WO2016084774A1 - 抗ウイルス性転写シートとその製造方法及び抗ウイルス性シュリンクフィルムとその製造方法 - Google Patents
抗ウイルス性転写シートとその製造方法及び抗ウイルス性シュリンクフィルムとその製造方法 Download PDFInfo
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- WO2016084774A1 WO2016084774A1 PCT/JP2015/082862 JP2015082862W WO2016084774A1 WO 2016084774 A1 WO2016084774 A1 WO 2016084774A1 JP 2015082862 W JP2015082862 W JP 2015082862W WO 2016084774 A1 WO2016084774 A1 WO 2016084774A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/06—Making preforms having internal stresses, e.g. plastic memory
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
- B32B37/025—Transfer laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/73—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of inorganic material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/12—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
Definitions
- the present invention relates to an antiviral transfer sheet for transferring an antiviral agent layer and an antibacterial layer onto the surface of an article made of synthetic resin, natural resin, wood, metal, glass or the like.
- the present invention also relates to a shrink film that covers the surface of an article, and the surface of the film relates to an antiviral shrink film having antiviral and antibacterial properties.
- a transfer sheet including a functional layer is transferred to a transfer substrate, the functional layer can be provided on the surface of the transfer target product.
- An example of the function of the functional layer is antiviral.
- the shrink film containing a functional layer can be used for the use which provides a functional coating to articles
- An example of the function of the functional layer is antiviral.
- an antibacterial transfer sheet is known.
- an antibacterial transfer sheet is known in which an active energy ray-curable composition is positioned in layers on a basic sheet, and a pattern layer and an adhesive layer are further laminated (see Patent Document 1).
- the active energy ray curable composition is composed of a surface energy activator in addition to the photocurable compound and the inorganic antibacterial agent.
- the surface energy activator acts on the sebum so that the contact area between the sebum and the hard coat layer is widened.
- the action efficiency of the inorganic antibacterial agent per unit is increased.
- the active energy ray curable composition layer may be present inside.
- the amount of the inorganic antibacterial agent must be increased uniformly.
- An antibacterial agent is an expensive material and is a material that inhibits the transparency of the active energy ray-curable composition layer in which it is mixed.
- the transfer sheet becomes expensive and the visibility of the display painted on the pattern layer is lowered.
- the visibility is lowered, the appealing power of the article derived from the display is lowered.
- an antibacterial shrink film is known.
- a shrink film is known which is manufactured by forming a resin or the like kneaded with an antibacterial agent into a film shape (see, for example, Patent Document 2).
- coating an antibacterial agent to the surface of the film base material which has shrink property is known (for example, refer patent document 3).
- the problem to be solved by the present invention is a method for producing an antiviral transfer sheet, which occurs in carrying out a production method for increasing the density of antiviral agents and antibacterial agents on the surface layer after transfer.
- the problem to be solved by the present invention is an antiviral transfer sheet, which requires a large amount of antiviral agent, etc., which arises when attempting to increase the density of the antiviral agent on the surface layer after transfer The opacity of the layer having antiviral function.
- an “antiviral transfer sheet” refers to a transfer sheet that provides a transferred product by imparting antiviral properties and antibacterial properties to a transferred surface of a transferred substrate.
- the problem to be solved by the present invention is a method for producing an antiviral shrink film, which requires a large amount of an antiviral agent or the like produced when the antiviral agent or the like is present at a high density on the surface layer of the shrink film.
- the problem to be solved by the present invention is an antiviral shrink film, which requires a large amount of an antiviral agent or the like generated when attempting to increase the density of the antiviral agent on the surface of the shrink film, antiviral The opacity of the functional layer.
- an inorganic antiviral agent powder is disposed on one side of a base sheet, and a hard coat agent is formed in a layer shape on the inorganic antiviral agent powder.
- a functional layer consisting of inorganic antiviral powder and hard coat on the base sheet.
- An adhesive layer is formed on the functional layer in contact with the functional layer or with another layer interposed therebetween.
- an adhesive layer may be formed directly on the functional layer.
- a picture layer may be formed on the functional layer, and an adhesive layer may be formed on the picture layer.
- an anchor layer may be formed on the functional layer, a picture layer may be formed on the anchor layer, and an adhesive layer may be formed on the picture layer.
- the pattern layer and the anchor layer are examples of other layers.
- the inorganic antiviral agent powder in the method for producing an antiviral transfer sheet, is a mixture of titanium oxide powder and cuprous oxide (copper oxide (I): Cu 2 O) powder.
- the amount of the inorganic antiviral agent powder disposed on the base sheet may be 0.01 g or more and 0.03 g or less per 1 m 2 of the antiviral transfer sheet.
- a picture layer may be formed on the functional layer, and the adhesive layer may be formed on the picture layer.
- the antiviral transfer sheet comprises a base sheet (31) and a transfer layer (32),
- the transfer layer is composed of a functional layer (37) on the base sheet in contact with one surface of the base sheet and an adhesive layer (39) which is the outermost layer side of the transfer layer
- the functional layer comprises an inorganic antiviral agent powder (33) and a hard coat agent (34),
- the amount of the inorganic antiviral agent powder is 0.01 g or more and 0.03 g or less per 1 m 2 of the antiviral transfer sheet.
- the surface where the functional layer comes into contact with the base sheet is the boundary surface of the functional layer (35)
- a particle in which a part of the particle surface is in contact with the boundary surface is defined as a contact effective powder particle
- an area where the contact effective powder particle is in contact with the boundary surface is defined as a single contact area.
- the total contact area is the total value of the single contact area of the contact effective powder particles existing in the boundary boundary constant section,
- the occupation percentage of the contact effective powder is 50% or more and 80% or less.
- the inorganic antiviral agent powder is composed of a mixture of titanium oxide powder and cuprous oxide (copper oxide (I): Cu 2 O) powder.
- the transfer layer (32) may include a pattern layer (38) positioned between the functional layer and the adhesive layer in addition to the functional layer (37) and the adhesive layer (39). It may be a thing.
- the method for producing an antiviral shrink film according to another embodiment of the present invention uses the shrink base material and the antiviral transfer sheet according to the present invention.
- an antiviral transfer sheet (11) according to the present invention is laminated on a shrink base material (26) to form a base material laminate ( 44).
- a base material transfer body (45) in which a transfer layer is transferred onto the shrink base material by applying pressure and heat to the base material laminate (44) is prepared.
- the substrate sheet (31) is removed from the substrate transfer body (45) to obtain an antiviral shrink film (1).
- 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 It may be 210 ° C.
- the antiviral shrink film (1) includes a shrink base material (26) and a functional layer (37) that is on one side of the shrink base material and is the outermost layer of the antiviral shrink film.
- Consists of The functional layer comprises an inorganic antiviral agent powder (33) and a hard coat agent (34), Containing 0.01 g or more and 0.03 g or less of the inorganic antiviral powder per 1 m 2 of the antiviral shrink film,
- the surface where the functional layer is in contact with the external environment is the exposed surface of the functional layer (41),
- a particle in which a part of the particle surface is exposed on the exposed surface is defined as an exposed effective powder particle, and an area where the exposed effective powder particle is exposed on the exposed surface is a single exposed area.
- the total exposed area is the total value of the single exposed area of the exposed active powder particles present in the exposed surface constant section, When the percentage of the total exposed area relative to the area of the constant section is the occupied percentage of the exposed active powder, The occupation percentage of the exposed effective powder is 50% or more and 80% or less.
- the exposed surface (41) is the surface of the antiviral shrink film (1).
- the inorganic antiviral agent powder comprises a mixture of titanium oxide powder and cuprous oxide (copper oxide (I): Cu 2 O) powder. It may also have a picture layer (38) located between the shrink base material and the functional layer.
- a transfer sheet in which an antiviral agent is localized on the surface that becomes the outermost layer after transfer is produced.
- most of the contained antiviral agent is positioned at a position where the antiviral action is exerted. Therefore, there is an advantage that an antiviral agent can be saved. Further, the degree to which the transparency of the functional layer is inhibited by the antiviral agent can be reduced. For this reason, there exists an advantage which can maintain the transparency of a functional layer.
- the occupation ratio of the effective particles of the antiviral agent on the surface that becomes the outermost layer after transfer is in a specific value range. Therefore, there is an advantage that many particles in the contained antiviral agent particles function effectively. Therefore, there is an advantage that an antiviral agent can be saved. Further, the degree to which the transparency of the functional layer is inhibited by the antiviral agent can be reduced. For this reason, the transparency of the functional layer can be maintained.
- the transferred product which is the result of transferring the transfer sheet, has the advantage that the visibility of the transferred product surface layer can be maintained well. Or when the pattern layer is provided in the transfer sheet, there exists an advantage which can maintain the visibility of a pattern layer favorable.
- the method for producing an antiviral shrink film of the present invention comprises using an antiviral transfer sheet according to the present invention or an antiviral transfer sheet produced by the method of producing an antiviral transfer sheet according to the present invention as a shrink substrate. It is produced by transcription. For this reason, there exists an advantage which can manufacture the antiviral shrink film with which the antiviral agent powder localizes on the surface and the surface is smooth. In addition, the method for producing an antiviral shrink film of the present invention does not cause curling in the antiviral shrink film, so that the production operation is facilitated during production, and the produced antiviral shrink film is of high quality. There are advantages.
- the manufacturing method of the antiviral shrink film of the present invention has an advantage that it is a simple manufacturing method of transferring a transfer sheet. Moreover, even if the pressure processing which transfers the transfer layer of a transfer sheet to a shrink base material is performed, there exists an advantage that the shrink process property which a shrink base material has remains in an antiviral shrink film.
- the antiviral shrink film of the present invention is positioned at a position where the antiviral agent is localized on the surface and a large number of particles in the antiviral agent powder particles exhibit antiviral ability in addition to the other invention-specific matters. Has the advantage of being. For this reason, there is an advantage that the amount of the antiviral agent required for imparting a certain antiviral performance to the antiviral shrink film is reduced, and the transparency of the functional layer is also within a reasonable range.
- FIG. 1 is a cross-sectional view schematically showing the configuration of an antiviral transfer sheet.
- FIG. 2 is a cross-sectional view schematically showing a configuration of a product to be transferred which is a result of transferring an antiviral transfer sheet.
- FIG. 3 is a cross-sectional view schematically showing the structure of the antiviral shrink film.
- FIG. 4 is an explanatory view schematically showing a method for producing an antiviral shrink film.
- antiviral is a collective term for antiviral and antimicrobial.
- antibacterial is a general term for antivirals and antibacterials. Unless otherwise specified, antiviral and antimicrobial means both independently.
- the antiviral transfer sheet 11 may be referred to as a transfer sheet 11.
- the transfer sheet 11 has a transfer layer 32 on one side of a base sheet 31.
- the transfer layer 32 includes a functional layer 37, a pattern layer 38, and an adhesive layer 39.
- the functional layer 37 is disposed in contact with one surface 61 of the base sheet 31.
- the functional layer 37 is disposed on the base sheet 31.
- the adhesive layer 39 is disposed on the outermost layer of the transfer layer 32.
- the adhesive layer 39 is disposed on the outermost layer of the transfer sheet 11.
- the functional layer 37 and the pattern layer 38 may be in contact with each other, and other layers may exist between them.
- the pattern layer 38 and the adhesive layer 39 may be in contact with each other, and there may be other layers between them.
- 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 that will be described in detail later.
- the antiviral agent powder 33 is disposed on the surface 61 of the base sheet 31.
- the antiviral agent powder is applied in the form of a suspension of an organic solvent, and then the organic solvent is removed and placed.
- the antiviral agent powder may be applied in the form of a suspension of a small amount of a hard coat agent and an organic solvent, and then the organic solvent is removed.
- the hard coat agent 34 is positioned on the antiviral agent powder 33.
- the functional layer 37 is formed.
- the method for positioning the hard coating agent include coating, spraying in the form of a mist, and printing.
- the pattern layer 38 and the adhesive layer 39 are sequentially laminated on the functional layer 37 thus formed.
- the method for forming the picture layer 38 and the adhesive layer 39 is the same as the method for forming the picture layer and the adhesive layer in a known transfer sheet.
- the pattern layer 38 is an optional component.
- the picture layer 38 may or may not be provided. If necessary, an anchor layer or the like may 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.
- FIG. 2 is a schematic cross-sectional view of a transferred product 22 manufactured by transferring the transfer sheet 11 to the transferred substrate 21.
- an adhesive layer 39 in contact with the transfer substrate 21.
- a pattern layer 38 is provided on the adhesive layer 39, and a functional layer 37 is provided on the pattern layer 38.
- the pattern layer imparts appealing power derived from the pattern to the article to be transferred 22.
- the design of the surface layer of the substrate to be transferred is observed through the transfer layer even in the product to be transferred.
- the transfer layer is black or the like and does not transmit light, the transferred product has the appearance of the transfer layer itself.
- the functional layer 37 is positioned on the outermost layer of the transferred product 22, and the exposed surface 62 of the functional layer 37 is in contact with the external environment.
- the antiviral agent powder 33 When the antiviral agent powder 33 is exposed in the functional layer 37, the antiviral agent powder 33 exhibits its function. When the antiviral powder is embedded in the functional layer 37, the function is not exhibited. Further, even when the antiviral agent powder is located in the vicinity of the back surface (surface opposite to the exposed surface 62) of the functional layer 37, the function is not exhibited.
- the exposed surface 62 of the article to be transferred 22 is a surface derived from the boundary surface 35 of the functional layer in the antiviral transfer sheet 11.
- the localization state of the antiviral powder in the functional layer 37 will be described.
- the area ratio of the antiviral agent powder in the area of the boundary surface 35 is expressed as a percentage, and is defined as “occupation percentage of the contact effective powder”.
- the definition and calculation method of “percentage of contact effective powder” will be described.
- the functional layer boundary surface 35 is a surface where the functional layer 37 is in contact with the surface 61 of the base sheet 31. Furthermore, let the area where a contact effective powder particle contacts a boundary surface be a single contact area.
- the single contact area is AR-T.
- a certain section is a continuous surface.
- the fixed section is a section divided by a single square drawn on the boundary surface 35.
- AROBS be the area of a certain section.
- n is the number of contact effective powder particles present in a certain section.
- the n individual contact areas AR-T are totaled to obtain the total contact area.
- Let the total contact area be ⁇ AR-T.
- OCC ⁇ T% ⁇ AR ⁇ T / AROBS ⁇ 100 ⁇ Formula (1)
- the occupation percentage of contact effective powder is calculated
- the boundary surface of the transfer sheet is positioned on the outermost layer, and the boundary surface is exposed.
- An enlarged image of the exposed surface is obtained using a scanning electron microscope.
- a square whose actual dimension in the test product is 700 nm (nanometer) is set as an observation target.
- Each of the two orthogonal sides of the observation target square is divided into 17 parts, and the observation target square is divided into 289 small sections by drawing a straight line from each division point.
- Each subsection is square.
- the contact area in the small compartment is 1, 0.9, 0.8, 0. .7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 are determined in 11 stages. That is, when the contact surface (product) covers the entire surface of the small section, the determination value of the small section is set to 1. When the contact area is half of the small area, the determination value of the small area is set to 0.5. When there is no contact surface (product) in the small section, the determination value of the small section is set to 0.
- the percentage of contact effective powder occupancy is calculated for three different observation target squares on the exposed surface (surface derived from the boundary surface 35) in the transferred test article.
- the length of one side of each observation target square is 700 nm (nanometers) in terms of the actual dimension in the transferred test article.
- the calculated value of 3 is obtained, the average value of the 3 calculated values is obtained, and the average value is set as the occupation percentage of the contact effective powder of the antiviral transfer sheet.
- the percentage occupied by the contact effective powder by the above simple method is 50% or more and 80% or less.
- the antiviral agent powder particles 33 a large number of particles are positioned in the functional layer in a state where they exhibit antiviral ability.
- the amount of the antiviral agent powder required for the transfer layer after the transfer to exhibit a certain level of antiviral force is reduced.
- the amount of the antiviral agent powder contained in the functional layer is reduced, and the transparency of the functional layer can be maintained within a reasonable range.
- the contact effective powder particles are firmly fixed to the functional layer because a part of them is surrounded by the hard coat agent. Therefore, even if the functional layer is placed on the surface layer of the article after transfer and a human finger or the like comes into contact with the exposed surface 62, the antiviral agent powder does not fall off.
- the surface of the functional layer 37 that is, the exposed surface 62 of the transferred product 22 is smooth.
- the total light transmittance of the functional layer is 88% or more, and the haze is 3% or less.
- the total light transmittance is measured in accordance with JIS K-7361 (Plastic-Test method for total light transmittance of transparent materials).
- the haze is measured according to JIS K7136 (Plastic—How to determine haze of transparent material).
- An antiviral molded article may be produced by an in-mold injection molding method using an antiviral transfer sheet. Further, the antiviral transfer sheet may be transferred to a transfer substrate using a transfer machine such as a roll transfer machine or an up-down transfer machine. Examples of the substrate to be transferred include resin molded products, shrink substrates, rubber products, metal products, wood products, glass products, ceramic products, and composite products made of various materials.
- an antiviral transfer sheet is placed in a molding die. At that time, the antiviral transfer sheet is adjusted so that the base sheet faces the mold cavity surface.
- the mold is closed, and the molten resin is filled into the mold cavity so that the molten resin contacts the adhesive layer of the antiviral transfer sheet.
- the molten resin is molded, and at the same time, the antiviral transfer sheet is adhered to the surface of the injection molded body.
- the mold is opened and the injection molded body is taken out, the transfer layer is bonded to the surface of the injection molded body. Subsequently, the base sheet is removed from the injection molded body.
- the manufacturing method and configuration of the antiviral shrink film will be described.
- the manufacturing method of an antiviral shrink film is a method of manufacturing by transferring an antiviral transfer sheet to a shrink substrate.
- the antiviral transfer sheet is an antiviral transfer sheet according to the present invention and an antiviral transfer sheet produced by the method for producing an antiviral transfer sheet according to the present invention.
- the antiviral shrink film 1 may be shortened and called the shrink film 1 in some cases.
- FIG. 4 is an explanatory view schematically showing a method for producing an antiviral shrink film.
- the transfer sheet 11 is laminated on one surface of the shrink substrate 26 to make a substrate laminate 44.
- the shrink base material 26 and the transfer layer 32 of the transfer sheet 11 are made to face each other.
- the adhesive layer contacts the shrink base material 26.
- the base laminate 44 is passed between the pressure roll 51 and the receiving roll 52. By passing, a part of the hot-melt resin constituting the adhesive layer 39 is melted and solidified, and the boundary surface 40 between the surface of the shrink base material 26 and the adhesive layer 39 is welded. In this way, a substrate transfer body 45 composed of the shrink substrate 26 and the transfer sheet 11 is created.
- the substrate sheet 31 is removed from the substrate transfer body 45 to obtain the shrink film 1.
- the temperature condition in the transfer is usually 170 ° C. to 210 ° C., preferably 180 ° C. to 200 ° C. If it is in this range, the melting of the resin of the adhesive layer is sufficient and transfer becomes good, and the shrink workability of the shrink base material is left in the shrink film 1.
- the pressure condition in the transfer is usually 0.3 MPa to 1.2 MPa, preferably 0.4 MPa to 0.8 MPa. If it exists in this range, heat
- the addition time of the pressure heat can be expressed by the relative moving speed of the laminate and the pressure roll, and is 0.5 m / min to 4.0 m / min.
- the speed is less than 0.5 m / min, the shrink workability of the manufactured shrink film 1 is deteriorated.
- the speed is higher than 4.0 m / min, the heat conduction is low, and the transfer layer is defective because the resin of the adhesive layer is not sufficiently melted.
- the shrink film 1 manufactured by the manufacturing method of the present invention was covered with a door knob, and hot air was blown.
- the shrink film contracted to match the shape of the doorknob, and the shrink film was attached to the doorknob. Even if the thermal processing for transferring the transfer sheet 11 to the shrink base material 26 is performed, the shrink workability of the shrink base material 26 remains in the shrink film 1.
- the shrink film 1 according to the present invention has an adhesive layer 39 positioned in contact with one surface of the shrink base material 26.
- the pattern layer 38 is positioned on the adhesive layer 39, and the functional layer 37 is positioned on the pattern layer 38.
- the pattern layer 38 is a selective component and may or may not be present.
- the pattern layer When the pattern layer is provided, the appealing power derived from the pattern is imparted to the body to which the shrink film 1 is attached. On the other hand, when there is no pattern layer, the appearance that the mounted body of the shrink film 1 originally has is maintained.
- the functional layer 37 is located on the surface layer of the shrink film 1, and 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 is a surface positioned on the surface of the mounted body in a state where the shrink film 1 is mounted on the mounted body.
- the other surface of the shrink film 1 is a surface where the shrink base material is in contact with the external environment.
- the functional layer 37 includes an antiviral agent powder 33 and a hard coat agent 34.
- the antiviral agent powder 33 is localized in the vicinity of the exposed surface 41 in contact with the external environment.
- the localization of the antiviral powder 33 in the functional layer 37 in the shrink film 1 will be described.
- the area ratio of the antiviral agent powder to the area of the exposed surface 41 is expressed as a percentage, and is defined as “percentage of the exposed effective powder”.
- the definition and calculation method of “percentage of exposed effective powder” will be described.
- particles in which part of the particle surface is exposed on the exposed surface 41 are defined as exposed effective powder particles.
- the exposed surface 41 is a surface where the functional layer 37 is in contact with the external environment.
- the area where the exposed effective powder particles are exposed on the exposed surface is defined as the single exposed area.
- the single exposed area is AR-E.
- a certain section is a continuous surface.
- the fixed section is a section divided by a single square drawn on the exposed surface 41.
- AROBS be the area of a certain section.
- n is the number of exposed effective powder particles present in a certain section.
- the individual exposed areas AR-E are summed up to obtain the total exposed area.
- ⁇ AR-E be the total exposed area.
- OCC ⁇ E% ⁇ AR ⁇ E / AROBS ⁇ 100 ⁇ Equation (3)
- the antiviral agent powder particles are fine, it is difficult to accurately measure the single exposed area. As a result, it is difficult to accurately calculate the occupation percentage of the exposed effective powder. For this reason, the occupation percentage of the exposed effective powder is determined by a simple method described below.
- the surface is the surface where the functional layer is exposed.
- a square having an actual dimension of 700 nm on one side (nanometer) in the shrink film is an observation object.
- Each of the two orthogonal sides of the observation target square is divided into 17 parts, and the observation target square is divided into 289 small sections by drawing a straight line from each division point.
- Each subsection is square.
- the exposed area in the small compartment is 1, 0.9, 0.8, 0. .7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 are determined in 11 stages. That is, when the exposed surface (product) covers the entire surface of the small section, the determination value of the small section is set to 1. When the exposed area is half of the small area, the determination value of the small area is set to 0.5. When there is no exposed surface (product) in the small section, the determination value of the small section is set to 0.
- the percentage of the effective exposure powder occupied is calculated for three observation target squares that differ on the exposed surface 41 of the antiviral shrink film.
- the length of one side of each observation target square is 700 nm (nanometer) in actual dimensions.
- the calculated value of 3 is obtained, the average value of the 3 calculated values is obtained, and the average value is set as the occupation percentage of the exposed effective powder of the antiviral shrink film.
- the occupation percentage of the exposed effective powder by the above simple method is 50% or more and 80% or less.
- the shrink film 1 a large number of particles among the 33 particles of the antiviral agent powder are positioned in the functional layer in a state where the antiviral ability is exhibited. Therefore, the amount of antiviral agent powder required for the shrink film 1 to exhibit a certain level of antiviral power is reduced. For the same reason, the amount of the antiviral agent powder disposed in the functional layer is reduced, and the transparency of the functional layer can be maintained within a reasonable range.
- the exposed effective powder particles are firmly fixed in the functional layer because a part of them is surrounded by the hard coat agent. Therefore, even if the shrink film 1 is positioned on the surface layer of the mounted product and a human finger or the like contacts the exposed surface 41, the antiviral agent powder does not fall off.
- the exposed surface of the functional layer 37 is smooth. That is, the surface of the shrink film 1 is smooth, and as a result, the surface of the shrink film mounting body is smooth.
- Inorganic antiviral agent examples include a photocatalytic material, a metal ion supported on an ion exchanger, and antibacterial ceramics.
- Photocatalytic materials are 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, oxide Examples thereof include oxides such as cobalt, rhodium oxide, nickel oxide, rhenium oxide, and zirconium oxide, oxides of these metals, and metal oxides doped with nitrogen or metal ions.
- supported on the surface is also mentioned.
- supported on the surface is also mentioned.
- metal ions include silver ions, copper ions (II), and zinc ions.
- ion exchangers include zeolites (crystalline aluminosilicates), silica gels, silicate carriers such as clay minerals, phosphate carriers such as zirconium phosphate and calcium phosphate, and soluble glass, activated carbon, and metal carriers. And organic metals.
- a part of the ion-exchangeable ions in the ion exchanger by immersing the ion exchanger in an aqueous solution of metal ions at a predetermined pH condition, a predetermined temperature for a predetermined time or A method in which the whole is substituted with metal ions, washed with water after completion of ion exchange, and heated and dried.
- Anakin ceramics composition formula a Ag-Ca u Zn v Al w (PO 4) X (OH) Y, as those of crystalline, silver zirconium phosphate, silver tripolyphosphate aluminum, silver hydroxyapatite and Examples include silver tricalcium phosphate.
- Noncrystalline materials include silver phosphate glass and silver phosphate double salt ceramics.
- These inorganic antiviral agents are powders having a particle size of 1 nm to 400 nm (nanometer).
- the titanium oxide powder having a particle diameter of 1 nm to 400 nm is used.
- cuprous oxide copper oxide (I): Cu 2 O
- powder having a particle diameter of 1 nm to 400 nm is used.
- titanium oxide is preferable. Titanium oxide is more preferably anatase type because rutile type is less transparent.
- cuprous oxide copper oxide (I): Cu 2 O
- titanium oxide As the cuprous oxide, it is preferable to use a powder that has been subjected to an anti-oxidation surface treatment.
- the mixing ratio of titanium oxide and cuprous oxide is preferably 45:55 to 75:25 (parts by weight). This is because when the titanium oxide ratio exceeds 75 parts by weight, the antiviral properties are insufficient, and when the cuprous oxide ratio exceeds 55 parts by weight, the haze value (% value) increases.
- the amount of the inorganic antiviral agent is preferably 0.01 g or more and 0.03 g or less per 1 m 2 (square meter) of the antiviral transfer sheet. This is because the antiviral properties are exhibited and the total light transmittance is within the practical range.
- the area 1 m 2 of the anti-viral transfer sheet is equal to the area 1 m 2 of the functional layer.
- the amount is preferably 0.01 g or more and 0.03 g or less per 1 m 2 of the area of the antiviral transfer sheet. This is because if it is less than 0.01 g / m 2 , the antiviral properties are insufficient, and if it exceeds 0.03 g / m 2 , the total light transmittance is less than 88%.
- the hard coating agent is an active energy ray-curable resin that is cured by ultraviolet rays or electron beams, which are typified by a photocurable resin such as an ultraviolet curable resin, and a radiation curable resin such as an electron beam curable resin.
- the hard coating agent may be a thermosetting and active energy ray curable resin.
- the active energy ray curable resin is, for example, a urethane acrylate resin or a cyanoacrylate resin.
- the thermosetting and active energy ray-curable resin is, for example, a resin obtained by adding an additive such as isocyanate to a urethane acrylate resin or a cyanoacrylate resin.
- thermosetting and active energy ray-curable resin When the thermosetting and active energy ray-curable resin is heated, some of the monomers and oligomers in the resin are cross-linked and become a semi-cured state.
- the semi-cured hard coat layer is cured when further irradiated with active energy rays such as ultraviolet rays.
- thermosetting and active energy ray-curable hard coat agent is used. It is only necessary to semi-cure by heating, and then to irradiate active energy rays to fully cure.
- active energy ray-curable hard coating agent a small amount of active energy rays may be irradiated for semi-curing, and then active energy rays may be irradiated again for full curing.
- ultraviolet curable resins and thermosetting and ultraviolet curable resins are preferred. This is because the equipment (tool) for performing the curing operation is easily and inexpensively available, and the curing operation is easy. Moreover, from the viewpoint of the transfer sheet, the transferred product, and the shrink film 1, it is because the functional layer is highly transparent and ultraviolet rays can easily enter.
- the hard coat agent may be cured at any production stage. That is, it may be cured at any stage of the following (1) to (3).
- (1) After functional layer formation during transfer sheet manufacturing (2) After transfer sheet manufacture (3)
- the transfer layer of the transfer sheet is transferred to the transfer product 21, preferably after the transfer process by pressure heat, that is, in the step (3). More preferably, it is semi-cured in the step (1) and is fully cured in the step (3).
- the hard coat agent may be cured at any production stage. In other words, it may be cured at any of the following stages (1) to (4).
- stages (1) to (4) (1) After functional layer formation during transfer sheet manufacturing (2) After transfer sheet manufacture (3) After manufacturing shrink film (4) After shrinking the shrink film and mounting it on the mounted body, preferably after performing the transfer process by pressure heat, that is, in the stage (3) or (4). More preferably, it is semi-cured in the step (1), and is fully cured in the step (3) or (4).
- the material of the base sheet is, for example, a resin sheet such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, polyvinyl chloride resin, metal foil such as aluminum foil or copper foil, glassine paper
- a base sheet such as a cellulosic sheet such as coated paper or cellophane, or a composite of each of the above sheets can be used.
- the material of the pattern layer is made of polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, etc. It is preferable to use a colored ink containing the above pigment or dye as a colorant. In the case of forming a metal color, a pearl pigment in which titanium oxide is coated on metal particles such as aluminum, titanium, bronze, or mica can be used. Examples of the method for forming the pattern layer include printing methods such as an offset printing method, a gravure printing method, and a screen printing method.
- the pattern layer may be formed from a metal thin film such as aluminum, tin, or copper.
- a metal vapor deposition method, a sputtering method, an ion beam method, or the like can be used.
- a heat-sensitive or pressure-sensitive resin suitable for the type of transfer target product or shrink substrate is used.
- the adhesive layer may be made of PMMA, PS, PA, or polyolefin resin that is compatible with these resins.
- the shrink base material is a polystyrene (PS) resin
- the adhesive layer may be made of PMMA, PS, PA, or polyolefin resin that has an affinity for these resins.
- the method for forming the adhesive layer include a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and an offset printing method.
- a release layer may be formed between the base sheet and the functional layer.
- the release layer is a layer that is removed from the transferred product or the shrink film together with the base sheet when the base sheet is peeled after the transfer.
- melamine resin release agent, silicone resin release agent, fluororesin release agent, cellulose derivative release agent, urea resin release agent, polyolefin resin release agent, Paraffin-type release agents and composite release agents thereof can be used.
- the method for forming the release layer include a coating method such as a roll coating method and a spray coating method, a gravure printing method, and a screen printing method.
- Shrink base materials are polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-propylene copolymer, ionomer, polypropylene, polystyrene, polyester, fluororesin, hydrochloric acid rubber, silicone rubber, EPDM, chloroprene rubber, nitrile-butadiene rubber, etc.
- the resin or rubber is molded into a film. After the film is formed, it is usually stretched uniaxially or biaxially and heat set. Stretching can be performed simultaneously with film forming by performing stretch blow molding or stretch inflation molding under such temperature conditions that the orientation is required.
- a transfer sheet was prepared and transferred by in-mold injection molding to produce an antiviral molded product, and the antiviral properties, total light transmittance, and haze of the antiviral molded product were measured.
- the production method of the transfer sheet was as follows.
- Antiviral agent The primary particle diameter of the powder TiO 2 powder (white powder) mixed with 60 parts by weight of TiO 2 powder and 40 parts by weight of Cu 2 O powder is 15 nm, and the primary particle diameter of Cu 2 O powder (brown powder) is 50 nm. Met.
- Hard coating agent Urethane acrylate UV curable resin Molding resin: Acrylic resin Molded product size: 50mm x 50mm x 1mm Molten resin temperature: 240 ° C to 260 ° C A suspension of an antiviral agent, methyl ethyl ketone, and a small amount of a hard coating agent was applied on the base sheet in an amount of 0.02 g / m 2 to remove the methyl ethyl ketone. A hard coat agent was applied in a layer shape having a dry thickness of 5.5 ⁇ m over the antiviral agent. The hard coating agent was half cured, the anchor agent was applied, and an adhesive layer was prepared by a gravure printing method using a polyolefin resin. Thereafter, the hard coat agent was cured by irradiation with ultraviolet rays.
- Sample Nos. 8, 9, 10 and 11, 12, 13 are obtained by changing the mixing ratio (parts by weight) of TiO 2 powder and Cu 2 O powder added as an antiviral agent.
- Sample No. 1 has a functional layer formed without adding an antiviral agent.
- an antiviral agent and a hard coat agent in the amounts shown in the table are mixed in advance to prepare a suspension, and the suspension is applied to form a functional layer.
- JIS R 1756 visible light responsive photocatalytic viral test method.
- the light conditions were as follows: light from a white fluorescent lamp was cut with an N113 filter, and ultraviolet rays of 400 nm or less were cut to an illuminance of 1000 lx.
- bacteriophage virus was attached to a sample, and the sample irradiated with light for 2 hours was collected with an SCDLP solution, and a moderately diluted sample was infected with E. coli and applied to an agar medium. The number of colonies after culture was counted and evaluated by calculating the degree of inactivation.
- the haze was measured according to JIS K-7136 (Plastic—How to determine haze of transparent material). It measured with the haze meter NDH5000 (made by Nippon Denshoku Industries Co., Ltd.).
- the antiviral property passed -2.0 or lower, the total light transmittance was 88.0% or higher, and the haze was 3.0% or lower.
- Sample Nos. 8 and 9 obtained high antiviral properties and high total light transmittance (% value).
- the measured value “ ⁇ 4.8>” of the antiviral property indicates that the measurement was impossible when the experiment was conducted, and it was determined that the measured value was ⁇ 4.8 or less which is the limit value of the measurement. Yes.
- Table 4 the same applies to Table 4.
- Example 2 Using the antiviral molded product prepared in Example 1, the antibacterial properties of the antiviral molded product were measured.
- the antiviral molded products used for the measurement are sample number 1 and sample number 9.
- the term “antibacterial” literally means antibacterial, and the term “antibacterial” does not mean antiviral.
- the measurement of antibacterial properties was based on JIS-R-1756 (visible light responsive photocatalyst, antiviral test method).
- the light conditions were such that the light from a white fluorescent lamp was cut with an N169 filter and ultraviolet rays of 380 nm or less were cut to an illuminance of 1000 lx.
- test method 50 ⁇ L (microliter) of a staphylococcus aureus bacterial solution was dropped onto a sample, and the sample irradiated with light for 24 hours was collected with an SCDLP solution. The recovered solution was mixed with NB medium, and the number of colonies after culture was counted for evaluation.
- Antibacterial activity value (Log of Staphylococcus aureus after test with sample)-(Log of Staphylococcus aureus after test with glass plate)
- the measured antibacterial value “ ⁇ 4.8>” indicates that the measurement was impossible when the experiment was performed, and the value was determined to be ⁇ 4.8 or less, which is the limit value of the measurement. The same applies to Table 5.
- Transfer sheet 11 was prepared, transfer conditions were examined, transferred to a shrink base material, antiviral shrink film 1 was prepared, and shrink processability was evaluated.
- the production method of the transfer sheet was as follows.
- Antiviral agent primary particle size of powder TiO 2 powder (white powder) mixed with 60 parts by weight of TiO 2 powder and 40 parts by weight of Cu 2 O powder is 15 nm, and primary particle size of Cu 2 O powder (brown powder) is 50 nm. Met.
- Shrink base material biaxially stretched polystyrene sheet, thickness 60 ⁇ m, heat shrinkage ratio was 14% in MD direction and 75% in TD direction when heated at 100 ° C. for 10 seconds.
- thermal shrinkage (%) 100 ⁇ (length before heating ⁇ length after heating) / length before heating.
- Hard coating agent Urethane acrylate UV curable resin A suspension of an antiviral agent, methyl ethyl ketone and a small amount of a hard coating agent was applied on a base sheet to an amount of 0.02 g / m 2 to remove the methyl ethyl ketone. . A hard coat agent was applied in a layer shape having a dry thickness of 5.5 ⁇ m over the antiviral agent. The hard coating agent was half cured, the anchor agent was applied, and an adhesive layer was prepared by a gravure printing method using a polyolefin resin. Thereafter, the hard coat agent was cured by irradiation with ultraviolet rays.
- the transfer was performed by placing a shrink base material and a transfer film on the stage, and applying pressure and heat from the top with a pressure roll.
- the temperature of the hot roll was 186 ° C.
- the transfer degree was measured by changing the moving speed of the pressure roller, the pressure, and the number of times of pressure application (number of times of passing between the stage and the roll). The degree of transfer was visually measured as a percentage of the transfer layer region present on the antiviral shrink film after the substrate sheet was removed.
- the finished antiviral shrink film was wrapped around the door knob, and heat was applied at 170 ° C. for 2 minutes to perform shrink processing.
- the processability of the antiviral shrink film was evaluated in two stages, visually (Yes) or not (X).
- Table 3 shows the experimental results of the transfer condition examination and shrink workability.
- the transfer sheet 11 was prepared and transferred to a shrink substrate to prepare an antiviral shrink film 1, and the antiviral properties, total light transmittance, and haze of the antiviral shrink film were measured.
- the base sheet, antiviral TiO 2 powder and Cu 2 O powder, hard coat agent, and adhesive used in Example 4 are the same as those used in Example 1.
- Sample Nos. 8, 9, 10 and 11, 12, 13 are obtained by changing the mixing ratio (parts by weight) of TiO 2 powder and Cu 2 O powder added as an antiviral agent.
- the transfer conditions were a pressure roll temperature: 186 ° C., a pressure: 0.55 Mpa, and a transfer speed: 3.4 m / min.
- Sample No. 1 has a functional layer formed without adding an antiviral agent.
- Comparative-1 is a functional layer obtained by preparing a suspension by previously mixing the amounts of antiviral agent and hard coat agent described in the table and applying the suspension.
- Antiviral evaluation, test method, inertness calculation formula, total light transmittance measurement, and haze measurement were the same as in Example 1.
- the antiviral property was -2.0 or less, and the total light transmittance was 88.0% or more. Haze was not considered in the overall evaluation.
- Sample Nos. 8 and 9 obtained high antiviral properties and high total light transmittance (% value).
- the antiviral properties of the antiviral shrink film 1 were measured using the antiviral shrink film 1 produced in Example 4.
- the antiviral shrink film 1 used for the measurement is sample number 1 and sample number 9.
- antibacterial literally means antibacterial, and the term “antibacterial” does not mean antiviral.
- Antibacterial measurement, test method, and calculation formula for antibacterial activity value were the same as in Example 2.
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Abstract
Description
前記機能層の上に、機能層に接して、あるいは他の層を介在して、接着層を形成するものである。
本発明にあっては、機能層の上に直接接着層を形成してもよい。また、機能層の上に絵柄層を形成し、絵柄層の上に接着層を形成してもよい。さらにまた、機能層の上に、アンカー層を形成し、アンカー層の上に絵柄層を形成し、絵柄層の上に接着層を形成してもよい。絵柄層とアンカー層は他の層の例示である。
前記転写層は基体シートの片面に接して基体シート上に在る機能層(37)と前記転写層の最表層側の層である接着層(39)からなり、
前記機能層は無機系抗ウイルス剤粉末(33)とハードコート剤(34)からなり、
前記無機系抗ウイルス剤粉末の量は、抗ウイルス性転写シート1m2当たり0.01g以上0.03g以下であり、
前記機能層が基体シートと接触する面を機能層の境界面(35)とし、
前記無機系抗ウイルス剤粉末の粒子の中で、粒子表面の一部分が境界面に接触している粒子を接触有効粉末粒子とし、接触有効粉末粒子が境界面と接している面積を単独接触面積とし、
境界面一定区画中に存在する接触有効粉末粒子の単独接触面積の合計値を合計接触面積とし、
前記一定区画の面積に対する合計接触面積の百分率を接触有効粉末の占有百分率としたとき、
接触有効粉末の占有百分率が50%以上80%以下である。
前記機能層は無機系抗ウイルス剤粉末(33)とハードコート剤(34)からなり、
抗ウイルス性シュリンクフィルム1m2当たり前記無機系抗ウイルス剤粉末を0.01g以上0.03g以下含んでいて、
機能層が外部環境と接する面を機能層の露出面(41)とし、
前記無機系抗ウイルス剤粉末の粒子の中で、粒子表面の一部分が露出面に露出している粒子を露出有効粉末粒子とし、露出有効粉末粒子が露出面に露出している面積を単独露出面積とし、
露出面一定区画中に存在する露出有効粉末粒子の単独露出面積の合計値を合計露出面積とし、
前記一定区画の面積に対する合計露出面積の百分率を露出有効粉末の占有百分率としたとき、
露出有効粉末の占有百分率が50%以上80%以下である。
OCC-T%=ΣAR-T/AROBS×100 -- 式(1) である。
「接触有効粉末の占有百分率」=判定値の合計値/289×100 -- 式(2) である。
OCC-E%=ΣAR-E/AROBS×100 -- 式(3) である。
「露出有効粉末の占有百分率」=判定値の合計値/289×100 -- 式(4) である。
無機系抗ウイルス剤としては、光触媒材料、金属イオンをイオン交換体に担持したもの、抗菌セラミックスなどが挙げられる。
ハードコート剤は、紫外線硬化性樹脂などの光硬化性樹脂、電子線硬化性樹脂などの放射線硬化性樹脂などに代表される紫外線や電子線などで硬化する活性エネルギー線硬化性樹脂である。ハードコート剤は熱硬化性かつ活性エネルギー線硬化性の樹脂であってもよい。活性エネルギー線硬化性樹脂は、例えば、ウレタンアクリレート系樹脂やシアノアクリレート系樹脂である。熱硬化性かつ活性エネルギー線硬化性の樹脂は、例えば、ウレタンアクリレート系樹脂やシアノアクリレート系樹脂にイソシアネートなどの添加剤を加えた樹脂である。熱硬化性かつ活性エネルギー線硬化性の樹脂は加熱することにより、樹脂中のモノマーやオリゴマーの一部が架橋され半硬化状態に成る。なお、半硬化状態のハードコート層は、さらに紫外線などの活性エネルギー線を照射すれば硬化状態となる。
(1)転写シート製造中の機能層形成後
(2)転写シート製造後
(3)転写シートの転写層を被転写品21に転写した後
好ましくは圧熱による転写加工を行った後、すなわち(3)の段階で行うことである。より一層好ましくは(1)の段階で半硬化し、(3)の段階で全硬化を行うことである。
(1)転写シート製造中の機能層形成後
(2)転写シート製造後
(3)シュリンクフィルム製造後
(4)シュリンクフィルムを収縮して被装着体に装着した後
好ましくは圧熱による転写加工を行った後、すなわち(3)又は(4)の段階で行うことである。より一層好ましくは(1)の段階で半硬化し、(3)又は(4)の段階で全硬化を行うことである。
基体シートの材質は、例えば、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、アクリル系樹脂、ポリ塩化ビニル系樹脂などの樹脂シート、アルミニウム箔、銅箔などの金属箔、グラシン紙、コート紙、セロハンなどのセルロース系シート、あるいは以上の各シートの複合体など、基体シートとして離型性を有するものを使用することができる。
絵柄層の材質は、ポリビニル系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、ポリエステルウレタン系樹脂、セルロースエステル系樹脂、アルキッド樹脂などの樹脂をバインダーとし、適切な色の顔料又は染料を着色剤として含有する着色インキを用いるとよい。また、金属発色させる場合には、アルミニウム、チタン、ブロンズなどの金属粒子やマイカに酸化チタンをコーティングしたパール顔料を用いることもできる。絵柄層の形成方法は、オフセット印刷法、グラビア印刷法、スクリーン印刷法などの印刷法を挙げることができる。
接着層は、被転写品又はシュリンク基材の種類に適した感熱性又は感圧性のある樹脂が使用される。例えば、被転写基材がPC、ポリスチレン(PS)系樹脂であれば、接着層は、これらの樹脂と親和性のある、PMMA、PS、PA、ポリオレフィン系樹脂を使用するとよい。例えば、シュリンク基材がポリスチレン(PS)系樹脂であれば、接着層は、これらの樹脂と親和性のある、PMMA、PS、PA、ポリオレフィン系樹脂を使用するとよい。接着層の形成方法は、グラビアコート法、ロールコート法、コンマコート法、グラビア印刷法、スクリーン印刷法、オフセット印刷法などを挙げることができる。
必要に応じて、離型層が基体シートと機能層との間に形成されていてもよい。離型層は、転写後、基体シートを剥離した際に、基体シートとともに被転写品又はシュリンクフィルムから取り除かれる層である。離型層の材質としては、メラミン樹脂系離型剤、シリコーン樹脂系離型剤、フッ素樹脂系離型剤、セルロース誘導体系離型剤、尿素樹脂系離型剤、ポリオレフィン樹脂系離型剤、パラフィン系離型剤およびこれらの複合型離型剤などを用いることができる。離型層の形成方法は、ロールコート法、スプレーコート法などのコート法、グラビア印刷法、スクリーン印刷法などを挙げることができる。
シュリンク基材は、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエチレン、エチレン-プロピレン共重合体、アイオノマー、ポリプロピレン、ポリスチレン、ポリエステル、フッ素系樹脂、塩酸ゴム、シリコーンゴム、EPDM、クロロプレンゴム、ニトリル-ブタジエンゴムなどの樹脂又はゴムをフィルム状に成形して製造される。フィルムを成形した後に、通常は、これを一軸又は二軸方向に延伸し熱セットする。延伸は、配向がかかるような温度条件で延伸ブロー成形したり延伸インフレーション成形したりすることにより、フィルムの成形と同時に行うこともできる。
抗ウイルス剤:TiO2粉末60重量部とCu2O粉末40重量部を混合した粉末
TiO2粉末の(白色粉末)一次粒子径は15nm、Cu2O粉末(茶褐色粉末)の一次粒子径は50nmであった。
成形樹脂:アクリル系樹脂
成形品サイズ:50mm×50mm×1mm
溶融樹脂温度:240℃~260℃
基体シートの上に抗ウイルス剤とメチルエチルケトンと少量のハードコート剤の懸濁液を抗ウイルス剤0.02g/m2になる量塗布し、メチルエチルケトンを除去した。抗ウイルス剤の上からハードコート剤を乾燥厚さ5.5μmの層形状に塗布した。ハードコート剤をハーフキュアしてアンカー剤を塗布し、ポリオレフィン系樹脂を使用したグラビア印刷法で接着層を作製した。その後、紫外線照射してハードコート剤をキュアした。
)に準拠した。光条件は、白色蛍光灯の光をN113フィルターにて、400nm以下の紫外線をカットし、照度1000lxとした。
全光線透過率の測定はJIS K 7361(プラスチック-透明材料の全光線透過率の試験方法)に準拠して行った。ヘイズメーターNDH5000(日本電色工業株式会社製)にて測定した。
(抗菌活性値)=(サンプルでの試験後黄色ブドウ球菌の対数)- (ガラス板での試験後黄色ブドウ球菌の対数)
抗ウイルス剤:TiO2粉末60重量部とCu2O粉末40重量部を混合した粉末
TiO2粉末(白色粉末)の一次粒子径は15nm、Cu2O粉末(茶褐色粉末)の一次粒子径は50nmであった。
基体シートの上に抗ウイルス剤とメチルエチルケトンと少量のハードコート剤の懸濁液を抗ウイルス剤0.02g/m2になる量塗布し、メチルエチルケトンを除去した。抗ウイルス剤の上からハードコート剤を乾燥厚さ5.5μmの層形状に塗布した。ハードコート剤をハーフキュアしてアンカー剤を塗布し、ポリオレフィン系樹脂を使用したグラビア印刷法で接着層を作製した。その後、紫外線照射してハードコート剤をキュアした。
11 抗ウイルス性転写シート
21 被転写基材
22 被転写品
26 シュリンク基材
31 基体シート
32 転写層
33 抗ウイルス剤粉末
34 ハードコート剤
35 機能層の境界面
37 機能層
38 絵柄層
39 接着層
40 境界面
41 露出面
44 基材積層体
45 基材転写体
51 圧熱ロール
52 受けロール
61 (基体シートの)表面
62 露出面
Claims (12)
- 抗ウイルス性転写シートの製造方法において、
基体シートの片面に無機系抗ウイルス剤粉末を配置し、前記無機系抗ウイルス剤粉末の上からハードコート剤を層形状に位置付けて、基体シートの上に無機系抗ウイルス剤粉末とハードコート剤からなる機能層を形成し、
前記機能層の上に、機能層に接して、あるいは他の層を介在して、接着層を形成することを特徴とする抗ウイルス性転写シートの製造方法。 - 前記無機系抗ウイルス剤粉末が酸化チタン粉末と亜酸化銅(酸化銅(I):Cu2O)粉末の混合物からなるものであることを特徴とする請求項1に記載した抗ウイルス性転写シートの製造方法。
- 基体シートに配置する前記無機系抗ウイルス剤粉末の量が、抗ウイルス性転写シート1m2当たり0.01g以上0.03g以下であることを特徴とする請求項1又は2のいずれかに記載した抗ウイルス性転写シートの製造方法。
- 前記機能層を形成した後に、
前記機能層の上に絵柄層を形成し、
前記絵柄層の上に前記接着層を形成することを特徴とする請求項1乃至3いずれかに記載した抗ウイルス性転写シートの製造方法。 - 抗ウイルス性転写シートにおいて、
基体シートと転写層からなり、
前記転写層は基体シートの片面に接して基体シート上に在る機能層と前記転写層の最表層側の層である接着層からなり、
前記機能層は無機系抗ウイルス剤粉末とハードコート剤からなり、
前記無機系抗ウイルス剤粉末の量は、抗ウイルス性転写シート1m2当たり0.01g以上0.03g以下であり、
前記機能層が基体シートと接触する面を機能層の境界面とし、
前記無機系抗ウイルス剤粉末の粒子の中で、粒子表面の一部分が境界面に接触している粒子を接触有効粉末粒子とし、接触有効粉末粒子が境界面と接している面積を単独接触面積とし、
境界面一定区画中に存在する接触有効粉末粒子の単独接触面積の合計値を合計接触面積とし、
前記一定区画の面積に対する合計接触面積の百分率を接触有効粉末の占有百分率としたとき、
接触有効粉末の占有百分率が50%以上80%以下である抗ウイルス性転写シート。 - 前記無機系抗ウイルス剤粉末が酸化チタン粉末と亜酸化銅(酸化銅(I):Cu2O)粉末の混合物からなるものであることを特徴とする請求項5に記載した抗ウイルス性転写シート。
- 前記転写層は前記機能層と前記接着層に加えて、前記機能層と前記接着層の間に位置する絵柄層を有することを特徴とする請求項5又は6いずれかに記載した抗ウイルス性転写シート。
- 抗ウイルス性シュリンクフィルムの製造方法において、
シュリンク基材の上に請求項5乃至7いずれかに記載した抗ウイルス性転写シートを積層して基材積層体を作成し、
前記基材積層体に圧力と熱を付加してシュリンク基材上に転写層を転写した基材転写体を作成し、
前記基材転写体から基体シートを取り除いて抗ウイルス性シュリンクフィルムを得る抗ウイルス性シュリンクフィルムの製造方法。 - 抗ウイルス性シュリンクフィルムの製造方法において、
前記積層物に付加する圧力は0.3MPa~1.2MPaであり、前記積層物に付加する熱は170℃~210℃であることを特徴とする請求項8に記載した抗ウイルス性シュリンクフィルムの製造方法。 - 抗ウイルス性シュリンクフィルムにおいて、
シュリンク基材と、シュリンク基材の片面側にあり、抗ウイルス性シュリンクフィルムの最も表層にある機能層からなり、
前記機能層は無機系抗ウイルス剤粉末とハードコート剤からなり、
抗ウイルス性シュリンクフィルム1m2当たり前記無機系抗ウイルス剤粉末を0.01g以上0.03g以下含んでいて、
機能層が外部環境と接する面を機能層の露出面とし、
前記無機系抗ウイルス剤粉末の粒子の中で、粒子表面の一部分が露出面に露出している粒子を露出有効粉末粒子とし、露出有効粉末粒子が露出面に露出している面積を単独露出面積とし、
露出面一定区画中に存在する露出有効粉末粒子の単独露出面積の合計値を合計露出面積とし、
前記一定区画の面積に対する合計露出面積の百分率を露出有効粉末の占有百分率としたとき、
露出有効粉末の占有百分率が50%以上80%以下である抗ウイルス性シュリンクフィルム。 - 前記無機系抗ウイルス剤粉末が酸化チタン粉末と亜酸化銅(酸化銅(I):Cu2O)粉末の混合物からなるものであることを特徴とする請求項10に記載した抗ウイルス性シュリンクフィルム。
- 前記シュリンク基材と前記機能層の間に位置する絵柄層を有することを特徴とする請求項10又は11いずれかに記載した抗ウイルス性シュリンクフィルム。
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EP3202552B1 (en) | 2023-08-30 |
EP3202552A4 (en) | 2018-02-21 |
JPWO2016084774A1 (ja) | 2017-04-27 |
CN107073808A (zh) | 2017-08-18 |
EP3202552A1 (en) | 2017-08-09 |
JP6159895B2 (ja) | 2017-07-05 |
KR20170088328A (ko) | 2017-08-01 |
US20180310553A1 (en) | 2018-11-01 |
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