WO2023048107A1 - Hard coat film - Google Patents
Hard coat film Download PDFInfo
- Publication number
- WO2023048107A1 WO2023048107A1 PCT/JP2022/034860 JP2022034860W WO2023048107A1 WO 2023048107 A1 WO2023048107 A1 WO 2023048107A1 JP 2022034860 W JP2022034860 W JP 2022034860W WO 2023048107 A1 WO2023048107 A1 WO 2023048107A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hard coat
- coat layer
- film
- coat film
- properties
- Prior art date
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- 239000002184 metal Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 10
- 239000011147 inorganic material Substances 0.000 claims abstract description 7
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- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
Definitions
- the present invention relates to a hard coat film having antibacterial and antiviral properties.
- antibacterial films such as face shield films, partition films, window films, touch panel films for electronic devices, etc., which may come into direct contact with the surface of human hands, ⁇ It is desired to have antiviral properties.
- antibacterial hard coat films As described above, various antibacterial hard coat films have been proposed in the past, but recently, there is a demand for not only antibacterial properties but also good antiviral properties.
- antibacterial and antiviral properties for example, antistatic performance, high hardness, antifog properties, heat shielding properties (that is, heat shielding or heat insulating properties) are required.
- functional requirements for hard coat films are increasing.
- an object of the present invention is, firstly, to provide a hard coat film with good antibacterial and antiviral properties, and secondly, to provide a hard coat film with good antibacterial and antiviral properties,
- An object of the present invention is to provide a hard coat film having an antibacterial property.
- Third, an object of the present invention is to provide a hard coat film having good antibacterial and antiviral properties and a high hardness.
- a hard coat film having good antibacterial and antiviral properties and heat shielding properties is provided. to provide.
- the present invention has been completed based on various findings obtained through intensive studies to solve the above problems. That is, the present invention has the following configurations.
- a hard coat film comprising a substrate and a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin provided on at least one surface of the substrate.
- At least one layer of a thin film made of a metal or metal oxide is laminated on the surface of the base material opposite to the hard coat layer or between the base material and the hard coat layer.
- the hard coat film according to any one of the first to seventh inventions.
- a hard coat film with good antibacterial and antiviral properties it is possible to provide a hard coat film with good antibacterial and antiviral properties. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antistatic properties. In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and high hardness. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antifogging properties. In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as heat shielding properties. Furthermore, according to the present invention, in addition to good antibacterial and antiviral properties, a hard coat film that also has multiple performances such as the above antistatic performance, high hardness, antifogging properties, and heat shielding properties. can provide.
- the hard coat film of the present invention is described below.
- the hard coat film of the present invention is a hard coat film characterized by having a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. be.
- the hard coat film of the present invention includes, for example, a face shield film, a partition film, a window film, a table cover film, a bus mirror film, a freezer/refrigerator window film, or a display or touch panel film for electronic devices, etc. can be preferably applied.
- a face shield film for example, a face shield film, a partition film, a window film, a table cover film, a bus mirror film, a freezer/refrigerator window film, or a display or touch panel film for electronic devices, etc.
- a display or touch panel film for electronic devices etc.
- a film substrate is generally used as the substrate to be coated with the hard coat film.
- the film substrate used in the present invention is not particularly limited, and examples thereof include acrylic resins, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polycarbonate, polyethylene naphthalate, polyethylene, polytrimethylene terephthalate, and polypropylene. , polybutylene terephthalate, polybutylene naphthalate, polystyrene, polymethyl methacrylate, polystyrene glycidyl methacrylate, aromatic polyimide, alicyclic polyimide, polyamideimide and mixtures thereof.
- polyester films, acrylic films, triacetyl cellulose, polyethylene terephthalate, and polycarbonate are particularly suitable.
- the film substrate is preferably triacetyl cellulose or polyethylene terephthalate from the viewpoint of transparency and cost advantage, and is a partition film or window film.
- the film substrate is preferably an acrylic resin film, or polycarbonate or polyethylene terephthalate from the viewpoint of impact resistance and cost advantage. It is also possible for the base material to have UV cut performance.
- the thickness of the film substrate varies depending on the application, so it cannot be generalized, but it is usually preferably in the range of 10 to 1000 ⁇ m, more preferably in the range of 20 to 300 ⁇ m.
- any resin that forms a film can be used without particular limitation. It is preferable to use an ionizing radiation-curable resin because it is possible to adjust the degree of cross-linking by adjusting the amount, and it is possible to adjust the surface hardness of the hard coat layer.
- the ionizing radiation-curable resin used in the present invention is a resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as “UV”) or electron beams (hereinafter abbreviated as “EB”), especially Can be cured by UV or EB having 3 or more (meth)acryloyloxy groups in one molecule to form a three-dimensional crosslinked structure in the coating film hardness and hard coat layer, although not limited thereto A polyfunctional acrylate is preferred.
- UV ultraviolet rays
- EB electron beams
- UV or EB curable multifunctional acrylates include urethane acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth) acrylates, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane ethoxy triacrylate, glycerin propoxy triacrylate, ditrimethylolpropane tetraacrylate, etc. can be done.
- the polyfunctional acrylates may not only be used alone, but may also be used in combination of two or more.
- the ionizing radiation curable resin used in the present invention is preferably a polymer having a weight average molecular weight in the range of 700 to 3600, and the weight average molecular weight divided by the number of functional groups is 50 to 1500. A range is preferred. If the number obtained by dividing the weight-average molecular weight by the number of functional groups is less than 50, the phenomenon (curling) in which the hard coat film warps toward the hard coat layer surface side increases, causing problems in subsequent processing steps and poor processability. . Further, when the number obtained by dividing the weight average molecular weight by the number of functional groups exceeds 1500, the hardness is insufficient, which is not suitable.
- the ionizing radiation-curable resin used in the present invention has a weight average molecular weight of less than 1,500, it is desirable that the number of functional groups per molecule is 3 or more and less than 10. Further, when the weight average molecular weight of the ionizing radiation-curable resin is 1500 or more, the number of functional groups in one molecule is desirably 3 or more and 20 or less. If it is within the above range, it is possible to suppress curling while suppressing the occurrence of cracks under high temperature conditions, and to maintain appropriate workability. For example, it is suitable for use as a window film.
- the resins contained in the hard coat layer include thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester, acrylic, styrene-acrylic, cellulose, and phenol.
- Thermosetting resins such as resins, urea resins, unsaturated polyesters, epoxies, silicone resins, etc. may be blended within a range that does not impair the hardness and scratch resistance of the hard coat layer.
- an inorganic metal in the hard coat layer by including an inorganic metal in the hard coat layer, it is possible to obtain a hard coat film having good antibacterial and antiviral properties (also referred to as “antibacterial and antiviral properties"). It is possible.
- the inorganic metal used in the present invention is a substance formed by incorporating metal ions such as silver, molybdenum, copper, and zinc into an inorganic compound (inorganic material), or silver, molybdenum, copper, zinc, and the like. is a substance in which a metal ion is supported on an inorganic compound (inorganic material).
- Specific examples of the inorganic metal used in the present invention include, for example, inorganic compounds such as zeolite, apatite, and zirconia.
- Inorganic antibacterial/antiviral agents such as antibacterial/antiviral zeolite, antibacterial/antiviral apatite, and antibacterial/antiviral zirconia can be used.
- a silver-based material containing silver ions is preferable from the viewpoint of being non-toxic to the body and excellent in safety.
- a phosphate-based glass-silver-supporting compound and a silver zeolite compound are more preferable because even a small amount thereof exhibits antibacterial and antiviral properties, and the addition amount thereof can be suppressed.
- a silver-molybdenum-based material containing both silver and molybdenum components can also be preferably used in the present invention, since it exhibits good antibacterial and antiviral properties.
- the inorganic metal in the present invention is preferably an inorganic material containing at least a silver component.
- the average particle size of the inorganic metal is, for example, preferably in the range of 1 to 30000 nm, more preferably in the range of 2.5 to 20000 nm. If the average particle size is less than 1 nm, the materials are limited and difficult to obtain. On the other hand, if the average particle size exceeds 30,000 nm, the dispersibility in the hard coat paint deteriorates, leaving a grainy feeling when applied.
- the amount of the inorganic metal added is not particularly limited in the present invention, but is, for example, in the range of 0.05% by mass to 30% by mass based on the solid content in the hard coat layer. If the amount added is less than 0.05% by mass, the antibacterial and antiviral properties are not sufficiently exhibited. On the other hand, if the amount added exceeds 30% by mass, the transparency becomes low, and the visibility is remarkably deteriorated when visibility is required for a face shield, a window film, or the like.
- the term "solid content in the hard coat layer” refers to "hard coat layer-forming coating solution (hard coat paint) for forming the hard coat layer. solids”. Moreover, solid content is solid content, such as resin and an additive, for example.
- the above-mentioned silver-based material and silver-molybdenum-based material exhibit good antibacterial and antiviral performance even with a small amount added, so the amount added is , 0.1 mass % to 10 mass %.
- the above inorganic metals may be used singly or in combination of two or more.
- the hard coat layer further contains an antistatic agent.
- an antistatic agent By further adding an antistatic agent to the hard coat layer containing the inorganic metal, it is possible to obtain a hard coat film having a hard coat layer having both good antibacterial/antiviral properties and antistatic performance.
- antistatic agents is not particularly limited, but for example, conductive fillers such as metallic conductive fillers, non-metallic conductive fillers, carbon-based conductive fillers, and organic antistatic agents.
- An antistatic agent dispersed in a binder made of an organic compound can be preferably used as needed.
- a quaternary ammonium salt-based antistatic agent can be preferably used.
- the amount added is not particularly limited in the present invention, but for example, 1% by mass with respect to the solid content in the hard coat layer. It is in the range of up to 20% by mass. If the amount added is less than 1% by mass, sufficient antistatic performance cannot be obtained. On the other hand, if the amount added exceeds 20% by mass, the strength of the coating film may decrease.
- the present invention it is possible to further improve the surface hardness (scratch resistance, pencil hardness) by including inorganic fine particles in the hard coat layer. That is, by adding inorganic fine particles to the hard coat layer containing the inorganic metal, it is possible to obtain a hard coat film having good antibacterial and antiviral properties and a high hardness. can.
- the average particle size of the inorganic fine particles is preferably in the range of 5-200 nm, more preferably in the range of 10-80 nm. If the average particle size is less than 5 nm, it is difficult to obtain sufficient surface hardness. On the other hand, if the average particle size exceeds 200 nm, the gloss and transparency of the hard coat layer are likely to be reduced, and the flexibility may also be reduced.
- examples of the inorganic fine particles include inorganic oxide fine particles such as silica and alumina.
- Alumina which is mainly composed of aluminum, has a high hardness, so that an effect can be obtained with a smaller addition amount than silica.
- the amount of the inorganic fine particles added is not particularly limited in the present invention, it is, for example, in the range of 10% by mass to 60% by mass with respect to the solid content in the hard coat layer. If the amount added is less than 10% by mass, it is difficult to obtain sufficient surface hardness. On the other hand, if the amount added exceeds 60% by mass, the transparency and appearance will be degraded, and visibility will be remarkably deteriorated when visibility is required for face shields, window films, and the like.
- the hard coat layer may contain an antifogging agent.
- an antifogging agent By adding an antifogging agent to the hard coat layer containing the inorganic metal, a hard coat film having a hard coat layer having both good antibacterial/antiviral properties and antifogging properties can be obtained.
- any substance that forms a hydrophilic region can be used without particular restrictions.
- Surfactants such as cationic surfactants having quaternary ammonium groups, amphoteric surfactants such as long-chain alkylamino acids, nonionic surfactants such as polyoxyethylene nonylphenyl ether, fluorine-based surfactants, , glycosylethyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxylethyl methacrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, N-(2-methacryloyloxyethyl)-2-pyrrolidone, glyceryl methacrylate, polyethylene Hydrophilic monomers such as glycol methacrylates, hydroxylalkyl (meth)acrylates such as polyethylene glycol acrylate, polyalkylene glycol mono(meth)acrylates, (meth)acrylamides, N-vinyllact
- a silane coupling agent having an anionic hydrophilic group for example, a sulfonic acid group
- a hydrophilic monomer and a vinyl group an acrylic group, a methacrylic group, a glycidyl group, an allyl group, an epoxy group
- a reactive surfactant having a reactive end group such as a mercapto group, cyano group, isocyano group, amino group, etc. and a hydrophilic moiety such as a sulfone group, hydroxyl group, ammonium chloride etc.
- a hydrophilic moiety such as a sulfone group, hydroxyl group, ammonium chloride etc.
- the amount of the antifogging agent added is not particularly limited in the present invention, but is, for example, in the range of 10% by mass to 70% by mass based on the solid content in the hard coat layer. If the amount added is less than 10% by mass, sufficient antifogging properties cannot be obtained. On the other hand, if the amount added exceeds 70% by mass, the scratch resistance of the film may decrease.
- At least one thin film made of metal or metal oxide can be laminated on the surface of the substrate opposite to the hard coat layer or between the substrate and the hard coat layer.
- the heat shielding effect (heat shielding property) of the hard coat film can be obtained.
- Specific metals or metal oxides include, for example, aluminum, silver, gold, nickel, cobalt, and stainless steel, and alloys thereof, titanium dioxide, tin oxide, indium oxide, zinc oxide, and tungsten oxide. .
- the layer (thin film) made of the metal or metal oxide described above for example, a known thin film forming method such as a vacuum vapor deposition method, a sputtering method, or a chemical vapor deposition method (CVD method) can be applied.
- the thickness of the layer (thin film) made of the metal or metal oxide described above is preferably in the range of 10 to 1000 nm. If the thickness is less than 10 nm, a sufficient heat shielding effect cannot be obtained, and if it exceeds 1000 nm or more, the transparency tends to decrease, and it is not suitable for applications such as window films that require visibility.
- the hard coat layer-forming coating liquid (hard coat paint) for forming the hard coat layer contains a known photopolymerization initiator.
- a photopolymerization initiator can include Acetophenones and benzophenones can be used as such a photopolymerization initiator.
- a leveling agent (surface modifier) can be used for the purpose of improving coatability.
- known leveling agents can be used.
- a fluorine-based or siloxane-based antifouling agent (leveling agent, surfactant, etc.) can be added to the hard coat layer.
- the amount of the antifouling agent to be added is not particularly limited, but is preferably 0.05% by mass to 2.0% by mass based on the resin solid content in the hard coat paint.
- the hard coat film of the present invention it is suitable, for example, to increase the haze value of the hard coat layer.
- organic fine particles include fine particles of acryl, melamine-formaldehyde condensate, polyethylene, styrene acryl, polyester, and the like.
- examples of inorganic fine particles include fine particles of alumina, zinc oxide, silica, titanium oxide, cerium oxide, and the like. can be exemplified.
- the amount of the fine particles to be added is preferably in the range of 10% by mass to 80% by mass based on the resin solid content in the hard coat paint.
- ultraviolet absorbers As other additives added to the hard coat layer, ultraviolet absorbers, antifoaming agents, surface tension modifiers, antioxidants, light stabilizers, etc. may be blended as needed.
- the hard coat layer contains antistatic agents, inorganic fine particles, organic fine particles, antifogging agents, photopolymerization initiators, other additives, etc. in an appropriate solvent.
- the solvent can be appropriately selected according to the solubility of the resin to be blended, and any solvent that can uniformly dissolve or disperse at least the solid content (resin, other additives described above, etc.) may be used.
- solvents include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetic acid.
- organic solvents such as ester solvents such as butyl and methyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol alone Alternatively, several types can be appropriately combined and used.
- the concentration (solid content concentration) of the coating liquid is not particularly limited, but can be, for example, in the range of about 10% by mass to 70% by mass.
- the irradiation amount of ionizing radiation (UV, EB, etc.) after coating and drying the hard coat layer forming coating solution on the substrate is the irradiation amount necessary to give the hard coat layer sufficient hardness. It may be set appropriately according to the type of the ionizing radiation curable resin.
- the method of applying the hard coat-forming coating liquid for forming the hard coat layer is not particularly limited, but gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, Known coating methods such as coating, screen printing, and spray coating can be used.
- drying temperature and heating time (drying time) in the drying process after coating can be set as appropriate.
- the coating thickness (after drying) of the hard coat layer varies depending on the application of the hard coat film, so it is not particularly limited, but is generally in the range of, for example, 1.0 ⁇ m to 20.0 ⁇ m. preferred. If the coating thickness is less than 1.0 ⁇ m, it is difficult to obtain the required surface hardness, which is not preferable. On the other hand, when the coating thickness exceeds 20.0 ⁇ m, curling is likely to occur, which is not preferable because the handleability in the manufacturing process is deteriorated.
- the hard coat film of the present invention has a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. ) are listed below. (Embodiment 1)
- the hard coat layer is provided on both sides of the substrate, and one layer contains the inorganic metal of the present invention and an antistatic agent, and has antibacterial/antiviral properties and antistatic performance.
- the other is a hard coat layer containing the inorganic metal of the present invention and an antifogging agent in the layer and having antibacterial/antiviral and antifogging properties.
- the same hard coat layer is provided on both surfaces of the substrate, and one contains the inorganic metal and inorganic fine particles of the present invention in the layer, has antibacterial / antiviral properties, and has high antibacterial and antiviral properties. It is a hard coat layer, and the other is a hard coat layer having the antibacterial/antiviral and antifog properties described above.
- An embodiment of such a hard coat film is suitable, for example, as a face shield film.
- a hard coat layer having antibacterial/antiviral properties and antistatic properties is provided on one surface of the substrate.
- a hard coat layer having the antibacterial/antiviral properties and high hardness is provided on one surface of the base material.
- a hard coat film is applied to members such as partitions, windows, table covers, and touch panels of electronic devices on the other surface of the substrate (the surface opposite to the surface on which the hard coat layer is provided).
- An adhesive layer for sticking can be provided.
- Such a hard coat film is suitable as, for example, a partition film, a window film, a table cover film, or a display or touch panel film for electronic devices.
- a hard coat layer having antibacterial/antiviral and antifogging properties is provided on one surface of the substrate.
- an adhesive layer is provided for attaching the hard coat film to members such as windows, bus mirrors, and freezer/refrigerator windows. can be provided.
- Embodiments of such hard coat films are suitable, for example, as window films, bus mirror films, and freezer-refrigerator window films.
- a hard coat layer having the above antibacterial/antiviral and antistatic properties is provided on one side of the base material, or one side of the base material has the above antibacterial/antiviral properties. and a hard coat layer having a high hardness is provided.
- the other surface of the substrate the surface opposite to the surface on which the hard coat layer is provided, or between the substrate and the hard coat layer, a metal or metal oxide At least one thin film can be laminated.
- Embodiments of such a hard coat film are suitable as, for example, partition films and window films that require a heat shielding effect.
- a hard coat film having good antibacterial and antiviral properties As described in detail above, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and antistatic properties. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and high hardness. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and antifogging properties. Furthermore, it is possible to provide a hard coat film having good antibacterial and antiviral properties and a heat shielding effect.
- a hard coat film that also has multiple properties among the above-mentioned antistatic performance, high hardness, antifogging properties, heat shielding properties, and the like.
- Example 1 [Preparation of Coating Solution for Forming Hard Coat Layer] Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 1.5% (based on solid content 0.5%) of a surface modifier (Megafac R-08MH; manufactured by DIC Corporation), and a silver-molybdenum compound as the inorganic metal of the present invention.
- Ionizing radiation curable resin Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.
- Irgacure 184 photopolymerization initiator, manufactured by BASF
- hard coat paint 30% hard coat layer-forming coating liquid
- a hard coat paint having the above composition was applied to one side of a polyethylene terephthalate (PET) base film (film thickness: 50 ⁇ m) using a bar coater, and then dried in a drying oven at 80° C. for 60 seconds.
- a hard coat layer having a thickness of 2 ⁇ m after drying was formed.
- this hard coat layer is cured by UV irradiation with a UV dose of 200 mJ/cm 2 using a UV irradiation device set at a height of 60 mm from the coated surface to prepare the hard coat film of this example. bottom.
- Example 2 The antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was replaced with an antibacterial/antiviral agent containing a silver compound (Zeomic HD10N (trade name); manufactured by Sinanen Zeomic Co., Ltd.).
- Zeomic HD10N trade name
- a hard coat film of Example 2 was produced using a hard coat paint prepared in the same manner except for changing to .
- Example 3 [Preparation of paint for hard coating] Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3.
- a hard coat film of Example 3 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 4 ⁇ m after drying.
- Example 4 [Preparation of paint for hard coating] Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3.
- a hard coat film of Example 4 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 ⁇ m after drying.
- Example 5 [Preparation of paint for hard coating] An ionizing radiation-curable resin (Aica Itron Z-942-4 (trade name); manufactured by Aica Kogyo Co., Ltd.) containing a fluorine-based surfactant (anti-fogging agent) and having urethane acrylate as a main component was added at 99%. 7%, and 0.3% (0.3% of the solid content) of an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention is blended, and propylene glycol monomethyl ether (PGME) is added. to prepare a hard coat paint having a final solid concentration of 40%.
- PGME propylene glycol monomethyl ether
- a hard coat film of Example 5 was produced in the same manner as in Example 1, except that the hard coat coating composition having the above composition was used and the hard coat layer had a thickness of 4 ⁇ m after drying.
- Example 6 [Preparation of paint for hard coating] Irgacure 184 (photopolymerization initiator, manufactured by BASF Co., Ltd.) containing 90 parts of ionizing radiation curable resin (Shikou UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) as the main component and urethane acrylate as the main component3.
- Irgacure 184 photopolymerization initiator, manufactured by BASF Co., Ltd.
- ionizing radiation curable resin Shikou UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.
- a hard coat film of Example 6 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 ⁇ m after drying.
- Example 7 On the opposite side of the hard coat layer on the substrate of the hard coat film of Example 3, an indium oxide/tin compound (ITO) layer was formed by a sputtering apparatus (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd. ), a hard coat film of Example 7 was prepared by coating to a thickness of 600 nm.
- ITO indium oxide/tin compound
- Example 8 An indium oxide/tin compound (ITO) layer was formed on one side of a polyethylene terephthalate (PET) substrate film (film thickness: 50 ⁇ m) using a sputtering device (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd.). was applied to a thickness of 600 nm. A hard coat layer having a thickness of 4 ⁇ m after drying was formed thereon by using the same hard coat paint as in Example 3, and a hard coat film of Example 8 was produced.
- a sputtering device magnetictron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd.
- Comparative example 1 Using a hard coat paint prepared in the same manner as in Example 1 except that the antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was not contained (omitted), A hard coat film of Comparative Example 1 was produced.
- ⁇ Thickness of coating film> The formed thickness of the coating film of the hard coat layer was measured using Thin-Film Analyzer F20 (trade name) (manufactured by FILMETRICS).
- Antibacterial properties It was measured by a method according to the JIS Z 2801:2010 standard. An antibacterial activity value of 2.0 or more was determined to be effective as an antibacterial activity value.
- Antiviral properties It was measured by a method according to the standard of ISO 21702:2019. An antiviral activity value of 2.0 or more was determined to be effective as an antiviral activity value.
- ⁇ Total light transmittance> Each hard coat film was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory. The measurement was performed based on the JIS-K7361 standard. As for the evaluation criteria, a light transmittance of 88% or more was considered acceptable.
- ⁇ Surface resistance> The surface resistance values of the hard coat films produced in Examples 3, 7 and 8 were measured using Hiresta-UX MCP-HT800 manufactured by Nitto Seiko Analytic Co., Ltd. A USR probe was used for the measurement, and the applied voltage was 500V. As for the evaluation criteria, a surface resistance value of less than 1.0 ⁇ 10 11 ⁇ / ⁇ was considered acceptable. 10 11 ⁇ / ⁇ is the level at which dust does not adhere due to static electricity.
- ⁇ Pencil hardness> For each hard coat film produced in Examples and Comparative Examples, pencil hardness was measured by a test method according to JIS-K-5600-5-4. The hardness without scratches on the surface is indicated. As for the judgment criteria, a hardness of 2H or more was regarded as acceptable.
- the heat shielding property of the hard coat film was evaluated by the "shielding coefficient".
- the shielding coefficient was measured according to JIS A 5759. If the shielding coefficient is less than 1.0, it has heat shielding properties (heat shielding effect).
- Example 3 in which the hard coat layer contains an antistatic agent, a hard coat film having both good antibacterial and antiviral properties and antistatic performance is obtained.
- Example 4 in which the hard coat layer contains inorganic fine particles, a hard coat film having good antibacterial and antiviral properties and high hardness can be obtained.
- Example 5 in which the hard coat layer contains an antifogging agent, a hard coat film having good antibacterial and antiviral properties and antifogging properties is obtained.
- Example 6 a hard coat film having good antibacterial and antiviral properties and high haze is obtained.
- Examples 7 and 8 hard coat films having good antibacterial and antiviral properties and heat shielding effects are obtained.
Landscapes
- Laminated Bodies (AREA)
Abstract
The present invention provides a hard coat film having satisfactory antibacterial properties and satisfactory antiviral properties. The hard coat film according to the present invention is configured such that a hard coat layer containing at least an inorganic metal and a ionizing-radiation-curable resin is provided on at least one surface of a base material. The inorganic metal is, for example, an inorganic material containing at least a silver component. The amount of the inorganic metal to be added is, for example, 0.05% by mass to 30% by mass relative to the solid content in the hard coat layer.
Description
本発明は、抗菌性・抗ウイルス性を有するハードコートフィルムに関するものである。
The present invention relates to a hard coat film having antibacterial and antiviral properties.
現在、特に感染症対策の観点から、人の手が表面に直接触れたりする可能性のある、たとえばフェイスシールド用フィルム、パーティション用フィルム、ウィンドウフィルム、電子機器等のタッチパネル用フィルムなどは、抗菌性・抗ウイルス性を有していることが要望されている。
At present, especially from the perspective of infectious disease control, antibacterial films such as face shield films, partition films, window films, touch panel films for electronic devices, etc., which may come into direct contact with the surface of human hands,・It is desired to have antiviral properties.
従来技術としては、たとえば、フィルム基材上に、抗菌剤等を含有する抗菌ハードコート層が積層されたハードコートフィルムが種々提案されている（例えば、特許文献１乃至３等を参照。）。
As a conventional technology, for example, various hard coat films have been proposed in which an antibacterial hard coat layer containing an antibacterial agent or the like is laminated on a film substrate (see, for example, Patent Documents 1 to 3, etc.).
上記のように、従来より、抗菌性を備えたハードコートフィルムは種々提案されているが、最近では、抗菌性だけではなく、良好な抗ウイルス性も兼ね備えたものが要望されている。また、用途によっては、抗菌性・抗ウイルス性に加えて、たとえば、帯電防止性能、高硬度、防曇性、遮熱性（つまり遮熱乃至は断熱性）なども要求されており、このようにハードコートフィルムに対する機能的要求は高まってきている。
As described above, various antibacterial hard coat films have been proposed in the past, but recently, there is a demand for not only antibacterial properties but also good antiviral properties. In addition, depending on the application, in addition to antibacterial and antiviral properties, for example, antistatic performance, high hardness, antifog properties, heat shielding properties (that is, heat shielding or heat insulating properties) are required. Functional requirements for hard coat films are increasing.
そこで、本発明の目的は、第１に、良好な抗菌性及び抗ウイルス性を備えたハードコートフィルムを提供することであり、第２に、良好な抗菌性及び抗ウイルス性を備え、さらに帯電防止性能を有するハードコートフィルムを提供することであり、第３に、良好な抗菌性及び抗ウイルス性を備え、さらに高硬度のハードコートフィルムを提供することであり、第４には、良好な抗菌性及び抗ウイルス性を備え、さらに防曇性を有するハードコートフィルムを提供することであり、第５には、良好な抗菌性及び抗ウイルス性を備え、さらに遮熱性を有するハードコートフィルムを提供することである。またさらには、良好な抗菌性及び抗ウイルス性に加え、上記の帯電防止性能、高硬度、防曇性や遮熱性等のうちの複数の性能をも兼備えるハードコートフィルムを提供することも目的とする。
Accordingly, an object of the present invention is, firstly, to provide a hard coat film with good antibacterial and antiviral properties, and secondly, to provide a hard coat film with good antibacterial and antiviral properties, An object of the present invention is to provide a hard coat film having an antibacterial property. Third, an object of the present invention is to provide a hard coat film having good antibacterial and antiviral properties and a high hardness. To provide a hard coat film having antibacterial and antiviral properties and also having antifogging properties. Fifthly, a hard coat film having good antibacterial and antiviral properties and heat shielding properties is provided. to provide. It is another object of the present invention to provide a hard-coated film that has not only good antibacterial properties and antiviral properties, but also multiple properties among the aforementioned antistatic properties, high hardness, antifogging properties, and heat shielding properties. and
本発明は、上記課題を解決するため鋭意検討を行い、得られた種々の知見に基づき完成したものである。
すなわち、本発明は以下の構成を有するものである。 The present invention has been completed based on various findings obtained through intensive studies to solve the above problems.
That is, the present invention has the following configurations.
すなわち、本発明は以下の構成を有するものである。 The present invention has been completed based on various findings obtained through intensive studies to solve the above problems.
That is, the present invention has the following configurations.
（第１の発明）
基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたことを特徴とするハードコートフィルム。 (First invention)
A hard coat film comprising a substrate and a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin provided on at least one surface of the substrate.
基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたことを特徴とするハードコートフィルム。 (First invention)
A hard coat film comprising a substrate and a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin provided on at least one surface of the substrate.
（第２の発明）
前記無機系金属は、少なくとも銀成分を含む無機材料であることを特徴とする第１の発明に記載のハードコートフィルム。 (Second invention)
The hard coat film according to the first invention, wherein the inorganic metal is an inorganic material containing at least a silver component.
前記無機系金属は、少なくとも銀成分を含む無機材料であることを特徴とする第１の発明に記載のハードコートフィルム。 (Second invention)
The hard coat film according to the first invention, wherein the inorganic metal is an inorganic material containing at least a silver component.
（第３の発明）
前記無機系金属の添加量は、前記ハードコート層中の固形分に対して、０．０５質量％～３０質量％の範囲であることを特徴とする第１又は第２の発明に記載のハードコートフィルム。 (Third invention)
The hard coat layer according to the first or second invention, wherein the amount of the inorganic metal added is in the range of 0.05% by mass to 30% by mass with respect to the solid content in the hard coat layer. coat film.
前記無機系金属の添加量は、前記ハードコート層中の固形分に対して、０．０５質量％～３０質量％の範囲であることを特徴とする第１又は第２の発明に記載のハードコートフィルム。 (Third invention)
The hard coat layer according to the first or second invention, wherein the amount of the inorganic metal added is in the range of 0.05% by mass to 30% by mass with respect to the solid content in the hard coat layer. coat film.
（第４の発明）
前記ハードコート層は、さらに帯電防止剤を含有することを特徴とする第１乃至第３の発明のいずれかに記載のハードコートフィルム。 (Fourth invention)
The hard coat film according to any one of the first to third inventions, wherein the hard coat layer further contains an antistatic agent.
前記ハードコート層は、さらに帯電防止剤を含有することを特徴とする第１乃至第３の発明のいずれかに記載のハードコートフィルム。 (Fourth invention)
The hard coat film according to any one of the first to third inventions, wherein the hard coat layer further contains an antistatic agent.
（第５の発明）
前記ハードコート層は、さらに無機微粒子を含有することを特徴とする第１乃至第４の発明のいずれかに記載のハードコートフィルム。 (Fifth Invention)
The hard coat film according to any one of the first to fourth inventions, wherein the hard coat layer further contains inorganic fine particles.
前記ハードコート層は、さらに無機微粒子を含有することを特徴とする第１乃至第４の発明のいずれかに記載のハードコートフィルム。 (Fifth Invention)
The hard coat film according to any one of the first to fourth inventions, wherein the hard coat layer further contains inorganic fine particles.
（第６の発明）
前記ハードコート層は、さらに防曇剤を含有することを特徴とする第１乃至第５の発明のいずれかに記載のハードコートフィルム。 (Sixth invention)
The hard coat film according to any one of the first to fifth inventions, wherein the hard coat layer further contains an antifogging agent.
前記ハードコート層は、さらに防曇剤を含有することを特徴とする第１乃至第５の発明のいずれかに記載のハードコートフィルム。 (Sixth invention)
The hard coat film according to any one of the first to fifth inventions, wherein the hard coat layer further contains an antifogging agent.
（第７の発明）
前記ハードコート層は、さらに有機微粒子を含有することを特徴とする第１乃至第６の発明のいずれかに記載のハードコートフィルム。 (Seventh invention)
The hard coat film according to any one of the first to sixth inventions, wherein the hard coat layer further contains organic fine particles.
前記ハードコート層は、さらに有機微粒子を含有することを特徴とする第１乃至第６の発明のいずれかに記載のハードコートフィルム。 (Seventh invention)
The hard coat film according to any one of the first to sixth inventions, wherein the hard coat layer further contains organic fine particles.
（第８の発明）
前記基材上の前記ハードコート層と反対の面、もしくは前記基材と前記ハードコート層との間に、金属または金属酸化物からなる薄膜が少なくとも1層以上積層されてなることを特徴とする第１乃至第７の発明のいずれかに記載のハードコートフィルム。 (Eighth invention)
At least one layer of a thin film made of a metal or metal oxide is laminated on the surface of the base material opposite to the hard coat layer or between the base material and the hard coat layer. The hard coat film according to any one of the first to seventh inventions.
前記基材上の前記ハードコート層と反対の面、もしくは前記基材と前記ハードコート層との間に、金属または金属酸化物からなる薄膜が少なくとも1層以上積層されてなることを特徴とする第１乃至第７の発明のいずれかに記載のハードコートフィルム。 (Eighth invention)
At least one layer of a thin film made of a metal or metal oxide is laminated on the surface of the base material opposite to the hard coat layer or between the base material and the hard coat layer. The hard coat film according to any one of the first to seventh inventions.
本発明によれば、良好な抗菌性及び抗ウイルス性を備えたハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに帯電防止性能を有するハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに高硬度のハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに防曇性を有するハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに遮熱性を有するハードコートフィルムを提供することができる。
さらには、本発明によれば、良好な抗菌性及び抗ウイルス性に加え、上記の帯電防止性能、高硬度、防曇性や遮熱性等のうちの複数の性能をも兼備えるハードコートフィルムを提供することができる。 According to the present invention, it is possible to provide a hard coat film with good antibacterial and antiviral properties.
Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antistatic properties.
In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and high hardness.
Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antifogging properties.
In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as heat shielding properties.
Furthermore, according to the present invention, in addition to good antibacterial and antiviral properties, a hard coat film that also has multiple performances such as the above antistatic performance, high hardness, antifogging properties, and heat shielding properties. can provide.
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに帯電防止性能を有するハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに高硬度のハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに防曇性を有するハードコートフィルムを提供することができる。
また、本発明によれば、良好な抗菌性及び抗ウイルス性を備え、さらに遮熱性を有するハードコートフィルムを提供することができる。
さらには、本発明によれば、良好な抗菌性及び抗ウイルス性に加え、上記の帯電防止性能、高硬度、防曇性や遮熱性等のうちの複数の性能をも兼備えるハードコートフィルムを提供することができる。 According to the present invention, it is possible to provide a hard coat film with good antibacterial and antiviral properties.
Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antistatic properties.
In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and high hardness.
Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as antifogging properties.
In addition, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties, as well as heat shielding properties.
Furthermore, according to the present invention, in addition to good antibacterial and antiviral properties, a hard coat film that also has multiple performances such as the above antistatic performance, high hardness, antifogging properties, and heat shielding properties. can provide.
以下、本発明の実施の形態について詳述する。
なお、本発明において、特に断りの無い限り、「○○～△△」との記載は「○○以上△△以下」を意味するものとする。 Embodiments of the present invention will be described in detail below.
In the present invention, unless otherwise specified, the description "○○ to △△" means "○○ or more and △△ or less".
なお、本発明において、特に断りの無い限り、「○○～△△」との記載は「○○以上△△以下」を意味するものとする。 Embodiments of the present invention will be described in detail below.
In the present invention, unless otherwise specified, the description "○○ to △△" means "○○ or more and △△ or less".
以下に、本発明のハードコートフィルムについて説明する。
本発明のハードコートフィルムは、上記のとおり、基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたことを特徴とするハードコートフィルムである。 The hard coat film of the present invention is described below.
As described above, the hard coat film of the present invention is a hard coat film characterized by having a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. be.
本発明のハードコートフィルムは、上記のとおり、基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたことを特徴とするハードコートフィルムである。 The hard coat film of the present invention is described below.
As described above, the hard coat film of the present invention is a hard coat film characterized by having a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. be.
本発明のハードコートフィルムは、例えば、フェイスシールド用フィルム、パーティション用フィルム、ウィンドウフィルム、テーブルカバー用フィルム、バスミラー用フィルム、冷凍冷蔵庫窓用フィルム、あるいは電子機器等のディスプレイ用またはタッチパネル用フィルム、等々に好ましく適用することができる。勿論、ここに挙げた用途はほんの一例であり、これらの用途に限定されるものではない。
The hard coat film of the present invention includes, for example, a face shield film, a partition film, a window film, a table cover film, a bus mirror film, a freezer/refrigerator window film, or a display or touch panel film for electronic devices, etc. can be preferably applied. Of course, the uses listed here are only examples, and the present invention is not limited to these uses.
このハードコートフィルムの被塗工基材としては、通常フィルム基材が用いられる。
本発明において使用されるフィルム基材は、特に限定されるものではなく、例えば、アクリル系樹脂、トリアセチルセルロース、ポリエチレンテレフタレート、シクロオレフィンポリマー、ポリカーボネート、ポリエチレンナフタレート、ポリエチレン、ポリトリメチレンテレフタレート、ポリプロピレン、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリスチレン、ポリメチルメタクリレート、ポリスチレングリシジルメタクリレート、芳香族式ポリイミド、脂環式ポリイミド、ポリアミドイミド及びこれらの混合物を例示することができる。これらのフィルム基材のなかでも、特にポリエステル系フィルム、アクリル系フィルム、トリアセチルセルロース、ポリエチレンテレフタレート、ポリカーボネートが好適である。 A film substrate is generally used as the substrate to be coated with the hard coat film.
The film substrate used in the present invention is not particularly limited, and examples thereof include acrylic resins, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polycarbonate, polyethylene naphthalate, polyethylene, polytrimethylene terephthalate, and polypropylene. , polybutylene terephthalate, polybutylene naphthalate, polystyrene, polymethyl methacrylate, polystyrene glycidyl methacrylate, aromatic polyimide, alicyclic polyimide, polyamideimide and mixtures thereof. Among these film substrates, polyester films, acrylic films, triacetyl cellulose, polyethylene terephthalate, and polycarbonate are particularly suitable.
本発明において使用されるフィルム基材は、特に限定されるものではなく、例えば、アクリル系樹脂、トリアセチルセルロース、ポリエチレンテレフタレート、シクロオレフィンポリマー、ポリカーボネート、ポリエチレンナフタレート、ポリエチレン、ポリトリメチレンテレフタレート、ポリプロピレン、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリスチレン、ポリメチルメタクリレート、ポリスチレングリシジルメタクリレート、芳香族式ポリイミド、脂環式ポリイミド、ポリアミドイミド及びこれらの混合物を例示することができる。これらのフィルム基材のなかでも、特にポリエステル系フィルム、アクリル系フィルム、トリアセチルセルロース、ポリエチレンテレフタレート、ポリカーボネートが好適である。 A film substrate is generally used as the substrate to be coated with the hard coat film.
The film substrate used in the present invention is not particularly limited, and examples thereof include acrylic resins, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polycarbonate, polyethylene naphthalate, polyethylene, polytrimethylene terephthalate, and polypropylene. , polybutylene terephthalate, polybutylene naphthalate, polystyrene, polymethyl methacrylate, polystyrene glycidyl methacrylate, aromatic polyimide, alicyclic polyimide, polyamideimide and mixtures thereof. Among these film substrates, polyester films, acrylic films, triacetyl cellulose, polyethylene terephthalate, and polycarbonate are particularly suitable.
本発明のハードコートフィルムを、例えば、フェイスシールド用フィルムとして用いる場合は、フィルム基材は、透明性や価格的に有利という観点から、トリアセチルセルロースやポリエチレンテレフタレートが好ましく、パーティション用フィルムやウィンドウフィルムとして用いる場合には、フィルム基材は、アクリル系樹脂フィルムや、耐衝撃性や価格的に有利という観点から、ポリカーボネートやポリエチレンテレフタレートが好ましい。基材には紫外線カット性能を有することも可能である。
When the hard coat film of the present invention is used as, for example, a face shield film, the film substrate is preferably triacetyl cellulose or polyethylene terephthalate from the viewpoint of transparency and cost advantage, and is a partition film or window film. When used as a film substrate, the film substrate is preferably an acrylic resin film, or polycarbonate or polyethylene terephthalate from the viewpoint of impact resistance and cost advantage. It is also possible for the base material to have UV cut performance.
上記フィルム基材の厚さは、用途によっても異なるので一概には言えないが、通常、１０～１０００μｍの範囲が好ましく、より好ましくは２０μｍ～３００μｍの範囲である。
The thickness of the film substrate varies depending on the application, so it cannot be generalized, but it is usually preferably in the range of 10 to 1000 μm, more preferably in the range of 20 to 300 μm.
次に、上記ハードコート層について説明する。
上記ハードコート層に含まれる樹脂としては、被膜を形成する樹脂であれば特に制限なく用いることができるが、特にハードコート層の表面硬度（耐擦傷性）を付与し、また、紫外線等の露光量によって架橋度合を調節することが可能であり、ハードコート層の表面硬度の調節が可能になるという点で電離放射線硬化型樹脂を用いることが好ましい。 Next, the hard coat layer will be described.
As the resin contained in the hard coat layer, any resin that forms a film can be used without particular limitation. It is preferable to use an ionizing radiation-curable resin because it is possible to adjust the degree of cross-linking by adjusting the amount, and it is possible to adjust the surface hardness of the hard coat layer.
上記ハードコート層に含まれる樹脂としては、被膜を形成する樹脂であれば特に制限なく用いることができるが、特にハードコート層の表面硬度（耐擦傷性）を付与し、また、紫外線等の露光量によって架橋度合を調節することが可能であり、ハードコート層の表面硬度の調節が可能になるという点で電離放射線硬化型樹脂を用いることが好ましい。 Next, the hard coat layer will be described.
As the resin contained in the hard coat layer, any resin that forms a film can be used without particular limitation. It is preferable to use an ionizing radiation-curable resin because it is possible to adjust the degree of cross-linking by adjusting the amount, and it is possible to adjust the surface hardness of the hard coat layer.
本発明に用いる電離放射線硬化型樹脂は、紫外線（以下、「ＵＶ」と略記する。）や電子線（以下、「ＥＢ」と略記する。）を照射することによって硬化する樹脂であれば、特に限定されるものではないが、塗膜硬度及びハードコート層が３次元的な架橋構造を形成するために１分子内に３個以上の（メタ）アクリロイルオキシ基を有するＵＶまたはＥＢにて硬化可能な多官能アクリレートからなるものが好ましい。ＵＶまたはＥＢ硬化可能な多官能アクリレートの具体例としては、ウレタンアクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパンエトキシトリアクリレート、グリセリンプロポキシトリアクリレート、ジトリメチロールプロパンテトラアクリレート等を挙げることができる。なお、多官能アクリレートは単独で使用するだけでなく、２種以上の複数を混合し使用してもよい。
The ionizing radiation-curable resin used in the present invention is a resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as “UV”) or electron beams (hereinafter abbreviated as “EB”), especially Can be cured by UV or EB having 3 or more (meth)acryloyloxy groups in one molecule to form a three-dimensional crosslinked structure in the coating film hardness and hard coat layer, although not limited thereto A polyfunctional acrylate is preferred. Specific examples of UV or EB curable multifunctional acrylates include urethane acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth) acrylates, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane ethoxy triacrylate, glycerin propoxy triacrylate, ditrimethylolpropane tetraacrylate, etc. can be done. The polyfunctional acrylates may not only be used alone, but may also be used in combination of two or more.
さらに、本発明に用いる電離放射線硬化型樹脂は、重量平均分子量が例えば７００～３６００の範囲内であるポリマーを用いることが好ましく、重量平均分子量を官能基数で割ったときの数字が５０～１５００の範囲のものが好ましい。重量平均分子量を官能基数で割ったときの数字が５０未満の場合、ハードコートフィルムがハードコート層面側に反りかえる現象（カール）が大きくなり、その後の加工工程に不具合が生じ、加工適性が悪い。また、重量平均分子量を官能基数で割ったときの数字が１５００を超えると、硬度が不足するため適さない。
Furthermore, the ionizing radiation curable resin used in the present invention is preferably a polymer having a weight average molecular weight in the range of 700 to 3600, and the weight average molecular weight divided by the number of functional groups is 50 to 1500. A range is preferred. If the number obtained by dividing the weight-average molecular weight by the number of functional groups is less than 50, the phenomenon (curling) in which the hard coat film warps toward the hard coat layer surface side increases, causing problems in subsequent processing steps and poor processability. . Further, when the number obtained by dividing the weight average molecular weight by the number of functional groups exceeds 1500, the hardness is insufficient, which is not suitable.
また、本発明に用いる電離放射線硬化型樹脂は、重量平均分子量が１５００未満である場合は、１分子中の官能基数は３個以上１０個未満であることが望ましい。また、上記電離放射線硬化型樹脂の重量平均分子量が１５００以上である場合は、１分子中の官能基数は３個以上２０個以下であることが望ましい。上記範囲内であれば、高温条件下でのクラックの発生を抑えつつ、カールが抑制でき、適切な加工適性を維持できる。例えば、ウィンドウフィルムの用途には好適である。
In addition, when the ionizing radiation-curable resin used in the present invention has a weight average molecular weight of less than 1,500, it is desirable that the number of functional groups per molecule is 3 or more and less than 10. Further, when the weight average molecular weight of the ionizing radiation-curable resin is 1500 or more, the number of functional groups in one molecule is desirably 3 or more and 20 or less. If it is within the above range, it is possible to suppress curling while suppressing the occurrence of cracks under high temperature conditions, and to maintain appropriate workability. For example, it is suitable for use as a window film.
また、上記ハードコート層に含まれる樹脂としては、上述の電離放射線硬化型樹脂の他に、ポリエチレン、ポリプロピレン、ポリスチレン、ポリカーボネート、ポリエステル、アクリル、スチレン－アクリル、繊維素等の熱可塑性樹脂や、フェノール樹脂、ウレア樹脂、不飽和ポリエステル、エポキシ、珪素樹脂等の熱硬化性樹脂をハードコート層の硬度、耐擦傷性を損なわない範囲内で配合してもよい。
In addition to the ionizing radiation-curable resins described above, the resins contained in the hard coat layer include thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester, acrylic, styrene-acrylic, cellulose, and phenol. Thermosetting resins such as resins, urea resins, unsaturated polyesters, epoxies, silicone resins, etc. may be blended within a range that does not impair the hardness and scratch resistance of the hard coat layer.
本発明では、上記ハードコート層に無機系金属を含有させることにより、良好な抗菌性及び抗ウイルス性（「抗菌性・抗ウイルス性」とも表記する。）を備えたハードコートフィルムを得ることが可能である。
In the present invention, by including an inorganic metal in the hard coat layer, it is possible to obtain a hard coat film having good antibacterial and antiviral properties (also referred to as "antibacterial and antiviral properties"). It is possible.
本発明に用いられる上記無機系金属とは、無機化合物（無機材料）に、例えば、銀、モリブデン、銅、亜鉛等の金属イオンを取り込んで形成した物質、あるいは、銀、モリブデン、銅、亜鉛等の金属イオンを無機化合物（無機材料）に担持させた物質である。
本発明に用いられる無機系金属の具体例としては、例えば、無機化合物のゼオライト、アパタイト、ジルコニア等の物質に銀、モリブデン、銅、亜鉛等のうちの少なくともいずれかの金属イオンを取り込んで形成した抗菌性・抗ウイルス性ゼオライト、抗菌性・抗ウイルス性アパタイト、抗菌性・抗ウイルス性ジルコニア等の無機系抗菌・抗ウイルス剤が使用できる。また、銀、モリブデン、銅、亜鉛等のうちの少なくともいずれかの金属イオンをゼオライト、アパタイト、ジルコニア、ガラス等に担持させた化合物なども好ましく挙げられる。これらの金属イオンを無機材料に担持させることで、経時での金属成分の脱落を防ぐことができる。 The inorganic metal used in the present invention is a substance formed by incorporating metal ions such as silver, molybdenum, copper, and zinc into an inorganic compound (inorganic material), or silver, molybdenum, copper, zinc, and the like. is a substance in which a metal ion is supported on an inorganic compound (inorganic material).
Specific examples of the inorganic metal used in the present invention include, for example, inorganic compounds such as zeolite, apatite, and zirconia. Inorganic antibacterial/antiviral agents such as antibacterial/antiviral zeolite, antibacterial/antiviral apatite, and antibacterial/antiviral zirconia can be used. Also preferred are compounds in which at least one metal ion of silver, molybdenum, copper, zinc, etc. is supported on zeolite, apatite, zirconia, glass, or the like. Detachment of the metal component over time can be prevented by supporting these metal ions on the inorganic material.
本発明に用いられる無機系金属の具体例としては、例えば、無機化合物のゼオライト、アパタイト、ジルコニア等の物質に銀、モリブデン、銅、亜鉛等のうちの少なくともいずれかの金属イオンを取り込んで形成した抗菌性・抗ウイルス性ゼオライト、抗菌性・抗ウイルス性アパタイト、抗菌性・抗ウイルス性ジルコニア等の無機系抗菌・抗ウイルス剤が使用できる。また、銀、モリブデン、銅、亜鉛等のうちの少なくともいずれかの金属イオンをゼオライト、アパタイト、ジルコニア、ガラス等に担持させた化合物なども好ましく挙げられる。これらの金属イオンを無機材料に担持させることで、経時での金属成分の脱落を防ぐことができる。 The inorganic metal used in the present invention is a substance formed by incorporating metal ions such as silver, molybdenum, copper, and zinc into an inorganic compound (inorganic material), or silver, molybdenum, copper, zinc, and the like. is a substance in which a metal ion is supported on an inorganic compound (inorganic material).
Specific examples of the inorganic metal used in the present invention include, for example, inorganic compounds such as zeolite, apatite, and zirconia. Inorganic antibacterial/antiviral agents such as antibacterial/antiviral zeolite, antibacterial/antiviral apatite, and antibacterial/antiviral zirconia can be used. Also preferred are compounds in which at least one metal ion of silver, molybdenum, copper, zinc, etc. is supported on zeolite, apatite, zirconia, glass, or the like. Detachment of the metal component over time can be prevented by supporting these metal ions on the inorganic material.
本発明に用いられる無機系金属としては、生体毒性が無く安全性に優れる観点から、銀イオン（銀成分）を含む銀系材料が好ましい。中でも、例えば、リン酸系ガラス銀担持化合物や、銀ゼオライト化合物は、少量でも抗菌性・抗ウイルス性能を発現することから添加量を抑制することができるため、より好ましい。また、銀とモリブデンの両成分を含む銀－モリブデン系材料も、良好な抗菌性・抗ウイルス性能を発現することから、本発明において好ましく用いることができる。本発明における上記無機系金属は、少なくとも銀成分を含む無機材料であることが好ましい。
As the inorganic metal used in the present invention, a silver-based material containing silver ions (silver component) is preferable from the viewpoint of being non-toxic to the body and excellent in safety. Among them, for example, a phosphate-based glass-silver-supporting compound and a silver zeolite compound are more preferable because even a small amount thereof exhibits antibacterial and antiviral properties, and the addition amount thereof can be suppressed. A silver-molybdenum-based material containing both silver and molybdenum components can also be preferably used in the present invention, since it exhibits good antibacterial and antiviral properties. The inorganic metal in the present invention is preferably an inorganic material containing at least a silver component.
上記無機系金属の平均粒子径は、例えば、１～３００００ｎｍの範囲であることが好ましく、更に好ましくは平均粒子径２．５～２００００ｎｍの範囲である。平均粒子径が１ｎｍ未満であると、材料が限定的で入手が困難である。一方、平均粒子径が３００００ｎｍを超えると、ハードコート塗料への分散性が悪化し、塗工した際に粒状感が残ってしまう。
The average particle size of the inorganic metal is, for example, preferably in the range of 1 to 30000 nm, more preferably in the range of 2.5 to 20000 nm. If the average particle size is less than 1 nm, the materials are limited and difficult to obtain. On the other hand, if the average particle size exceeds 30,000 nm, the dispersibility in the hard coat paint deteriorates, leaving a grainy feeling when applied.
上記無機系金属の添加量は、本発明では特に限定される必要はないが、例えば、上記ハードコート層中の固形分に対して、０．０５質量％～３０質量％の範囲である。添加量が０．０５質量％未満であると、抗菌性・抗ウイルス性が十分に発現されない。一方、添加量が３０質量％を超えると、透明性が低くなり、フェイスシールドやウィンドウフィルム等の視認性が求められる場合には、著しく視認性が劣ってしまう。
なお、本発明において、特に断りの無い限り、「ハードコート層中の固形分」との記載は「ハードコート層を形成するためのハードコート層形成用塗工液（ハードコート用塗料）中の固形分」を意味するものとする。また、固形分とは、例えば樹脂、添加剤等の固形分である。 The amount of the inorganic metal added is not particularly limited in the present invention, but is, for example, in the range of 0.05% by mass to 30% by mass based on the solid content in the hard coat layer. If the amount added is less than 0.05% by mass, the antibacterial and antiviral properties are not sufficiently exhibited. On the other hand, if the amount added exceeds 30% by mass, the transparency becomes low, and the visibility is remarkably deteriorated when visibility is required for a face shield, a window film, or the like.
In the present invention, unless otherwise specified, the term "solid content in the hard coat layer" refers to "hard coat layer-forming coating solution (hard coat paint) for forming the hard coat layer. solids”. Moreover, solid content is solid content, such as resin and an additive, for example.
なお、本発明において、特に断りの無い限り、「ハードコート層中の固形分」との記載は「ハードコート層を形成するためのハードコート層形成用塗工液（ハードコート用塗料）中の固形分」を意味するものとする。また、固形分とは、例えば樹脂、添加剤等の固形分である。 The amount of the inorganic metal added is not particularly limited in the present invention, but is, for example, in the range of 0.05% by mass to 30% by mass based on the solid content in the hard coat layer. If the amount added is less than 0.05% by mass, the antibacterial and antiviral properties are not sufficiently exhibited. On the other hand, if the amount added exceeds 30% by mass, the transparency becomes low, and the visibility is remarkably deteriorated when visibility is required for a face shield, a window film, or the like.
In the present invention, unless otherwise specified, the term "solid content in the hard coat layer" refers to "hard coat layer-forming coating solution (hard coat paint) for forming the hard coat layer. solids”. Moreover, solid content is solid content, such as resin and an additive, for example.
特に、前記の銀系材料や、銀－モリブデン系材料は、少量の添加量でも良好な抗菌性・抗ウイルス性能を発現することから、添加量は、上記ハードコート層中の固形分に対して、０．１質量％～１０質量％の範囲とすることができる。
なお、上記無機系金属は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 In particular, the above-mentioned silver-based material and silver-molybdenum-based material exhibit good antibacterial and antiviral performance even with a small amount added, so the amount added is , 0.1 mass % to 10 mass %.
The above inorganic metals may be used singly or in combination of two or more.
なお、上記無機系金属は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 In particular, the above-mentioned silver-based material and silver-molybdenum-based material exhibit good antibacterial and antiviral performance even with a small amount added, so the amount added is , 0.1 mass % to 10 mass %.
The above inorganic metals may be used singly or in combination of two or more.
本発明において、上記ハードコート層にさらに帯電防止剤を含有させることが好ましい実施形態である。上記無機系金属を含有するハードコート層にさらに帯電防止剤を含有させることにより、良好な抗菌性・抗ウイルス性と帯電防止性能を兼ね備えたハードコート層を有するハードコートフィルムを得ることができる。
In a preferred embodiment of the present invention, the hard coat layer further contains an antistatic agent. By further adding an antistatic agent to the hard coat layer containing the inorganic metal, it is possible to obtain a hard coat film having a hard coat layer having both good antibacterial/antiviral properties and antistatic performance.
このような帯電防止剤の種類としては、特に制約はされないが、例えば金属系導電性フィラー、非金属性導電性フィラー、カーボン系導電性フィラーのような導電性フィラーや有機系帯電防止剤からなる帯電防止剤を必要に応じて有機化合物からなるバインダー中に分散させたものを好ましく用いることができる。本発明においては、例えば４級アンモニウム塩系の帯電防止剤を好ましく用いることができる。
The type of such antistatic agents is not particularly limited, but for example, conductive fillers such as metallic conductive fillers, non-metallic conductive fillers, carbon-based conductive fillers, and organic antistatic agents. An antistatic agent dispersed in a binder made of an organic compound can be preferably used as needed. In the present invention, for example, a quaternary ammonium salt-based antistatic agent can be preferably used.
上記帯電防止剤、例えば４級アンモニウム塩系の帯電防止剤を用いる場合、その添加量は、本発明では特に制約はされないが、例えば、上記ハードコート層中の固形分に対して、１質量％～２０質量％の範囲である。添加量が１質量％未満であると、十分な帯電防止性能が得られない。一方、添加量が２０質量％を超えると、塗膜強度が低下するおそれがある。
When the antistatic agent, such as a quaternary ammonium salt-based antistatic agent, is used, the amount added is not particularly limited in the present invention, but for example, 1% by mass with respect to the solid content in the hard coat layer. It is in the range of up to 20% by mass. If the amount added is less than 1% by mass, sufficient antistatic performance cannot be obtained. On the other hand, if the amount added exceeds 20% by mass, the strength of the coating film may decrease.
また、本発明では、上記ハードコート層に無機微粒子を含有させ、表面硬度（耐擦傷性、鉛筆硬度）の更なる向上を図ることが可能である。すなわち、上記無機系金属を含有するハードコート層にさらに無機微粒子を含有させることにより、良好な抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層を有するハードコートフィルムを得ることができる。
In addition, in the present invention, it is possible to further improve the surface hardness (scratch resistance, pencil hardness) by including inorganic fine particles in the hard coat layer. That is, by adding inorganic fine particles to the hard coat layer containing the inorganic metal, it is possible to obtain a hard coat film having good antibacterial and antiviral properties and a high hardness. can.
この場合、無機微粒子の平均粒子径は５～２００ｎｍの範囲であることが好ましく、更に好ましくは平均粒子径１０～８０ｎｍの範囲である。平均粒子径が５ｎｍ未満であると、十分な表面硬度を得ることが困難である。一方、平均粒子径が２００ｎｍを超えると、ハードコート層の光沢及び透明性が低下し易く、また可撓性も低下するおそれがある。
In this case, the average particle size of the inorganic fine particles is preferably in the range of 5-200 nm, more preferably in the range of 10-80 nm. If the average particle size is less than 5 nm, it is difficult to obtain sufficient surface hardness. On the other hand, if the average particle size exceeds 200 nm, the gloss and transparency of the hard coat layer are likely to be reduced, and the flexibility may also be reduced.
上記無機微粒子としては、例えばシリカやアルミナなどの無機酸化物微粒子を挙げることができる。アルミニウムを主成分とするアルミナは高硬度を有するため、シリカよりも少ない添加量で効果を得られる。
Examples of the inorganic fine particles include inorganic oxide fine particles such as silica and alumina. Alumina, which is mainly composed of aluminum, has a high hardness, so that an effect can be obtained with a smaller addition amount than silica.
上記無機微粒子の添加量は、本発明では特に制約はされないが、例えば、上記ハードコート層中の固形分に対して、１０質量％～６０質量％の範囲である。添加量が１０質量％未満であると、十分な表面硬度が得られ難い。一方、添加量が６０質量％を超えると、透明性や見映えの低下が生じ、フェイスシールドやウィンドウフィルム等の視認性が求められる場合には、著しく視認性が劣ってしまう。
Although the amount of the inorganic fine particles added is not particularly limited in the present invention, it is, for example, in the range of 10% by mass to 60% by mass with respect to the solid content in the hard coat layer. If the amount added is less than 10% by mass, it is difficult to obtain sufficient surface hardness. On the other hand, if the amount added exceeds 60% by mass, the transparency and appearance will be degraded, and visibility will be remarkably deteriorated when visibility is required for face shields, window films, and the like.
本発明において、上記ハードコート層に防曇剤を含有させることができる。上記無機系金属を含有するハードコート層にさらに防曇剤を含有させることにより、良好な抗菌性・抗ウイルス性と防曇性を兼ね備えたハードコート層を有するハードコートフィルムを得ることができる。
In the present invention, the hard coat layer may contain an antifogging agent. By adding an antifogging agent to the hard coat layer containing the inorganic metal, a hard coat film having a hard coat layer having both good antibacterial/antiviral properties and antifogging properties can be obtained.
このような防曇剤としては、親水性領域を形成するような物質であれば特に制約されることなく使用可能であるが、例えば、脂肪酸石鹸、アルキルベンゼンスルホン酸塩等の陰イオン界面活性剤、第４アンモニウム基を持つ陽イオン界面活性剤、長鎖アルキルアミノ酸等の両性界面活性剤、ポリオキシエチレンノニルフェニルエーテル等の非イオン界面活性剤、等の界面活性剤や、フッ素系界面活性剤や、グリコシルエチルメタクリレート、メタクリル酸、アクリル酸、２－ヒドロキシルエチルメタクリレート、アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－ビニルピロリドン、Ｎ－（２－メタクロイルオキシエチル）－２－ピロリドン、グリセリルメタクリレート、ポリエチレングリコールメタクリレート、ポリエチレングリコールアクリレート等のヒドロキシルアルキル（メタ）アクリレート類、ポリアルキレングリコールモノ（メタ）アクリレート類、（メタ）アクリルアミド類、Ｎ－ビニルラクタム類、等の親水性モノマー及びこれらのモノマーからなるポリマー等を挙げることができる。また、親水性物質として、アニオン系の親水基（例えばスルホン酸基など）を有するシランカップリング剤や、親水性のモノマー及びビニル基、アクリル基、メタクリル基、グリシジル基、アリル基、エポキシ基、メルカプト基、シアノ基、イソシアノ基、アミノ基等の反応性末端基とスルホン基、水酸基、アンモニウムクロライドなどの親水性部分を持つ反応性界面活性剤を用いることもできる。
As such an antifogging agent, any substance that forms a hydrophilic region can be used without particular restrictions. Surfactants such as cationic surfactants having quaternary ammonium groups, amphoteric surfactants such as long-chain alkylamino acids, nonionic surfactants such as polyoxyethylene nonylphenyl ether, fluorine-based surfactants, , glycosylethyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxylethyl methacrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, N-(2-methacryloyloxyethyl)-2-pyrrolidone, glyceryl methacrylate, polyethylene Hydrophilic monomers such as glycol methacrylates, hydroxylalkyl (meth)acrylates such as polyethylene glycol acrylate, polyalkylene glycol mono(meth)acrylates, (meth)acrylamides, N-vinyllactams, and polymers composed of these monomers etc. can be mentioned. Further, as a hydrophilic substance, a silane coupling agent having an anionic hydrophilic group (for example, a sulfonic acid group), a hydrophilic monomer and a vinyl group, an acrylic group, a methacrylic group, a glycidyl group, an allyl group, an epoxy group, A reactive surfactant having a reactive end group such as a mercapto group, cyano group, isocyano group, amino group, etc. and a hydrophilic moiety such as a sulfone group, hydroxyl group, ammonium chloride etc. can also be used.
上記防曇剤の添加量は、本発明では特に制約はされないが、例えば、上記ハードコート層中の固形分に対して、１０質量％～７０質量％の範囲である。添加量が１０質量％未満であると、防曇性が十分に得られない。一方、添加量が７０質量％を超えると、フィルムの耐擦傷性が低下するおそれがある。
The amount of the antifogging agent added is not particularly limited in the present invention, but is, for example, in the range of 10% by mass to 70% by mass based on the solid content in the hard coat layer. If the amount added is less than 10% by mass, sufficient antifogging properties cannot be obtained. On the other hand, if the amount added exceeds 70% by mass, the scratch resistance of the film may decrease.
本発明において、基材上のハードコート層と反対の面、もしくは基材とハードコート層との間に、金属または金属酸化物からなる薄膜を少なくとも１層以上積層させることができる。金属または金属酸化物からなる層を設けることにより、ハードコートフィルムの遮熱効果（遮熱性）が得られる。
具体的な金属または金属酸化物としては、例えば、アルミニウム、銀、金、ニッケル、コバルト、及びステンレス、及びそれらの合金、二酸化チタン、酸化錫、酸化インジウム、酸化亜鉛、及び酸化タングステンなどが挙げられる。 In the present invention, at least one thin film made of metal or metal oxide can be laminated on the surface of the substrate opposite to the hard coat layer or between the substrate and the hard coat layer. By providing a layer made of metal or metal oxide, the heat shielding effect (heat shielding property) of the hard coat film can be obtained.
Specific metals or metal oxides include, for example, aluminum, silver, gold, nickel, cobalt, and stainless steel, and alloys thereof, titanium dioxide, tin oxide, indium oxide, zinc oxide, and tungsten oxide. .
具体的な金属または金属酸化物としては、例えば、アルミニウム、銀、金、ニッケル、コバルト、及びステンレス、及びそれらの合金、二酸化チタン、酸化錫、酸化インジウム、酸化亜鉛、及び酸化タングステンなどが挙げられる。 In the present invention, at least one thin film made of metal or metal oxide can be laminated on the surface of the substrate opposite to the hard coat layer or between the substrate and the hard coat layer. By providing a layer made of metal or metal oxide, the heat shielding effect (heat shielding property) of the hard coat film can be obtained.
Specific metals or metal oxides include, for example, aluminum, silver, gold, nickel, cobalt, and stainless steel, and alloys thereof, titanium dioxide, tin oxide, indium oxide, zinc oxide, and tungsten oxide. .
上述の金属または金属酸化物からなる層（薄膜）の形成方法としては、例えば、真空蒸着法、スパッタ法、化学蒸着法（ＣＶＤ法）等の公知の薄膜形成方法を適用することができる。
上述の金属または金属酸化物からなる層（薄膜）の厚みは、１０～１０００ｎｍの範囲であることが好ましい。厚みが１０ｎｍ未満であると、十分な遮熱効果が得られず、また、１０００ｎｍ以上を超えると透明性が低下する傾向が認められ、ウィンドウフィルム等の視認性が求められる用途には適さない場合がある。 As a method for forming the layer (thin film) made of the metal or metal oxide described above, for example, a known thin film forming method such as a vacuum vapor deposition method, a sputtering method, or a chemical vapor deposition method (CVD method) can be applied.
The thickness of the layer (thin film) made of the metal or metal oxide described above is preferably in the range of 10 to 1000 nm. If the thickness is less than 10 nm, a sufficient heat shielding effect cannot be obtained, and if it exceeds 1000 nm or more, the transparency tends to decrease, and it is not suitable for applications such as window films that require visibility. There is
上述の金属または金属酸化物からなる層（薄膜）の厚みは、１０～１０００ｎｍの範囲であることが好ましい。厚みが１０ｎｍ未満であると、十分な遮熱効果が得られず、また、１０００ｎｍ以上を超えると透明性が低下する傾向が認められ、ウィンドウフィルム等の視認性が求められる用途には適さない場合がある。 As a method for forming the layer (thin film) made of the metal or metal oxide described above, for example, a known thin film forming method such as a vacuum vapor deposition method, a sputtering method, or a chemical vapor deposition method (CVD method) can be applied.
The thickness of the layer (thin film) made of the metal or metal oxide described above is preferably in the range of 10 to 1000 nm. If the thickness is less than 10 nm, a sufficient heat shielding effect cannot be obtained, and if it exceeds 1000 nm or more, the transparency tends to decrease, and it is not suitable for applications such as window films that require visibility. There is
上記ハードコート層に含有される電離放射線硬化型樹脂を硬化させるため、上記ハードコート層を形成するためのハードコート層形成用塗工液（ハードコート用塗料）には、公知の光重合開始剤を含むことができる。そのような光重合開始剤としては、アセトフェノン類やベンゾフェノン類を使用できる。
In order to cure the ionizing radiation-curable resin contained in the hard coat layer, the hard coat layer-forming coating liquid (hard coat paint) for forming the hard coat layer contains a known photopolymerization initiator. can include Acetophenones and benzophenones can be used as such a photopolymerization initiator.
また、上記ハードコート層には、塗工性の改善を目的にレベリング剤（表面改質剤）の使用が可能であり、たとえばフッ素系、アクリル系、シロキサン系、及びそれらの付加物或いは混合物などの公知のレベリング剤を使用可能である。
In addition, in the hard coat layer, a leveling agent (surface modifier) can be used for the purpose of improving coatability. known leveling agents can be used.
また、本発明のハードコートフィルムに防汚性を付与するためには、上記ハードコート層に、フッ素系やシロキサン系等の防汚剤（レベリング剤または界面活性剤など）を添加することができる。防汚剤の添加量としては、特に制約はされないが、ハードコート用塗料中の樹脂固形分に対して、０．０５質量％～２．０質量％が好ましい。
In order to impart antifouling properties to the hard coat film of the present invention, a fluorine-based or siloxane-based antifouling agent (leveling agent, surfactant, etc.) can be added to the hard coat layer. . The amount of the antifouling agent to be added is not particularly limited, but is preferably 0.05% by mass to 2.0% by mass based on the resin solid content in the hard coat paint.
また、本発明のハードコートフィルムに不透明性を付与するためには、例えば上記ハードコート層のヘイズ値を高めることが好適である。そのためには、上記ハードコート層に有機微粒子や無機微粒子を添加する方法が挙げられる。ハードコート層中に有機微粒子や無機微粒子が存在することに起因し光が屈折、散乱することでヘイズが発現する。有機微粒子としては、アクリル、メラミン・ホルムアルデヒド縮合物、ポリエチレン、スチレンアクリル、ポリエステル等の微粒子を例示することができ、無機微粒子としては、アルミナ、酸化亜鉛、シリカ、酸化チタン、酸化セリウム等の微粒子を例示することができる。
ヘイズ値を高めるために、上記微粒子の添加量は、ハードコート用塗料中の樹脂固形分に対して、１０質量％～８０質量％の範囲が好適である。 In order to impart opacity to the hard coat film of the present invention, it is suitable, for example, to increase the haze value of the hard coat layer. For that purpose, there is a method of adding organic fine particles or inorganic fine particles to the hard coat layer. Haze occurs when light is refracted and scattered due to the presence of organic fine particles and inorganic fine particles in the hard coat layer. Examples of organic fine particles include fine particles of acryl, melamine-formaldehyde condensate, polyethylene, styrene acryl, polyester, and the like. Examples of inorganic fine particles include fine particles of alumina, zinc oxide, silica, titanium oxide, cerium oxide, and the like. can be exemplified.
In order to increase the haze value, the amount of the fine particles to be added is preferably in the range of 10% by mass to 80% by mass based on the resin solid content in the hard coat paint.
ヘイズ値を高めるために、上記微粒子の添加量は、ハードコート用塗料中の樹脂固形分に対して、１０質量％～８０質量％の範囲が好適である。 In order to impart opacity to the hard coat film of the present invention, it is suitable, for example, to increase the haze value of the hard coat layer. For that purpose, there is a method of adding organic fine particles or inorganic fine particles to the hard coat layer. Haze occurs when light is refracted and scattered due to the presence of organic fine particles and inorganic fine particles in the hard coat layer. Examples of organic fine particles include fine particles of acryl, melamine-formaldehyde condensate, polyethylene, styrene acryl, polyester, and the like. Examples of inorganic fine particles include fine particles of alumina, zinc oxide, silica, titanium oxide, cerium oxide, and the like. can be exemplified.
In order to increase the haze value, the amount of the fine particles to be added is preferably in the range of 10% by mass to 80% by mass based on the resin solid content in the hard coat paint.
上記ハードコート層に添加するその他の添加剤として、紫外線吸収剤、消泡剤、表面張力調整剤、酸化防止剤、光安定剤等を必要に応じて配合してもよい。
As other additives added to the hard coat layer, ultraviolet absorbers, antifoaming agents, surface tension modifiers, antioxidants, light stabilizers, etc. may be blended as needed.
上記ハードコート層は、上述の無機系金属、電離放射線硬化型樹脂の他に、帯電防止剤、無機微粒子、有機微粒子、防曇剤、光重合開始剤、その他の添加剤等を適当な溶媒に溶解、分散したハードコート層形成用塗工液を、上記被塗工基材上に塗工、乾燥した後、ＵＶ又はＥＢ等の電離放射線を照射することにより、光重合が起こりハード性に優れるハードコート層を得ることができる。
In addition to the above inorganic metals and ionizing radiation curable resins, the hard coat layer contains antistatic agents, inorganic fine particles, organic fine particles, antifogging agents, photopolymerization initiators, other additives, etc. in an appropriate solvent. After the dissolved and dispersed hard coat layer forming coating solution is applied onto the base material to be coated and dried, photopolymerization occurs by irradiating ionizing radiation such as UV or EB, resulting in excellent hard properties. A hard coat layer can be obtained.
溶媒としては、配合される上記樹脂の溶解性に応じて適宜選択でき、少なくとも固形分（樹脂、その他の上記添加剤等）を均一に溶解あるいは分散できる溶媒であればよい。そのような溶媒としては、例えば、トルエン、キシレン、ｎ－ヘプタンなどの芳香族系溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂肪族系溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、乳酸メチル等のエステル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール系等のアルコール系溶剤等の公知の有機溶媒を単独或いは適宜数種類組み合わせて使用することもできる。
The solvent can be appropriately selected according to the solubility of the resin to be blended, and any solvent that can uniformly dissolve or disperse at least the solid content (resin, other additives described above, etc.) may be used. Examples of such solvents include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetic acid. Known organic solvents such as ester solvents such as butyl and methyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol alone Alternatively, several types can be appropriately combined and used.
また、上記塗工液の濃度（固形分濃度）については、特に制約はされないが、例えば１０質量％～７０質量％程度の範囲とすることができる。
In addition, the concentration (solid content concentration) of the coating liquid is not particularly limited, but can be, for example, in the range of about 10% by mass to 70% by mass.
上記ハードコート層形成用塗工液を基材上に塗工、乾燥した後の電離放射線（ＵＶ、ＥＢ等）の照射量は、ハードコート層に十分なハード性を持たせるに必要な照射量であればよく、電離放射線硬化型樹脂の種類等に応じて適宜設定することができる。
The irradiation amount of ionizing radiation (UV, EB, etc.) after coating and drying the hard coat layer forming coating solution on the substrate is the irradiation amount necessary to give the hard coat layer sufficient hardness. It may be set appropriately according to the type of the ionizing radiation curable resin.
上記ハードコート層を形成するためのハードコート形成用塗工液の塗工方法については、特に限定はないが、グラビア塗工、マイクログラビア塗工、ファウンテンバー塗工、スライドダイ塗工、スロットダイ塗工、スクリーン印刷法、スプレーコート法等の公知の塗工方式が挙げられる。
The method of applying the hard coat-forming coating liquid for forming the hard coat layer is not particularly limited, but gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, Known coating methods such as coating, screen printing, and spray coating can be used.
また、塗工後の乾燥工程における乾燥温度、加熱時間（乾燥時間）については適宜設定することができる。
In addition, the drying temperature and heating time (drying time) in the drying process after coating can be set as appropriate.
上記ハードコート層の塗膜厚さ（乾燥後）は、ハードコートフィルムの用途によっても異なるため、特に制約される必要はないが、一般には例えば１．０μｍ～２０．０μｍの範囲であることが好適である。塗膜厚さが１．０μｍ未満では、必要な表面硬度が得られ難いため好ましくない。また、塗膜厚さが２０．０μｍを超えた場合は、カールが発生しやすく製造工程などで取扱い性が低下するため好ましくない。
The coating thickness (after drying) of the hard coat layer varies depending on the application of the hard coat film, so it is not particularly limited, but is generally in the range of, for example, 1.0 μm to 20.0 μm. preferred. If the coating thickness is less than 1.0 μm, it is difficult to obtain the required surface hardness, which is not preferable. On the other hand, when the coating thickness exceeds 20.0 μm, curling is likely to occur, which is not preferable because the handleability in the manufacturing process is deteriorated.
本発明のハードコートフィルムは、基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたものであるが、層構成の具体例（実施態様）を以下に挙げる。
（実施態様１）
基材上の両方の面にそれぞれ上記ハードコート層を設け、一方は、層中に本発明の無機系金属と帯電防止剤を含有し、抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層であり、他方は、層中に本発明の無機系金属と防曇剤を含有し、抗菌性・抗ウイルス性と防曇性を有するハードコート層である。あるいは、同じく基材上の両方の面にそれぞれ上記ハードコート層を設け、一方は、層中に本発明の無機系金属と無機微粒子を含有し、抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層であり、他方は、上記の抗菌性・抗ウイルス性と防曇性を有するハードコート層である。
このようなハードコートフィルムの実施態様は、例えば、フェイスシールド用フィルムとして好適である。 The hard coat film of the present invention has a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. ) are listed below.
(Embodiment 1)
The hard coat layer is provided on both sides of the substrate, and one layer contains the inorganic metal of the present invention and an antistatic agent, and has antibacterial/antiviral properties and antistatic performance. The other is a hard coat layer containing the inorganic metal of the present invention and an antifogging agent in the layer and having antibacterial/antiviral and antifogging properties. Alternatively, the same hard coat layer is provided on both surfaces of the substrate, and one contains the inorganic metal and inorganic fine particles of the present invention in the layer, has antibacterial / antiviral properties, and has high antibacterial and antiviral properties. It is a hard coat layer, and the other is a hard coat layer having the antibacterial/antiviral and antifog properties described above.
An embodiment of such a hard coat film is suitable, for example, as a face shield film.
（実施態様１）
基材上の両方の面にそれぞれ上記ハードコート層を設け、一方は、層中に本発明の無機系金属と帯電防止剤を含有し、抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層であり、他方は、層中に本発明の無機系金属と防曇剤を含有し、抗菌性・抗ウイルス性と防曇性を有するハードコート層である。あるいは、同じく基材上の両方の面にそれぞれ上記ハードコート層を設け、一方は、層中に本発明の無機系金属と無機微粒子を含有し、抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層であり、他方は、上記の抗菌性・抗ウイルス性と防曇性を有するハードコート層である。
このようなハードコートフィルムの実施態様は、例えば、フェイスシールド用フィルムとして好適である。 The hard coat film of the present invention has a hard coat layer containing at least an inorganic metal and an ionizing radiation-curable resin on at least one surface of a substrate. ) are listed below.
(Embodiment 1)
The hard coat layer is provided on both sides of the substrate, and one layer contains the inorganic metal of the present invention and an antistatic agent, and has antibacterial/antiviral properties and antistatic performance. The other is a hard coat layer containing the inorganic metal of the present invention and an antifogging agent in the layer and having antibacterial/antiviral and antifogging properties. Alternatively, the same hard coat layer is provided on both surfaces of the substrate, and one contains the inorganic metal and inorganic fine particles of the present invention in the layer, has antibacterial / antiviral properties, and has high antibacterial and antiviral properties. It is a hard coat layer, and the other is a hard coat layer having the antibacterial/antiviral and antifog properties described above.
An embodiment of such a hard coat film is suitable, for example, as a face shield film.
（実施態様２）
基材上の一方の面に、上記の抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層を設ける。あるいは、基材上の一方の面に、上記の抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層を設ける。いずれの実施態様においても、基材上の他方の面（ハードコート層を設けた面とは反対面）には、ハードコートフィルムを、パーティション、ウィンドウ、テーブルカバー、電子機器のタッチパネル等の部材に貼着するための粘着層を設けることができる。
このようなハードコートフィルムの実施態様は、例えば、パーティション用フィルム、ウィンドウフィルム、テーブルカバー用フィルム、あるいは電子機器等のディスプレイ用またはタッチパネル用フィルムとして好適である。 (Embodiment 2)
A hard coat layer having antibacterial/antiviral properties and antistatic properties is provided on one surface of the substrate. Alternatively, a hard coat layer having the antibacterial/antiviral properties and high hardness is provided on one surface of the base material. In any embodiment, a hard coat film is applied to members such as partitions, windows, table covers, and touch panels of electronic devices on the other surface of the substrate (the surface opposite to the surface on which the hard coat layer is provided). An adhesive layer for sticking can be provided.
Such a hard coat film is suitable as, for example, a partition film, a window film, a table cover film, or a display or touch panel film for electronic devices.
基材上の一方の面に、上記の抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層を設ける。あるいは、基材上の一方の面に、上記の抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層を設ける。いずれの実施態様においても、基材上の他方の面（ハードコート層を設けた面とは反対面）には、ハードコートフィルムを、パーティション、ウィンドウ、テーブルカバー、電子機器のタッチパネル等の部材に貼着するための粘着層を設けることができる。
このようなハードコートフィルムの実施態様は、例えば、パーティション用フィルム、ウィンドウフィルム、テーブルカバー用フィルム、あるいは電子機器等のディスプレイ用またはタッチパネル用フィルムとして好適である。 (Embodiment 2)
A hard coat layer having antibacterial/antiviral properties and antistatic properties is provided on one surface of the substrate. Alternatively, a hard coat layer having the antibacterial/antiviral properties and high hardness is provided on one surface of the base material. In any embodiment, a hard coat film is applied to members such as partitions, windows, table covers, and touch panels of electronic devices on the other surface of the substrate (the surface opposite to the surface on which the hard coat layer is provided). An adhesive layer for sticking can be provided.
Such a hard coat film is suitable as, for example, a partition film, a window film, a table cover film, or a display or touch panel film for electronic devices.
（実施態様３）
基材上の一方の面に、上記の抗菌性・抗ウイルス性と防曇性を有するハードコート層を設ける。また、基材上の他方の面（ハードコート層を設けた面とは反対面）には、ハードコートフィルムを、ウィンドウ、バスミラー、冷凍冷蔵庫窓等の部材に貼着するための粘着層を設けることができる。
このようなハードコートフィルムの実施態様は、例えば、ウィンドウフィルム、バスミラー用フィルム、冷凍冷蔵庫窓用フィルムとして好適である。 (Embodiment 3)
A hard coat layer having antibacterial/antiviral and antifogging properties is provided on one surface of the substrate. On the other side of the substrate (the side opposite to the side on which the hard coat layer is provided), an adhesive layer is provided for attaching the hard coat film to members such as windows, bus mirrors, and freezer/refrigerator windows. can be provided.
Embodiments of such hard coat films are suitable, for example, as window films, bus mirror films, and freezer-refrigerator window films.
基材上の一方の面に、上記の抗菌性・抗ウイルス性と防曇性を有するハードコート層を設ける。また、基材上の他方の面（ハードコート層を設けた面とは反対面）には、ハードコートフィルムを、ウィンドウ、バスミラー、冷凍冷蔵庫窓等の部材に貼着するための粘着層を設けることができる。
このようなハードコートフィルムの実施態様は、例えば、ウィンドウフィルム、バスミラー用フィルム、冷凍冷蔵庫窓用フィルムとして好適である。 (Embodiment 3)
A hard coat layer having antibacterial/antiviral and antifogging properties is provided on one surface of the substrate. On the other side of the substrate (the side opposite to the side on which the hard coat layer is provided), an adhesive layer is provided for attaching the hard coat film to members such as windows, bus mirrors, and freezer/refrigerator windows. can be provided.
Embodiments of such hard coat films are suitable, for example, as window films, bus mirror films, and freezer-refrigerator window films.
（実施態様４）
基材上の一方の面に、上記の抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層を設け、あるいは、基材上の一方の面に、上記の抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層を設ける。このいずれの実施態様においても、さらに、基材上の他方の面（ハードコート層を設けた面とは反対面）、もしくは基材とハードコート層との間には、金属または金属酸化物からなる薄膜を少なくとも１層以上積層させることができる。
このようなハードコートフィルムの実施態様は、遮熱効果が求められる例えば、パーティション用フィルム、ウィンドウフィルムとして好適である。 (Embodiment 4)
A hard coat layer having the above antibacterial/antiviral and antistatic properties is provided on one side of the base material, or one side of the base material has the above antibacterial/antiviral properties. and a hard coat layer having a high hardness is provided. In any of these embodiments, the other surface of the substrate (the surface opposite to the surface on which the hard coat layer is provided), or between the substrate and the hard coat layer, a metal or metal oxide At least one thin film can be laminated.
Embodiments of such a hard coat film are suitable as, for example, partition films and window films that require a heat shielding effect.
基材上の一方の面に、上記の抗菌性・抗ウイルス性と帯電防止性能を有するハードコート層を設け、あるいは、基材上の一方の面に、上記の抗菌性・抗ウイルス性を有し、かつ高硬度のハードコート層を設ける。このいずれの実施態様においても、さらに、基材上の他方の面（ハードコート層を設けた面とは反対面）、もしくは基材とハードコート層との間には、金属または金属酸化物からなる薄膜を少なくとも１層以上積層させることができる。
このようなハードコートフィルムの実施態様は、遮熱効果が求められる例えば、パーティション用フィルム、ウィンドウフィルムとして好適である。 (Embodiment 4)
A hard coat layer having the above antibacterial/antiviral and antistatic properties is provided on one side of the base material, or one side of the base material has the above antibacterial/antiviral properties. and a hard coat layer having a high hardness is provided. In any of these embodiments, the other surface of the substrate (the surface opposite to the surface on which the hard coat layer is provided), or between the substrate and the hard coat layer, a metal or metal oxide At least one thin film can be laminated.
Embodiments of such a hard coat film are suitable as, for example, partition films and window films that require a heat shielding effect.
以上詳細に説明したように、本発明によれば、良好な抗菌性及び抗ウイルス性を有するハードコートフィルムを提供することができる。また、本発明によれば、良好な抗菌性及び抗ウイルス性と帯電防止性能を有するハードコートフィルムを提供することができる。また、本発明によれば、良好な抗菌性及び抗ウイルス性を有し、かつ高硬度のハードコートフィルムを提供することができる。また、本発明によれば、良好な抗菌性及び抗ウイルス性と防曇性を有するハードコートフィルムを提供することができる。さらには、良好な抗菌性及び抗ウイルス性と遮熱効果を有するハードコートフィルムを提供することができる。またさらには、良好な抗菌性及び抗ウイルス性に加え、上記の帯電防止性能、高硬度、防曇性や遮熱性等のうちの複数の性能をも兼備えるハードコートフィルムを提供することができる。
As described in detail above, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and antistatic properties. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and high hardness. Moreover, according to the present invention, it is possible to provide a hard coat film having good antibacterial and antiviral properties and antifogging properties. Furthermore, it is possible to provide a hard coat film having good antibacterial and antiviral properties and a heat shielding effect. Furthermore, in addition to good antibacterial properties and antiviral properties, it is possible to provide a hard coat film that also has multiple properties among the above-mentioned antistatic performance, high hardness, antifogging properties, heat shielding properties, and the like. .
以下、実施例を挙げて、本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、下記の記載中、「部」は別途記載がない限り質量部を、「％」は別途記載がない限り質量％を意味する。
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the descriptions below, "parts" means parts by mass unless otherwise stated, and "%" means % by mass unless otherwise stated.
（実施例１）
［ハードコート層形成用塗工液の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液（以下、「ハードコート用塗料」とも呼ぶ。）を調製した。 (Example 1)
[Preparation of Coating Solution for Forming Hard Coat Layer]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 1.5% (based on solid content 0.5%) of a surface modifier (Megafac R-08MH; manufactured by DIC Corporation), and a silver-molybdenum compound as the inorganic metal of the present invention. 0.09% (0.3% of solid content) of antibacterial / antiviral agent, diluted with butyl acetate / n-propyl alcohol = 50/50 (parts by weight) to final solid content concentration A 30% hard coat layer-forming coating liquid (hereinafter also referred to as "hard coat paint") was prepared.
［ハードコート層形成用塗工液の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液（以下、「ハードコート用塗料」とも呼ぶ。）を調製した。 (Example 1)
[Preparation of Coating Solution for Forming Hard Coat Layer]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 1.5% (based on solid content 0.5%) of a surface modifier (Megafac R-08MH; manufactured by DIC Corporation), and a silver-molybdenum compound as the inorganic metal of the present invention. 0.09% (0.3% of solid content) of antibacterial / antiviral agent, diluted with butyl acetate / n-propyl alcohol = 50/50 (parts by weight) to final solid content concentration A 30% hard coat layer-forming coating liquid (hereinafter also referred to as "hard coat paint") was prepared.
［ハードコートフィルムの作製］
ポリエチレンテレフタレート（ＰＥＴ）からなる基材フィルム（フィルム厚５０μｍ）の片面に、上記組成からなるハードコート用塗料を、バーコーターを用いて塗工した後、８０℃の乾燥炉で６０秒間乾燥させ、乾燥後の膜厚が２μｍのハードコート層を形成した。次いで、このハードコート層に対して、塗布面より６０ｍｍの高さにセットされたＵＶ照射装置を用い、ＵＶ照射量２００ｍＪ／ｃｍ２の紫外線照射により硬化させ、本実施例のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat paint having the above composition was applied to one side of a polyethylene terephthalate (PET) base film (film thickness: 50 μm) using a bar coater, and then dried in a drying oven at 80° C. for 60 seconds. A hard coat layer having a thickness of 2 μm after drying was formed. Next, this hard coat layer is cured by UV irradiation with a UV dose of 200 mJ/cm 2 using a UV irradiation device set at a height of 60 mm from the coated surface to prepare the hard coat film of this example. bottom.
ポリエチレンテレフタレート（ＰＥＴ）からなる基材フィルム（フィルム厚５０μｍ）の片面に、上記組成からなるハードコート用塗料を、バーコーターを用いて塗工した後、８０℃の乾燥炉で６０秒間乾燥させ、乾燥後の膜厚が２μｍのハードコート層を形成した。次いで、このハードコート層に対して、塗布面より６０ｍｍの高さにセットされたＵＶ照射装置を用い、ＵＶ照射量２００ｍＪ／ｃｍ２の紫外線照射により硬化させ、本実施例のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat paint having the above composition was applied to one side of a polyethylene terephthalate (PET) base film (film thickness: 50 μm) using a bar coater, and then dried in a drying oven at 80° C. for 60 seconds. A hard coat layer having a thickness of 2 μm after drying was formed. Next, this hard coat layer is cured by UV irradiation with a UV dose of 200 mJ/cm 2 using a UV irradiation device set at a height of 60 mm from the coated surface to prepare the hard coat film of this example. bottom.
（実施例２）
実施例１におけるハードコート用塗料中の銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を、銀化合物を含有する抗菌・抗ウイルス剤（ゼオミック ＨＤ１０Ｎ（商品名）；（株）シナネンゼオミック製）に変更したこと以外は同様にして調製したハードコート用塗料を用いて、実施例２のハードコートフィルムを作製した。 (Example 2)
The antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was replaced with an antibacterial/antiviral agent containing a silver compound (Zeomic HD10N (trade name); manufactured by Sinanen Zeomic Co., Ltd.). A hard coat film of Example 2 was produced using a hard coat paint prepared in the same manner except for changing to .
実施例１におけるハードコート用塗料中の銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を、銀化合物を含有する抗菌・抗ウイルス剤（ゼオミック ＨＤ１０Ｎ（商品名）；（株）シナネンゼオミック製）に変更したこと以外は同様にして調製したハードコート用塗料を用いて、実施例２のハードコートフィルムを作製した。 (Example 2)
The antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was replaced with an antibacterial/antiviral agent containing a silver compound (Zeomic HD10N (trade name); manufactured by Sinanen Zeomic Co., Ltd.). A hard coat film of Example 2 was produced using a hard coat paint prepared in the same manner except for changing to .
（実施例３）
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、４級アンモニウム塩系帯電防止剤（１ＳＸ－１０５５Ｆ(商品名)；大成ファインケミカル（株）製）５部、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 3)
[Preparation of paint for hard coating]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 1.5% surface modifier (Megafac R-08MH; manufactured by DIC Corporation) (based on solid content 0.5%), quaternary ammonium salt antistatic agent (1SX-1055F (product Name); manufactured by Taisei Fine Chemical Co., Ltd.) 5 parts, 0.09% (based on solid content 0.3%) of an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention These were blended and diluted with butyl acetate/n-propyl alcohol=50/50 (parts by weight) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、４級アンモニウム塩系帯電防止剤（１ＳＸ－１０５５Ｆ(商品名)；大成ファインケミカル（株）製）５部、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 3)
[Preparation of paint for hard coating]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 1.5% surface modifier (Megafac R-08MH; manufactured by DIC Corporation) (based on solid content 0.5%), quaternary ammonium salt antistatic agent (1SX-1055F (product Name); manufactured by Taisei Fine Chemical Co., Ltd.) 5 parts, 0.09% (based on solid content 0.3%) of an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention These were blended and diluted with butyl acetate/n-propyl alcohol=50/50 (parts by weight) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコートフィルムの作製］
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例３のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 3 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 4 μm after drying.
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例３のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 3 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 4 μm after drying.
（実施例４）
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、シリカ微粒子（平均粒子径５０ｎｍ）３０部、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 4)
[Preparation of paint for hard coating]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 30 parts of silica fine particles (average particle diameter 50 nm), 1.5% (based on solid content 0.5%) of a surface modifier (Megafac R-08MH; manufactured by DIC Corporation), and the present invention An antibacterial/antiviral agent containing a silver-molybdenum compound as an inorganic metal is blended at a ratio of 0.09% (0.3% of the solid content), and butyl acetate/n-propyl alcohol = 50/50 (weight Part) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９５部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、シリカ微粒子（平均粒子径５０ｎｍ）３０部、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．０９％（対固形分０．３％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 4)
[Preparation of paint for hard coating]
Ionizing radiation curable resin (Shiko UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) containing urethane acrylate as a main component and 95 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF)3. 5 parts, 30 parts of silica fine particles (average particle diameter 50 nm), 1.5% (based on solid content 0.5%) of a surface modifier (Megafac R-08MH; manufactured by DIC Corporation), and the present invention An antibacterial/antiviral agent containing a silver-molybdenum compound as an inorganic metal is blended at a ratio of 0.09% (0.3% of the solid content), and butyl acetate/n-propyl alcohol = 50/50 (weight Part) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコートフィルムの作製］
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が５μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例４のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 4 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 μm after drying.
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が５μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例４のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 4 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 μm after drying.
（実施例５）
［ハードコート用塗料の調製］
フッ素系界面活性剤（防曇剤）を含有し、ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（アイカアイトロンＺ－９４２－４（商品名）；アイカ工業（株）製）を９９．７％、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．３％（対固形分０．３％）の割合で配合し、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）にて希釈して最終固形分濃度４０％のハードコート用塗料を調製した。 (Example 5)
[Preparation of paint for hard coating]
An ionizing radiation-curable resin (Aica Itron Z-942-4 (trade name); manufactured by Aica Kogyo Co., Ltd.) containing a fluorine-based surfactant (anti-fogging agent) and having urethane acrylate as a main component was added at 99%. 7%, and 0.3% (0.3% of the solid content) of an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention is blended, and propylene glycol monomethyl ether (PGME) is added. to prepare a hard coat paint having a final solid concentration of 40%.
［ハードコート用塗料の調製］
フッ素系界面活性剤（防曇剤）を含有し、ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（アイカアイトロンＺ－９４２－４（商品名）；アイカ工業（株）製）を９９．７％、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．３％（対固形分０．３％）の割合で配合し、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）にて希釈して最終固形分濃度４０％のハードコート用塗料を調製した。 (Example 5)
[Preparation of paint for hard coating]
An ionizing radiation-curable resin (Aica Itron Z-942-4 (trade name); manufactured by Aica Kogyo Co., Ltd.) containing a fluorine-based surfactant (anti-fogging agent) and having urethane acrylate as a main component was added at 99%. 7%, and 0.3% (0.3% of the solid content) of an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention is blended, and propylene glycol monomethyl ether (PGME) is added. to prepare a hard coat paint having a final solid concentration of 40%.
［ハードコートフィルムの作製］
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例５のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 5 was produced in the same manner as in Example 1, except that the hard coat coating composition having the above composition was used and the hard coat layer had a thickness of 4 μm after drying.
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例５のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 5 was produced in the same manner as in Example 1, except that the hard coat coating composition having the above composition was used and the hard coat layer had a thickness of 4 μm after drying.
（実施例６）
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９０部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、有機微粒子（ＫＭＰ－６０５；信越シリコーン社製：平均粒子径２μｍ）３０部、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．１８％（対固形分０．６％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 6)
[Preparation of paint for hard coating]
Irgacure 184 (photopolymerization initiator, manufactured by BASF Co., Ltd.) containing 90 parts of ionizing radiation curable resin (Shikou UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) as the main component and urethane acrylate as the main component3. 5 parts, organic fine particles (KMP-605; manufactured by Shin-Etsu Silicone Co., Ltd.: average particle size 2 μm) 30 parts, surface modifier (Megaface R-08MH; manufactured by DIC Corporation) 1.5% (relative to solid content 0.5%), and an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention is blended at a ratio of 0.18% (0.6% relative to the solid content), and butyl acetate/n -Propyl alcohol = 50/50 (parts by weight) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコート用塗料の調製］
ウレタンアクリレートを主成分とする電離放射線硬化型樹脂（紫光ＵＶ－７６３０Ｂ（商品名）；日本合成化学（株）製）９０部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ社製）３．５部と、有機微粒子（ＫＭＰ－６０５；信越シリコーン社製：平均粒子径２μｍ）３０部、表面改質剤（メガファックＲ－０８ＭＨ；ＤＩＣ（株）製）を１．５％（対固形分０．５％）、本発明の無機系金属として銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を０．１８％（対固形分０．６％）の割合で配合し、酢酸ブチル／ｎ－プロピルアルコール＝５０／５０（重量部）にて希釈して最終固形分濃度３０％のハードコート層形成用塗工液を調製した。 (Example 6)
[Preparation of paint for hard coating]
Irgacure 184 (photopolymerization initiator, manufactured by BASF Co., Ltd.) containing 90 parts of ionizing radiation curable resin (Shikou UV-7630B (trade name); manufactured by Nippon Synthetic Chemical Co., Ltd.) as the main component and urethane acrylate as the main component3. 5 parts, organic fine particles (KMP-605; manufactured by Shin-Etsu Silicone Co., Ltd.: average particle size 2 μm) 30 parts, surface modifier (Megaface R-08MH; manufactured by DIC Corporation) 1.5% (relative to solid content 0.5%), and an antibacterial/antiviral agent containing a silver-molybdenum compound as the inorganic metal of the present invention is blended at a ratio of 0.18% (0.6% relative to the solid content), and butyl acetate/n -Propyl alcohol = 50/50 (parts by weight) to prepare a coating solution for forming a hard coat layer having a final solid concentration of 30%.
［ハードコートフィルムの作製］
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が５μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例６のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 6 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 μm after drying.
上記組成からなるハードコート用塗料を用い、乾燥後の膜厚が５μｍのハードコート層としたこと以外は、実施例１と同様にして、実施例６のハードコートフィルムを作製した。 [Preparation of hard coat film]
A hard coat film of Example 6 was produced in the same manner as in Example 1, except that the hard coat paint having the above composition was used and the hard coat layer had a thickness of 5 μm after drying.
（実施例７）
実施例３のハードコートフィルムの基材上のハードコート層と反対面に、酸化インジウム・錫化合物（ＩＴＯ）層を、スパッタ装置（マグネトロンスパッタＭＳＰ－４０Ｔ（商品名）；（株）真空デバイス製）にて、厚み６００ｎｍを塗設し、実施例７のハードコートフィルムを作製した。 (Example 7)
On the opposite side of the hard coat layer on the substrate of the hard coat film of Example 3, an indium oxide/tin compound (ITO) layer was formed by a sputtering apparatus (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd. ), a hard coat film of Example 7 was prepared by coating to a thickness of 600 nm.
実施例３のハードコートフィルムの基材上のハードコート層と反対面に、酸化インジウム・錫化合物（ＩＴＯ）層を、スパッタ装置（マグネトロンスパッタＭＳＰ－４０Ｔ（商品名）；（株）真空デバイス製）にて、厚み６００ｎｍを塗設し、実施例７のハードコートフィルムを作製した。 (Example 7)
On the opposite side of the hard coat layer on the substrate of the hard coat film of Example 3, an indium oxide/tin compound (ITO) layer was formed by a sputtering apparatus (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd. ), a hard coat film of Example 7 was prepared by coating to a thickness of 600 nm.
（実施例８）
ポリエチレンテレフタレート（ＰＥＴ）からなる基材フィルム（フィルム厚５０μｍ）の片面に、酸化インジウム・錫化合物（ＩＴＯ）層を、スパッタ装置（マグネトロンスパッタＭＳＰ－４０Ｔ（商品名）；（株）真空デバイス製）にて、厚み６００ｎｍを塗設した。その上に、実施例３と同様のハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層を設け、実施例８のハードコートフィルムを作製した。 (Example 8)
An indium oxide/tin compound (ITO) layer was formed on one side of a polyethylene terephthalate (PET) substrate film (film thickness: 50 μm) using a sputtering device (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd.). was applied to a thickness of 600 nm. A hard coat layer having a thickness of 4 μm after drying was formed thereon by using the same hard coat paint as in Example 3, and a hard coat film of Example 8 was produced.
ポリエチレンテレフタレート（ＰＥＴ）からなる基材フィルム（フィルム厚５０μｍ）の片面に、酸化インジウム・錫化合物（ＩＴＯ）層を、スパッタ装置（マグネトロンスパッタＭＳＰ－４０Ｔ（商品名）；（株）真空デバイス製）にて、厚み６００ｎｍを塗設した。その上に、実施例３と同様のハードコート用塗料を用い、乾燥後の膜厚が４μｍのハードコート層を設け、実施例８のハードコートフィルムを作製した。 (Example 8)
An indium oxide/tin compound (ITO) layer was formed on one side of a polyethylene terephthalate (PET) substrate film (film thickness: 50 μm) using a sputtering device (magnetron sputtering MSP-40T (trade name); manufactured by Vacuum Device Co., Ltd.). was applied to a thickness of 600 nm. A hard coat layer having a thickness of 4 μm after drying was formed thereon by using the same hard coat paint as in Example 3, and a hard coat film of Example 8 was produced.
（比較例１）
実施例１におけるハードコート用塗料中の銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を含有しない（省いた）こと以外は実施例１と同様にして調製したハードコート用塗料を用いて、比較例１のハードコートフィルムを作製した。 (Comparative example 1)
Using a hard coat paint prepared in the same manner as in Example 1 except that the antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was not contained (omitted), A hard coat film of Comparative Example 1 was produced.
実施例１におけるハードコート用塗料中の銀－モリブデン系化合物を含有する抗菌・抗ウイルス剤を含有しない（省いた）こと以外は実施例１と同様にして調製したハードコート用塗料を用いて、比較例１のハードコートフィルムを作製した。 (Comparative example 1)
Using a hard coat paint prepared in the same manner as in Example 1 except that the antibacterial/antiviral agent containing a silver-molybdenum compound in the hard coat paint in Example 1 was not contained (omitted), A hard coat film of Comparative Example 1 was produced.
＜評価＞
以上のようにして作製された実施例及び比較例の各ハードコートフィルムを次の項目について評価し、その結果を纏めて表１に示した。 <Evaluation>
The hard coat films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 1.
以上のようにして作製された実施例及び比較例の各ハードコートフィルムを次の項目について評価し、その結果を纏めて表１に示した。 <Evaluation>
The hard coat films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 1.
＜塗膜の厚み＞
ハードコート層の塗膜の形成厚みは、Ｔｈｉｎ－Ｆｉｌｍ Ａｎａｌｙｚｅｒ Ｆ２０（商品名）（ＦＩＬＭＥＴＲＩＣＳ社製）を用いて測定した。 <Thickness of coating film>
The formed thickness of the coating film of the hard coat layer was measured using Thin-Film Analyzer F20 (trade name) (manufactured by FILMETRICS).
ハードコート層の塗膜の形成厚みは、Ｔｈｉｎ－Ｆｉｌｍ Ａｎａｌｙｚｅｒ Ｆ２０（商品名）（ＦＩＬＭＥＴＲＩＣＳ社製）を用いて測定した。 <Thickness of coating film>
The formed thickness of the coating film of the hard coat layer was measured using Thin-Film Analyzer F20 (trade name) (manufactured by FILMETRICS).
＜抗菌性＞
ＪＩＳ Ｚ ２８０１：２０１０の規格に準じた方法にて測定した。抗菌活性値２．０以上を抗菌活性値として有効であると判定した。 <Antibacterial properties>
It was measured by a method according to the JIS Z 2801:2010 standard. An antibacterial activity value of 2.0 or more was determined to be effective as an antibacterial activity value.
ＪＩＳ Ｚ ２８０１：２０１０の規格に準じた方法にて測定した。抗菌活性値２．０以上を抗菌活性値として有効であると判定した。 <Antibacterial properties>
It was measured by a method according to the JIS Z 2801:2010 standard. An antibacterial activity value of 2.0 or more was determined to be effective as an antibacterial activity value.
＜抗ウイルス性＞
ＩＳＯ ２１７０２：２０１９の規格に準じた方法にて測定した。抗ウイルス活性値２．０以上を抗ウイルス活性値として有効であると判定した。 <Antiviral properties>
It was measured by a method according to the standard of ISO 21702:2019. An antiviral activity value of 2.0 or more was determined to be effective as an antiviral activity value.
ＩＳＯ ２１７０２：２０１９の規格に準じた方法にて測定した。抗ウイルス活性値２．０以上を抗ウイルス活性値として有効であると判定した。 <Antiviral properties>
It was measured by a method according to the standard of ISO 21702:2019. An antiviral activity value of 2.0 or more was determined to be effective as an antiviral activity value.
＜全光線透過率＞
各ハードコートフィルムについて、村上色彩技術研究所（株）製ヘイズメータＨＭ－１５０Ｎを用いて測定した。測定は、ＪＩＳ－Ｋ７３６１の規格に基づき実施した。評価基準については、光線透過率８８％以上を合格とした。 <Total light transmittance>
Each hard coat film was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory. The measurement was performed based on the JIS-K7361 standard. As for the evaluation criteria, a light transmittance of 88% or more was considered acceptable.
各ハードコートフィルムについて、村上色彩技術研究所（株）製ヘイズメータＨＭ－１５０Ｎを用いて測定した。測定は、ＪＩＳ－Ｋ７３６１の規格に基づき実施した。評価基準については、光線透過率８８％以上を合格とした。 <Total light transmittance>
Each hard coat film was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory. The measurement was performed based on the JIS-K7361 standard. As for the evaluation criteria, a light transmittance of 88% or more was considered acceptable.
＜ヘイズ＞
実施例、比較例で作製した各ハードコートフィルムのヘイズは、ＪＩＳ－Ｋ７１３６に基づき、村上色彩技術研究所（株）製ヘイズメータＨＭ－１５０Ｎを用いて測定した。 <Haze>
The haze of each hard coat film produced in Examples and Comparative Examples was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS-K7136.
実施例、比較例で作製した各ハードコートフィルムのヘイズは、ＪＩＳ－Ｋ７１３６に基づき、村上色彩技術研究所（株）製ヘイズメータＨＭ－１５０Ｎを用いて測定した。 <Haze>
The haze of each hard coat film produced in Examples and Comparative Examples was measured using a haze meter HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. based on JIS-K7136.
＜表面抵抗＞
実施例３、７、８で作製したハードコートフィルムの表面抵抗値は、日東精工アナリテック（株）製ハイレスタ-ＵＸ ＭＣＰ－ＨＴ８００を用いて測定した。測定にはＵＳＲプローブを用い、引加電圧を５００Ｖとした。評価基準については、表面抵抗値１．０×１０１１Ω／□未満を合格とした。なお、１０１１Ω／□は、静電気などでほこりが付着しないレベルである。 <Surface resistance>
The surface resistance values of the hard coat films produced in Examples 3, 7 and 8 were measured using Hiresta-UX MCP-HT800 manufactured by Nitto Seiko Analytic Co., Ltd. A USR probe was used for the measurement, and the applied voltage was 500V. As for the evaluation criteria, a surface resistance value of less than 1.0×10 11 Ω/□ was considered acceptable. 10 11 Ω/□ is the level at which dust does not adhere due to static electricity.
実施例３、７、８で作製したハードコートフィルムの表面抵抗値は、日東精工アナリテック（株）製ハイレスタ-ＵＸ ＭＣＰ－ＨＴ８００を用いて測定した。測定にはＵＳＲプローブを用い、引加電圧を５００Ｖとした。評価基準については、表面抵抗値１．０×１０１１Ω／□未満を合格とした。なお、１０１１Ω／□は、静電気などでほこりが付着しないレベルである。 <Surface resistance>
The surface resistance values of the hard coat films produced in Examples 3, 7 and 8 were measured using Hiresta-UX MCP-HT800 manufactured by Nitto Seiko Analytic Co., Ltd. A USR probe was used for the measurement, and the applied voltage was 500V. As for the evaluation criteria, a surface resistance value of less than 1.0×10 11 Ω/□ was considered acceptable. 10 11 Ω/□ is the level at which dust does not adhere due to static electricity.
＜鉛筆硬度＞
実施例、比較例で作製した各ハードコートフィルムについて、ＪＩＳ－Ｋ－５６００－５－４に準じた試験法により鉛筆硬度を測定した。表面に傷の発生なき硬度を標記した。判定基準については、硬度２Ｈ以上は合格とした。 <Pencil hardness>
For each hard coat film produced in Examples and Comparative Examples, pencil hardness was measured by a test method according to JIS-K-5600-5-4. The hardness without scratches on the surface is indicated. As for the judgment criteria, a hardness of 2H or more was regarded as acceptable.
実施例、比較例で作製した各ハードコートフィルムについて、ＪＩＳ－Ｋ－５６００－５－４に準じた試験法により鉛筆硬度を測定した。表面に傷の発生なき硬度を標記した。判定基準については、硬度２Ｈ以上は合格とした。 <Pencil hardness>
For each hard coat film produced in Examples and Comparative Examples, pencil hardness was measured by a test method according to JIS-K-5600-5-4. The hardness without scratches on the surface is indicated. As for the judgment criteria, a hardness of 2H or more was regarded as acceptable.
＜水接触角＞
ＪＩＳ－３２５７の規格に準じた方法にて測定した。 <Water contact angle>
It was measured by a method according to the JIS-3257 standard.
ＪＩＳ－３２５７の規格に準じた方法にて測定した。 <Water contact angle>
It was measured by a method according to the JIS-3257 standard.
＜防曇性＞
８０℃に熱したお湯にハードコート層面をかざし、湯気で曇りが発生するかを目視観察した。
○：曇りの発生なし
×：曇りの発生あり <Anti-fogging property>
The surface of the hard coat layer was held over hot water heated to 80° C., and it was visually observed whether fogging was caused by the steam.
○: No clouding ×: Cloudy
８０℃に熱したお湯にハードコート層面をかざし、湯気で曇りが発生するかを目視観察した。
○：曇りの発生なし
×：曇りの発生あり <Anti-fogging property>
The surface of the hard coat layer was held over hot water heated to 80° C., and it was visually observed whether fogging was caused by the steam.
○: No clouding ×: Cloudy
＜遮熱性（遮蔽係数）＞
ハードコートフィルムの遮熱性は「遮蔽係数」によって評価した。遮蔽係数は、ＪＩＳ Ａ ５７５９に準拠し測定した。遮蔽係数が１．０未満であれば、遮熱性（遮熱効果）を有している。 <Heat shielding (shielding coefficient)>
The heat shielding property of the hard coat film was evaluated by the "shielding coefficient". The shielding coefficient was measured according to JIS A 5759. If the shielding coefficient is less than 1.0, it has heat shielding properties (heat shielding effect).
ハードコートフィルムの遮熱性は「遮蔽係数」によって評価した。遮蔽係数は、ＪＩＳ Ａ ５７５９に準拠し測定した。遮蔽係数が１．０未満であれば、遮熱性（遮熱効果）を有している。 <Heat shielding (shielding coefficient)>
The heat shielding property of the hard coat film was evaluated by the "shielding coefficient". The shielding coefficient was measured according to JIS A 5759. If the shielding coefficient is less than 1.0, it has heat shielding properties (heat shielding effect).
表１の結果から、本発明の実施例によれば、良好な抗菌性及び抗ウイルス性を有するハードコートフィルムが得られることがわかる。特に、ハードコート層に帯電防止剤を含有する実施例３では、良好な抗菌性及び抗ウイルス性と帯電防止性能を兼ね備えるハードコートフィルムが得られる。また、ハードコート層に無機微粒子を含有する実施例４では、良好な抗菌性及び抗ウイルス性を有し、かつ高硬度のハードコートフィルムが得られる。また、ハードコート層に防曇剤を含有する実施例５では、良好な抗菌性及び抗ウイルス性と防曇性を有するハードコートフィルムが得られる。また、実施例６では、良好な抗菌性及び抗ウイルス性と高ヘイズなハードコートフィルム得られる。また、実施例７及び実施例８では、良好な抗菌性及び抗ウイルス性と遮熱効果を有するハードコートフィルムが得られる。
From the results in Table 1, it can be seen that the examples of the present invention provide hard coat films having good antibacterial and antiviral properties. In particular, in Example 3, in which the hard coat layer contains an antistatic agent, a hard coat film having both good antibacterial and antiviral properties and antistatic performance is obtained. Moreover, in Example 4, in which the hard coat layer contains inorganic fine particles, a hard coat film having good antibacterial and antiviral properties and high hardness can be obtained. In Example 5, in which the hard coat layer contains an antifogging agent, a hard coat film having good antibacterial and antiviral properties and antifogging properties is obtained. Moreover, in Example 6, a hard coat film having good antibacterial and antiviral properties and high haze is obtained. Moreover, in Examples 7 and 8, hard coat films having good antibacterial and antiviral properties and heat shielding effects are obtained.
From the results in Table 1, it can be seen that the examples of the present invention provide hard coat films having good antibacterial and antiviral properties. In particular, in Example 3, in which the hard coat layer contains an antistatic agent, a hard coat film having both good antibacterial and antiviral properties and antistatic performance is obtained. Moreover, in Example 4, in which the hard coat layer contains inorganic fine particles, a hard coat film having good antibacterial and antiviral properties and high hardness can be obtained. In Example 5, in which the hard coat layer contains an antifogging agent, a hard coat film having good antibacterial and antiviral properties and antifogging properties is obtained. Moreover, in Example 6, a hard coat film having good antibacterial and antiviral properties and high haze is obtained. Moreover, in Examples 7 and 8, hard coat films having good antibacterial and antiviral properties and heat shielding effects are obtained.
Claims (8)
- 基材上の少なくとも一方の面に、少なくとも無機系金属および電離放射線硬化型樹脂を含有するハードコート層を設けたことを特徴とするハードコートフィルム。 A hard coat film characterized by providing a hard coat layer containing at least an inorganic metal and an ionizing radiation curable resin on at least one surface of a base material.
- 前記無機系金属は、少なくとも銀成分を含む無機材料であることを特徴とする請求項１に記載のハードコートフィルム。 The hard coat film according to claim 1, wherein the inorganic metal is an inorganic material containing at least a silver component.
- 前記無機系金属の添加量は、前記ハードコート層中の固形分に対して、０．０５質量％～３０質量％の範囲であることを特徴とする請求項１又は２に記載のハードコートフィルム。 3. The hard coat film according to claim 1, wherein the amount of the inorganic metal added is in the range of 0.05% by mass to 30% by mass with respect to the solid content in the hard coat layer. .
- 前記ハードコート層は、さらに帯電防止剤を含有することを特徴とする請求項１乃至３のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 3, wherein the hard coat layer further contains an antistatic agent.
- 前記ハードコート層は、さらに無機微粒子を含有することを特徴とする請求項１乃至４のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 4, wherein the hard coat layer further contains inorganic fine particles.
- 前記ハードコート層は、さらに防曇剤を含有することを特徴とする請求項１乃至５のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 5, wherein the hard coat layer further contains an antifogging agent.
- 前記ハードコート層は、さらに有機微粒子を含有することを特徴とする請求項１乃至６のいずれか一項に記載のハードコートフィルム。 The hard coat film according to any one of claims 1 to 6, wherein the hard coat layer further contains organic fine particles.
- 前記基材上の前記ハードコート層と反対の面、もしくは前記基材と前記ハードコート層との間に、金属または金属酸化物からなる薄膜が少なくとも1層以上積層されてなることを特徴とする請求項１乃至７のいずれか一項に記載のハードコートフィルム。
At least one layer of a thin film made of a metal or metal oxide is laminated on the surface of the base material opposite to the hard coat layer or between the base material and the hard coat layer. The hard coat film according to any one of claims 1 to 7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-153591 | 2021-09-21 | ||
| JP2021153591 | 2021-09-21 | ||
| JP2021-182477 | 2021-11-09 | ||
| JP2021182477 | 2021-11-09 |
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| WO2023048107A1 true WO2023048107A1 (en) | 2023-03-30 |
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| PCT/JP2022/034860 WO2023048107A1 (en) | 2021-09-21 | 2022-09-19 | Hard coat film |
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| Country | Link |
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| TW (1) | TW202328356A (en) |
| WO (1) | WO2023048107A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021066874A (en) * | 2019-10-23 | 2021-04-30 | アイカ工業株式会社 | Photocurable resin composition and hard coat film |
| WO2021251329A1 (en) * | 2020-06-09 | 2021-12-16 | 日本製紙株式会社 | Antiviral sheet |
-
2022
- 2022-09-19 WO PCT/JP2022/034860 patent/WO2023048107A1/en active Application Filing
- 2022-09-20 TW TW111135430A patent/TW202328356A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021066874A (en) * | 2019-10-23 | 2021-04-30 | アイカ工業株式会社 | Photocurable resin composition and hard coat film |
| WO2021251329A1 (en) * | 2020-06-09 | 2021-12-16 | 日本製紙株式会社 | Antiviral sheet |
| WO2021251328A1 (en) * | 2020-06-09 | 2021-12-16 | 日本製紙株式会社 | Cellulose fiber-containing antiviral sheet |
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