WO2022025136A1 - Article antiviral et composition de résine antivirale - Google Patents

Article antiviral et composition de résine antivirale Download PDF

Info

Publication number
WO2022025136A1
WO2022025136A1 PCT/JP2021/027968 JP2021027968W WO2022025136A1 WO 2022025136 A1 WO2022025136 A1 WO 2022025136A1 JP 2021027968 W JP2021027968 W JP 2021027968W WO 2022025136 A1 WO2022025136 A1 WO 2022025136A1
Authority
WO
WIPO (PCT)
Prior art keywords
antiviral
cured product
layer
resin
resin composition
Prior art date
Application number
PCT/JP2021/027968
Other languages
English (en)
Japanese (ja)
Inventor
孝 遠藤
晴香 中村
亮介 西垣
陽亮 住田
功之 森山
勝二 中村
Original Assignee
大日本印刷株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021113041A external-priority patent/JP7211458B2/ja
Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Publication of WO2022025136A1 publication Critical patent/WO2022025136A1/fr

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present disclosure relates to antiviral articles and antiviral resin compositions.
  • an antibacterial composition is applied to the surface of objects that are touched by humans, such as building interior materials, vehicle interior materials, information appliances, and touch panels, and antibacterial treatment is applied. That was being done.
  • Patent Documents 1 to 3 have been proposed with respect to an antibacterial composition or an antibacterial article. However, it is not enough to have antibacterial properties against viruses such as influenza virus. That is, the compositions or articles having antibacterial properties of Patent Documents 1 to 3 may not be able to satisfy the antiviral properties.
  • patent documents 4 to 5 have been proposed as compositions or articles having antiviral properties.
  • the antiviral resin composition of Patent Document 4 contains cuprous oxide particles and the like. Therefore, the tint derived from the color of cuprous oxide (reddish brown) could not be prevented.
  • the interior decorative sheet having antiviral properties of Patent Document 5 is formed by blending a silver-based inorganic additive or a zinc-based inorganic additive in a coating resin on the outermost surface of the decorative sheet.
  • the latter zinc-based inorganic additive has a health problem when ingested in a large amount.
  • the former silver-based inorganic additive is expensive, but has no health problem.
  • Patent Document 5 does not examine the problem of discoloration due to an increase in the amount of the silver-based inorganic additive added.
  • the present disclosure is an object of suppressing discoloration of a silver-based antiviral article and an antiviral resin composition due to light.
  • the present disclosure provides the following [1] to [2].
  • An antiviral article comprising a phosphorus-based antioxidant as the antioxidant.
  • an antiviral article and an antiviral resin composition that suppresses discoloration due to light (visible light, ultraviolet rays) of a silver-based antiviral agent.
  • the antiviral article of the present disclosure is an article having a cured product layer, wherein the cured product layer is a cured product of a curable resin composition and an antiviral agent supporting or containing silver ions in a carrier. , An antioxidant, and a phosphorus-based antioxidant as the antioxidant.
  • the antiviral article of the present disclosure may be applicable not only to antiviral use but also to antibacterial use depending on the type of bacteria, environmental conditions, and required level of antibacterial property. be. Since mold is a type of fungus, the antiviral article of the present disclosure is also applied to antifungal uses according to the type of mold, environmental conditions, and the required level of antifungal property. In some cases it can be done.
  • FIGS. 2 (A) to 2 (D), and FIG. 3 are cross-sectional views showing typical embodiments of the antiviral article 100 of the present disclosure.
  • the antiviral article 100 of FIGS. 1 (A) to 1 (E), FIGS. 2 (A) to (D), and FIG. 3 carries or contains silver ions on the cured product 11 and the carrier of the curable resin composition. It has a cured product layer 10 containing the antiviral agent 12.
  • the cured product layer 10 of the antiviral article 100 of FIGS. 1 (A) to 1 (E), FIGS. 2 (A) to (D), and FIG. 3 contains a phosphorus-based antioxidant (not shown). be.
  • the antiviral article 100 of FIGS. 1A to 1E is formed of a single layer of the cured product layer 10.
  • the cured product layer 10 of FIG. 1 (A) contains the antiviral agent 12 in the entire cured product layer 10.
  • the antiviral agent 12 is applied to the cured product layer in both the thickness direction (Z-axis direction in the figure) and the in-plane direction (each direction in the XY plane in the figure). It is included on the surface side (upper side of the figure) of 10.
  • the cured product layer 10 of FIG. 1C contains the antiviral agent 12 on the front surface side (upper side of the figure) and the back surface side (lower side of the figure) of the cured product layer 10.
  • the cured product layer 10 of FIG. 1 (D) contains the antiviral agent 12 in a part of the region in the in-plane direction on the surface side (upper side of the figure) of the cured product layer 10.
  • the antiviral agent 12 is applied to a part of the surface side (upper side of the figure) of the cured product layer 10 and the back surface side (lower side of the figure) of the cured product layer 10. Included in some areas.
  • the location of the antiviral agent 12 in the cured product layer 10 is not particularly limited. However, from the viewpoint of enhancing the antiviral property, it is preferable that the antiviral agent 12 is present on the surface on the side touched by a person.
  • the antiviral article 100 composed of a single layer of the cured product layer 10 as shown in FIGS. 1 (A) to 1 (E) is laminated by forming the cured product layer 10 on a substrate having releasability, for example. After producing the body, it can be obtained by peeling the base material having releasability from the laminated body.
  • the antiviral article 100 of FIGS. 2A to 2D has a cured product layer 10 on the base material 20.
  • the antiviral article 100 of FIG. 2A has a cured product layer 10 on the entire surface of one side of the base material 20.
  • the antiviral article 100 of FIG. 2B has a cured product layer 10 on both sides of the base material 20.
  • the antiviral article 100 of FIG. 2C has a cured product layer 10 in a part of a region on one side (Z-axis direction + side in the figure) of the base material 20.
  • the antiviral article 100 of FIG. 2D has a part of a region on one side of the base material 20 (Z-axis direction + side in the figure) and the other side of the base material 20 (Z in the figure).
  • the cured product layer 10 is provided in a part of the region (axial-side). As shown in FIGS. 2A to 2D, the cured product layer 10 may be formed on the entire surface of the base material 20 or may be formed on a part of the base material 20. Further, as shown in FIGS. 2A to 2D, the cured product layer 10 may be formed on only one surface of the base material 20 or may be formed on both sides of the base material 20. good.
  • the antiviral article 100 of FIG. 3 has a cured product layer 10 on a three-dimensional base material 20.
  • the three-dimensional base material 20 in FIG. 3 is a handle for a door, and FIG. 3 shows a cross-sectional view thereof.
  • the cured product layer contains a cured product of the curable resin composition.
  • the "cured product of a curable resin composition” may be abbreviated as "cured product”.
  • the cured product of the curable resin composition mainly has a role as a binder resin.
  • Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionized radiation curable resin composition, and among them, an ionized radiation curable resin from the viewpoint of scratch resistance and production efficiency.
  • a cured product of the composition is preferred.
  • the thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
  • the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like.
  • a curing agent, a curing catalyst, and the like are added to the thermosetting resin composition, if necessary.
  • Typical examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet curable resin composition.
  • a polymerization initiator is not required, so that the resin composition has less odor and is colored.
  • An electron beam curable resin composition is preferable from the viewpoint of difficulty.
  • the electron beam curable resin composition tends to have a higher crosslink density of the cured product layer, and it is easier to improve scratch resistance and stain resistance. preferable.
  • the ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”).
  • the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group is preferable.
  • examples of the ionizing radiation curable functional group include an epoxy group and an oxetanyl group.
  • a (meth) acryloyl group means an acryloyl group or a metachloroyl group.
  • (meth) acrylate means acrylate or methacrylate.
  • ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and ⁇ -rays, and charged particle beams such as ⁇ -rays and ion-rays are also included.
  • the ionizing radiation curable compound is appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") conventionally used as ionizing radiation curable resins. Can be used.
  • the ionizing radiation curable compound is more preferably a compound having two or more ethylenically unsaturated bonding groups, and more preferably a polyfunctional (meth) acrylate compound having two or more ethylenically unsaturated bonding groups.
  • the polyfunctional (meth) acrylate compound either a monomer or an oligomer can be used.
  • the oligomer of the polyfunctional (meth) acrylate compound has a weight average molecular weight of preferably 1000 or more and 10000 or less in order to make the obtained article have good scratch resistance, processing suitability, and antiviral expression. More preferably, it is 2000 or more and 6000 or less.
  • the number of functional groups per molecule of oligomer is preferably 2 or more and 10 or less, and more preferably 2 or more and 6 or less.
  • the bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexane. Examples thereof include diol diacrylate.
  • the trifunctional or higher functional (meth) acrylate-based monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and di.
  • Examples thereof include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
  • Examples of the polyfunctional (meth) acrylate-based oligomer include acrylate-based polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
  • Urethane (meth) acrylate is obtained, for example, by reacting a polyhydric alcohol or an organic diisocyanate with a hydroxy (meth) acrylate.
  • the preferred epoxy (meth) acrylate is a (meth) acrylate obtained by reacting a trifunctional or higher aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or the like with a (meth) acrylic acid, and a bifunctional or higher functional one.
  • the ionizing radiation curable resin can be used alone or in combination of two or more.
  • the ionizing radiation curable resin composition preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator.
  • a photopolymerization initiator include one or more selected from acetophenone, benzophenone, ⁇ -hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethylketal, benzoylbenzoate, ⁇ -acyloxime ester, thioxanthones and the like.
  • the photopolymerization accelerator can reduce the polymerization inhibition due to air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.
  • the content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more with respect to the total amount of the binder resin. It is preferably 100% by mass, most preferably 100% by mass.
  • the cured product layer contains an antiviral agent that carries or contains silver ions on the carrier.
  • an antiviral agent carrying or containing silver ions on a carrier may be abbreviated as “antiviral agent”.
  • antiviral agent As shown in FIGS. 1A to 1E, it is preferable that at least a part of the antiviral agent 12 protrudes from the cured product layer 10 in order to enhance the antiviral property.
  • inorganic compounds such as zeolite, apatite, glass, zirconium phosphate and titanium phosphate are preferable, and among them, a porous inorganic compound is preferable.
  • Zeolites are aluminosilicates of alkali metals or alkaline earth metals, and either natural zeolites or synthetic zeolites can be used. Zeolites are classified into A type, faujasite type (X type, Y type), mordenite type, clinoptilolite type and the like according to the crystal structure, and any of them can be used.
  • Apatite is a general term for minerals having a composition represented by the following general formula.
  • M 10 (ZO 4 ) 3 X 2 In the above formula, M represents Ca, Ba, Mg, Na, K, Fe, Al and the like, Z represents P, S, Si and As and the like, and X represents F, Cl, O and OH and the like. show.
  • Typical examples corresponding to the above formula include fluorine apatite "Ca 10 (PO 4 ) 6 F 2 " and hydroxyapatite "Ca 10 (PO 4 ) 6 (OH) 2 ".
  • the glass examples include soda glass, borosilicate glass, lead glass, aluminosilicate glass, borate glass and phosphoric acid glass.
  • containing silver ions means holding silver ions or a substance capable of generating silver ions in the carrier in some form.
  • substance capable of generating silver ions means a substance that generates silver ions due to an external factor, a time-dependent factor, or the like, for example, a substance that generates silver ions by dissolving in water or the like. do.
  • Specific supporting or containing forms include a method of supporting by physical adsorption or chemical adsorption; a method of supporting by an ion exchange reaction; a method of supporting by a binder; a method of incorporating a silver compound into a carrier; vapor deposition and dissolution. Examples thereof include a method of supporting or containing a thin layer of a silver compound on the surface of a carrier by a thin film forming method such as a precipitation reaction or sputtering.
  • the antiviral agent is preferably in the form of particles.
  • the shape of the particles of the antiviral agent includes a sphere, an ellipsoid, a polyhedron, a scaly shape, and the like, and is not particularly limited.
  • the average particle size of the antiviral agent is preferably 0.1 to 10.0 ⁇ m, more preferably 0.5 to 5.0 ⁇ m, and even more preferably 1.0 to 4.0 ⁇ m.
  • the average particle size is preferably 0.1 to 10.0 ⁇ m, more preferably 0.5 to 5.0 ⁇ m, and even more preferably 1.0 to 4.0 ⁇ m.
  • the stability of the ink for the cured product layer can be easily obtained.
  • by setting the average particle size to 10.0 ⁇ m or less it is possible to suppress poor appearance, deterioration of scratch resistance and stain resistance, and whitening of the coating film due to excessive protrusion of the antiviral agent from the surface of the cured product layer. It can be easily done, and moreover, it is possible to easily suppress the wear of the members of the coating device (coating roll, doctor blade, etc.).
  • the D / T is preferably 1.0 or less, more preferably 0.7 or less, and 0. It is more preferably 4 or less.
  • the lower limit of D / T is not particularly limited, but is usually 0.01 or more, preferably 0.05 or more.
  • the average particle size means the one measured as the mass average value d50 in the particle size distribution measurement by the laser light diffraction method.
  • the amount of silver ions in the antiviral agent is preferably 0.1 to 30.0 parts by mass, more preferably 0.5 to 25.0 parts by mass with respect to 100 parts by mass of the carrier, and 1 It is more preferably 0.0 to 20.0 parts by mass.
  • the "amount of silver ions” means both the carried silver ions and the contained silver ions.
  • the content of the antiviral agent is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and more preferably 1.0 part by mass or more with respect to 100 parts by mass of the cured product.
  • the upper limit is preferably 20.0 parts by mass or less, more preferably 17.0 parts by mass or less, more preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, and more preferably 5.0 parts by mass. It is less than a part.
  • the content of the antiviral agent is preferably set to a large value in the above range.
  • the cured product layer contains an antioxidant, and further contains a phosphorus-based antioxidant as the antioxidant. If the cured product layer does not contain a phosphorus-based antioxidant, it will turn brown. In particular, when the antiviral resin composition does not contain a phosphorus-based antioxidant, discoloration due to irradiation with light (visible light, ultraviolet light) is remarkable. Further, even after the cured product layer is formed, if the cured product layer does not contain a phosphorus-based antioxidant, it tends to turn brown due to strong light (sunlight or the like). It is considered that the phosphorus-based antioxidant can easily capture the radicals generated by light, and thus can easily suppress the alteration of silver ions.
  • Examples of the phosphorus-based antioxidant include a compound having a phosphorous acid structure represented by the following formula (1), a compound having a phosphonic acid structure represented by the following formula (2), and a phosphinic acid structure represented by the following formula (3). Examples thereof include a compound having a phosphine oxide structure represented by the following formula (4).
  • a compound having a phosphorous acid structure represented by the following formula (1) is preferable because it easily exhibits the effect of suppressing discoloration due to light in the state of the antiviral resin composition.
  • the compound represented by the following general formula (1-2-1) is more preferable.
  • the phosphorus-based antioxidant one kind or two or more kinds can be used.
  • Examples of the compound having a phosphorous acid structure represented by the formula (1) include compounds represented by the following general formulas (1-1) to (1-3).
  • the general formulas (1-1) to (1-3) those of the general formulas (1-1) and (1-2) tend to have good solubility in the ink for the cured product layer. Is preferable.
  • the phosphorus-based antioxidant is diffused throughout the cured product layer, which is preferable in that discoloration can be more easily suppressed.
  • R 11 , R 12 and R 13 are hydrocarbons which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, respectively. Groups are shown, which may have substituents. Further, two selected from R 11 , R 12 and R 13 may be combined to form a ring.
  • R 11 , R 12 and R 13 is a linear alkyl group.
  • the linear alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 15 carbon atoms, and even more preferably 8 to 10 carbon atoms.
  • the remaining R 11 , R 12 and R 13 are preferably phenyl groups.
  • R 11 , R 12 and R 13 do not bind to each other (two selected from R 11 , R 12 and R 13 are bonded and ringed. It is preferable not to form).
  • R 23 is a hydrocarbon group which may contain a hetero atom and may further have a substituent.
  • R 21 , R 22 , R 24 and R 25 are hydrocarbon groups which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, respectively. Further, it may have a substituent.
  • R 21 and R 22 may be bonded to form a ring.
  • R 24 and R 25 may be bonded to form a ring.
  • R 21 , R 22 , R 22 and R 24 is a linear alkyl group, and it is more preferable that all of them are linear alkyl groups.
  • the linear alkyl group preferably has 6 to 18 carbon atoms, more preferably 12 to 15 carbon atoms.
  • R 21 , R 22 , R 24 and R 25 do not bind to each other (R 21 , R 22 , R 24 and R 25 bind to each other). It is preferable not to form a ring).
  • R independently represents a linear alkyl group having 12 to 15 carbon atoms.
  • R 32 is a hydrocarbon group which may contain a hetero atom and may further have a substituent.
  • Each of R 31 and R 33 is a hydrocarbon group which may independently contain a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, or a hetero atom, and further has a substituent. May be good.
  • the phosphorus-based antioxidant may or may not have a polymerizable ethylenic double bond with the curable resin composition, but preferably does not. Since the phosphorus-based antioxidant does not have a polymerizable ethylenic double bond with the curable resin composition, the degree of freedom of movement of the phosphorus-based antioxidant in the cured product layer is increased, and the degree of freedom of movement of the phosphorus-based antioxidant in the cured product layer is increased. It is considered that the phosphorus-based antioxidant is diffused throughout and the discoloration can be easily suppressed.
  • the molecular weight of the phosphorus-based antioxidant is preferably 1500 or less, more preferably 1300 or less, still more preferably 1200 or less, from the viewpoint of facilitating good solubility in the cured product layer ink.
  • the lower limit of the molecular weight of the phosphorus-based antioxidant is not particularly limited, but is usually 270 or more, preferably 300 or more, and more preferably 330 or more.
  • the lower limit of the content of the phosphorus-based antioxidant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass with respect to 100 parts by mass of the antiviral agent. More than parts, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and the upper limit is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, more preferably 600 parts by mass or less, and more preferably 400 parts by mass. It is not less than parts by mass, more preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and more preferably 70 parts by mass or less.
  • the content of the phosphorus-based antioxidant By setting the content of the phosphorus-based antioxidant to 1 part by mass or more, discoloration can be easily suppressed. Further, by setting the content of the phosphorus-based antioxidant to 1000 parts by mass or less, the crosslink density of the cured product of the curable resin composition is lowered, and the scratch resistance and stain resistance of the cured product layer are lowered. Can be easily suppressed.
  • the cured product layer may contain other antioxidants as long as the effects of the present disclosure are not impaired.
  • examples of other antioxidants include phenolic antioxidants, sulfur-based antioxidants and amine-based antioxidants. It should be noted that antioxidants other than phosphorus-based antioxidants are difficult to suppress discoloration. Therefore, it is preferable that the cured product layer does not substantially contain other antioxidants (antioxidants other than phosphorus-based antioxidants).
  • the term "substantially free" means that the content of the other antioxidant is 0.1% by mass or less, preferably 0.01% by mass or less, based on the total solid content of the cured product layer. More preferably, it is 0.001% by mass or less.
  • the cured product layer preferably further contains a light stabilizer.
  • a light stabilizer By including a light stabilizer, discoloration can be further suppressed.
  • the light stabilizer is superior in suppressing discoloration in the state of the cured product layer rather than in the state of the composition.
  • the light stabilizer include hindered amine compounds.
  • the hindered amine compound has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.
  • the hindered amine compound examples include NH type hindered amine compound, NR type hindered amine compound and NOR type hindered amine compound.
  • these hindered amine compounds NH-type hindered amine compounds and NR-type hindered amine compounds are preferable, and NR-type hindered amine compounds are more preferable, from the viewpoint of making it easier to suppress discoloration.
  • the cured product layer preferably contains one or more hindered amine compounds selected from NH-type hindered amine compounds and NR-type hindered amine compounds, and preferably contains one or more hindered amine compounds selected from NR-type hindered amine compounds. Is more preferable.
  • the reason why the NH-type hindered amine compound and the NR-type hindered amine compound are likely to suppress discoloration is considered to be that the NH-type hindered amine-based compound and the NR-type hindered amine-based compound are likely to form a complex with silver ions.
  • the NH-type hindered amine compound is a hydrogen atom bonded to a nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton that remains as a hydrogen atom.
  • Specific examples of the NH-type hindered amine compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
  • the NR-type hindered amine compound refers to a compound in which a hydrogen atom bonded to a nitrogen atom is replaced with an alkyl group in the 2,2,6,6-tetramethylpiperidine skeleton.
  • the alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 (the alkyl group is a methyl group).
  • NR-type hindered amine compound examples include 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylpropanediacid bis [1,2, 2,6,6-Pentamethyl-4-piperidinyl], bissebacate (1,2,2,6,6-pentamethyl-4-piperidinyl), 1-methyl sebacate 10- (1,2,2,6,, 6-Pentamethyl-4-piperidyl), 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate and the like.
  • the NOR-type hindered amine compound refers to a compound in which the hydrogen atom bonded to the nitrogen atom in the 2,2,6,6-tetramethylpiperidine skeleton is replaced with OR 1 or OCOR 2 .
  • R 1 and R 2 are an alkyl group and / or a cycloalkyl group, preferably an alkyl group having 5 to 12 carbon atoms and / or a cycloalkyl group.
  • the hindered amine compound preferably has a base dissociation constant (pkb) of 8.5 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.
  • pkb base dissociation constant
  • the lower limit of pkb of the hindered amine compound is not particularly limited, but is preferably 4.0 or more, and more preferably 4.5 or more.
  • the hindered amine compound may or may not have an ethylenic double bond that can be polymerized with the curable resin composition.
  • the molecular weight of the hindered amine compound is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, from the viewpoint of facilitating good solubility in the cured product layer ink.
  • the lower limit of the molecular weight of the hindered amine compound is not particularly limited, but is usually 200 or more, preferably 215 or more, and more preferably 230 or more.
  • the content of the light stabilizer is preferably 20 to 1000 parts by mass, more preferably 30 to 500 parts by mass, and further preferably 50 to 200 parts by mass with respect to 100 parts by mass of the antiviral agent. preferable.
  • the light stabilizer preferably contains a hindered amine compound in the above range.
  • the cured product layer preferably further contains an ultraviolet absorber.
  • the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and the like, and a triazine-based ultraviolet absorber is preferable.
  • the ultraviolet absorber one kind or two or more kinds can be used.
  • the hydroxyphenyltriazine-based ultraviolet absorber in which at least one organic group selected from a hydroxyphenyl group, an alkoxyphenyl group and an organic group containing these groups is linked to the triazine ring is one. More preferably, a hydroxyphenyltriazine-based ultraviolet absorber represented by the following general formula (A) is further preferable. Since the hydroxyphenyltriazine-based ultraviolet absorber has a branched structure, it is expected that it will be difficult to bleed out from the cured product layer, and excellent weather resistance will be obtained over a longer period of time. Further, an ultraviolet absorber having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group is preferable because it is easy to suppress bleed-out.
  • R 11 is a divalent organic group
  • R 13 , R 14 and R 15 are independent of each other. It is a monovalent organic group
  • n 11 and n 12 are independently integers of 1 to 5.
  • Examples of the divalent organic group of R 11 include an aliphatic hydrocarbon group such as an alkylene group and an alkaneylene group, and an alkylene group is preferable from the viewpoint of weather resistance, and the carbon number thereof is preferably 1 or more and 20 or less. 1 or more and 12 or less are more preferable, 1 or more and 8 or less are further preferable, and 1 or more and 4 or less are particularly preferable.
  • the alkylene group and the alkenylene group may be linear, branched or cyclic, but the linear or branched group is preferable.
  • alkylene group having 1 or more and 20 or less carbon atoms examples include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,3-propylene, a 1,2-propylene and a 2,2-propylene group.
  • Various propylene groups (hereinafter, "various" means linear, branched, and those containing isomers thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, Various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecilene groups, various icosilene groups. The group is mentioned.
  • Examples of the monovalent organic group of R 13 and R 14 include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group can be used.
  • Aryl groups are preferred. Of these, a phenyl group is preferable as the monovalent organic group of R 13 and R 14 .
  • the aryl group preferably has 6 or more and 20 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms, for example, a phenyl group, various methylphenyl groups, and various ethylphenyl groups. Groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and the like can be mentioned.
  • the arylalkyl group preferably has 7 or more and 20 or less carbon atoms, more preferably 7 or more and 12 or less carbon atoms, and more preferably 7 or more and 10 or less carbon atoms, for example, a benzyl group, a phenethyl group, and various phenylpropyl groups.
  • Groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, various hexylbenzyl groups and the like can be mentioned.
  • Examples of the monovalent organic group of R15 include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group is preferable. Is more preferable. That is, as R 12 , an alkyl ester group and an alkenyl ester group are preferable, and an alkyl ester group is more preferable.
  • the alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 2 or more and 16 or less, and further preferably 6 or more and 12 or less, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, and various types.
  • alkenyl group an alkenyl group having preferably 2 or more and 20 or less carbon atoms, more preferably 3 or more and 16 or less, still more preferably 6 or more and 12 or less, for example, a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, Various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadesenyl groups. Examples include groups and various icosenyl groups.
  • R 11 is an alkylene group having 1 or more carbon atoms and 20 or less carbon atoms
  • R 12 and R 15 are alkyl groups having 1 or more carbon atoms and 20 or less carbon atoms. It is an alkyl ester group as a group
  • R 13 and R 14 are aryl groups having 6 or more carbon atoms and 20 or less carbon atoms
  • a hydroxyphenyltriazine compound having n 11 and n 12 of 1 is preferable
  • R 11 has 1 or more carbon atoms and 12 carbon atoms.
  • R 12 and R 15 are alkyl ester groups having 2 or more and 16 or less carbon atoms
  • R 13 and R 14 are aryl groups having 6 or more and 12 or less carbon atoms
  • R 11 is an alkylene group having 1 or more and 8 or less carbon atoms
  • R 12 is an alkyl ester group having R 15 and 6 or more and 12 or less carbon atoms.
  • R 13 and R 14 are aryl groups having 6 or more and 10 or less carbon atoms, hydroxyphenyltriazine compounds having n 11 and n 12 of 1 are more preferable, and R 11 is an alkylene group having 1 or more and 4 or less carbon atoms.
  • R 12 and R 15 are ester groups which are alkyl groups having 8 carbon atoms
  • R 13 and R 14 are phenyl groups, and hydroxyphenyl triazine compounds having n 11 and n 12 of 1 are particularly preferable.
  • the content of the ultraviolet absorber is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the cured product. Is even more preferable.
  • the cured product layer may contain an extender pigment.
  • the extender pigment is used, for example, to adjust the design of the antiviral article.
  • examples of the extender pigment include inorganic particles such as silica, alumina, calcium carbonate, aluminosilicate and barium sulfate, and organic particles such as polyethylene, urethane resin, polycarbonate and polyamide (nylon).
  • the shape of the extender pigment is not particularly limited, but is preferably polyhedral, spherical, or scaly.
  • the average particle size of the extender pigment is usually about 1 to 10 ⁇ m, preferably 3 to 8 ⁇ m.
  • the cured product layer may contain a colorant and be colored to a desired hue, lightness, and saturation.
  • the colorant may be appropriately selected from those of the same color as those used for the colorant and the pattern layer described later.
  • the thickness of the cured product layer can be, for example, 1.0 ⁇ m or more and 10,000 ⁇ m or less from the viewpoint of the balance between processing characteristics and scratch resistance.
  • the thickness of the cured product layer is preferably thick.
  • the base material is responsible for self-supporting property and durability against external force, and the effect is saturated if the antiviral property has a certain thickness or more.
  • the thickness of the cured product layer is a thin film, in consideration of the fact that the thickness of the cured product layer is increased, which causes disadvantages such as a decrease in post-processing suitability and an increase in material cost.
  • the thickness of the cured product layer is preferably 1.5 ⁇ m or more and 30 ⁇ m or less, more preferably 2 ⁇ m or more and 20 ⁇ m or less, and further preferably 3 ⁇ m or more and 15 ⁇ m or less, from the viewpoint of the balance between processing characteristics and scratch resistance.
  • the cured product layer is, for example, an ink for a cured product layer containing a material constituting the cured product layer (curable resin composition, antiviral agent, phosphorus-based antioxidant, etc.), a solvent to be added as necessary, and the like. It can be formed by applying, drying and curing on a substrate. An ink for a cured product layer is applied, dried, and cured on a base material having releasability to form a cured product layer, and the cured product layer is transferred to another substrate or the like to form a cured product layer. It can also be formed.
  • a material constituting the cured product layer curable resin composition, antiviral agent, phosphorus-based antioxidant, etc.
  • the antiviral article of the present disclosure may be a single layer of a cured product layer, or may have a layer other than the cured product layer.
  • An antiviral article composed of a single layer of a cured product layer is, for example, a group having a mold releasable property from a laminated body obtained by forming a cured product layer on a substrate having a releasable property. It can be obtained by peeling off the material.
  • the layer other than the cured product layer of the antiviral article include a base material, a primer layer, a decorative layer, a transparent resin layer, an adhesive layer and the like.
  • Examples of the laminated structure of the antiviral article include the following (1) to (12).
  • the layers other than the cured product layer of the antiviral article include a magnetic material layer for magnetic recording; a conductor layer that functions as a circuit, a copper wire for current, or an electromagnetic wave shielding layer; a gas such as water vapor or oxygen.
  • Functional layers such as a gas barrier layer for suppressing transmission; a light reflecting layer for reflecting visible light with a high reflectance; an antireflection layer for suppressing the reflection of visible light; and the like can also be mentioned.
  • These functional layers can be formed at any of the following laminated configurations (1) to (12) depending on the function of each layer.
  • Hardened material layer (2) Base material / Hardened material layer (3) Base material / Primer layer / Hardened material layer (4) Base material / Decorative layer / Hardened material layer (5) Base material / Transparent resin layer / Hardened material layer (6) Base material / Adhesive layer / Transparent resin layer / Hardened material layer (7) Base material / Adhesive layer / Decorative layer / Transparent resin layer / Hardened material layer (8) Base material / Decorative layer / Adhesive layer / Transparent resin layer / Hardened material layer (9) Base material / Transparent resin layer / Primer layer / Hardened material layer (10) Base material / Adhesive layer / Transparent resin layer / Primer layer / Hardened material Layer (11) Base material / Adhesive layer / Decorative layer / Transparent resin layer / Primer layer / Hardened material layer (12) Base material / Decorative layer / Adhesive layer / Transparent resin layer / Primer layer / Hardened material layer (12)
  • the antiviral article preferably has a cured product layer on the substrate from the viewpoint of handleability.
  • Base material The form of the base material may be a flat plate such as a film, a sheet or a plate, or a three-dimensional shape such as a polyhedron, a polygonal prism, a cylinder, a spherical surface or a spheroidal surface, and is not particularly limited.
  • films, sheets and boards are often referred to as films, sheets and boards in order from the one having a relatively thin thickness, but in the present specification, these three are not distinguished unless otherwise specified. ..
  • constituent material of the base material examples include resin, metal, non-metal inorganic material, fibrous material, wood-based material, etc., which can be appropriately selected according to the intended use.
  • the base material may be a single layer, or may be a laminated layer of two or more layers made of the above materials. In the case of a laminated body having two or more layers of the base material, it is preferable that two or more layers of different materials are laminated to complement each other's various performances of the materials of each layer. Examples of the base material formed by laminating two or more layers include the following A to J. In addition, "/" indicates the interface of each layer.
  • A Resin / wood-based material
  • B resin / metal
  • C resin / fibrous material
  • D resin / non-metal inorganic material
  • E resin 1 / resin 2
  • F Metal / Wood-based material
  • G Metal / Non-metal Inorganic material
  • H Metal / Fibrous material
  • I Metal 1 / Metal 2
  • J Non-metal inorganic material / fibrous material
  • the resin 1 and the resin 2 represent different types of resins (for example, the resin 1 is an olefin resin and the resin 2 is an acrylic resin). Further, in the above H, the metal 1 and the metal 2 represent different kinds of metals (for example, the metal 1 is copper and the metal 2 is chromium).
  • the base material is a laminated body such as A to J
  • a layer (adhesive layer or the like) for strengthening the adhesive force may be provided between the layers of each constituent layer of the laminated body. ..
  • the resin used as the base material examples include those made of various synthetic resins or natural resins.
  • the synthetic resin a thermoplastic resin and a curable resin can be used.
  • thermoplastic resin examples include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers, polyvinyl chloride containing an appropriate amount of a plasticizer as required, polyvinylidene chloride, and vinyl chloride-vinyl acetate.
  • Vinyl chloride resin such as copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester resin such as polyester thermoplastic elastomer, poly (meth) methyl acrylate, Acrylic resins such as ethyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) butyl acrylate-(meth) butyl acrylate copolymers, polyamide resins typified by nylon 6 or nylon 66, etc.
  • Tricellulose resin such as cellulose acetate, cellophane, celluloid, polystyrene, styrene resin such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene -Vinyl alcohol copolymerization, polycarbonate resin, polyallylate resin, polyimide resin and the like can be mentioned.
  • the curable resin include the thermosetting resin and the ionizing radiation curable resin exemplified in the cured product layer.
  • the natural resin include natural rubber, pine fat, amber and the like.
  • Metals used as a base material include, for example, alloys containing aluminum such as aluminum or duralumin, alloys containing iron such as iron or carbon steel and stainless steel, alloys containing copper such as copper or brass and bronze, gold and silver. , Chromium, nickel, cobalt, tin, titanium and the like. Further, as the metal base material, those obtained by plating or the like with these metals can also be used.
  • non-metal inorganic materials used as a base material examples include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), gypsum, calcium silicate, and wood piece cement, and ceramic materials such as ceramics, earthenware, glass, and amber. Examples include ceramic materials, natural stones such as limestone (including marble), granite, and Anshan rock.
  • Fibrous materials used as base materials include, for example, thin leaf paper, kraft paper, high-quality paper, Japanese paper, titanium paper, linter paper, sulfate paper, paraffin paper, parchment paper, glassin paper, wallpaper backing paper, board paper and gypsum board.
  • base materials include, for example, thin leaf paper, kraft paper, high-quality paper, Japanese paper, titanium paper, linter paper, sulfate paper, paraffin paper, parchment paper, glassin paper, wallpaper backing paper, board paper and gypsum board.
  • base paper polyester resin fibers, acrylic resin fibers, protein-based or cellulose-based natural fibers such as silk, cotton and linen, glass fibers, carbon fibers and the like.
  • acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin are used to increase the interfiber strength between the fibers of the paper base material or between other layers and the paper, to prevent fluffing, and to prevent fluffing.
  • the above resin may be added (impregnated with resin after papermaking, or filled in at the time of papermaking).
  • Examples of the paper to which the resin is added include inter-paper reinforced paper and resin-impregnated paper.
  • a resin such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is formed on the surface of a backing paper for wallpaper, which is often used in the field of building materials.
  • a resin such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is formed on the surface of a backing paper for wallpaper, which is often used in the field of building materials.
  • Examples include wallpaper with laminated layers.
  • the shape and dimensions of the base material are not particularly limited and may be appropriately selected according to the intended use, desired performance and processing suitability.
  • the thickness is a typical design dimension of the article.
  • the thickness is not particularly limited, but is generally set to about 10 ⁇ m or more and 10 cm or less from the viewpoint of manufacturing processability, mechanical strength, usability, and economy.
  • a film having a size of 20 ⁇ m or more and 500 ⁇ m or less is usually selected, and in the case of a plate form, a film having a size of 1 mm or more and 2 cm or less is usually selected.
  • the base material is subjected to an oxidation method or unevenness on one or both sides of the base material in order to improve the adhesion with other layers constituting the antiviral article or the adhesion between the antiviral article and the member to be laminated.
  • a physical surface treatment such as a law or a surface treatment such as a chemical surface treatment can be applied.
  • the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment method is preferably used from the viewpoint of the effectiveness and operability of the surface treatment.
  • the antiviral article preferably has a primer layer in contact with the surface of the cured product layer on the substrate side.
  • the primer layer improves the adhesion between the base material and the cured product layer, and makes it easy to secure long-term interlayer adhesion (so-called weather resistance) and scratch resistance when exposed to ultraviolet rays.
  • Examples of cases where antiviral articles are exposed to ultraviolet rays include places where sunlight including an ultraviolet spectrum such as near a window enters; inside a kitchen, refrigerator and cupboard where a mercury lamp for sterilization is installed; in direct sunlight. Examples include the installation, construction, or use of anti-virus articles outdoors where they are exposed to direct sunlight.
  • the primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.
  • a binder resin urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (carbonate bond to the polymer main chain).
  • a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent.
  • a polyol resin such as an acrylic polyol resin is preferably cross-linked and cured with an isocyanate-based curing agent, and a acrylic polyol resin is more preferably cross-linked and cured with an isocyanate-based curing agent.
  • the primer layer preferably contains an ultraviolet absorber and / or a light stabilizer in order to further improve weather resistance.
  • an ultraviolet absorber and the light stabilizer general-purpose ones can be used.
  • the thickness of the primer layer is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, more preferably 0.7 ⁇ m or more and 8 ⁇ m or less, and further preferably 1.0 ⁇ m or more and 6 ⁇ m or less.
  • the antiviral article may have a back surface primer layer on the side opposite to the cured product layer of the base material for the purpose of improving the adhesiveness with the adherend. Further, the antiviral article may have an adhesive layer on the side opposite to the cured product layer of the base material for the purpose of adhering it to the adherend. It is preferable to form a peelable separator on the surface of the pressure-sensitive adhesive layer opposite to the base material.
  • the antiviral article may have a transparent resin layer between the base material and the cured product layer from the viewpoint of increasing the strength and the like.
  • the base material is a resin base material
  • the transparent resin layer is preferably located between the substrate and the primer layer.
  • the transparent resin layer is preferably located between the decorative layer and the cured product layer from the viewpoint of protecting the decorative layer.
  • the resin constituting the transparent resin layer examples include a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), an acrylic resin, and a vinyl chloride resin.
  • a polyolefin resin is preferable from the viewpoint of processability.
  • two or more kinds of these exemplified various resins may be laminated or mixed and used.
  • the content of the polyolefin-based resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total resin components of the transparent resin layer, from the viewpoint of processability. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
  • the polyolefin resin of the transparent resin layer includes polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-vinyl acetate.
  • examples thereof include polymers, ethylene-acrylic acid copolymers, and ethylene-propylene-butene copolymers.
  • polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, propylene-butene copolymer are preferable, and polypropylene is more preferable.
  • the transparent resin layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant.
  • the thickness of the transparent resin layer is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 40 ⁇ m or more and 120 ⁇ m or less, and further preferably 60 ⁇ m or more and 100 ⁇ m or less, from the viewpoint of the balance between scratch resistance, processing suitability and weather resistance.
  • the antiviral article preferably has a decorative layer at any position on the antiviral article.
  • the location where the decorative layer is formed is preferably on the side closer to the base material from the viewpoint of enhancing the weather resistance of the decorative layer.
  • the decorative layer is preferably located between the substrate and the primer layer.
  • the decorative layer is preferably located between the base material and the transparent resin layer.
  • the decorative layer may be formed on the entire surface of the antiviral article or may be formed only on a part thereof. In the case where the outer surface of the cured product layer is covered with the decorative layer, it is preferable to form the decorative layer only in a part of the region in order not to inhibit the expression of antiviral property.
  • the decorative layer examples include a colored layer formed by solid coating with ink; a pattern layer formed by printing ink as a pattern; a metal thin film; and the like.
  • the patterns expressed by the decorative layer include wood grain patterns such as annual rings and conduit grooves on the surface of the wood board; stone grain patterns on the surface of stone boards such as marble and granite; cloth grain patterns on the surface of the fabric; leather grain patterns on the leather surface; Tile-pasted pattern including joint groove; Brick stack pattern including joint groove; Sand grain pattern; Pear-skin pattern; "Pattern” or "ray carved pattern”); Geometric patterns, letters, figures, polka dots, floral patterns and other abstract patterns; etc.
  • a binder resin is appropriately mixed with a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer and the like. Is used.
  • the binder resin for the coloring layer and the pattern layer is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-acetic acid.
  • resins such as vinyl copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin.
  • resins such as vinyl copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin.
  • various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.
  • the colorant is not particularly limited, and is, for example, an inorganic pigment such as carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue; , Isoindolinon yellow, nickel azo complex, phthalocyanine blue, azomethine azo black and other organic pigments or dyes; metal pigments consisting of scaly foil pieces such as aluminum and brass; titanium dioxide coated mica, scaly foil such as basic lead carbonate Pearl gloss (pearl) pigment consisting of one piece; and the like.
  • an inorganic pigment such as carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue
  • metal pigments consisting of scaly foil
  • the content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more with respect to 100 parts by mass of the resin constituting the coloring layer and the pattern layer. 70 parts by mass or less is more preferable.
  • the coloring layer and the pattern layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a coloring agent.
  • the thickness of the colored layer and the pattern layer may be appropriately selected according to the desired pattern, but is preferably 0.5 ⁇ m or more and 20 ⁇ m or less from the viewpoint of concealing the ground color of the adherend and improving the design. It is more preferably 1 ⁇ m or more and 10 ⁇ m or less, and further preferably 2 ⁇ m or more and 5 ⁇ m or less.
  • the metal thin film examples include a thin film of a single metal element such as gold, silver, copper, tin, iron, indium, nickel, chromium, and cobalt; and a thin film of an alloy containing two or more of the metal elements.
  • the alloy examples include brass, bronze, stainless steel and the like.
  • the film thickness of the metal thin film can be about 0.1 ⁇ m to 1 ⁇ m.
  • the antiviral article may have an adhesive layer.
  • the antiviral article has a transparent resin layer
  • a decorative layer is further provided between the base material and the transparent resin layer
  • the positional relationship between the adhesive layer and the decorative layer is not particularly limited.
  • the decorative layer, the adhesive layer and the transparent resin layer may be provided in this order from the side closer to the base material, or the adhesive layer, the decorative layer and the transparent resin may be provided from the side closer to the base material layer.
  • the layers may be provided in this order.
  • an adhesive layer may be provided between the layers constituting the base material.
  • the adhesive layer can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, or a rubber-based adhesive.
  • an adhesive such as a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, or a rubber-based adhesive.
  • urethane-based adhesives are preferable in terms of adhesive strength.
  • the urethane-based adhesive include an adhesive using a two-component curable urethane resin containing various polyol compounds such as a polyether polyol, a polyester polyol, and an acrylic polyol, and a curing agent such as an isocyanate compound.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 15 ⁇ m or less, and further preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the above-mentioned decorative layer, adhesive layer and primer layer are known methods such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma coating method and the like, in which a coating liquid containing a composition forming each layer is applied. It can be formed by applying with, and if necessary, drying and curing.
  • the antiviral article may be given a desired uneven shape (also referred to as an uneven pattern) by a shaping treatment such as embossing.
  • embossing for example, the antiviral article is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 200 ° C. or lower, and further preferably 100 ° C. or higher and 180 ° C. or lower to obtain an antiviral article.
  • Embossing can be performed by pressing the embossed plate. The portion where the embossed plate is pressed is preferably on the cured product layer side of the antiviral article.
  • the antiviral article of the present disclosure preferably has an antiviral activity value of more than 0.0 as measured by the following method.
  • the antiviral activity value is more preferably 1.0 or more, further preferably 2.0 or more.
  • the following method is an ISO 21702 compliant method.
  • ⁇ Measurement method of antiviral activity value >> 0.4 ml of virus solution is added dropwise to a 5 cm square test piece (antiviral processed product and unprocessed product), and the test piece is covered with a 4 cm square film. This test piece was allowed to stand at 25 ° C for 24 hours. After standing, the virus on the test piece is washed out and collected, and the virus infectivity titer is measured.
  • the antiviral activity value is calculated by the following formula (1).
  • R Ut-At (1)
  • R Antiviral activity value
  • Ut Average of common logarithms of virus infectious titer (PFU / cm 2 ) after 24 hours of unprocessed product
  • PFU virus infectious titer of antiviral processed product after 24 hours of standing (PFU) / Cm 2 )
  • the antiviral article of the present disclosure can be used for various purposes. Specific uses include the following (1) to (12). When the antiviral article of the present disclosure is used as the following various surface materials, known adhesion is required between the surface material and the adherend to which the surface material is laminated, if necessary. An agent layer may be interposed.
  • Usable adhesives include heat-sealing adhesives that adhere by cooling and solidifying after heating and melting, heat-curing adhesives that adhere by polymerization or cross-linking reaction by heating, and ionizing radiation irradiation such as ultraviolet rays and electron beams.
  • Examples thereof include an ionizing radiation-curable adhesive that adheres by polymerization or cross-linking reaction, and an adhesive that adheres only by pressurization by utilizing the adhesiveness of the adhesive itself.
  • Surface materials for interior parts such as walls, floors, and ceilings of buildings such as houses, offices, stores, hospitals, and clinics.
  • Surface materials for exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics.
  • Surface materials for fittings internal or exterior parts
  • fittings such as windows, window frames, doors, door frames; surface materials for accessories (handles, etc.) of fittings; surface materials for jigs for fittings.
  • OA equipment such as various computer equipment such as electronic copiers, facsimiles, printers, and personal computers; Surface materials for housings of various OA equipment for ATM equipment of financial institutions such as banks and post offices; Surface material for auxiliary equipment (keyboard keyboard, touch panel, etc.) of OA equipment; Surface material for jigs of various OA equipment.
  • OA equipment such as various computer equipment such as electronic copiers, facsimiles, printers, and personal computers
  • Surface materials for housings of various OA equipment for ATM equipment of financial institutions such as banks and post offices Surface material for auxiliary equipment (keyboard keyboard, touch panel, etc.) of OA equipment
  • Surface material for jigs of various OA equipment Surface materials for interior or exterior parts (walls, floors, ceilings, handrails, columns, operation panels, levers, handles, steering wheels, etc.) of vehicles such as automobiles and railroad vehicles, ships, and aircraft. ..
  • the antiviral resin composition of the present disclosure is a resin composition containing a curable resin composition, an antiviral agent supporting or containing silver ions on a carrier, and an antioxidant, and the antioxidant. It contains a phosphorus-based antioxidant as an agent.
  • the antiviral resin composition of the present disclosure may contain a light stabilizer, an ultraviolet absorber and the like, if necessary.
  • the embodiments of the "light stabilizer” and the “ultraviolet absorber” in the antiviral resin composition of the present disclosure are the implementation of the "light stabilizer” and the “ultraviolet absorber” in the antiviral article of the present disclosure described above. It is similar to the form of.
  • the antiviral resin composition of the present disclosure preferably contains a solvent.
  • the solvent may be, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.).
  • Etc. aromatic hydrocarbons (toluene, xylene, etc.), carbon halides (di dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (isopropanol, butanol, cyclohexanol, etc.) ), Cellosolves (methyl cellosolve, ethyl cellosolve, etc.), glycol ethers (propylene glycol monomethyl ether acetate, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. It can be exemplified and may be a mixture thereof.
  • the content of the solvent is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, based on the total amount of the antiviral resin composition (ink for cured product layer).
  • the step of dew condensation for 4 hours was regarded as one cycle, and the test in which the cycle was repeated) was carried out for 2 cycles (48 hours). Then, the L * a * b * value after the accelerated weather resistance test was measured. Then, the color difference ( ⁇ E * ab) was calculated from the measured value immediately after production and the measured value after the accelerated weathering test. The results are shown in Table 2.
  • Antiviral activity value According to "Measuring method of antiviral activity value" in the main text of the specification, the antiviral activity value was measured with respect to the antiviral articles of Examples B1 to B3 and Comparative Examples B1 to B3. Two types of antiviral activity values, influenza virus and feline calicivirus, were measured.
  • Example A1 An ink a (antiviral resin composition a) for a cured product layer of Example A1 was prepared by mixing and stirring the following compositions.
  • ⁇ Ink a for cured product layer (antiviral resin composition a)> 100 parts by mass of ionizing radiation curable resin composition (trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000) -Antiviral agent containing silver ions in the carrier 3 parts by mass (product number "PG711" manufactured by Koa Glass Co., Ltd., carrier is glass, average particle diameter 3 ⁇ m) -Phosphorus-based antioxidant 1 part by mass (phosphorus-based antioxidant of the above formula 1-1-1) -UV absorber 2 parts by mass (hydroxyphenyltriazine, TINUVIN479, manufactured by BASF) 16 parts by mass of extender pigment (atypical silica) (average particle size: 10 ⁇ m) ⁇ Solvent 50 parts by mass (ethyl acetate)
  • Example A2 For the cured product layer of Example A2, which comprises changing the phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) to the phosphorus-based antioxidant of the above formula 1-1-2. Ink b (antiviral resin composition b) was prepared.
  • Example A3 For the cured product layer of Example A3, which comprises changing the phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) to the phosphorus-based antioxidant of the above formula 1-1-3. Ink c (antiviral resin composition c) was prepared.
  • Example A4 For the cured product layer of Example A4, which comprises changing the phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) to the phosphorus-based antioxidant of the above formula 1-2-1. Ink d (antiviral resin composition d) was prepared.
  • Example A5 The phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) was changed to the phosphorus-based antioxidant of the following formula 1-3-1 (ADEKA Corporation, product number "PEP-36").
  • the ink e (antiviral resin composition e) for the cured product layer of Example A5 was prepared.
  • Example A6 The phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) is changed to the phosphorus-based antioxidant of the following formula 1-1-4 (ADEKA, product number "TPP"). , Ink f (antiviral resin composition f) for the cured product layer of Example A6 was prepared.
  • Example A7 An ink g (antiviral resin composition g) for a cured product layer was prepared.
  • Example A8 Ink h (anti-virus resin composition h) for the cured product layer was prepared.
  • Example A9 An ink i for a cured product layer (antiviral resin composition i) was prepared.
  • Comparative Example A1 Curing of Comparative Example A1 in which the phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) is changed to a phenol-based antioxidant (ADEKA Corporation, product number "AO-20"). An ink j for a material layer (antiviral resin composition j) was prepared.
  • Comparative Example A2 Curing of Comparative Example A2 in which the phosphorus-based antioxidant of the cured product layer ink a (antiviral resin composition a) is changed to a sulfur-based antioxidant (ADEKA Corporation, product number "AO-503").
  • An ink k (antiviral resin composition k) for a material layer was prepared.
  • Comparative Example A3 The cured product layer ink l (anti-virus resin composition kl) of Comparative Example A3 was prepared by removing the phosphorus-based antioxidant from the cured product layer ink a (anti-virus resin composition a).
  • the cured product layer ink (antiviral resin composition) of the examples can suppress discoloration.
  • Example B1 A two-component curable acrylic-urethane resin and a decorative layer ink containing a colorant are applied by gravure printing to one surface of a substrate (polypropylene resin sheet containing titanium oxide with a thickness of 60 ⁇ m) that has undergone double-sided corona discharge treatment. After drying, a decorative layer having a wood grain pattern having a thickness of 3 ⁇ m was formed. Next, an adhesive layer having a thickness of 3 ⁇ m made of a urethane resin-based adhesive is formed on the decorative layer, and a polypropylene-based resin is heated and melt-extruded onto the adhesive layer by a T-die extruder to have a transparency of 80 ⁇ m.
  • a resin layer was formed.
  • the surface of the transparent resin layer was subjected to a corona discharge treatment, and then an ink for a primer layer having the following composition was applied onto the transparent resin layer by a gravure printing method and dried to form a primer layer having a thickness of 2 ⁇ m.
  • the cured product layer ink g antioxidant resin composition g was applied onto the primer layer by a roll coating method to form an uncured cured product layer, which was then dried at 60 ° C. for 1 minute.
  • Electron beam (acceleration voltage: 175 kV, 5Mrad (50 kGy)) is irradiated to crosslink and cure the curable resin composition (ionized radiation curable resin composition) to form a cured product layer having a thickness of 15 ⁇ m.
  • the antiviral article of Example 1 was obtained.
  • the cured product layer ink g (antiviral resin composition g) was applied onto the primer layer immediately after preparation.
  • ⁇ Ink for primer layer ⁇ 100 parts by mass of a mixture of urethane-acrylic copolymer and acrylic polyol ⁇ 5 parts by mass of hexamethylene diisocyanate
  • Example B2 The antiviral properties of Example B2 are the same as in Example B1 except that the cured product layer ink g (antiviral resin composition g) is changed to the cured product layer ink h (antiviral resin composition h). Obtained a viral article.
  • Example B3 The antiviral properties of Example B3 are the same as in Example B1 except that the cured product layer ink g (antiviral resin composition g) is changed to the cured product layer ink i (antiviral resin composition i). Obtained a viral article.
  • Comparative Example B1 The antiviral property of Comparative Example B1 is the same as that of Example B1 except that the cured product layer ink g (antiviral resin composition g) is changed to the cured product layer ink j (antiviral resin composition j). Obtained a viral article.
  • Comparative Example B2 The antiviral properties of Comparative Example B2 are the same as in Example B1 except that the cured product layer ink g (antiviral resin composition g) is changed to the cured product layer ink k (antiviral resin composition k). Obtained a viral article.
  • Comparative Example B3 Anti-virus of Comparative Example B3 in the same manner as in Example B1 except that the cured product layer ink g (antiviral resin composition g) was changed to the cured product layer ink l (antiviral resin composition l). Obtained a viral article.
  • the antiviral article of the example can suppress discoloration. Further, as shown in Table 2, it can be confirmed that the antiviral article of the example has good antiviral property. It is considered that antioxidants such as phosphorus-based antioxidants do not affect the antiviral activity value.
  • Antiviral article 10 Cured product layer 11: Cured product of curable resin composition 12: Antiviral agent supporting or containing silver ions on a carrier 20: Substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne un article antiviral qui présente une décoloration à la lumière réduite.　L'article antiviral a une couche de produit durci, la couche de produit durci comprenant un produit durci d'une composition de résine durcissable, un agent antiviral comprenant un support et des ions argent supportés sur le support ou contenus dans celui-ci et un agent antioxydant, et l'agent antioxydant comprenant un agent antioxydant à base de phosphore. De préférence, la couche de produit durci de l'article antiviral est placée sur un matériau de base.
PCT/JP2021/027968 2020-07-30 2021-07-28 Article antiviral et composition de résine antivirale WO2022025136A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2020129742 2020-07-30
JP2020-129742 2020-07-30
JP2021-113041 2021-07-07
JP2021113041A JP7211458B2 (ja) 2020-07-30 2021-07-07 抗ウイルス性物品及び抗ウイルス性物品の製造方法

Publications (1)

Publication Number Publication Date
WO2022025136A1 true WO2022025136A1 (fr) 2022-02-03

Family

ID=80035666

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/027968 WO2022025136A1 (fr) 2020-07-30 2021-07-28 Article antiviral et composition de résine antivirale

Country Status (3)

Country Link
JP (1) JP2023033309A (fr)
TW (1) TW202214759A (fr)
WO (1) WO2022025136A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63265958A (ja) * 1987-04-22 1988-11-02 Shinagawa Nenryo Kk 抗菌性樹脂組成物
JPH11171704A (ja) * 1997-12-10 1999-06-29 Co-Op Chem Co Ltd 抗菌抗かび剤
US6485735B1 (en) * 1999-08-31 2002-11-26 Phelps Dodge High Performance Conductors Of Sc & Ga, Inc. Multilayer thermoset polymer matrix and structures made therefrom
WO2005037296A1 (fr) * 2003-10-16 2005-04-28 Toagosei Co., Ltd. Agent luttant contre le coronavirus
JP2008081884A (ja) * 2006-09-27 2008-04-10 Dainippon Printing Co Ltd 発泡壁紙
JP2013180459A (ja) * 2012-03-01 2013-09-12 Dainippon Printing Co Ltd 光触媒機能を有する積層シート
JP2013180233A (ja) * 2012-03-01 2013-09-12 Dainippon Printing Co Ltd 光触媒機能を付加した積層シート
US20140170238A1 (en) * 2012-12-18 2014-06-19 Basf Se Antimicrobial effects in polymers
WO2019172041A1 (fr) * 2018-03-09 2019-09-12 富士フイルム株式会社 Membrane antibactérienne, composition antibactérienne, matériau de base équipé d'une membrane antibactérienne, et procédé pour conférer une propriété antibactérienne

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63265958A (ja) * 1987-04-22 1988-11-02 Shinagawa Nenryo Kk 抗菌性樹脂組成物
JPH11171704A (ja) * 1997-12-10 1999-06-29 Co-Op Chem Co Ltd 抗菌抗かび剤
US6485735B1 (en) * 1999-08-31 2002-11-26 Phelps Dodge High Performance Conductors Of Sc & Ga, Inc. Multilayer thermoset polymer matrix and structures made therefrom
WO2005037296A1 (fr) * 2003-10-16 2005-04-28 Toagosei Co., Ltd. Agent luttant contre le coronavirus
JP2008081884A (ja) * 2006-09-27 2008-04-10 Dainippon Printing Co Ltd 発泡壁紙
JP2013180459A (ja) * 2012-03-01 2013-09-12 Dainippon Printing Co Ltd 光触媒機能を有する積層シート
JP2013180233A (ja) * 2012-03-01 2013-09-12 Dainippon Printing Co Ltd 光触媒機能を付加した積層シート
US20140170238A1 (en) * 2012-12-18 2014-06-19 Basf Se Antimicrobial effects in polymers
WO2019172041A1 (fr) * 2018-03-09 2019-09-12 富士フイルム株式会社 Membrane antibactérienne, composition antibactérienne, matériau de base équipé d'une membrane antibactérienne, et procédé pour conférer une propriété antibactérienne

Also Published As

Publication number Publication date
TW202214759A (zh) 2022-04-16
JP2023033309A (ja) 2023-03-10

Similar Documents

Publication Publication Date Title
JP7226635B2 (ja) 抗ウイルス性物品及び抗ウイルス性樹脂組成物
WO2011081201A1 (fr) Composition de revêtement et feuille utilisant celle-ci
JP5830857B2 (ja) シート
WO2016125907A1 (fr) Feuille décorative et élément décoratif pourvu d'une feuille décorative
WO2016125906A1 (fr) Élément décoratif
KR20200059265A (ko) 화장 시트 및 이것을 이용한 화장재
WO2019065801A1 (fr) Feuille décorative et matériau décoratif l'utilisant
JP2017202674A (ja) 化粧シート及び該化粧シートを備える化粧部材
JP5035058B2 (ja) 化粧シート及び該化粧シートを用いた化粧板
JP2022026338A (ja) 抗ウイルス性物品及び抗ウイルス性樹脂組成物
WO2022025136A1 (fr) Article antiviral et composition de résine antivirale
JP2022027514A (ja) 抗ウイルス性物品及び抗ウイルス性樹脂組成物
WO2022059676A1 (fr) Article antiviral et composition de résine antivirale
JP2022097957A (ja) 積層体
JP2022026339A (ja) 抗ウイルス性物品及び抗ウイルス性樹脂組成物
JP2007204966A (ja) 化粧シート及び該化粧シートを用いた化粧板
JP2022053446A (ja) 化粧材
JP4797328B2 (ja) 化粧シート及びそれを用いた化粧鋼板
US20220347983A1 (en) Decorative sheet and decorative material using same
JP2022138582A (ja) 抗ウイルス性化粧シート
JP2022086791A (ja) 抗ウイルス性粘着シート
JP2022086747A (ja) 抗ウイルス性粘着シート
WO2023190478A1 (fr) Feuille de transfert et article résistant aux intempéries
JP2023084528A (ja) 抗ウイルス性粘着シート及び抗ウイルス性粘着シート付の物品
JP2023084526A (ja) 抗ウイルス性粘着シート及び抗ウイルス性粘着シート付の物品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21850265

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21850265

Country of ref document: EP

Kind code of ref document: A1