of Resin Composition] · Ultraviolet curable resin composition (UV Carton Dry Off Gloss OP Ink, manufactured by DIC Graphics Co., Ltd.): 100 parts by mass · Silver-based antiviral agent (Neosintol AV-18F, particle size 3.0 μm, manufactured by Sumika Environmental Science Co., Ltd.): 2.0 parts by mass

[0161] As the base material, a polyester film (Crisper K2323 manufactured by Toyobo Co., Ltd.) was used. On the polyester film, the above resin composition was applied using a color developing device for UV ink (RIT-03 manufactured by Shibabashi Co., Ltd.), and then irradiated with UV using a UV irradiation device to be cured, thereby forming a resin layer. Thus, a laminate was obtained.

[0162] [Example 2] The following materials were mixed and stirred to prepare a resin composition. [Composition of Resin Composition] · Acrylic resin composition (Hakuriniss Silk No. 25 manufactured by Showa Ink Industry Co., Ltd.): 100 parts by mass · Solvent (SS-E Solvent (slow evaporation) <14K manufactured by DIC Graphics Co., Ltd.): 30 parts by mass · Silver-based antiviral agent (Neosintol AV-18F with a particle size of 3.0 μm manufactured by Sumika Environmental Science Co., Ltd.): 0.79 parts by mass

[0163] As the base material, a polyester film (Crisper K2323 manufactured by Toyobo Co., Ltd.) was used. On the polyester film, the above resin composition was printed using a desktop silk printing machine to form a resin layer. Thus, a laminate was obtained.

[0164] [Evaluation] 1. Arithmetic mean height Sa The arithmetic mean height Sa of the surface on the resin layer side of the laminate was measured using a non-contact surface and layer cross-section shape measurement system VertScan2.0 R5500GML-A150-AC manufactured by Hishikawa System Co., Ltd. Various parameters were determined based on ISO 25178, and measurements were taken at 10 arbitrary locations, and the arithmetic mean value of these was determined. The measurement conditions were as follows. · Measurement area: 94.96 μm × 71.22 μm · Objective lens: 50 times · Measurement mode: Wave · Wavelength filter: 530White

[0165] 2. Arithmetic mean roughness Ra The arithmetic mean roughness Ra of the surface on the resin layer side of the laminate was measured using a non-contact surface and layer cross-section shape measurement system VertScan2.0 R5500GML-A150-AC manufactured by Rhombus Systems. The measurement conditions were as follows. · Measurement area: 94.96 μm × 71.22 μm · Objective lens: 50x · Measurement mode: Wave · Wavelength filter: 530White

[0166] 3. Contact angle of water The contact angle of the surface on the resin layer side of the laminate with respect to water was measured by the θ / 2 method using a contact angle meter (DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, 3 μL of a droplet of pure water was dropped onto the surface of the resin layer of the laminate, and the contact angle 2000 microseconds after droplet deposition was measured.

[0167] 4. Antiviral property An antiviral test was conducted on the surface on the resin layer side of the laminate in accordance with ISO 21702, and the antiviral activity value was calculated. Specifically, influenza A virus H3N2 was used, and a test virus solution was obtained by culturing this virus in MDCK cells (dog kidney-derived cells). An unprocessed sample and an antiviral-treated sample cut into 5 cm × 5 cm were placed in a sterilized petri dish, 0.4 ml of the above test virus solution was inoculated onto the sample, and after covering with a sterilized polyethylene film cut into 4 cm × 4 cm, it was gently pressed down so that the test virus suspension spread over the entire film, and the lid of the petri dish was covered. After storing these petri dishes in an environment at 25°C and a relative humidity of 90% or more for 24 hours, the test pieces were taken out from the petri dishes, 10 ml of SCDLP medium was added to wash away the virus, and the virus infectivity titer was measured by the plaque measurement method. The antiviral activity value was determined by the following formula. R = Ut - At Each symbol is as follows. R: Antiviral activity value Ut: Average of the common logarithm of the virus infectivity titer (PFU / cm 2 ) after standing the unprocessed sample for 24 hours At: Logarithmic mean of virus infectivity titer (PFU / cm 2 ) of antiviral processed product sample after 24-hour static placement

[0168] Antiviral property was evaluated according to the following criteria. A: Antiviral activity value is 2.0 or more B: Antiviral activity value is less than 2.0

[0169]

Table 1

[0170] It was confirmed from Table 1 that antiviral property can be obtained when the arithmetic mean height Sa of the surface on the side opposite to the base material of the resin layer is within a predetermined range.

Explanation of reference signs

[0171] 1 … Laminate 2 … Base material 3 … Resin layer

Claims

1. A base material, A resin layer disposed on one surface of the base material and containing at least one of resin, particles of an antibacterial agent (excluding calcium hydroxide), and particles of an antiviral agent (excluding calcium hydroxide), A laminate having, The arithmetic mean height Sa of the surface of the resin layer opposite to the base material is 0.3 μm or more and 2.0 μm or less. The laminate.

2. A base material, A resin layer disposed on one surface of the base material and containing at least one of resin, particles of an antibacterial agent, and particles of an antiviral agent, A laminate having, The arithmetic mean height Sa of the surface of the resin layer opposite to the base material is 0.3 μm or more and 2.0 μm or less, The antibacterial agent includes at least one of an organic antibacterial agent and a photocatalytic antibacterial agent, The antiviral agent includes at least one of an organic antiviral agent and a photocatalytic antiviral agent. The laminate.

3. A base material, A resin layer disposed on one surface of the base material and containing at least one of resin, particles of an antibacterial agent, and particles of an antiviral agent, A laminate having, The arithmetic mean height Sa of the surface of the resin layer opposite to the base material is 0.3 μm or more and 2.0 μm or less, The antibacterial agent includes at least one of a silver-based antibacterial agent, a zinc-based antibacterial agent, and a copper-based antibacterial agent, The antiviral agent includes at least one of a silver-based antiviral agent, a zinc-based antiviral agent, and a copper-based antiviral agent. The laminate.

4. The contact angle of the surface of the resin layer opposite to the base material with respect to water is 70° or more and 100° or less. The laminate according to any one of Claims 1 to 3.

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