ANTIVIRAL TRANSFER SHEET AND METHOD FOR MANUFACTURING SAME, AND ANTIVIRAL SHRINK FILM AND METHOD FOR MANUFACTURING SAME

Abstract

Provided is an antiviral transfer sheet manufacturing method for increasing the density of an antiviral agent or antibacterial agent in a surface which becomes an upper-most layer after transfer. In particular, a manufacturing method that eliminates the need for a large amount of an antiviral agent and the like, and the opacity of the layer having antiviral function is provided. A functional layer 37 including an inorganic antiviral agent powder and a hard coat agent is formed on one surface of a base material sheet 31 by disposing on the base material sheet the inorganic antiviral agent powder 33, and positioning the hard coat agent 34 in layer shape from over the inorganic antiviral agent powder 33. Then, an adhesive layer 39 is formed on the functional layer 37 in contact with the functional layer 37 or via another layer, thereby manufacturing an antiviral transfer sheet 11.

Claims

1. An antiviral transfer sheet manufacturing method comprising disposing an inorganic antiviral agent powder on one surface of a base material sheet, positioning a hard coat agent from over the inorganic antiviral agent powder in layer shape, and forming a functional layer including the inorganic antiviral agent powder and the hard coat agent on the base material sheet, wherein an adhesive layer is formed on the functional layer, in contact with the functional layer or via another layer.

2. The antiviral transfer sheet manufacturing method according to claim 1, wherein the inorganic antiviral agent powder includes a mixture of a titanium oxide powder and a cuprous oxide (copper oxide (I):Cu.sub.2O) powder.

3. The antiviral transfer sheet manufacturing method according to claim 1, wherein the inorganic antiviral agent powder disposed on the base material sheet has an amount of not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 of an antiviral transfer sheet.

4. The antiviral transfer sheet manufacturing method according to claim 1, comprising: after the functional layer is formed, forming a picture layer on the functional layer; and forming the adhesive layer on the picture layer.

5. An antiviral transfer sheet comprising a base material sheet and a transfer layer, wherein the transfer layer includes a functional layer which is in contact with one surface of the base material sheet and which is on the base material sheet, and an adhesive layer which is an upper-most layer of the transfer layer, the functional layer includes an inorganic antiviral agent powder and a hard coat agent, the inorganic antiviral agent powder has an amount of not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 of the antiviral transfer sheet, the functional layer has a boundary surface in contact with the base material sheet, of particles of the inorganic antiviral agent powder, a particle of which a part of the particle surface is in contact with the boundary surface provides an contact-effective powder particle, and the contact-effective powder particle has an independent contact area in contact with the boundary surface, a total value of the independent contact areas of the contact-effective powder particles present in a certain section of the boundary surface is a total contact area, and when the percentage of the total contact area with respect to an area of the certain section is an contact-effective powder-occupied percentage, the contact-effective powder-occupied percentage is not less than 50% and not more than 80%.

6. The antiviral transfer sheet according to claim 5, wherein the inorganic antiviral agent powder includes a mixture of a titanium oxide powder and a cuprous oxide (copper oxide (I):Cu.sub.2O) powder.

7. The antiviral transfer sheet according to claim 5, wherein the transfer layer includes, in addition to the functional layer and the adhesive layer, a picture layer positioned between the functional layer and the adhesive layer.

8. An antiviral shrink film manufacturing method comprising: preparing a base material laminated body by laminating the antiviral transfer sheet according to claim 5 on a shrink base material; preparing, by applying pressure and heat to the base material laminated body, a base material transfer body including a transfer layer transferred onto the shrink base material; and obtaining an antiviral shrink film by removing the base material sheet from the base material transfer body.

9. The antiviral shrink film manufacturing method according to claim 8, wherein the pressure applied to the laminate is 0.3 MPa to 1.2 MPa, and the heat applied to the laminate is 170 C. to 210 C.

10. An antiviral shrink film comprising a shrink base material and a functional layer which is disposed on one surface side of the shrink base material and which is on an upper-most layer of the antiviral shrink film, wherein the functional layer includes an inorganic antiviral agent powder and a hard coat agent, and contains the inorganic antiviral agent powder by an amount of not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 of the antiviral shrink film, the functional layer has an exposed surface in contact with an external environment, the inorganic antiviral agent powder includes particles of which a particle having a particle surface partly exposed on the exposed surface provides an effective exposed powder particle, the effective exposed powder particle has an independent exposed area exposed on the exposed surface, a total value of the independent exposed areas of the effective exposed powder particles present in a certain section of the exposed surface is a total exposed area, and when the percentage of the total exposed area with respect to an area of the certain section is an effective exposed powder-occupied percentage, the effective exposed powder-occupied percentage is not less than 50% and not more than 80%.

11. The antiviral shrink film according to claim 10, wherein the inorganic antiviral agent powder includes a mixture of a titanium oxide powder and a cuprous oxide (copper oxide (I):Cu.sub.2O) powder.

12. The antiviral shrink film according to claim 10, comprising a picture layer positioned between the shrink base material and the functional layer.

13. The antiviral transfer sheet manufacturing method according to claim 2, wherein the inorganic antiviral agent powder disposed on the base material sheet has an amount of not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 of an antiviral transfer sheet.

14. The antiviral transfer sheet manufacturing method according to claim 2, comprising: after the functional layer is formed, forming a picture layer on the functional layer; and forming the adhesive layer on the picture layer.

15. The antiviral transfer sheet manufacturing method according to claim 3, comprising: after the functional layer is formed, forming a picture layer on the functional layer; and forming the adhesive layer on the picture layer.

16. The antiviral transfer sheet manufacturing method according to claim 13, comprising: after the functional layer is formed, forming a picture layer on the functional layer; and forming the adhesive layer on the picture layer.

17. The antiviral transfer sheet according to claim 6, wherein the transfer layer includes, in addition to the functional layer and the adhesive layer, a picture layer positioned between the functional layer and the adhesive layer.

18. An antiviral shrink film manufacturing method comprising: preparing a base material laminated body by laminating the antiviral transfer sheet according to claim 6 on a shrink base material; preparing, by applying pressure and heat to the base material laminated body, a base material transfer body including a transfer layer transferred onto the shrink base material; and obtaining an antiviral shrink film by removing the base material sheet from the base material transfer body.

19. An antiviral shrink film manufacturing method comprising: preparing a base material laminated body by laminating the antiviral transfer sheet according to claim 7 on a shrink base material; preparing, by applying pressure and heat to the base material laminated body, a base material transfer body including a transfer layer transferred onto the shrink base material; and obtaining an antiviral shrink film by removing the base material sheet from the base material transfer body.

20. The antiviral shrink film according to claim 11, comprising a picture layer positioned between the shrink base material and the functional layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] FIG. 1 is a cross sectional view schematically illustrating a configuration of an antiviral transfer sheet.

[0033] FIG. 2 is a cross sectional view schematically illustrating a configuration of a transferred item which is obtained as a result of transferring an antiviral transfer sheet.

[0034] FIG. 3 is a cross sectional view schematically illustrating a configuration of an antiviral shrink film.

[0035] FIG. 4 is a figure schematically illustrating an antiviral shrink film manufacturing method.

DESCRIPTION OF THE EMBODIMENTS

[0036] In the following, an antiviral transfer sheet manufacturing method, antiviral transfer sheet, antiviral shrink film manufacturing method, and, antiviral shrink film according to embodiments of the present invention will be further described with reference to the drawings. In the drawing figures that will be referenced in the present description, some of the constituent elements may be schematically depicted in an exaggerated manner, for example, for facilitating an understanding of the present invention. Accordingly, the relative sizes, ratios and the like of the constituent elements may differ from those of an actual product. In addition, the sizes, materials, shapes, relative positions and the like of the members or portions described with reference to the examples of the present invention are not intended to limit the scope of the invention thereto unless otherwise specifically noted. The examples are merely illustrative examples.

[0037] In the present invention and the present description, the term antiviral is a general term for antiviral and antibacterial. The term antibacterial is also a general term for antiviral and antibacterial. Unless otherwise specifically noted, antiviral and antibacterial may each independently refer to both.

[0038] With reference to FIG. 1, an antiviral transfer sheet manufacturing method and a configuration and the like thereof will be described. An antiviral transfer sheet 11 may be referred to as a transfer sheet 11.

[0039] The transfer sheet 11 includes a transfer layer 32 disposed on one surface of a base material sheet 31. The transfer layer 32 includes a functional layer 37, a picture layer 38, and an adhesive layer 39. The functional layer 37 is disposed in contact with one surface 61 of the base material sheet 31. The functional layer 37 is disposed on the base material sheet 31. The adhesive layer 39 is disposed as an upper-most layer of the transfer layer 32. The adhesive layer 39 is disposed as an upper-most layer of the transfer sheet 11.

[0040] The functional layer 37 is located under the picture layer 38, and the adhesive layer 39 is located over the picture layer 38. The functional layer 37 and the picture layer 38 may contact each other. Between these layers, another layer may also be present. The picture layer 38 and the adhesive layer 39 may contact each other. Between these layers, another layer may be present.

[0041] The functional layer 37 includes an antiviral agent powder 33 and a hard coat agent 34. The antiviral agent powder 33 is a powder of an inorganic antiviral agent as will be described later.

[0042] An antiviral transfer sheet manufacturing method will be described. First, the antiviral agent powder 33 is disposed on the surface 61 of the base material sheet 31. The antiviral agent powder is disposed by applying a suspension of organic solvent containing the powder, and later removing the organic solvent. Alternatively, the antiviral agent powder may be disposed by applying a suspension of organic solvent containing the powder and a small amount of hard coat agent, and later removing the organic solvent.

[0043] Then, the hard coat agent 34 is positioned on the antiviral agent powder 33. By this operation, the functional layer 37 is formed. The hard coat agent may be positioned by various methods, such as coating, dispersing in mist, and printing.

[0044] Over the functional layer 37 thus formed, the picture layer 38 and the adhesive layer 39 are laminated in that order. The picture layer 38 and the adhesive layer 39 may be formed by the same method as the method by which a picture layer and an adhesive layer of a known transfer sheet are formed. The picture layer 38 of the transfer sheet 11 is a selective constituent element. The picture layer 38 may or may not be provided. Between the functional layer 37 and the picture layer 38, between the picture layer 38 and the adhesive layer 39, or between the functional layer and the adhesive layer, an anchor layer and the like may be provided as needed.

[0045] By transferring the transfer sheet 11 thus manufactured onto a transferred base material, a transferred item can be provided with antiviral property.

[0046] FIG. 2 is a schematic cross sectional view of a transferred item 22 manufactured by transferring the transfer sheet 11 onto a transferred base material 21. Referring to FIG. 2, the adhesive layer 39 is in contact with the transferred base material 21. On the adhesive layer 39, the picture layer 38 is present. On the picture layer 38, the functional layer 37 is present. The picture layer provides the transferred item 22 with an appeal deriving from a picture.

[0047] When the picture layer is absent, the design of the upper layer of the transferred base material is observed even on the transferred item through the transfer layer. If the transfer layer is black and the like and does not transmit light, for example, the transferred item has the appearance of the transfer layer per se.

[0048] The functional layer 37 is positioned in the upper-most layer of the transferred item 22. An exposed surface 62 of the functional layer 37 is in contact with the external environment.

[0049] The antiviral agent powder 33 of the functional layer 37 exerts its function when exposed. If the antiviral agent powder is buried in the functional layer 37, the function will not be exerted. The function will not be exerted, either, if the antiviral agent powder is positioned in the vicinity of the rear surface (on the opposite side from the exposed surface 62) of the functional layer 37.

[0050] The exposed surface 62 of the transferred item 22 is a surface derived from a boundary surface 35 of the functional layer in the antiviral transfer sheet 11.

[0051] The localized presence state of the antiviral powder in the functional layer 37 will be described. The area ratio of the antiviral agent powder to the area of the boundary surface 35 expressed in percentage is defined as a contact-effective powder-occupied percentage. The definition and method for calculating the contact-effective powder-occupied percentage will be described in the following.

[0052] Among the individual particles of the antiviral agent powder 33, the particles of which a part of the particle surface is in contact with the boundary surface 35 are defined as contact-effective powder particles. The boundary surface 35 of the functional layer is a surface via which the functional layer 37 contacts the surface 61 of the base material sheet 31. Further, the area of the boundary surface which is in contact with the contact-effective powder particles will be referred to as independent contact area. The independent contact area is denoted as AR-T.

[0053] A certain section of the boundary surface 35 will be considered. The certain section is a single continuous surface. For example, the certain section is a section demarcated by a single square drawn on the boundary surface 35. The area of the certain section is referred to as AROBS.

[0054] Suppose the number of the contact-effective powder particles present in the certain section is n. A total of n individual independent contact areas AR-T is calculated to determine a total contact area. The total contact area will be referred to as AR-T.

[0055] The contact-effective powder-occupied percentage, referred to as OCC-T %, is expressed by the following expression (1).

OCC-T %=AR-T/AROBS100(1)

[0056] However, because the antiviral powder particles are fine, it is difficult to accurately measure the independent contact area. It is also difficult to accurately calculate the contact-effective powder-occupied percentage. Accordingly, the contact-effective powder-occupied percentage is determined by a simplified method as will be described below.

[0057] By transferring the antiviral transfer sheet onto the transferred base material, a transferred specimen is prepared. In the transferred specimen, the boundary surface of the transfer sheet is positioned on the upper-most layer. Accordingly, the boundary surface is exposed.

[0058] A magnified image of the exposed surface is obtained using a scanning electron microscope. In the magnified image, a square with a side of 700 nm (nanometers) in actual size in the specimen is considered to be an observation object. Each of two mutually perpendicular sides of the square as the observation object is divided into 17 parts. Lines are drawn from the division points to divide the observation object square into 289 small sections. Each of the small sections is a square.

[0059] The small sections are observed. Then, the contact area of the contact-effective powder particles present in the small section, and the area of the small section are compared. In this way, the contact area in the small section is determined on a scale of 11 levels of 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, and 0. Specifically, if the contact surface (area) extends throughout the surface of the small section, the small section is determined to have a determination value of 1. If the contact area is one half the small section area, the small section is determined to have a determination value of 0.5. If there is no contact surface (area) in the small section, the small section is determined to have a determination value of 0.

[0060] All of the 289 small sections are observed. By making the determination for all of the small sections, determination values are given. Thereafter, the total value of the 289 determination values is calculated according to the following expression (2).

contact-effective powder-occupied percentage=total value of determination values/289100(2)

[0061] On the exposed surface (the surface derived from the boundary surface 35) of the transferred specimen, the contact-effective powder-occupied percentages for three different observation object squares are calculated. The length of a side of each of the observation object squares is 700 nm (nanometers) in actual size of the transferred specimen. Three calculated values are obtained. Then, an average value of the three calculated values is determined. The average value is defined as the contact-effective powder-occupied percentage of the antiviral transfer sheet.

[0062] In the antiviral transfer sheet according to the present invention, the contact-effective powder-occupied percentage according to the simplified method (determined according to expression (2)) is not less than 50% and not more than 80%.

[0063] By the above-described simplified method, a magnified image of the boundary surface may be obtained through the base material sheet of the antiviral transfer sheet. Then, in the magnified image, the contact-effective powder-occupied percentage may be calculated by the same determination method from an observation object square with a side of 700 nm (nanometers) in actual size.

[0064] Thus, the antiviral agent powder particles 33 are positioned in the functional layer in a state such that a number of the particles can exert their antiviral capability. In the transfer layer after transfer, the amount of antiviral agent powder required to exert antiviral power of certain capability is decreased. For the same reason, as the amount of antiviral agent powder included in the functional layer decreases, the transparency of the functional layer can be maintained in an appropriate range.

[0065] Meanwhile, the contact-effective powder particles are partly surrounded by the hard coat agent, whereby the contact-effective powder particles are strongly fixedly attached to the functional layer. Accordingly, the functional layer after transfer is placed on the upper layer of the article. As a result, even when the exposed surface 62 is contacted by a human finger and the like, the antiviral agent powder will not fall off.

[0066] Gaps of the antiviral agent powder are filled with the hard coat agent. Accordingly, the surface of the functional layer 37, i.e., the exposed surface 62 of the transferred item 22, is smooth. The functional layer has a total light transmittance of not less than 88%, and a haze of not more than 3%.

[0067] The total light transmittance is measured in accordance with JIS K 7361 (testing method for total light transmittance of plastic-transparent materials). Haze is measured in accordance with JIS K 7136 (method for determining the haze of plastic-transparent materials).

[0068] Using the antiviral transfer sheet, an antiviral molded article may be manufactured according to an in-mold injection molding process. The antiviral transfer sheet may also be transferred onto the transferred base material using a transfer machine, such as a roll transfer machine or an up-down transfer machine. Examples of the transferred base material include resin molded articles, shrink base materials, rubber products, metal products, wood products, glass products, and composite products of ceramics products or various materials.

[0069] An in-mold injection molding process will be described. First, the antiviral transfer sheet is installed in molding dies. The antiviral transfer sheet is aligned in a direction such that the base material sheet faces the die cavity surface.

[0070] Then, the dies are closed, and molten resin is filled into the cavity of the dies so that the molten resin contacts the adhesive layer of the antiviral transfer sheet. As a result, the molten resin is molded, while the antiviral transfer sheet is adhered onto the surface of the injection molding. After the resin is cooled or allowed to cool, the dies are opened and the injection molding is extracted where the transfer layer is adhered to the surface of the injection molding. Thereafter, the base material sheet is removed from the injection molding.

[0071] A method for manufacturing the antiviral shrink film and a configuration thereof, for example, will be described. The antiviral shrink film manufacturing method is a manufacturing method involving a transfer of the antiviral transfer sheet onto the shrink base material. The antiviral transfer sheet includes an antiviral transfer sheet according to the present invention, and an antiviral transfer sheet manufactured by the antiviral transfer sheet manufacturing method according to the present invention. The antiviral shrink film 1 may be referred to as the shrink film 1 for short.

[0072] FIG. 4 is a figure schematically illustrating the antiviral shrink film manufacturing method. The transfer sheet 11 is laminated on one surface of the shrink base material 26 to make a base material laminated body 44. In the base material laminated body 44, the shrink base material 26 and the transfer layer 32 of the transfer sheet 11 face each other. In the base material laminated body 44, the adhesive layer contacts the shrink base material 26.

[0073] The base material laminated body 44 is passed between a press-heat roll 51 and a backing roll 52. During the passage, part of the heated molten resin of the adhesive layer 39 is melted and then solidified, whereby a boundary surface 40 between the surface of the shrink base material 26 and the adhesive layer 39 is fused. In this way, a base material transfer body 45 including the shrink base material 26 and the transfer sheet 11 is prepared.

[0074] By removing the base material sheet 31 from the base material transfer body 45, the shrink film 1 is obtained.

[0075] The temperature condition during transfer is normally 170 C. to 210 C. and preferably 180 C. to 200 C. When the temperature is in this range, the resin of the adhesive layer sufficiently melts. Accordingly, satisfactory transfer can be performed. In addition, the shrink-processability of the shrink base material can be left in the shrink film 1.

[0076] The pressure condition during transfer is normally 0.3 MPa to 1.2 MPa and preferably 0.4 MPa to 0.8 MPa. When the pressure is in this range, satisfactory heat conduction can be obtained. As a result, the resin of the adhesive layer can be melted to an appropriate degree, and satisfactory transfer can be performed. In addition, the shrink-processability of the shrink base material can be left in the shrink film 1.

[0077] The time of application of press-heating can be expressed by the relative speed of movement of the laminate and the press-heat roll. The application time is 0.5 m/min to 4.0 m/min. If the speed is less than 0.5 m/min, the shrink-processability of the manufactured shrink film 1 may deteriorate. If the speed is more than 4.0 m/min, heat conduction may be decreased. As a result, the resin of the adhesive layer may fail to be sufficiently melted, and transfer failure may be caused.

[0078] The shrink film 1 manufactured according to the manufacturing method of the present invention was covered on a door knob. This was followed by a process of blowing hot air. The shrink film was shrunk so as to conform to the shape of door knob, whereby the shrink film was mounted on the door knob. Even when the press-heat processing for transferring the transfer sheet 11 onto the shrink base material 26 is performed, the shrink-processability of the shrink base material 26 is left in the shrink film 1.

[0079] Referring to FIG. 3, the adhesive layer 39 is positioned in the shrink film 1 according to the present invention in such a way as to adjoin one surface of the shrink base material 26. On the adhesive layer 39, the picture layer 38 is positioned, and further on the picture layer 38, the functional layer 37 is positioned. The picture layer 38 of the shrink film 1 according to the present invention is a selective constituent member. Accordingly, the picture layer 38 may or may not be present.

[0080] When the picture layer is provided, the mounted body of the shrink film 1 is provided with an appeal derived from the picture. On the other hand, when the picture layer is absent, the original appearance of the mounted body of the shrink film 1 is retained.

[0081] The functional layer 37 is positioned in the upper layer of the shrink film 1. The exposed surface 41 of the functional layer 37 is in contact with the external environment. The exposed surface 41 is one surface of the shrink film 1. The exposed surface 41, when the shrink film 1 is mounted on the mounted body, is also the face positioned on the surface of the mounted body. The other surface of the shrink film 1 is a face in contact with the external environment of the shrink base material.

[0082] The functional layer 37 includes the antiviral agent powder 33 and the hard coat agent 34. The antiviral agent powder 33 is locally present in the vicinity of the exposed surface 41 in contact with the external environment.

[0083] The localization of the antiviral agent powder 33 in the functional layer 37 of the shrink film 1 will be described. The area ratio of the antiviral agent powder to the area of the exposed surface 41 expressed in percentage is defined as an effective exposed powder-occupied percentage. The definition and a method for calculating the effective exposed powder-occupied percentage will be described.

[0084] Among the individual particles of the antiviral powder 33, the particles of which the particle surface is partly exposed on the exposed surface 41 are defined as effective exposed powder particles. The exposed surface 41 is the surface of the functional layer 37 that is in contact with the external environment. In addition, the area of the exposed surface in which the effective exposed powder particles are exposed is defined as an independent exposed area. The independent exposed area is referred to as AR-E.

[0085] A certain section of the exposed surface 41 is considered. The certain section is a single continuous surface. For example, the certain section is a section demarcated by a single square drawn on the exposed surface 41. The certain section has an area AROBS.

[0086] The number of effective exposed powder particles in the certain section is expressed by n. A total of n individual independent exposed areas AR-E is calculated, and a total exposed area is determined. The total exposed area is expressed by AR-E.

[0087] When the effective exposed powder-occupied percentage is referred to as OCC-E %, the percentage is expressed by the following expression (3).

OCC-E %=AR-E/AROBS100(3)

[0088] However, because the antiviral powder particles are fine, it is difficult to accurately measure the independent exposed area. It is also difficult to accurately calculate the exposed-effective powder-occupied percentage. Accordingly, the exposed-effective powder-occupied percentage is determined by a simplified method as will be described below.

[0089] A magnified image of the surface of the antiviral shrink film is obtained using a scanning electron microscope. The surface is an exposed surface of the functional layer. In the magnified image, a square with a side of 700 nm (nanometers) in actual size of the shrink film in the specimen is considered to be an observation object. Each of two mutually perpendicular sides of the square as the observation object is divided into 17 parts. Lines are drawn from the division points to divide the observation object square into 289 small sections. Each of the small sections is a square.

[0090] The small sections are observed. Then, the exposed area of the exposed-effective powder particles present in the small section, and the area of the small section are compared. In this way, the exposed area in the small section is determined on a scale of 11 levels of 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, and 0. Specifically, if the exposed surface (area) extends throughout the surface of the small section, the small section is determined to have a determination value of 1. If the exposed area is one half the small section area, the small section is determined to have a determination value of 0.5. If there is no exposed surface (area) in the small section, the small section is determined to have a determination value of 0.

[0091] All of the 289 small sections are observed. By making the determination for all of the small sections, determination values are given. Thereafter, the total value of the 289 determination values is calculated according to the following expression (4).

contact-effective powder-occupied percentage=total value of determination values/289100(4)

[0092] On the exposed surface 41 of the antiviral shrink film, the exposed-effective powder-occupied percentages for three different observation object squares are calculated. The length of a side of each of the observation object squares is 700 nm (nanometers) in actual size of the transferred specimen. Three calculated values are obtained. Then, an average value of the three calculated values is determined. The average value is defined as the exposed-effective powder-occupied percentage of the antiviral shrink film.

[0093] In the antiviral shrink film according to the present invention, the exposed-effective powder-occupied percentage according to the simplified method (determined according to expression (4)) is not less than 50% and not more than 80%.

[0094] Thus, the antiviral agent powder particles 33 are positioned in the functional layer in a state such that a number of the particles can exert their antiviral capability in the antiviral shrink film 1. Accordingly, in the antiviral shrink film 1, the amount of antiviral agent powder required to exert antiviral power of certain capability is decreased. For the same reason, as the amount of antiviral agent powder included in the functional layer decreases, the transparency of the functional layer can be maintained in an appropriate range.

[0095] Meanwhile, the exposed-effective powder particles are partly surrounded by the hard coat agent, whereby the exposed-effective powder particles are strongly fixedly attached to the functional layer. Accordingly, the antiviral shrink film 1 is placed on the upper layer of the article. As a result, even when the exposed surface 41 is contacted by a human finger and the like, the antiviral agent powder will not fall off.

[0096] The exposed surface of the functional layer 37 is smooth. That is, the surface of the shrink film 1 is smooth, and therefore the surface of the shrink film mounted body is smooth.

[0097] The materials of the layers and a method for forming the same and the like will be described.

<Inorganic Antiviral Agent>

[0098] Examples of the inorganic antiviral agent include photocatalyst materials, metal ions in which metal ion is carried on an ion exchanger, and antibacterial ceramics.

[0099] Examples of the photocatalyst material include oxides such as titanium oxide, tin oxide, tungsten oxide, iron oxide, zinc oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, rhenium oxide, and zirconium oxide; oxides of a plurality of metals therefrom; and metal oxides doped with nitrogen or a metal ion. Other examples include metal oxides on a surface of which a co-catalyst, such as a metal or a metal salt, is carried. Further examples include metal oxides having a surface on which a photosensitization dye or the like is carried.

[0100] An ion exchanger carrying a metal ion will be described.

[0101] Examples of the metal ion include silver ion, copper ion (II), and zinc ion. Examples of the ion exchanger include silicate carriers, such as zeolite (crystalline aluminosilicate), silica gel, and clay minerals; phosphate-based carriers such as zirconium phosphate and calcium phosphate; soluble glass; activated charcoal; metal carriers; and organic metals.

[0102] A metal ion may be carried on the ion exchanger by the following method, for example. First, the ion exchanger is immersed in an aqueous solution of the metal ion under a predetermined pH condition at a predetermined temperature for a predetermined time, thereby substituting some or all of ion-exchangeable ions in the ion exchanger with the metal ion. After completion of the ion exchange, the ion exchanger is washed with water and dried by heating.

[0103] The composition of antibacterial ceramics is expressed by Ag-Cau Znv Alw (PO4)X (OH) Y. Examples of crystalline antibacterial ceramics include silver zirconium phosphate, silver tripolyphosphate aluminum, silver hydroxyapatite, and silver phosphate tricalcium. Examples of non-crystalline antibacterial ceramics include silver phosphate glass and silver phosphate double salt ceramics.

[0104] As the inorganic antiviral agent, a powder with a particle size of 1 nm to 400 nm (nanometers) is used. As the titanium oxide, a powder with a particle size of 1 nm to 400 nm is used. As the cuprous oxide (copper oxide (I): Cu.sub.2O), a powder with a particle size of 1 nm to 400 nm is used.

[0105] Among the inorganic antiviral agents, titanium oxide is preferable. Rutile-type titanium oxide decreases transparency. Accordingly, anatase type is more preferable.

[0106] Even more preferably, cuprous oxide (copper oxide (I): Cu.sub.2O) is mixed in titanium oxide. As the cuprous oxide, preferably, a powder which is surface-treated for oxidation resistance is used.

[0107] The mixing ratio of titanium oxide and cuprous oxide is preferably 45:55 to 75:25 (parts by weight). This is because if the titanium oxide ratio is greater than 75 parts by weight, antiviral property is insufficient. Also, if the cuprous oxide ratio is greater than 55 parts by weight, the haze value (% value) is increased.

[0108] The amount of inorganic antiviral agent is preferably not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 (square meters) area of the antiviral transfer sheet. This is so that antiviral property can be exerted, and the total light transmittance can be in a practical range. The 1 m.sup.2 area of the antiviral transfer sheet is equal to the 1 m.sup.2 area of the functional layer.

[0109] When a mixture of titanium oxide and cuprous oxide is used as the inorganic antiviral agent, the amount of the mixture is preferably not less than 0.01 g and not more than 0.03 g per 1 m.sup.2 area of the antiviral transfer sheet. This is because if less than 0.01 g/m.sup.2, antiviral property is insufficient. If greater than 0.03 g/m.sup.2, the total light transmittance becomes less than 88%.

<Hard Coat Agent>

[0110] The hard coat agent is an active energy-ray curable resin that is curable with ultraviolet ray, electron beam and the like, as represented by a photo-curable resin such as ultraviolet ray curable resin, or a radiation curable resin such as electron beam curable resin. The hard coat agent may be a thermally curable and active energy-ray curable resin. Examples of the active energy-ray curable resin include urethane acrylate resins and cyanoacrylate resins. An example of the thermally curable and active energy-ray curable resin is a resin obtained by adding an additive such as isocyanate into urethane acrylate resin or cyanoacrylate resin. By heating the thermally curable and active energy-ray curable resin, some of the monomers or oligomers in the resin are cross-linked, whereby the resin is half-cured. The half-cured hard coat layer becomes cured by being irradiated with active energy ray such as ultraviolet ray.

[0111] When a thermally curable and active energy-ray curable hard coat agent is used commonly in the antiviral transfer sheet manufacturing method according to the present invention and the antiviral shrink film manufacturing method according to the present invention, heating may be performed for half-curing and then active energy ray irradiation may be performed for full-curing. When an active energy-ray curable hard coat agent is used, a small amount of active energy ray irradiation may be performed for half-curing, and then active energy ray irradiation may be again performed for full-curing.

[0112] Among the hard coat agents, an ultraviolet ray curable resin and a thermally curable and ultraviolet ray curable resin are preferable. This is because of easy access to inexpensive equipment (tools) for the curing operation, ease of curing operation. This is also because, from the viewpoint of the transfer sheet, transferred item, and shrink film 1, of high transparency of the functional layer and easy penetration of ultraviolet ray.

[0113] The hard coat agent in the transfer sheet manufactured by the manufacturing method of the present invention may be cured at any stage of the manufacturing process. That is, the hard coat agent may be cured in any of the following stages (1) to (3).

(1) After formation of the functional layer during manufacture of the transfer sheet
(2) After manufacture of the transfer sheet
(3) After transfer of the transfer layer of the transfer sheet onto the transferred item 21

[0114] Preferably, curing is performed after the press-heat transfer processing, i.e., stage (3). More preferably, half-curing is performed in stage (1) and full-curing is performed in stage (3).

[0115] In the antiviral shrink film manufacturing method according to the present invention, the hard coat agent may be cured in any manufacturing stage. That is, the hard coat agent may be cured in any of the following stages (1) to (4).

(1) After formation of the functional layer during manufacture of the transfer sheet
(2) After manufacture of the transfer sheet
(3) After manufacture of the shrink film
(4) After the shrink film is shrunk and mounted on the mounted body

[0116] Preferably, curing is performed after the press-heat transfer processing, i.e., in stage (3) or (4). More preferably, half-curing is performed in stage (1), and full-curing is performed in stage (3) or (4).

<Base Material Sheet>

[0117] As the material of the base material sheet, materials having releasable property as a base material sheet may be used. Examples include resin sheets of polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, and polyvinyl chloride resin; metal foils such as aluminum foil and copper foil; cellulose sheets such as glassine paper, coated paper, and cellophane; and composite materials of the above sheets.

<Picture Layer>

[0118] Among the material of the picture layer, resins such as polyvinyl resins, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, or alkyd resin may be used as a binder. A coloring ink containing an appropriate color of pigment or dye as a coloring agent may be used. For a metallic color, metal particles of aluminum, titanium, bronze and the like, or a pearl pigment obtained by coating mica with titanium oxide may be used. Examples of the method for forming the picture layer include printing processes such as offset printing, gravure printing, and screen printing.

[0119] The picture layer may be formed of a metal thin film of aluminum, tin, copper and the like. In this case, the forming method may include metal evaporation, sputtering, or ion beam method.

<Adhesive Layer>

[0120] For the adhesive layer, a resin having appropriate thermosensitivity or pressure sensitivity for the type of the transferred item or shrink base material is used. For example, when the transferred base material is PC or polystyrene (PS) resin, the adhesive layer may use PMMA, PS, PA, or polyolefin resin having affinity with the PC or PS resin. For example, when the shrink base material is polystyrene (PS) resin, the adhesive layer may use PMMA, PS, PA, or polyolefin resin having affinity with the PS resin. Examples of the method for forming the adhesive layer include gravure coating, roll coating, comma coating, gravure printing, screen printing, and offset printing.

<Release Layer>

[0121] As needed, a release layer may be formed between the base material sheet and the functional layer. The release layer is a layer that is removed from the transferred item or shrink film together with the base material sheet when the base material sheet is peeled after transfer. Examples of the material of the release layer include melamine resin-based mold release agent, silicone resin-based mold release agent, fluorine resin-based mold release agent, cellulose derivative-based mold release agent, urea resin-based mold release agent, polyolefin resin-based mold release agent, paraffin-based mold release agent, and composite mold release agent thereof. Examples of the method for forming the release layer include coating methods such as roll coating and spray coating; gravure printing; and screen printing.

<Shrink Base Material>

[0122] The shrink base material is manufactured by molding a resin or rubber, such as polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-propylene copolymer, ionomer, polypropylene, polystyrene, polyester, fluorine resin, hydrochloride rubber, silicone rubber, EPDM, chloroprene rubber, and nitrile-butadiene rubber, into film shape. After the film is molded, normally the molded film is stretched in a single-axis direction or double-axis directions, and then thermally set. The stretching may be performed by stretch blow molding or stretch inflation molding under a temperature condition such that orientation is exerted, simultaneously with the molding of the film.

[0123] An embodiment of the present invention has been described with reference to the drawings. However, specific configuration examples are not limited to the embodiment. The present invention may include design modifications and the like without departing from the gist of the present invention.

Example 1

[0124] A transfer sheet was fabricated. Transfer was performed by in-mold injection molding. An antiviral molded article was prepared. The antiviral property, total light transmittance, and haze of the antiviral molded article were measured.

[0125] The transfer sheet manufacturing method and the like were as follows.

[0126] Base material sheet: PET film, thickness 50 m (micrometers) Antiviral agent: Mix powder of 60 parts by weight of TiO.sub.2 powder and 40 parts by weight of Cu.sub.2O powder

[0127] TiO.sub.2 powder (white powder) had a primary particle size of 15 nm. Cu.sub.2O powder (brownish-red powder) had a primary particle size of 50 nm.

[0128] Hard coat agent: Urethane acrylate-based ultraviolet ray cure resin

[0129] Molding resin: Acrylic resin

[0130] Molded article size: 50 mm50 mm1 mm

[0131] Molten resin temperature: 240 C. to 260 C.

[0132] Onto the base material sheet, a suspension including antiviral agent, methyl ethyl ketone, and a small amount of hard coat agent was applied by an amount such that the antiviral agent was 0.02 g/m.sup.2. Then, methyl ethyl ketone was removed. From over the antiviral agent, the hard coat agent was applied in a layer shape having a dry thickness of 5.5 Thereafter, an anchor agent was applied onto the half-cured hard coat agent. The adhesive layer was fabricated by gravure printing using polyolefin resin. Thereafter, ultraviolet ray irradiation was performed to cure the hard coat agent.

[0133] Between the sample numbers 8, 9, and 10 and 11, 12, and 13, the mixing ratio (parts by weight) of the TiO.sub.2 powder and Cu.sub.2O powder added as the antiviral agent was changed.

[0134] The functional layer with sample number 1 was formed without adding the antiviral agent.

[0135] In the comparative example, the suspension was fabricated by mixing the antiviral agent and hard coat agent of the amounts indicated in a table in advance. The functional layer was formed by applying the suspension.

[0136] Antiviral property was evaluated in accordance with JIS R 1756 (visible light responsive photocatalyst viral testing method). As a light condition, illuminance was set at 1000 lx by cutting ultraviolet rays of 400 nm or below included in the light of a white fluorescent lamp by means of a N113 filter.

[0137] The test was conducted by the following method. First, a sample with attached bacteriophage virus was optically irradiated for two hours. From the sample, virus was collected using a SCDLP solution. Escherichia coli infected with the virus that was appropriately diluted were applied to an agar medium. The number of colonies after cultivation was counted. Then, the inactivation degree was calculated for evaluation.

[0138] As the inactivation degree calculation formula, the following expression was used.

(inactivation degree)=(logarithm of bacteriophage infectivity titer after test)(logarithm of initial bacteriophage infectivity titer)

[0139] The total light transmittance measurement was performed in accordance with JIS K 7361 (method for testing total light transmittance of plastic-transparent materials). For the measurement, the NDH 5000 haze meter (from Nippon Denshoku Industries Co., Ltd) was used.

[0140] Haze measurement was performed in accordance with JIS K 7136 (method for determining haze of plastic-transparent materials). The measurement was performed using the NDH 5000 haze meter (from Nippon Denshoku Industries Co., Ltd).

[0141] Measurement results are shown in Table 1.

[0142] In the overall evaluation, antiviral property of 2.0 or below was evaluated as being acceptable. Total light transmittance of 88.0% or more was also evaluated as being acceptable. Haze of 3.0% or below was also evaluated as being acceptable.

TABLE-US-00001 TABLE 1 Amount of Titanium Anti- Total light Overall Sample antiviral copper viral transmit- Haze evalu- number agent g/m.sup.2 ratio property tance % % ation 1 0 None 0.2 92.0 1.1 Poor 8 0.02 50/50 3.9 91.2 2.2 Good 9 0.02 60/40 2.2 91.3 2.3 Good 10 0.02 70/30 1.4 91.4 1.8 Poor 11 0.04 50/50 4.8> 89.9 4.0 Poor 12 0.04 60/40 4.8> 89.6 3.9 Poor 13 0.04 70/30 4.8> 90.0 3.3 Poor Compar- 0.02 60/40 0.3 91.3 2.6 Poor ison-1 Note 1: Titanium copper ratio indicates TiO.sub.2/Cu.sub.2O (weight ratio). Note 2: The value 4.8> of antiviral property indicates measurement limit.

[0143] Sample numbers 8 and 9 provided the results indicating high antiviral property and large total light transmittance (% value). In Table 1, the antiviral property measurement value 4.8> indicates that, because the antiviral property was not measurable in the actually performed experiment, the measurement value was determined to be not more than a measurement limit value of 4.8. The same applies to Table 4.

Example 2

[0144] Using the antiviral molded articles prepared in Example 1, the antibacterial property of the antiviral molded article was measured. The antiviral molded articles used for measurement included sample number 1 and sample number 9. In the paragraphs describing Example 2, the term antibacterial property literally means antibacterial property. The term antibacterial property does not mean antiviral property.

[0145] The antibacterial property measurement was performed in accordance with JIS-R-1756 (method for testing antiviral property of visible light responsive photocatalysts). As a light condition, illuminance was set to 1000 lx by cutting ultraviolet rays of 380 nm or below included in light of a white fluorescent lamp by means of an N169 filter.

[0146] The test was conducted by the following method. First, 50 L (microliters) of the sample was irradiated with light for 24 hours while a bacterial liquid of Staphylococcus aureus was added dropwise thereto. From the sample, Staphylococcus aureus was collected using a SCDLP solution. The collected liquid was mixed in an NB medium. The number of colonies after cultivation was counted for evaluation.

[0147] As an antibacterial activity value calculation formula, the following expression was used.

(antibacterial activity value)=(logarithm of Staphylococcus aureus in sample after test)(logarithm of Staphylococcus aureus on glass plate after test)

TABLE-US-00002 TABLE 2 Amount of antiviral agent Titanium Antibacterial Sample number g/m.sup.2 copper ratio property Evaluation 1 0 None 0.7 Poor 9 0.02 60/40 4.8> Good Note 1: Titanium copper ratio indicates TiO.sub.2/Cu.sub.2O (weight ratio). Note 2: The value 4.8> of antiviral property indicates measurement limit.

[0148] In Table 2, the antibacterial property measurement value 4.8> indicates that, because the antibacterial property was not measurable in the actually performed experiment, the measurement value was determined to be not more than a measurement limit value of 4.8. The same applies to Table 5.

Example 3

[0149] The antiviral shrink film 1 was fabricated by fabricating the transfer sheet 11, analyzing the transfer condition, and performing transfer onto the shrink base material. The shrink-processability of the film was evaluated.

[0150] The manufacturing method and the like of the transfer sheet were as follows.

[0151] Base material sheet: PET film, thickness 50 m

[0152] Antiviral agent: Mixed powder of 60 parts by weight of TiO.sub.2 powder and 40 parts by weight of Cu.sub.2O powder

[0153] The TiO.sub.2 powder (white powder) had a primary particle size of 15 nm. The Cu.sub.2O powder (brownish-red powder) had a primary particle size of 50 nm.

[0154] The shrink base material was a dual-axis stretched polystyrene sheet having a thickness of 60 m, and exhibited, upon heating at 100 C. for 10 seconds, a thermal shrinkage in the MD direction of 14% and a thermal shrinkage in the TD direction of 75%. The thermal shrinkage was determined according to the following expression.

Thermal shrinkage (%)=100(pre-heating lengthpost-heating length)/pre-heating length

[0155] Hard coat agent: Urethane acrylate-based ultraviolet ray cure resin

[0156] Onto the base material sheet, a suspension including antiviral agent, methyl ethyl ketone, and a small amount of hard coat agent was applied by an amount such that the antiviral agent was 0.02 g/m.sup.2. Then, methyl ethyl ketone was removed. From over the antiviral agent, the hard coat agent was applied in a layer shape having a dry thickness of 5.5 m. Thereafter, an anchor agent was applied onto the half-cured hard coat agent. The adhesive layer was fabricated by gravure printing using polyolefin resin. Thereafter, ultraviolet ray irradiation was performed to cure the hard coat agent.

[0157] The transfer was performed by applying pressure and heat using a press-heat roll from above the shrink base material and transfer film placed overlapping with each other on a stage. The temperature of the press-heat roll was 186 C.

[0158] The transfer degree was measured by changing the movement speed, pressure, and number of times of press-heat application (number of times of passage between the stage and the roll) of the press-heat roll. The transfer degree was measured in percentage through visual observation of the degree of the transfer layer region present on the antiviral shrink film after the base material sheet had been removed.

[0159] The completed antiviral shrink film was wound on a door knob. The antiviral shrink film was heated at 170 C. for 2 minutes to perform shrink processing. The processability of the antiviral shrink film was evaluated visually in terms of either OK (good) or not OK (poor).

[0160] Table 3 shows the experiment results of transfer condition analysis and shrink-processability.

TABLE-US-00003 TABLE 3 Transfer Number of Sample speed times of Pressure Transfer number m/min transfer Mpa degree % Processability 21 2.1 1 0.55 100 Good 22 2.1 2 0.55 100 Poor 23 2.1 3 0.55 100 Poor 24 2.1 5 0.55 100 Poor 25 3.4 1 0.55 100 Good 26 3.4 1 0.26 70 Good 27 3.4 1 0.37 100 Good 28 3.4 1 0.77 100 Good 29 4.7 1 0.55 5 Good 30 9.9 1 0.55 0 Good Note 1: Transfer degree of 0% indicates absence of transfer.

[0161] Even when the transfer processing involving the application of press-heat was performed, shrink-processability was good. As the number of times of transfer was increased, shrink-processability decreased.

Example 4

[0162] The antiviral shrink film 1 was fabricated by fabricating the transfer sheet 11 and performing transfer onto the shrink base material. The antiviral property, total light transmittance, and haze of the antiviral shrink film were measured.

[0163] The base material sheet, TiO.sub.2 powder and Cu.sub.2O powder of the antiviral agent, hard coat agent, and adhesive used in Example 4 were the same as those used in Example 1.

[0164] Between sample numbers 8, 9, 10, 11, 12, and 13, the mixing ratio (parts by weight) of the TiO.sub.2 powder and Cu.sub.2O powder added as the antiviral agent was changed.

[0165] With regard to the transfer condition, the press-heat roll temperature was 186 C., pressure was 0.55 Mpa, and transfer speed was 3.4 m/min.

[0166] The functional layer of sample number 1 was formed without adding the antiviral agent.

[0167] The functional layer of comparison-1 was formed by applying a suspension prepared by mixing in advance the antiviral agent and hard coat agent of the amounts indicated in the table.

[0168] The methods of evaluation of antiviral property and testing, inactivity degree calculation formula, total light transmittance measurement, and haze measurement were the same as those of Example 1.

[0169] The measure results are shown in Table 4.

[0170] For comprehensive evaluation, antiviral property of 2.0 or below was evaluated as being acceptable. Total light transmittance of 88.0% or above was evaluated as being acceptable. Haze was not considered in the comprehensive evaluation.

TABLE-US-00004 TABLE 4 Amount of Titanium Anti- Total light Overall Sample antiviral copper viral transmit- Haze evalu- number agent g/m.sup.2 ratio property tance % % ation 1 0 None 0.2 89.8 2.8 Poor 8 0.02 50/50 3.8 89.1 5.7 Good 9 0.02 60/40 2.5 89.1 5.9 Good 10 0.02 70/30 1.5 89.2 4.6 Poor 11 0.04 50/50 4.8> 87.8 10.3 Poor 12 0.04 60/40 4.8> 87.5 10.0 Poor 13 0.04 70/30 4.8> 87.9 8.5 Poor Compar- 0.02 60/40 0.3 89.1 6.7 Poor ison-1 Note 1: Titanium copper ratio indicates TiO.sub.2/Cu.sub.2O (weight ratio). Note 2: The value 4.8> of antiviral property indicates measurement limit.

[0171] For sample numbers 8 and 9, the results indicating high antiviral property and large total light transmittance (% value) were obtained.

Example 5

[0172] Using the antiviral shrink film 1 prepared in Example 4, the antibacterial property of the antiviral shrink film 1 was measured. The antiviral shrink film 1 used for measurement included sample number 1 and sample number 9. In the paragraphs describing Example 5, the term antibacterial property literally means antibacterial property. The term antibacterial property does not mean antiviral property.

[0173] Antibacterial property measurement and testing methods, and antibacterial activity value calculation formula were the same as those of Example 2.

TABLE-US-00005 TABLE 5 Amount of antiviral agent Titanium Antibacterial Sample number g/m.sup.2 copper ratio property Evaluation 1 0 None 0.6 Poor 9 0.02 60/40 4.8> Good Note 1: Titanium copper ratio indicates TiO.sub.2/Cu.sub.2O (weight ratio). Note 2: The value 4.8 > of antiviral property indicates measurement limit.

LIST OF REFERENCE NUMERALS

[0174] 1 Antiviral shrink film [0175] 11 Antiviral transfer sheet [0176] 21 Transferred base material [0177] 22 Transferred item [0178] 26 Shrink base material [0179] 31 Base material sheet [0180] 32 Transfer layer [0181] 33 Antiviral agent powder [0182] 34 Hard coat agent [0183] 35 Functional layer boundary surface [0184] 37 Functional layer [0185] 38 Picture layer [0186] 39 Adhesive layer [0187] 40 Boundary surface [0188] 41 Exposed surface [0189] 44 Base material laminated body [0190] 45 Base material transfer body [0191] 51 Press-heat roll [0192] 52 Backing roll [0193] 61 Surface (of base material sheet) [0194] 62 Exposed surface