Antiviral urethane resin sheet

Abstract

To provide an antiviral urethane resin sheet having high antiviral properties, excellent in scratch resistance, abrasion resistance and designability.SOLUTION: An antiviral urethane resin sheet comprises a skin layer containing a urethane resin and an antivirus layer disposed on one face of the skin layer. The antivirus layer contains an alkoxysilane-based quaternary ammonium salt, a solvent-based urethane resin binder, and an additive made of silicone resin, and a delustering agent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to an antiviral urethane resin sheet. [Background technology]

[0002] In recent years, due to growing awareness of environmental hygiene, there has been a demand for imparting antiviral properties to highly durable synthetic leathers used for automobile interior parts, railway vehicle and aircraft interior parts, furniture, shoes, footwear, bags, interior and exterior building materials, clothing coverings and linings, wall coverings, and the like. As for urethane resin sheets, their application to synthetic leather, such as synthetic resin skin materials, has been studied. Synthetic leather has an uneven pattern, i.e., a grain pattern, similar to that of natural leather on its outermost surface, and is required to have a matte appearance with fine unevenness. For example, with regard to automobile interiors, as vehicles become more luxurious, it has become important to impart antiviral properties to synthetic leather, which is a skin material for interiors, without reducing the luxurious feel.

[0003] In order to produce synthetic leather imparted with functionality such as antibacterial properties, a process release sheet for synthetic leather production, which is applied as a surface layer of synthetic leather and has a layer containing functional particles, and a method for producing synthetic leather have been proposed (see, for example, Patent Document 1). Furthermore, a functional quaternary ammonium organosilane composition has been proposed as a functional material that imparts antiviral properties (see, for example, Patent Document 2).

[0004] [Patent Document 1] Patent Publication No. 2021-30683 [Patent Document 2] Special Publication No. 2013-501742 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the technology described in Patent Document 1, the functional particles contained in the functional particle-containing layer are mainly antibacterial metal particles, which causes problems such as the surface appearance being limited to a glossy appearance, and there is a concern that the metal particles may fall off if stress is applied to the outermost surface, etc. Patent Document 1 does not pay attention to the abrasion resistance, wear resistance, etc. when used in, for example, vehicle interior materials. The antibacterial particles described in Patent Document 2 are antibacterial granules containing carrier particles aggregated with a binder containing a quaternary ammonium organosilane composition, and have the problem that when used as the outermost layer of synthetic leather, etc., they do not have sufficient abrasion resistance, wear resistance, etc.

[0006] An object of an embodiment of the present invention is to provide an antiviral urethane resin sheet that has good antiviral properties, as well as excellent abrasion resistance, wear resistance, and design properties. [Means for solving the problem]

[0007] The means for solving the problem include the following embodiments. <1> An antiviral urethane resin sheet comprising: a surface layer containing a urethane resin; and an antiviral layer provided on one surface of the surface layer, wherein the antiviral layer contains an alkoxysilane-based quaternary ammonium salt, a solvent-based urethane resin binder, an additive made of a silicone resin, and a matting agent.

[0008] <2> It is synthetic leather <1> The antiviral urethane resin sheet according to claim 1. <3> The antiviral layer contains 17 to 26 parts by mass of the alkoxysilane-based quaternary ammonium salt per 100 parts by mass of the total solid content of the antiviral layer. <1> or <2> The antiviral urethane resin sheet according to claim 1.

[0009] <4> The antiviral layer contains 4 to 6 parts by mass of the additive made of the silicone resin with respect to 100 parts by mass of the total solid content of the antiviral layer. <1> ~ <3> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less. <5> The antiviral layer contains 11 to 14 parts by mass of the matting agent relative to 100 parts by mass of the total solid content of the antiviral layer. <1> ~ <4> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less.

[0010] <6> The thickness of the antiviral layer is 6.5 μm to 10.5 μm. <1> ~ <5> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less. <7> The antiviral layer further contains an acrylic resin binder. <1> ~ <6> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less.

[0011] <8> The matting agent contains at least one kind of particles selected from the group consisting of inorganic fillers and organic fillers, the particles having an average particle size of 2 μm to 12 μm. <1> ~ <7> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less.

[0012] <9> After conducting the scratch resistance test under the following conditions, no whitening is visually confirmed. <1> ~ <8> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less. -Abrasion resistance test- An antiviral urethane resin sheet with a diameter of 120 mm, which is the test specimen, is glued and fixed onto the turntable of a Taber scratch tester (manufactured by Taber Industries), and the tip of a tungsten carbide cutter is brought into contact with the surface of the specimen, and the test specimen is rotated once at a load of 1.96 N and a rotation speed of 0.5 revolutions per minute (hereinafter referred to as rpm). <10> The surface gloss value measured using Method 3 "60° specular gloss measurement method" in accordance with JIS Z 8741 (1997) is less than 1.4. <1> ~ <9> 10. The antiviral urethane resin sheet according to claim 9, wherein the antiviral urethane resin sheet is a urethane resin sheet having a thickness of 100 nm or less. [Effects of the Invention]

[0013] According to an embodiment of the present invention, it is possible to provide an antiviral urethane resin sheet that has good antiviral properties and also excellent abrasion resistance and wear resistance. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one embodiment of an antiviral urethane resin sheet according to the present disclosure. [Figure 2] FIG. 1 is a schematic cross-sectional view showing the layer structure of the antiviral urethane resin sheet of Example 11. DETAILED DESCRIPTION OF THE INVENTION

[0015] The antiviral urethane resin sheet of the present disclosure will be described in detail below. The following description of the components may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments. In the present disclosure, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit. In the present disclosure, in the numerical ranges described in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, combinations of preferred aspects are more preferred aspects. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0016] In the present disclosure, the term "total solid content" refers to, for example, the amount of components excluding the solvent out of all components contained in the composition. In the present disclosure, the term "layer containing a resin" refers to a "layer formed containing a resin that is the main component of the layer." That is, in the present disclosure, the term "layer containing a resin" is used to encompass both a resin layer containing only a resin, and a layer formed from a resin composition that contains, in addition to the resin that is the main component, optional components such as a plasticizer, a colorant, and an ultraviolet absorber. In the present disclosure, the term "resin that is the main component" refers to a resin that is contained in an amount of 60 mass % or more relative to the total amount of the resin composition containing that component.

[0017] <Antiviral urethane resin sheet> The antiviral urethane resin sheet of the present disclosure includes a surface layer containing a urethane resin, and an antiviral layer provided on one surface of the surface layer, and the antiviral layer contains an alkoxysilane-based quaternary ammonium salt, a solvent-based urethane resin binder, an additive made of a silicone resin, and a matting agent.

[0018] An antiviral urethane resin sheet according to the present disclosure (hereinafter sometimes referred to as the "resin sheet according to the present disclosure") will be described with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing one embodiment of the layer structure of an antiviral urethane resin sheet 10 according to the present disclosure. The antiviral urethane resin sheet 10 shown in Fig. 1 includes a surface layer 12 containing a urethane resin, and an antiviral layer 14 provided on one surface of the surface layer 12. The antiviral urethane resin sheet 10 shown in Fig. 1 is preferably used so that the antiviral layer 14, which exhibits antiviral properties during use, is the outermost surface.

[0019] The antiviral urethane resin sheet of the present disclosure may be used as a resin sheet as is, or may be applied to synthetic leather. There are no particular limitations on the manner in which the resin sheet of the present disclosure is applied to synthetic leather. For example, the resin sheet of the present disclosure may be bonded to one surface of a base fabric via an adhesive layer to form synthetic leather, or may be applied as a skin layer to the surface of a resin laminate comprising known layers such as a substrate layer, a foam layer, and a base fabric. When laminating the resin sheet of the present disclosure with a base fabric or another resin layer, a squeezing roll having an uneven surface can be used to perform laminate embossing so that the squeezing roll is in contact with the antiviral layer side of the resin sheet of the present disclosure, thereby forming an uneven pattern on the surface of the antiviral layer opposite to the skin layer side. By applying the resin sheet of the present disclosure to the surface of synthetic leather, antiviral properties can be imparted to the surface of the synthetic leather.

[0020] The resin sheet of the present disclosure will be described below in order along with the materials constituting the resin sheet and the method for producing the resin sheet.

[0021] (1. Epidermal layer) The surface layer in the resin sheet of the present disclosure contains a urethane resin. -Urethane resin- The urethane resin contained in the surface layer is not particularly limited as long as it can be formed into a sheet. Examples of the urethane resin include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. Among these, polycarbonate-based polyurethanes are preferred from the viewpoint of better long-term durability. Because of their good long-term durability, the resin sheet of the present disclosure can be suitably used for applications such as automobile interior materials, and can impart good antiviral properties to automobile interior materials. As an example of a preferable physical property of the urethane resin, the 100% modulus value of the urethane resin measured under the condition of 20°C is 2 MPa (2 × 10 6 N / m 2 ) to 40 MPa. Here, the 100% modulus value is a value indicating hardness measured at 20°C in accordance with JIS K 6253 (1997). When the 100% modulus value is within the above range, the surface layer containing a urethane resin, and in turn the resin sheet of the present disclosure having the surface layer, tends to exhibit favorable stretch properties.

[0022] The surface layer may contain only one type of urethane resin, or may contain two or more types. The content of the urethane resin in the surface layer can be 80 to 100 parts by mass, and preferably 85 to 95 parts by mass, per 100 parts by mass of the total solid content of the surface layer.

[0023] -Other ingredients- In addition to the urethane resin that is the main component, the surface layer may contain other components, such as known additives, as desired, as long as the effects of the present disclosure are not impaired. Examples of other components that the surface layer may contain include colorants, processing aids, plasticizers, fillers, etc. When the surface layer contains other components in addition to the urethane resin, the content of the other components is preferably within a range that does not reduce the adhesion between the surface layer and the antiviral layer.

[0024] -Other ingredients: coloring agent- The skin layer may include a colorant. When the surface layer contains a colorant, the colorant is not particularly limited, and dyes, pigments, etc. can be appropriately selected and used. Examples of colorants include inorganic pigments such as titanium white (titanium dioxide), zinc white, ultramarine, cobalt blue, red iron oxide, vermilion, yellow lead, titanium yellow, and carbon black; organic pigments or dyes such as quinacridone, permanent red 4R, isoindolinone, Hansa Yellow A, phthalocyanine blue, indanthrene blue RS, and aniline black; metal pigments selected from the group consisting of foil powders of metals such as aluminum and brass; and pearlescent (pearl) pigments selected from the group consisting of foil powders of titanium dioxide-coated mica and basic lead carbonate. Among these, pigments that are colorants with excellent weather resistance and durability are preferred.

[0025] When the skin layer contains a colorant, it may contain only one type of colorant, or may contain two or more types of colorants for the purpose of color matching or the like. There are no particular restrictions on the content of the colorant in the composition for forming the surface layer used to form the surface layer, and the type, content, etc. of the colorant to be used may be appropriately selected depending on the desired hue, etc. of the resin sheet. From the viewpoint of uniformity of the surface skin layer, the content of the colorant is preferably 20% by mass or less based on the total solid content of the surface skin layer-forming composition.

[0026] -Thickness of the epidermis- From the viewpoint of improving durability and design, the thickness of the surface layer is preferably in the range of 20 μm to 70 μm, and more preferably in the range of 20 μm to 50 μm. The thickness of the epidermis layer, the antiviral layer described below in the resin sheet of the present disclosure, and other layers that may be provided as needed can be measured by observing a cross section obtained by cutting the resin sheet perpendicular to the surface direction. Therefore, the thickness of each layer in the resin sheet of the present disclosure refers to the thickness after drying.

[0027] -Method for forming the epidermal layer- The surface layer can be formed by applying a known film-forming method, such as a method of applying a surface layer-forming composition containing a urethane resin onto a temporary support such as release paper, or a method of forming the surface layer-forming composition into a sheet by a known film-forming method such as a calendar method, an extrusion method, or a casting method. As the coating method, known coating methods such as knife coater method, blade coater method, roll coater method, bar coater method, curtain coater method, gravure coater method, etc. can be used, with knife coater method being preferred.

[0028] (2. Antiviral layer) The antiviral layer in the resin sheet according to the present disclosure contains an alkoxysilane-based quaternary ammonium salt as an antiviral component, a solvent-based urethane resin binder, an additive made of a silicone resin, and a matting agent that imparts a matte appearance to the antiviral layer.

[0029] -Alkoxysilane-based quaternary ammonium salt- The antiviral layer in the resin sheet of the present disclosure contains an alkoxysilane-based quaternary ammonium salt as an antiviral component. Alkoxysilane-based quaternary ammonium salts are compounds that have antiviral properties and contain an ammonium group with an alkyl group that has good adsorptive properties, and an alkoxysilyl group. Examples of anions that react with an ammonium group to form a salt include chloride ions, bromide ions, fluoride ions, iodide ions, arylsulfonyl ions, and acetyl ions. From the viewpoint of antiviral activity, chloride ions, bromide ions, and acetyl ions are preferred. Examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group. The alkoxysilyl group and the ammonium salt may be linked together via an alkylene group having 2 to 5 carbon atoms. Specific examples of alkoxysilane-based quaternary ammonium salts include the compounds shown below, but the alkoxysilane-based quaternary ammonium salts of the present disclosure are not limited to the following specific examples. (CH3O)3Si(CH2)3N + (CH3)2C 18 H 37 Cl - (CH3O)3Si(CH2)3N + (CH3)2(C 10 H 21 )Cl - (CH3O)3Si(CH2)3N + (CH3)2C 18 H 37 Br - (CH3O)3Si(CH2)3N + (CH3)2(C 10 H 21 )Br - (C2H5O)3Si(CH2)3N + (CH3)2C 18 H 37 Cl - (C2H5O)3Si(CH2)3N + (CH3)2CH2C6H5Cl -

[0030] From the viewpoint of easily imparting sufficient antiviral properties, the content of the alkoxysilane-based quaternary ammonium salt in the antiviral layer is preferably 17 to 26 parts by mass, and more preferably 18 to 22 parts by mass, relative to 100 parts by mass of the total solids content of the antiviral layer.

[0031] -Solvent-based urethane resin binder- The antiviral layer contains a solvent-based urethane resin as a binder in order to achieve uniform layer formation. The solvent-based urethane resin may be at least one solvent-based polyurethane selected from the group consisting of polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof, which are soluble in organic solvents. The solvent-based polyurethane may be a one-component system or a two-component system. From the viewpoints of durability, resistance to hydrolysis, resistance to heat degradation, etc., polycarbonate-based polyurethanes, silicone-modified polycarbonate-based polyurethanes, etc. are preferred, with polycarbonate-based polyurethanes being more preferred. The antiviral layer may contain only one type of solvent-based urethane resin, or may contain two or more types. The solvent-based urethane resin refers to a urethane resin that can dissolve at least 10% by mass in methyl ethyl ketone, an organic solvent, in an atmosphere of 25°C.

[0032] The antiviral layer may contain a thermoplastic resin other than the solvent-based urethane resin (hereinafter referred to as "other resin") as a binder. Examples of other resins that can be used in the antiviral layer include acrylic resins, and acrylic resins are preferred from the viewpoints of compatibility with the solvent-based urethane resin and transparency. Specific examples of acrylic resins used as binders include polymers or copolymers of methacrylic acid or methacrylic acid esters, such as polymethyl methacrylate (PMMA), and copolymers of alkyl methacrylate, alkyl acrylate, and styrene. When the antiviral layer contains an acrylic resin as the other resin, it may contain only one type of acrylic resin, or may contain two or more types of acrylic resin. When the antiviral layer contains other resins, the content of the acrylic resin is preferably 15 parts by mass or less per 100 parts by mass of the total amount of the resins serving as binders.

[0033] The content of the resin binder in the antiviral layer is preferably 54 parts by mass to 68 parts by mass per 100 parts by mass of the solid content of the antiviral layer.

[0034] -Silicone resin additive- The antiviral layer contains at least one additive made of a silicone resin (hereinafter, may be referred to as a specific additive). When the antiviral layer contains the specific additive, the antiviral layer has good scratch resistance and abrasion resistance. The silicone resin may be appropriately selected from the group consisting of known silicone resins and modified silicone resins. The silicone resin may be any resin having a siloxane structural unit, and may be a homopolymer of the siloxane structural unit or a copolymer of the siloxane structural unit and a structural unit derived from acrylic acid. As the modified silicone resin, a urethane-modified silicone resin, an ester-modified silicone resin, or the like can be used.

[0035] The antiviral layer may contain only one type of specific additive, or may contain two or more types. From the viewpoint of further improving abrasion resistance and the like, the content of the specific additive in the antiviral layer is preferably 4 parts by mass to 6 parts by mass, and more preferably 5 parts by mass to 6 parts by mass, per 100 parts by mass of the solid content of the antiviral layer.

[0036] -Matting agent- The antiviral layer contains a matting agent. By containing the matting agent in the antiviral layer, the resin sheet of the present disclosure has excellent design properties. Here, design properties refer to the resin sheet having reduced surface gloss and a matte appearance. The matting agent preferably contains at least one type of particles selected from the group consisting of inorganic fillers and organic fillers, and having an average particle size of 2 μm to 12 μm. From the viewpoint of achieving a better matting effect, the matting agent preferably has an average particle size of 2 μm to 12 μm, more preferably 4 μm to 10 μm. The average particle size of matting agent particles was measured using an automatic particle size measuring device (model number: CAPA-300) manufactured by Horiba Ltd., using a light transmission centrifugal sedimentation method with water as the dispersion medium at a disk rotation speed of 3000 rpm, and the value measured using the method of measuring the volume-based median diameter was used. Examples of inorganic fillers as matting agents include silica particles, glass beads, etc. Examples of organic fillers include resin particles, resin beads, etc. More specific examples of organic fillers include urethane beads, acrylic beads, collagen particles, etc. The matting agent may be transparent particles or colored particles.

[0037] The antiviral layer may contain only one type of matting agent, or may contain two or more types depending on the purpose. From the viewpoint of further improving design properties, the content of the matting agent in the antiviral layer is preferably 11 parts by mass to 14 parts by mass, and more preferably 12 parts by mass to 13 parts by mass, per 100 parts by mass of the solid content of the antiviral layer.

[0038] -Other ingredients- In addition to the above essential components, the antiviral layer may contain other components depending on the purpose. Examples of other components include antiviral agents other than alkoxysilane-based quaternary ammonium salts, antibacterial agents or disinfectants, and colorants.

[0039] -Thickness of the antiviral layer- From the viewpoint of improving the antiviral property, scratch resistance, abrasion resistance, and design property, the thickness of the antiviral layer is preferably 6.5 μm to 10.5 μm, and more preferably 7 μm to 9 μm. The thickness of the antiviral layer can be measured in the same manner as the thickness of the epidermal layer described above.

[0040] -Method for forming antiviral layer- In the resin sheet of the present disclosure, an example of a method for forming an antiviral layer is to apply an antiviral layer-forming composition containing the antiviral agent, resin binder, specific additive, matting agent, and other components as desired to one surface of the aforementioned surface layer, followed by drying. Any known application method may be used as the application method. Examples of known application methods include a knife coater method, a blade coater method, a roll coater method, a bar coater method, a curtain coater method, and a gravure coater method. From the viewpoint of uniformity of the resulting layer, the knife coater method, a direct gravure coater method, which is an embodiment of the gravure coater method, and a reverse gravure coater method are preferred. The amount of the antiviral layer-forming composition applied by the coating method is set to 7 g / m as the amount applied when dried, from the viewpoint of improving antiviral properties, scratch resistance, abrasion resistance, and design properties. 2 ~11g / m 2 It is preferable that the thickness is 7.5 g / m 2 ~9.5g / m 2 It is more preferable that:

[0041] (3. Preferred physical properties of the resin sheet of the present disclosure) 3-1. Scratch resistance The resin sheet of the present disclosure may be used as it is as a resin sheet, synthetic leather, etc., or may be used as a surface material for existing synthetic leather. From the viewpoint of maintaining antiviral properties for a long period of time, it is preferable that the resin sheet of the present disclosure has good durability. As a measure of durability, it is preferable that the film has a scratch resistance such that no whitening is visually confirmed after carrying out an abrasion resistance test under the following conditions. The test is carried out at room temperature (20°C). Here, "whitening" refers to the surface of the test piece that comes into contact with the cutting edge of the cutter becoming roughened by friction and appearing white to the naked eye. -Abrasion resistance test- An antiviral urethane resin sheet with a diameter of 120 mm is glued and fixed to the turntable of a Taber scratch tester (manufactured by Taber Industries), and the tip of a tungsten carbide cutter is brought into contact with the surface of the test piece, and the test piece is rotated once at a load of 1.96 N and a rotation speed of 0.5 rpm.

[0042] 3-2.Appearance The resin sheet of the present disclosure preferably has a matte appearance with reduced gloss. The matte appearance is preferably such that the surface gloss value measured by Method 3 "60° specular gloss measurement method" in accordance with JIS Z 8741 (1997) is less than 1.4, and more preferably 1.2 or less. When the surface gloss value measured by the 60° specular gloss measurement method is less than 1.4, when the resin sheet of the present disclosure is applied to, for example, synthetic leather, it can give the surface a matte, heavy appearance.

[0043] The resin sheet of the present disclosure has the above-described configuration, and therefore has excellent antiviral properties while also having excellent scratch resistance and abrasion resistance, making it applicable to various applications requiring antiviral properties. Furthermore, because the antiviral layer, which is the outermost layer, contains an appropriate amount of a matting agent, the resin sheet has a matte appearance and is excellent in design.

[0044] (4. Other layers) The resin sheet of the present disclosure may have, in addition to the above-described surface layer and antiviral layer, other layers depending on the purpose of the resin sheet. Examples of other layers include an adhesive layer, a base fabric, a resin foam layer, a substrate layer, and a design layer.

[0045] 4-1.Adhesive layer The resin sheet of the present disclosure may have an adhesive layer. The adhesive layer is useful for adhering the laminate of the skin layer and the antiviral layer to other layers such as a base fabric, a substrate layer, etc. The adhesive layer also allows the resin sheet of the present disclosure to be directly adhered to the surface of a hard material such as a wall surface.

[0046] The adhesive layer can be formed from a resin having adhesive properties. The adhesive layer can be formed by applying a known adhesive to the surface of the surface layer of the resin sheet opposite to the antiviral layer side. The adhesive used to form the adhesive layer provided on the resin sheet as desired is not particularly limited and may be appropriately selected depending on the purpose. Suitable adhesives include, for example, urethane resin adhesives, polyvinyl chloride adhesives, polyvinylidene chloride adhesives, and styrene resin adhesives. The adhesive layer can be formed by applying a resin as an adhesive to the surface of the epidermis layer opposite the antiviral layer side. The application method can be any of the known application methods described above. The thickness of the adhesive layer is preferably in the range of 5 μm to 50 μm, more preferably 10 μm to 50 μm, from the viewpoint of adhesiveness between adjacent layers and the texture of the resin sheet.

[0047] 4-2. Base fabric The resin sheet of the present disclosure may have a base fabric. The resin sheet has improved strength due to the presence of the base fabric, and can be used as synthetic leather as is. The base fabric is not particularly limited as long as it has the necessary strength and flexibility and a certain degree of stretchability, and any of woven fabric, knitted fabric and nonwoven fabric can be used. From the viewpoint of stretchability, knitted fabrics are preferred, and known knitted fabrics such as warp knitting, warp knitting, raschel knitting, and terry knitting can be used as appropriate.

[0048] Fibers constituting the base fabric may be synthetic fibers such as polyester fibers, polyamide fibers, polyacrylonitrile fibers, acrylic fibers, and polyurethane fibers; natural fibers such as cotton and hemp; and regenerated fibers such as rayon fibers, depending on the purpose. The base fabric may be made of one type of fiber or two or more types of fibers. For example, the use of polyurethane fibers in combination with the fibers constituting the base fabric can further improve the stretchability of the base fabric, and the use of Kevlar fibers, a high-strength polyamide fiber, can also improve the strength of the base fabric.

[0049] The thickness of the base fabric can be appropriately selected depending on the purpose, and is preferably 650 μm to 1200 μm, more preferably 700 μm to 1100 μm, from the viewpoint of the strength and durability of the resin sheet.

[0050] 4-3.Foamed resin layer The resin sheet of the present disclosure may have a foamed resin layer. When the resin sheet has a foamed resin layer, the flexibility and elasticity of the resin sheet are improved. There are no particular limitations on the foamed resin layer, so long as it is a resin layer that is flexible and contains bubbles therein. Examples of the resin contained in the foamed resin layer include the resins shown below. Polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene (PB), Polyurethane (PUR), Polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). The resin may be modified, or may be a resin having a crosslinked structure formed by a crosslinking agent or the like. The foamed resin layer can be formed by incorporating bubbles formed by a known method into these resins. The foamed resin layer may contain only one type of thermoplastic resin, or may contain two or more types of thermoplastic resin. When the resin sheet has a foamed resin layer, the thickness of the foamed resin layer is preferably 100 μm to 500 μm.

[0051] 4-4.Base material layer The resin sheet of the present disclosure may have a substrate layer. By having the substrate layer, the resin sheet has an increased thickness, and the strength and feel are improved. The base layer preferably contains a thermoplastic resin. There are no particular restrictions on the thermoplastic resin that can be used for the base layer, and the resin can be appropriately selected from known thermoplastic resins in consideration of various conditions such as the affinity between adjacent layers and the stretchability of the resin sheet. Examples of thermoplastic resins that can be used for the base layer include polyethylene (PE), PP resin, PVC resin, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (urethane resin), ABS resin, acrylonitrile-styrene copolymer (AS resin), polycarbonate (PC), acrylic resins such as polymethyl methacrylate (PMMA), and fluororesins such as polytetrafluoroethylene (PTFE). The substrate layer can be formed by a known film-forming method. The substrate layer may contain only one type of thermoplastic resin, or may contain two or more types of thermoplastic resin.

[0052] 4-5. Design layer The resin sheet may have a design layer. The design layer is a layer that further imparts design properties to the resin sheet, and may be a printed layer formed by printing, a colored layer containing a colorant, or a layer that combines these. The design layer can be provided, if desired, on the surface of the above-mentioned skin layer facing the antiviral layer or on the surface opposite to the antiviral layer.

[0053] The design layer can be formed, for example, by a printing method on the surface of the aforementioned surface layer. Examples of printing methods for forming the design layer include a method in which the design layer is formed by a known printing method using a printing ink containing a resin. From the viewpoint of being able to form a clear printed image, the printing ink containing a resin preferably contains at least one resin selected from acrylic resin, urethane resin, polyolefin resin, polyamide resin, and vinyl chloride-vinyl acetate copolymer. When the design layer is a printed layer, there are no particular limitations on the printing method that can be used to form the design layer, and any printing method can be used, such as gravure printing (intaglio printing), letterpress printing, offset printing, inkjet printing, screen printing, etc. The design layer formed by a printing method may be a discontinuous layer that includes areas where the printing ink is adhered, or may be a continuous, uniform layer made of the printing ink.

[0054] (5. Layer structure of resin sheet) As shown in FIG. 1, the resin sheet of the present disclosure includes a surface layer and an antiviral layer on one side of the surface layer, and can be used for a variety of purposes. Alternatively, an embodiment such as that shown in FIG. 2 may be adopted, in which an adhesive layer, an epidermal layer, and an antiviral layer are attached to a base fabric via an optional adhesive layer. FIG. 2 is a schematic cross-sectional view showing one embodiment of an antiviral urethane resin sheet having a base fabric and an adhesive layer as optional layers. The antiviral urethane resin sheet 20 shown in FIG. 2 comprises a surface layer 12 and an antiviral layer 14 on one side of a base fabric 16 with an adhesive layer 18 interposed therebetween. The resin sheet provided with the base fabric as shown in FIG. 2 can be used as synthetic leather in its original form for automobile interior materials, building interior materials, bags, shoes, clothing, and the like.

[0055] (6. Manufacturing method of resin sheet) There are no particular limitations on the method for producing the resin sheet of the present disclosure, and any known production method can be appropriately adopted. An example of the manufacturing method will be described below, but the manufacturing method is not limited to the following.

[0056] The method for producing a resin sheet according to the present disclosure includes a step (step A) of forming a surface layer using a surface layer-forming composition containing at least a urethane resin, and a step (step B) of applying an antiviral layer-forming composition containing an alkoxysilane-based quaternary ammonium salt, a solvent-based urethane resin binder, a specific additive, and a matting agent to one surface of the obtained surface layer to form an antiviral layer. The method for producing a resin sheet can further include any steps, such as a step of forming an adhesive layer on the surface of the epidermis layer opposite the antiviral layer side (step C), and a step of adhering a base fabric to the surface of the adhesive layer obtained in step C opposite the epidermis layer side (step D).

[0057] (Process A) In step A, a surface layer containing a urethane resin is formed. Examples of the formation method include a method in which a surface layer-forming composition containing a urethane resin is applied to a temporary support such as release paper and dried to form a surface layer, and a method in which a surface layer-forming composition containing a urethane resin is formed into a sheet using a known film-forming method. When applying the coating method, the wet coating amount is determined depending on the thickness of the surface layer to be formed. For example, 2 ~200g / m 2 It can be said that: Step A may include a step of applying a skin layer-forming composition containing a urethane resin onto a temporary support such as release paper, and then drying the formed skin layer-forming composition layer. Drying can be carried out using a hot air dryer, warm air dryer, etc. The drying temperature can be 80° C. to 120° C., preferably 90° C. to 100° C. The drying time can be 1 minute to 3 minutes under the above temperature conditions. The thickness of the formed skin layer is preferably 5 μm to 200 μm, more preferably 30 μm to 150 μm, in terms of film thickness after drying, as described above. After drying, the coating is aged preferably at a temperature of 40° C. to 50° C. for 24 to 48 hours, and then the temporary support such as release paper is peeled off to obtain the surface layer.

[0058] (Process B) In step B, the prepared composition for forming an antiviral layer is applied to one surface of the epidermis layer obtained in step A to obtain a composition layer for forming an antiviral layer. The application may be performed by a known method, such as a knife coater method. When applying the coating method, the wet coating amount is determined depending on the thickness of the antiviral layer to be formed. For example, 2~50g / m 2 It can be said that: Drying can be carried out using a hot air dryer, warm air dryer, etc. The drying temperature can be 80° C. to 100° C., preferably 80° C. to 90° C. The drying time can be 40 seconds to 2 minutes under the above temperature conditions. The thickness of the formed skin layer is preferably 5 μm to 200 μm, more preferably 30 μm to 150 μm, in terms of film thickness after drying, as described above. [Example]

[0059] Hereinafter, the resin sheet of the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited to the following specific examples, and various modifications are possible.

[0060] (Manufacturing antiviral urethane resin sheets) Example 1 Components 1 to 5 were mixed according to the following formulation to prepare a composition for forming an epidermal layer. The solid content of the skin layer-forming composition was about 13% by mass. -Composition for forming epidermal layer- 1. One-component solvent-based polycarbonate-based urethane resin (Solvent-based urethane resin: resin solid content 20% by mass) 100 parts by mass 2. Solvent (dimethylformamide: DMF) 20 parts by mass 3. Solvent (propylene glycol monomethyl ether: PGM) 15 parts by mass 4. Solvent (isopropyl alcohol: IPA) 5 parts by weight 5. Colorant (carbon black) 15 parts by mass

[0061] The obtained composition for forming a surface skin layer was applied onto the surface of the prepared release paper using a knife coater in a wet coating amount of 150 g / m 2 The composition was applied in an amount of 1000 ppm to form a skin layer-forming composition layer. The formed skin layer-forming composition layer was dried at 100°C for 2 minutes using a hot air dryer to form a skin layer on the release paper. The dried skin layer had a thickness of 20µm. The dried surface layer was further aged at 50°C for 48 hours, and then the release paper was peeled off. (Step A)

[0062] Components 6 to 10 were mixed according to the following formulation to prepare a composition for forming an antiviral layer. The solid content of the composition for forming an antiviral layer was approximately 30% by mass. -Composition for forming antiviral layer- 6. Antiviral solution 20 parts by mass 7. One-component polycarbonate-based urethane resin (Solvent-based urethane resin: resin solid content 18% by mass) 100 parts by mass 8. Solvent (MEK) 10 parts by mass 9. Specific additive (urethane-modified silicone resin) 5 parts by mass 10. Matting agent (silica particles: average particle diameter 7 μm) 12 parts by mass

[0063] As the alkoxysilane-based quaternary ammonium salt, which is an antiviral agent, a methanol solution of trimethoxysilylpropyldimethyloctadecylammonium chloride was used. The content of the methoxysilane-based quaternary ammonium salt per 100 parts by mass of the solid content of the obtained composition for forming an antiviral layer was 20.6 parts by mass.

[0064] The obtained composition for forming an antiviral layer was applied to one side of the surface layer obtained in step A using a gravure coater in a wet coating amount of 30 g / m 2 The antiviral layer-forming composition layer was formed on one surface of the epidermal layer. Thereafter, the sheet was heated at 90°C for 1 minute using a hot air dryer to form an antiviral layer with a thickness of 9 µm on the surface of the epidermis layer, thereby obtaining a resin sheet of Example 1.

[0065] Example 2 A resin sheet of Example 2 was obtained in the same manner as in Example 1, except that in the antiviral layer-forming composition used in Example 1, the amount of the antiviral agent solution of Component 6 was changed from 20 parts by mass to 30 parts by mass. The content of the methoxysilane-based quaternary ammonium salt per 100 parts by mass of the solid content of the obtained composition for forming an antiviral layer was 25.7 parts by mass.

[0066] Example 3 A resin sheet of Example 3 was obtained in the same manner as in Example 1, except that in the antiviral layer-forming composition used in Example 1, the amount of the antiviral agent solution of Component 6 was changed from 20 parts by mass to 15 parts by mass. The content of the methoxysilane-based quaternary ammonium salt per 100 parts by mass of the solid content of the obtained composition for forming an antiviral layer was 17.8 parts by mass.

[0067] Example 4 A resin sheet of Example 4 was obtained in the same manner as in Example 1, except that in the composition for forming an antiviral layer used in Example 1, the amount of the specific additive of Component 9 was changed from 5 parts by mass to 6 parts by mass.

[0068] Example 5 A resin sheet of Example 5 was obtained in the same manner as in Example 1, except that in the composition for forming an antiviral layer used in Example 1, the blending amount of the specific additive of Component 9 was changed from 5 parts by mass to 4 parts by mass.

[0069] Example 6 A resin sheet of Example 6 was obtained in the same manner as in Example 1, except that in the antiviral layer-forming composition used in Example 1, the amount of the matting agent of Component 10 was changed from 12 parts by mass to 14 parts by mass.

[0070] Example 7 A resin sheet of Example 7 was obtained in the same manner as in Example 1, except that in the antiviral layer-forming composition used in Example 1, the amount of the matting agent of Component 10 was changed from 12 parts by mass to 11 parts by mass.

[0071] Example 8 In Example 1, the wet coating amount of the composition for forming the antiviral layer was 30 g / m 2 from 36g / m 2A resin sheet of Example 8 was obtained in the same manner as in Example 1, except that the above-mentioned procedure was changed to the following.

[0072] Example 9 In Example 1, the wet coating amount of the composition for forming the antiviral layer was 30 g / m 2 from 23 g / m 2 A resin sheet of Example 9 was obtained in the same manner as in Example 1, except that the above-mentioned conditions were changed.

[0073] Example 10 A resin sheet of Example 10 was obtained in the same manner as in Example 1, except that a composition for forming an antiviral layer obtained by further adding 2 parts by mass of a fluorine-modified acrylic resin as a binder to the composition for forming an antiviral layer used in Example 1 was used.

[0074] Example 11 In the same manner as in Example 1, a layer of the composition for forming a surface skin layer was formed on the surface of the release paper and dried. Thereafter, the following steps C and D were carried out to form a laminate of the surface layer, adhesive layer and base fabric on the surface of the release paper. (Process C) A composition for forming an adhesive layer was obtained by mixing the following components 11 to 13. The solid content concentration in the composition for forming an adhesive layer was 45 mass %. -Adhesive layer forming composition- 11. Two-component polycarbonate polyurethane resin (resin solid content 70% by mass) 100 parts by mass 12. Solvent (DMF) 50 parts by mass 13. Isocyanate crosslinking agent 6 parts by mass

[0075] The adhesive layer-forming composition was applied in a wet amount of 100 g / m onto the surface of the surface layer formed on the release paper. 2 The adhesive layer was heated at 120°C for 2 minutes using a hot air dryer to form an adhesive layer with a thickness of 45 µm, and a laminate having a release liner, a skin layer, and an adhesive layer was obtained.

[0076] (Process D) -Base fabric lamination- A base fabric (knitted polyester fabric: thickness 1100 μm) was attached and laminated to the adhesive layer side of the laminate obtained in step C. The heating temperature during lamination was 130°C. The resulting laminate of the base fabric, adhesive layer and surface layer was aged in the same manner as in Example 1, and the release paper was peeled off. An antiviral layer was formed on the surface of the skin layer opposite the adhesive layer from which the release paper had been peeled, in the same manner as in Example 1, to obtain a resin sheet of Example 11 having an adhesive layer, skin layer, and antiviral layer in this order on a base fabric. The thickness of the obtained resin sheet was 1174 μm.

[0077] Comparative Example 1 A resin sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that in the antiviral layer-forming composition used in Example 1, the antiviral agent contained in the antiviral agent solution of component 6 was changed to an alkoxysilane-based quaternary ammonium salt, and an antiviral layer was formed using a composition for forming an antiviral layer in which 30 parts by mass of monovalent copper compound nanoparticles were blended. Nanoparticles refer to particles with an average particle size of 1 nm to 100 nm or less.

[0078] Comparative Example 2 A resin sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that an antiviral layer was formed using a composition for forming an antiviral layer in which 100 parts by mass of polyvinyl chloride (average degree of polymerization 1300) was blended instead of the solvent-based urethane resin used as the binder in Component 7 in the composition for forming an antiviral layer used in Example 1.

[0079] Comparative Example 3 A resin sheet of Comparative Example 3 was obtained in the same manner as in Example 1, except that an antiviral layer was formed using a composition for forming an antiviral layer that did not contain the specific additive of Component 9 in the composition for forming an antiviral layer used in Example 1.

[0080] Comparative Example 4 A resin sheet of Comparative Example 4 was obtained in the same manner as in Example 1, except that an antiviral layer was formed using a composition for forming an antiviral layer that did not contain the matting agent of Component 10 in the composition for forming an antiviral layer used in Example 1.

[0081] (Evaluation of resin sheets) The antiviral urethane resin sheets obtained in the examples and comparative examples were evaluated by the following methods, and the results are shown in Tables 1 and 2 below. In Tables 1 and 2, the antiviral agent is abbreviated as "methoxysilane-based quaternary ammonium salt," the one-component solvent-based polycarbonate-based urethane resin is abbreviated as "urethane resin A," and the two-component polycarbonate-based polyurethane resin is abbreviated as "urethane resin B."

[0082] (1. Antiviral) The antiviral activity value of the resin sheet was measured in accordance with ISO 21702. The virus strain used was influenza virus (H3N2). A 50 mm square antiviral urethane resin sheet test piece was inoculated with 0.4 ml of virus liquid and then covered with a liquid-impermeable covering film. After inoculation with the virus solution, the test specimen was left to stand for 24 hours in an environment with a temperature of 25±1°C and a humidity of 90% RH or higher. After leaving it to stand for 24 hours, the covering film was peeled off, the virus was recovered from the test piece, and the virus infectivity (antiviral activity value) was measured by the plaque method and evaluated according to the following criteria. Rank A is an evaluation that the antiviral properties are good and at a level that is not problematic. -Evaluation criteria- A: Antiviral activity value is 2.0 or higher B: Antiviral activity value less than 2.0

[0083] (2. Scratch resistance) The device used was a Taber scratch tester (manufactured by Taber Industries). The resin sheets of the examples and comparative examples were cut into pieces with a diameter of 120 mm to prepare test pieces, and a hole with a diameter of 15 mm was drilled in the center of each test piece. The obtained test piece was adhesively fixed on the turntable of a Taber scratch tester, and the tip of a tungsten carbide cutter was brought into contact with the surface of the test piece. The scratch resistance was evaluated by rotating the test piece and scratching it over a length of 15 mm. The load was 1.96 N, and the turntable was rotated once at a rotation speed of 0.5 rpm. After the test, each test piece was visually observed from the front and in the dark, and the state of whitening was evaluated. The evaluation was carried out by 10 professional monitors, and the evaluation was based on the following criteria. -Evaluation criteria- A: 10 monitors evaluated that no bleaching was observed. B: At least one of the monitors evaluated that slight bleaching was observed. C: One or more monitors evaluated that significant bleaching was observed. A is an evaluation level that presents no practical problems. In this evaluation, even if one or more monitors evaluate the product as "slightly bleached," if one or more monitors evaluate the product as "significantly bleached," the product will be rated as C rank.

[0084] (3. Abrasion resistance) For the test, a flat surface abrasion tester (manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) was used. Each resin sheet of the examples and comparative examples was cut into a width of 70 mm and a length of 300 mm to prepare a test piece. The obtained test piece was fixed to a flat surface abrasion tester, and a load was applied to a friction element covered with cotton cloth (No. 6 canvas) to abrade the surface of the test piece. The friction element was abraded 10,000 times on the surface of the test piece at a load of 9.8 N and a speed of 60 reciprocations / minute. After the test, each test piece was visually inspected to evaluate the appearance for damage. The evaluation was carried out by 10 expert monitors and evaluated according to the following criteria: -Evaluation criteria- A: 10 monitors evaluated that no damage to the exterior was observed. B: At least one of the monitors evaluated that slight damage to the exterior was observed. C: One or more monitors evaluated that significant damage to the exterior was observed. A is an evaluation level that presents no practical problems. In this evaluation, even if one or more monitors rated the product as "slight damage to the exterior was observed," if one or more monitors rated the product as "significant damage to the exterior was observed," the product will be rated as C rank.

[0085] (4. Design) The gloss value (60° specular gloss) of the antiviral layer surface of each resin sheet in the Examples and Comparative Examples was measured in accordance with JIS Z 8741 (1997). The measuring device used was a micro-TRI-gloss (manufactured by BYK). -Evaluation criteria- A: Gloss value less than 1.4 B: Gloss value is 1.4 or more A is an evaluation level that presents no practical problems.

[0086] [Table 1]

[0087] [Table 2]

[0088] The results in Tables 1 and 2 show that the resin sheets of the examples have good antiviral properties, excellent scratch resistance and abrasion resistance, and good design properties with reduced gloss. Furthermore, a comparison between Example 1 and Example 10 shows that even if the resin binder contains an acrylic resin in addition to a urethane resin, an excellent effect can be achieved as long as the binder contains a solvent-based urethane resin. On the other hand, the resin sheets of Comparative Example 1, which contained an antiviral agent other than an alkoxysilane-based quaternary ammonium salt, and Comparative Example 2, which used a polyvinyl chloride resin as a binder resin, had problematic levels of antiviral property, and the resin sheet of Comparative Example 1 was glossy and had practically problematic design properties. Furthermore, the resin sheet of Comparative Example 3, which had an antiviral layer that did not contain a specific additive, had poor abrasion resistance and wear resistance. The resin sheet of Comparative Example 4, which did not contain a matting agent, was inferior in scratch resistance and abrasion resistance compared to the examples, and furthermore, had a glossy appearance and was inferior in design. [Explanation of symbols]

[0089] 10, 20 Antiviral urethane resin sheet (resin sheet) 12 Epidermal layer 14 Antiviral Layer 16 Base fabric 18 Adhesive layer

Claims

1. a surface layer containing a urethane resin; and an antiviral layer provided on one surface of the epidermis layer, The antiviral layer is an antiviral urethane resin sheet containing an alkoxysilane-based quaternary ammonium salt, a solvent-based urethane resin binder, an additive made of a silicone resin, and a matting agent.

2. 2. The antiviral urethane resin sheet according to claim 1, which is synthetic leather.

3. 3. The antiviral urethane resin sheet according to claim 1 or 2, wherein the antiviral layer contains 17 parts by mass to 26 parts by mass of the alkoxysilane-based quaternary ammonium salt per 100 parts by mass of a total solids content of the antiviral layer.

4. 4. The antiviral urethane resin sheet according to claim 1, wherein the antiviral layer contains 4 parts by mass to 6 parts by mass of the additive made of the silicone resin per 100 parts by mass of a total solid content of the antiviral layer.

5. 5. The antiviral urethane resin sheet according to claim 1, wherein the antiviral layer contains 11 parts by mass to 14 parts by mass of the matting agent per 100 parts by mass of a total solid content of the antiviral layer.

6. The antiviral urethane resin sheet according to any one of claims 1 to 5, wherein the antiviral layer has a thickness of 6.5 µm to 10.5 µm.

7. 7. The antiviral urethane resin sheet according to claim 1, wherein the antiviral layer further contains an acrylic resin binder.

8. The antiviral urethane resin sheet according to any one of claims 1 to 7, wherein the matting agent comprises at least one kind of particles selected from the group consisting of inorganic fillers and organic fillers, the particles having an average particle diameter of 2 µm to 12 µm.

9. The antiviral urethane resin sheet according to any one of claims 1 to 8, wherein no whitening is confirmed visually after an abrasion resistance test under the following conditions: - Scratch resistance test - An antiviral urethane resin sheet with a diameter of 120 mm, which is the test specimen, is adhesively fixed onto the turntable of a Taber scratch tester (manufactured by Taber Industries), and the tip of a tungsten carbide cutter is brought into contact with the surface of the specimen, and the test specimen is rotated once at a load of 1.96 N and a rotation speed of 0.5 rotations / minute.

10. The antiviral urethane resin sheet according to any one of claims 1 to 9, wherein the surface gloss value measured by Method 3 "60° specular gloss measurement method" in accordance with JIS Z 8741 (1997) is less than 1.4.

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