WO2022059676A1 - 抗ウイルス性物品及び抗ウイルス性樹脂組成物 - Google Patents
抗ウイルス性物品及び抗ウイルス性樹脂組成物 Download PDFInfo
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- WO2022059676A1 WO2022059676A1 PCT/JP2021/033773 JP2021033773W WO2022059676A1 WO 2022059676 A1 WO2022059676 A1 WO 2022059676A1 JP 2021033773 W JP2021033773 W JP 2021033773W WO 2022059676 A1 WO2022059676 A1 WO 2022059676A1
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- antiviral
- particles
- cured product
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- resin
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Images
Classifications
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Definitions
- the present invention relates to an antiviral article and an antiviral resin composition.
- 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.
- composition having antibacterial property or the antibacterial article for example, the techniques described in Patent Documents 1 to 3 have been proposed. 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 for 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 the coating resin on the outermost surface of the decorative sheet.
- the former silver-based inorganic additive has a problem of turning brown due to light (visible light, ultraviolet light).
- the amount of the silver-based inorganic additive added was increased in order to exhibit antiviral properties, the problem of discoloration due to light was remarkable.
- An object of the present invention is to provide an antiviral article and an antiviral resin composition capable of suppressing a problem of color such as discoloration due to light.
- the present invention provides the following [1] to [13].
- An article having a cured product layer contains a cured product of a curable resin composition and antiviral particles, and the antiviral particles are 1) particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound.
- At least one kind of antiviral particles selected from the group consisting of 2) mixed particles of particles containing a styrene polymer derivative compound and particles containing an unsaturated carboxylic acid derivative compound, and 3) particles containing a styrene resin.
- An antiviral article comprising A.
- the antiviral article according to Item 1 which contains 0.5 to 20.0 parts by mass of the antiviral particles A with respect to 100 parts by mass of the cured product.
- the antiviral article according to Item 1 or 2 above which has the cured product layer on a substrate.
- the antiviral particles A of 1) and / or 2) have at least one structure selected from the group whose constituent components are styrene, sodium sulfonate, acrylic acid, maleic acid and fumaric acid. , The antiviral article according to any one of the above items 1 to 3.
- the antiviral article according to any one of Items 1 to 4 wherein the cured product layer further contains a phenyl ether derivative compound.
- the curable resin composition and antiviral particles are contained, and the antiviral particles are 1) particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound, and 2) a styrene polymer derivative compound.
- a characteristic antiviral resin composition [10] The antiviral resin composition according to Item 9, further containing a phenyl ether derivative compound. [11] The antiviral resin composition according to Item 9 or 10, further comprising at least one selected from the group consisting of an antibacterial agent and an antiallergen agent. [12] The antiviral resin composition according to any one of Items 9 to 11, wherein the antiviral particles further contain antiviral particles B different from the antiviral particles A. [13] The antiviral resin composition according to any one of Items 9 to 12, wherein the antiviral particles have two different particle size peaks.
- an antiviral article and an antiviral resin composition that can suppress color problems such as discoloration due to light.
- the antiviral article of the present invention is an article having a cured product layer, wherein the cured product layer contains a cured product of a curable resin composition and antiviral particles, and the antiviral particles are: 1) Particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound, 2) Mixed particles of particles containing a styrene polymer derivative compound and particles containing an unsaturated carboxylic acid derivative compound, and 3) Styrene resin. It is characterized by containing at least one kind of antiviral particle A selected from the group consisting of particles containing styrene.
- the antiviral particles in the present invention contain antiviral particles A, and the antiviral particles A are 1) particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound together. It may be 2) mixed particles containing particles containing a styrene polymer derivative compound and particles containing an unsaturated carboxylic acid derivative compound separately, and different from these 3) particles containing a styrene resin. It may be any combination of these 1) to 3).
- antiviral particles B different from the antiviral particles A may be used in combination as long as the effects of the present invention are not affected.
- anti-viral particles is used as a term that includes the anti-viral particles A and the anti-viral particles B.
- FIGS. 2 (A) to 2 (D), and FIG. 3 are cross-sectional views showing typical embodiments of the antiviral article 100 of the present invention.
- the antiviral article 100 of FIGS. 1A to 2E, FIGS. 2A to 2D, and FIG. 3 shows a cured product containing a cured product 11 and antiviral particles 12 of the curable resin composition. It has a layer 10.
- 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. 1A is a cured product of the antiviral particles 12 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 in the entire layer 10.
- the cured product layer 10 of FIG. 1 (B) contains the antiviral particles 12 on the surface side (upper side of the figure) of the cured product layer 10.
- the cured product layer 10 of FIG. 1 (C) contains antiviral particles 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.
- 1 (D) contains the antiviral particles 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 particles 12 are placed in 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. It is included in some areas of.
- the location of the antiviral particles 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 particle 12 is present on the surface on the side touched by a human.
- 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, for example, laminated by forming the cured product layer 10 on a substrate having releasability. 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 is a part of one side of the base material 20 (the Z-axis direction + side in the figure, the direction indicated by the arrow in the drawing is the + side).
- the region has a cured product layer 10.
- the antiviral article 100 of FIG. 2 (D) 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).
- 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 illustrates a plan 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 curable resin composition substantially means a curable resin, but the additive (curing agent, curing catalyst, photopolymerization initiator, photopolymerization accelerator, etc.) for curing the curable resin is this. include.
- the cured product of the curable resin composition mainly has a role as a binder resin.
- the scratch resistance of the antiviral article is improved, and the antiviral property can be easily maintained for a long period of time.
- Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and / or a cured product of the ionizing radiation curable resin composition, and among them, ionizing radiation curing from the viewpoint of scratch resistance and production efficiency.
- a cured product of the sex resin composition is preferable.
- thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
- thermosetting resin examples 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 there is little odor and it is difficult to color.
- an electron beam curable resin composition is preferable.
- 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. Further, 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 rays (UV) and / or electron beams (EB) are 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.
- a polyfunctional (meth) acrylate compound either a monomer or an oligomer can be used.
- 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.
- Examples of 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.
- polyfunctional (meth) acrylate-based oligomer examples 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 epoxy resin.
- the above ionizing radiation curable resin can be used alone or in combination of two or more.
- the ionizing radiation curable compound is an ultraviolet curable compound
- the ionizing radiation curable resin composition preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator.
- photopolymerization initiator examples 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.
- p-dimethylaminobenzoic acid isoamyl ester p-dimethylaminobenzoic acid ethyl ester and the like can be used.
- 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 binder resin in the present specification is a general term for resin components including a curable resin contained in a curable resin composition and a non-curable resin that can function as a binder in the cured product layer.
- the cured product layer contains a cured product of a curable resin composition and antiviral particles, and the antiviral particles are 1) particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound, and 2). At least one type of antiviral particles A selected from the group consisting of () particles containing a styrene polymer derivative compound and particles containing an unsaturated carboxylic acid derivative compound, and 3) particles containing a styrene resin. It is characterized by containing. Here, 3) the particles containing the styrene resin are the particles not containing the unsaturated carboxylic acid derivative compound.
- the antiviral particles A in the present invention may be 1) particles containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound together, and 2) particles containing a styrene polymer derivative compound. It may be a mixed particle containing the particles containing the unsaturated carboxylic acid derivative compound separately, or it may be a particle containing 3) styrene resin, which is different from these, and these 1) to 3). It may be any combination.
- the antiviral particles A of 1) and / or 2) contain a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound, and the constituents thereof are hydrogen, hydroxyl group, carboxy group, sulfonic acid group, and carboxy group. It is preferable to have at least one structure selected from the group consisting of a salt of the above, a salt of a sulfonic acid group, a derivative of a carboxy group and a derivative of a sulfonic acid group.
- the content ratio of the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound in the whole particles of the antiviral particles A of 1) and / or 2) is not limited, but the antivirus is applied only to the enveloped virus. If it is sufficient to have the performance, it is sufficient to contain only the styrene polymer derivative compound. In this regard, if it is sufficient to have antiviral performance only against enveloped viruses, the antiviral particles A in the present invention may be an embodiment in which particles containing at least 3) styrene resin are used.
- the antiviral particles A of 1) and / or 2) have antiviral performance against non-enveloped viruses whose activity is difficult to inhibit
- unsaturated carboxylic acids are added to the styrene polymer derivative compound. It is preferable to contain an acid derivative compound, and in the present invention, the mass ratio of the styrene polymer derivative compound: the unsaturated carboxylic acid derivative compound is set to, for example, 30:70 to 70:30, and further set to 40:60 to 60:40. be able to.
- the antiviral particle A of the present invention contains both components of a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound in order to have antiviral performance against both enveloped virus and non-enveloped virus. It is preferable to use the antiviral particles A of 1) and / or 2) above.
- the particles containing the styrene polymer derivative compound (particles Aa) and the particles containing the unsaturated carboxylic acid derivative compound (particles Ab) are separately separated.
- the mass ratio of particles Aa: particles Ab can be set to 30:70 to 70:30, and further 40:60 to 60:40.
- particles containing the respective components and marketed for various purposes may be used as they are, or particles commercially available in a solvent-based state may be dried and molded. It may be converted and used.
- antiviral particles B different from the antiviral particles A may be further contained as long as the effects of the present invention are not affected.
- the antiviral particle B is not particularly limited as long as it is an antiviral particle that does not correspond to the antiviral particle A specified in 1), 2) and 3) above.
- the mass ratio of the antiviral particle A: the antiviral particle B is not limited, but is in the range of 10: 1 to 50:40. It is preferable to set it.
- the influenza virus is a sugar on the surface of the host cell.
- the copolymer containing styrene sulfonate has an ionic group similar to that of neuromic acid, so that it is a virus instead of the host cell.
- the unsaturated carboxylic acid derivative compound generates a hydroxyl group (OH ⁇ ) when it comes into contact with water, and the hydroxyl group exerts an antiviral effect.
- the reason why the antiviral particles A in 3) above exert antiviral properties against enveloped viruses is not limited by the mechanism, but for example, the above-mentioned copolymer containing styrene sulfonate. It is considered that it is due to the same action as.
- the antiviral particles exist in the state of particles in the cured product layer.
- the antiviral particles exist in the state of particles without being dissolved in the cured product layer ink (antiviral resin composition). Therefore, in the process of forming the cured product layer, the particles of the antiviral particles are likely to emerge, and the antiviral particles can be easily unevenly distributed on one surface side of the cured product layer. Then, by unevenly distributing the antiviral particles on one surface side of the cured product layer, the amount of the antiviral particles added in order to obtain a predetermined antiviral property can be suppressed, so that the cured product layer can be suppressed. It is possible to easily suppress the deterioration of the scratch resistance of the virus.
- a curable resin composition that satisfies the relationship of "specific gravity of antiviral particles ⁇ specific gravity of curable resin composition”. Is preferable. Further, it is preferable to use the antiviral particles having a high degree of polarity in that the antiviral particles can be easily unevenly distributed on the surface of the cured product layer. Further, when the solvent contained in the ink for the cured product layer volatilizes, the antiviral particles can be easily floated on the surface of the cured product layer, and the antiviral particles are unevenly distributed near the surface of the cured product layer. It can be done easily.
- the shape of the antiviral particles is not particularly limited, and examples thereof include spheres, ellipsoids, polyhedra, and scales.
- the average particle size of the antiviral particles is preferably 0.1 to 10.0 ⁇ m, more preferably 0.5 to 8.0 ⁇ m, and even more preferably 1.0 to 7.0 ⁇ m.
- the average particle size By setting the average particle size to 0.1 ⁇ m or more, the stability of the ink for the cured product layer can be easily obtained. Further, by setting the average particle diameter to 10.0 ⁇ m or less, it is possible to suppress deterioration of appearance, scratch resistance and stain resistance due to the antiviral particles protruding from the surface of the cured product layer, and whitening of the coating film. It can be done easily.
- the average particle size of the antiviral particles is preferably in the above range, but the antiviral particles in the cured product layer ink are aggregated until the cured product layer is completely cured, and the particles. Even if the diameter is apparently large, there is no problem in developing antiviral performance.
- the D / T is preferably 1.0 or less, more preferably 0.7 or less, and 0. It is more preferably 5.5 or less.
- the D / T By setting the D / T to 1.0 or less, it is possible to easily suppress poor appearance, deterioration of scratch resistance and stain resistance due to the antiviral particles protruding from the surface of the cured product layer, and whitening of the coating film. ..
- 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 antiviral particles may have two different particle size peaks.
- the two different particle size peaks are derived from, for example, the combined use of two or more kinds of antiviral particles having different components (and correspondingly different particle sizes).
- the antiviral particles A may be derived from the combination of the particles 1) to 3) above, and are derived from further containing the antiviral particles B in addition to the antiviral particles A. It may be a thing.
- the content of the antiviral particles A is preferably 0.5 to 20.0 parts by mass, more preferably 1.0 to 13.0 parts by mass with respect to 100 parts by mass of the cured product. It is more preferably 0.0 to 10.0 parts by mass.
- the antiviral properties can be easily improved.
- the content of the antiviral particles A By setting the content of the antiviral particles A to 20.0 parts by mass or less, it is possible to suppress deterioration of the physical properties of the coating film such as the strength and scratch resistance of the coating film. Furthermore, by setting the content of the antiviral particles to 20.0 parts by mass or less, it is easy to suppress deterioration of stain resistance and whitening of the coating film due to the antiviral particles protruding from the surface of the cured product layer. can.
- the cured product layer is added with a phenyl ether derivative compound, an antioxidant, a light stabilizer, an ultraviolet absorber, an extender pigment, an antibacterial agent, an antiallergen agent, an antifungal agent, a flame retardant, a lubricant, a foaming agent, a deodorant and the like. It may contain an agent.
- Phenyl ether derivative compound can be contained in the cured product layer to complement the antiviral performance.
- phenyl ether derivative compound examples include polyoxyethylene alkyl ether, which is known to exhibit antiviral performance as an ether type nonionic surfactant.
- the content of the phenyl ether derivative compound is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the cured product.
- the antiviral performance of the cured product layer can be complemented, and by containing 5.0 parts by mass or less, the surface performance such as scratch resistance and stain resistance of the cured product layer is maintained. can do.
- Antioxidant examples of the antioxidant include phosphorus-based antioxidants, sulfur-based antioxidants, phenol-based antioxidants, and the like.
- the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the cured product. It is more preferably by mass.
- Light stabilizer examples include aromatic compounds, amine compounds, organic acid compounds, catechin compounds and hindered amine compounds, with hindered amine compounds being preferred.
- the hindered amine compound has a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.
- the content of the light stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8.0 parts by mass, and 1.0 to 5 parts by mass with respect to 100 parts by mass of the cured product. It is more preferably 9.0 parts by mass.
- the light stabilizer preferably contains a hindered amine compound in the above range.
- UV absorber examples 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.
- 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 linear or branched are 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” refers to 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.
- 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 and 20 or less carbon atoms
- R 12 and R 15 are alkyl groups having 1 or more 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.
- Examples of the extender pigment include inorganic particles and / or organic particles.
- the extender pigment can be added according to the purpose of adjusting the design of the antiviral article, the purpose of imparting scratch resistance, abrasion resistance, and the like.
- Inorganic particles include silica, alumina, silicon carbide, silicon nitride, boron nitride, calcium titanate, barium titanate, magnesium pyrobolate, zinc oxide, zirconium oxide, chromium oxide, iron oxide, diamond, gold sand, glass fiber, and carbon dioxide. Calcium, aluminosilicate, barium sulfate and the like can be mentioned.
- Examples of the organic particles include polyethylene, urethane resin, polycarbonate, polyamide (nylon) and the like.
- the antibacterial agent examples include an inorganic antibacterial agent and an organic antibacterial agent.
- Inorganic antibacterial agents are particularly desirable because they are generally safer, more durable, and more heat resistant than organic antibacterial agents.
- the inorganic antibacterial agent is one in which an antibacterial metal such as silver, copper, zinc and the like is supported on various inorganic carriers.
- the content of the antibacterial agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the cured product, but the details can be appropriately adjusted according to the type of the antibacterial agent.
- the anti-allergen agent contains either an inorganic compound or an organic compound, and each of them may be used alone or may be a mixture of two or more different substances.
- the inorganic compound is preferably a material that supports a metal.
- the content of the anti-allergen agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the cured product, but the details can be appropriately adjusted according to the type of the anti-allergen agent.
- the inorganic material of the inorganic compound for example, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate and magnesium phosphate is preferable, and among them, titanium oxide and phosphorus are preferable. Zirconium phosphate or the like is preferable.
- the metal supported on the inorganic material for example, at least one selected from the group consisting of gold, silver, platinum, zinc and copper is preferable, and among these, silver, zinc and the like are preferable.
- the metal supported on the inorganic material for example, at least one selected from the group consisting of gold, silver, platinum, zinc and copper is preferable, and among these, silver, zinc and the like are preferable.
- "Parafine ANV-100: silver-supported inorganic compound” manufactured by Ohara Palladium, "Atomy Ball TZ-R: zinc-supported on titanium oxide” manufactured by JGC Catalysts and Chemicals can be preferably used.
- Anti-allergen agents are those that act effectively against various allergens such as mites and pollen.
- the organic compound at least one monomer component selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group or a polyphenol compound supported by an inorganic solid acid, styrene sulfonic acid and a salt thereof. It is preferably a polymer containing.
- water-insoluble polymer containing a phenolic hydroxyl group for example, "Allerbuster (trade name)” manufactured by Sekisui Chemical Co., Ltd., "Marcalinker M (trade name)” manufactured by Maruzen Petroleum Co., Ltd., etc. are used as commercial products. can do.
- examples of the combination of the polyphenol compound and the zirconium compound include "Allelimove (trade name)” manufactured by Toagosei Co., Ltd.
- At least one monomer component selected from the group consisting of styrene sulfonic acid and a salt thereof a material as shown in Japanese Patent No. 6136433 can be used.
- an organic compound and an inorganic compound are mixed, for example, an anionic phenol-based material and a zinc-based material having anti-allergenic properties can be mentioned.
- anionic phenolic materials include tannin, tannic acid-sulfuric acid, phenol sulfonic acid formaldehyde resin, noboratec type resin sulfone compound, noboratsk type resin methanesulfonic acid, resole type resin methanesulfonic acid, and benzylated phenolsulfone. It is appropriately selected and used from an acid, a thiophenol-based compound, a dihydroxydiphenylsulfone-based compound, a ligant compound, a metal chelate compound thereof, and the like.
- the zinc-based material is appropriately selected from a water-soluble zinc compound, a water-insoluble zinc compound, a zinc / metal oxide composite material, and the like, and the water-insoluble zinc compound and / or the water-insoluble zinc-metal oxide composite particles are used. It is preferable that the metal oxide is dispersed in water, has a particle size of 50 ⁇ m or less, and contains at least one of titania, silica, and alumina.
- 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.
- an ink for the cured product layer containing a material constituting the cured product layer (curable resin composition, antiviral particles, etc.), a solvent to be added as necessary, etc. is applied onto the substrate. It can be formed by drying and curing. 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 (curable resin composition, antiviral particles, etc.) constituting the cured product layer, an ink for the cured product layer containing a solvent, etc. is applied onto the substrate, dried, cured, and cured.
- the antiviral particles can be easily floated on the surface of the cured product layer when the solvent volatilizes, and the antiviral particles can be easily unevenly distributed near the surface of the cured product layer.
- the antiviral article of the present invention 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.
- Examples of 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). In the following (1) to (12), "/" indicates the interface of each layer.
- 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.
- 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 materials of the base material include resins, metals, non-metal inorganic materials, fibrous materials, wood-based materials, 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, vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers, and polyethylene.
- olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers
- vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers
- polyethylene examples include polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers, vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and
- polyester resin such as polyester-based thermoplastic elastomer, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, poly ( Acrylic resin such as butyl acrylate, methyl (meth) butyl acrylate-(meth) butyl acrylate copolymer, polyamide resin typified by nylon 6 or nylon 66, cellulose
- Stylized resin polystyrene, acrylonitrile-styrene copolymer, styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, poly Examples thereof include allylate resin and polyimide resin.
- curable resin examples include the thermosetting resin and / or the ionizing radiation curable resin exemplified in the cured product layer.
- Examples of natural resins 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. It may be the one to which the resin such as the above is added (impregnated with resin after making or filled in at the time of making). Examples of the paper to which the resin is added include inter-paper reinforced paper and resin-impregnated paper.
- a resin layer 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 layer 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 the original wallpaper made by laminating.
- 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 aptitude.
- the base material When the base material is a flat plate of film, sheet or plate, it has a thickness as a typical dimension in the design 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 300 ⁇ 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.
- Examples of 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.
- 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.
- 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.
- ultraviolet absorbers and light stabilizers General-purpose light 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.
- 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.
- the base material is a resin base material, it is preferable to have a transparent resin layer.
- the transparent resin layer is preferably located between the base material and the primer layer. Further, when the antiviral article has a decorative 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.
- ABS resin acrylonitrile-butadiene-styrene resin
- acrylic resin acrylic resin
- vinyl chloride resin 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-based 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 anti-virus article preferably has a decorative layer at any position on the anti-virus 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.
- Examples of the decorative layer include a colored layer formed by solid coating 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 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, etc. are appropriately mixed with the binder resin. 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.
- examples thereof include 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, nickel, chromium, cobalt, indium, and aluminum; and a thin film of an alloy containing two or more of the metal elements.
- a single metal element such as gold, silver, copper, tin, iron, nickel, chromium, cobalt, indium, and aluminum
- a thin film of an alloy containing two or more of the metal elements 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
- 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.
- urethane-based adhesive examples 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.
- 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 invention can be used for various purposes. Specific uses include the following (1) to (12). (1) Surface materials for interior parts such as walls, floors, and ceilings of buildings such as houses, offices, stores, hospitals, and clinics. (2) Surface materials for exterior walls, roofs, eaves ceilings, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics. (3) Surface materials for fittings (interior or exterior parts) such as windows, window frames, doors, door frames; surface materials for accessories (handles, etc.) of fittings; surface materials for jigs for fittings. (4) Surface materials for handrails, waist walls, surrounding edges, thresholds, Kamoi, and Kasagi.
- Surface material for outdoor (exterior) parts such as fences, gates, pillars of drying stands, and handrails.
- Surface materials for furniture such as chests of drawers, desks, chairs, cupboards, and kitchen sinks; surface materials for furniture accessories (handles, etc.); surface materials for furniture jigs.
- Surface materials for housings of various home appliances such as television receivers, radio receivers, refrigerators, microwave ovens, washing machines, fans, air conditioners, etc .; Accessories (handles, switches, touch panels, etc.) of home appliances Surface material; Surface material for home appliance jigs.
- OA equipment such as various computer equipment such as electronic copying machines, 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 copying machines, 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.
- 9 Surface materials for interior or exterior parts (walls, floors, ceilings, handrails, columns, control panels, levers, handles, steering wheels, etc.) of vehicles such as automobiles and railroad vehicles, ships, and aircraft. ..
- the antiviral article of the present invention may have a single layer of a cured product layer or may have a layer other than the cured product layer, but various additives added to each layer are vesicled. It is preferable to have.
- the method for vesicle-forming various additives is not particularly limited, and vesicles can be formed by a known method, and the supercritical reverse-phase evaporation method is particularly preferable.
- Examples of the vesicle treatment method include a Bangham method, an extrusion method, a hydration method, a reverse phase evaporation method, and a freeze-thaw method, in addition to the supercritical reverse phase evaporation method.
- a Bangham method chloroform or chloroform / methanol mixed solvent is put in a container such as a flask, and phospholipid is further put in and dissolved. Then, the solvent is removed using an evaporator to form a thin film composed of lipids, a dispersion liquid of the additive is added, and then hydrated and dispersed with a vortex mixer to obtain a vesicle.
- the extrusion method is a method of preparing a thin-film phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain a vesicle.
- the hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining a vesicle by gently stirring and dispersing without using a mixer.
- phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to form a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added.
- This is a method of obtaining vesicles.
- the freeze-thaw method is a method that uses cooling and heating as an external perturbation, and is a method of obtaining a vesicle by repeating this cooling and heating.
- the supercritical reverse phase evaporation method is water-soluble or hydrophilic in a mixture in which the substance forming the outer film of the vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure condition above the supercritical point.
- This is a method of adding an aqueous phase containing various additives as an encapsulating substance to form a capsule-shaped vesicle containing various additives as an encapsulating substance in a single layer of a film.
- the carbon dioxide in the supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or higher, and the temperature is equal to or higher than the critical point.
- Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions.
- vesicles are a general term for those containing a liquid phase inside vesicles having a closed membrane structure like a spherical shell, and in particular, those in which the outer membrane is composed of biolipids such as phospholipids are referred to as liposomes. ..
- phospholipids examples include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yellow egg lecithin, hydrogenated yellow egg lecithin, soy lecithin, hydrogenated soybean lecithin and other glycerophospholipids, and sphingomyelin.
- Sphingophospholipids such as ceramide phosphorylethanolamine and ceramidephosphorylglycerol.
- a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.
- nonionic surfactant examples include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene-.
- One or two types such as polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactum copolymer, etc. The above can be used.
- Examples of the cholesterol include one or more of cholesterol, ⁇ -cholestanol, ⁇ -cholestanol, cholestane, desmosterol (5,24-cholestadien-3 ⁇ -ol), sodium cholic acid, choleciferol and the like. Can be used.
- the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant.
- the outer membrane by forming the outer membrane into liposomes formed from phospholipids, the compatibility between the resin composition which is the main component of each layer and various additives can be improved.
- the antiviral resin composition of the present invention contains a curable resin composition and antiviral particles.
- Embodiments of the "curable resin composition” and “antiviral particles” in the antiviral resin composition of the present invention are the “curable resin composition” and “anti-virus” in the antiviral article of the present invention described above. It is the same as the embodiment of "viral particles”.
- the antiviral resin composition of the present invention comprises, if necessary, a phenyl ether derivative compound, an antioxidant, a light stabilizer, an ultraviolet absorber, an extender pigment (inorganic particles, organic particles), an antibacterial agent, an antiallergen agent, and the like. It may contain additives such as a fungicide, a flame retardant, a lubricant, a foaming agent, and a deodorant.
- Anti-allergen agent is an embodiment of the above-mentioned “antioxidant”, “light stabilizer”, “ultraviolet absorber”, “constituent pigment (inorganic particles, organic particles) in the antiviral article of the present invention. ) ”,“ Antibacterial agent ”, and“ Anti-allergen agent ”.
- the antiviral resin composition of the present invention preferably contains a solvent.
- the antiviral particles can be easily floated on the surface of the cured product layer when the solvent volatilizes, and the antiviral particles can be formed near the surface of the cured product layer. Particles can be easily unevenly distributed.
- 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.).
- 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.
- methyl ethyl ketone and ethyl acetate are preferable from the viewpoint of maintaining the shape of the antiviral particles.
- 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 sample was placed on a desk and left in a room under fluorescent lighting for 24 hours, and then the color of the cured product layer ink (antiviral resin composition) in the sample was visually evaluated.
- the brightness of the fluorescent lamp on the desk was in the range of 500 to 1000 lux. The results are shown in Table 1.
- the antiviral articles of Examples and Comparative Examples are subjected to an accelerated weather resistance test using a metal halide lamp (MWOM) (a step of irradiating ultraviolet rays for 20 hours under the following irradiation conditions and then dew condensation for 4 hours under the following condensation conditions. (Test in which the cycle is repeated) was carried out for 8 cycles (192 hours). Then, the L * a * b * value after the accelerated weather resistance test was measured.
- MWOM metal halide lamp
- the color difference ( ⁇ E * ab) is when the measured values immediately after production are L * 1 , a * 1 and b * 1 , and the measured values after the accelerated weathering test are L * 2 , a * 2 and b * 2 .
- ⁇ E * ab [(L * 2 -L * 1 ) 2 + (a * 2 -a * 1 ) 2 + (b * 2-a * 2 ) 2 ] 1/2
- Example 1 Preparation of ink for cured product layer (anti-virus resin composition) and preparation of anti-virus article [Example 1]
- An ink a (antiviral resin composition a) for a cured product layer of Example 1 was prepared by mixing and stirring the following composition.
- ⁇ Ink a for cured product layer (antiviral resin composition a)> 100 parts by mass of ionizing radiation curable resin composition (100 parts by mass of urethane acrylate resin consisting of 70 parts by mass of polyfunctional urethane oligomer and 30 parts by mass of bifunctional oligomer) 5 parts by mass of antiviral particles A (including the following particles A1 and particles A2 in a mass ratio of 1: 1) (Particles containing a styrene polymer derivative compound (particle A1): polystyrene sulfonic acid derivative manufactured by Shima Trading Co., Ltd., trade name "VERSA-TL3”) (Particles containing an unsaturated carboxylic acid derivative compound (particles A2): Particles formed by drying a solvent-based unsaturated polycarboxylic acid polymer manufactured by BYK, trade name "BYK-P104".
- ionizing radiation curable resin composition 100 parts by mass of urethane acrylate resin consist
- a decorative layer ink containing a two-component curable acrylic-urethane resin and a colorant was applied to one surface of a substrate (polypropylene resin sheet containing titanium oxide having a thickness of 60 ⁇ m) subjected to double-sided corona discharge treatment by a gravure printing method. And dried to form a decorative layer having a wood grain pattern with a thickness of 3 ⁇ m.
- 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.
- an ink for a primer layer 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 a (antiviral resin composition a) is applied onto the primer layer by a roll coating method to form an uncured cured product layer, which is then dried at 60 ° C. for 1 minute.
- An electron beam (pressurized voltage: 125 kV, 5Mrad (50 kGy)) was 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.
- Example 1 The antiviral particles A are removed from the cured product layer ink a (antiviral resin composition a) used in Example 1, and instead, the antiviral particles B (cinanenzeomic) in which silver ions are carried on zeolite are carried.
- Ink b (anti-virus resin composition b) for a cured product layer of Comparative Example 1 was prepared by adding 3 parts by mass of product No. "AJ10N", average particle diameter 2.5 ⁇ m).
- Comparative Example 1 was carried out in the same manner as in Example 1 except that the cured product layer ink a (anti-virus resin composition a) was changed to the cured product layer ink b (anti-virus resin composition b). Antiviral article was obtained.
- Example 1 As shown in Table 1, it can be confirmed that the cured product layer ink (anti-virus resin composition) of Example 1 and the anti-virus article can suppress discoloration.
- Example 2 Evaluation of antiviral performance and antiallergen performance
- the antiviral particles A are styrene resin-containing particles (particles A3) (styrene resin particles manufactured by polysciences, trade name: microsphere (particle diameter 4.5 ⁇ m). ) ”, An antiviral article was obtained in the same manner as in Example 1.
- Example 3 An anionic phenolic material having anti-allergenicity (“EXP20530A” manufactured by DIC) and a zinc-based material having anti-allergenicity (“EXP20530B” manufactured by DIC) with respect to the ink a for the cured product layer of Example 1.
- An antiviral article was obtained in the same manner as in Example 1 except that it was blended.
- the anionic phenolic material and the zinc-based material were blended so as to have a solid content ratio of 23% by mass in 100% by mass of the ink for the cured product layer after blending.
- Example 4 In the cured product layer ink a of Example 1, the antiviral particles A are a mixture of the particles A1, the particles A2 and the particles A3, and further, an antiviral additive: polyoxyethylene alkyl ether manufactured by Kao Chemicals, commercial product. An antiviral article was obtained in the same manner as in Example 1 except that the name "Emargen 707" was blended.
- the antiviral particle A contains the particle A1, the particle A2, and the particle A3 in a mass ratio of 3: 2: 3. Further, the antiviral particles A were blended in an amount of 4 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition. Further, the content of the antiviral additive was 4 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition (the same is true for 100 parts by mass with respect to 100 parts by mass of the cured product).
- Example 5 In the cured product layer ink a of Example 1, the antiviral particles A were designated as the particles A3, and an antiviral additive: polyoxyethylene alkyl ether manufactured by Kao Chemicals, trade name "Emulgen 707" was blended. , An antiviral article was obtained in the same manner as in Example 1.
- the antiviral particles A were blended in an amount of 1.5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition. Further, the content of the antiviral additive was 3 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition (the same is true for 100 parts by mass with respect to 100 parts by mass of the cured product).
- Example 6 In the cured product layer ink a of Example 1, the antiviral property is the same as that of Example 1 except that an antiviral additive: polyoxyethylene alkyl ether manufactured by Kao Chemicals, trade name "Emulgen 707" is further blended. I got the goods.
- an antiviral additive polyoxyethylene alkyl ether manufactured by Kao Chemicals, trade name "Emulgen 707" is further blended. I got the goods.
- the antiviral particle A contains the particle A1 and the particle A2 in a mass ratio of 2: 3. Further, the antiviral particles A were blended in an amount of 2.5 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition. Further, the content of the antiviral additive was 3 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin composition (the same is true for 100 parts by mass with respect to 100 parts by mass of the cured product).
- Antiviral performance The antiviral articles prepared in Examples 1, 2, 4 to 6 and Comparative Example 1 were subjected to an antiviral performance test by a method in accordance with an antiviral test method (ISO21702), and antiviral activity values for the following virus species were performed. Was evaluated based on the following evaluation criteria.
- the evaluation criteria are as follows.
- Virus type Envelope virus (influenza virus), non-enveloped virus (feline calicivirus)
- Anti-virus activity value for 2 virus species is 2.0 or more
- Anti-virus activity value for 1 virus species is 2.0 or more-: Anti-virus activity value for 2 virus species is less than 2.0
- the allergen performance of the antiviral articles prepared in Examples 1 and 3 was evaluated. Specifically, the antiviral articles prepared in Examples 1 and 3 were cut into small pieces and immersed in an aqueous mite allergen solution for 1 day, and then the amount of allergen was visually measured by a horizontal expansion chromatograph (mighty checker). It was confirmed and evaluated according to the following evaluation criteria.
- the evaluation criteria are as follows. +: A decrease in the amount of allergen was confirmed (the mite allergen level judgment was + judgment or less (that is, about 100 animals / m 2 or less). -: Decrease in the amount of allergen could not be confirmed (tick allergen level judgment + judgment exceeded)
- Antiviral article 10 Cured product layer 11: Cured product of curable resin composition 12: Antiviral particles 20: Substrate
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Abstract
Description
[1]硬化物層を有する物品であって、
前記硬化物層は、硬化性樹脂組成物の硬化物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする、抗ウイルス性物品。
[2]前記硬化物100質量部に対して、前記抗ウイルス性粒子Aを0.5~20.0質量部含む、上記項1に記載の抗ウイルス性物品。
[3]基材上に前記硬化物層を有してなる、上記項1又は2に記載の抗ウイルス性物品。
[4]前記1)及び/又は2)の抗ウイルス性粒子Aは、その構成成分がスチレン、スルホン酸ナトリウム、アクリル酸、マレイン酸及びフマル酸からなる群から選択される少なくとも一種の構造を有する、上記項1~3のいずれかに記載の抗ウイルス性物品。
[5]前記硬化物層は、更にフェニルエーテル誘導体化合物を含有する、上記項1~4のいずれかに記載の抗ウイルス性物品。
[6]前記硬化物層は、更に抗菌剤及び抗アレルゲン剤からなる群から選択される少なくとも一種を含有する、上記項1~5のいずれかに記載の抗ウイルス性物品。
[7]前記抗ウイルス性粒子は、前記抗ウイルス性粒子Aとは異なる抗ウイルス性粒子Bを更に含有する、上記項1~6のいずれかに記載の抗ウイルス性物品。
[8]前記抗ウイルス性粒子は、異なる2つの粒子径ピークを有する、上記項1~7のいずれかに記載の抗ウイルス性物品。
[9]硬化性樹脂組成物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする、抗ウイルス性樹脂組成物。
[10]更にフェニルエーテル誘導体化合物を含有する、上記項9に記載の抗ウイルス性樹脂組成物。
[11]更に抗菌剤及び抗アレルゲン剤からなる群から選択される少なくとも一種を含有する、上記項9又は10に記載の抗ウイルス性樹脂組成物。
[12]前記抗ウイルス性粒子は、前記抗ウイルス性粒子Aとは異なる抗ウイルス性粒子Bを更に含有する、上記項9~11のいずれかに記載の抗ウイルス性樹脂組成物。
[13]前記抗ウイルス性粒子は、異なる2つの粒子径ピークを有する、上記項9~12のいずれかに記載の抗ウイルス性樹脂組成物。
本発明の抗ウイルス性物品は、硬化物層を有する物品であって、前記硬化物層は、硬化性樹脂組成物の硬化物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする。
硬化物層は、硬化性樹脂組成物の硬化物を含む。本明細書において、「硬化性樹脂組成物の硬化物」のことを「硬化物」と略称する場合がある。なお、硬化性樹脂組成物は、実質的に硬化性樹脂を意味するが、硬化性樹脂を硬化させるための添加剤(硬化剤、硬化触媒、光重合開始剤、光重合促進剤等)はこれに含まれる。
硬化物層は、硬化性樹脂組成物の硬化物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする。ここで、3)スチレン樹脂を含有する粒子は、前記不飽和カルボン酸誘導体化合物を含有していない粒子である。前述の通り、本発明における抗ウイルス性粒子Aは、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを一緒に含有する粒子であってもよく、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子とを別々に含有する混合粒子であってもよく、これらとは異なる3)スチレン樹脂を含有する粒子であってもよく、これら1)~3)の任意の組み合わせであってもよい。
硬化物層は、フェニルエーテル誘導体化合物、酸化防止剤、光安定剤、紫外線吸収剤、体質顔料、抗菌剤、抗アレルゲン剤、防カビ剤、難燃剤、滑剤、発泡剤、消臭剤等の添加剤を含んでいてもよい。
フェニルエーテル誘導体化合物は、抗ウイルス性能を補完するために硬化物層に含有することができる。
酸化防止剤としては、リン系酸化防止剤、硫黄系酸化防止剤及びフェノール系酸化防止剤等が挙げられる。
光安定剤としては、芳香族系化合物、アミン系化合物、有機酸系化合物、カテキン系化合物及びヒンダードアミン系化合物が挙げられ、中でもヒンダードアミン系化合物が好ましい。ヒンダードアミン系化合物とは、2,2,6,6-テトラメチルピペリジン骨格を分子内に含む構造を有するものである。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤等が挙げられ、トリアジン系紫外線吸収剤が好ましい。紫外線吸収剤は、1種又は2種以上を用いることができる。
体質顔料としては、無機粒子及び/又は有機粒子が挙げられる。体質顔料は、抗ウイルス性物品の意匠性を調整する目的、耐擦傷性、耐摩耗性等を付与する目的等に応じて添加することができる。
抗菌剤としては、無機系抗菌剤、及び有機系抗菌剤がある。特に無機系抗菌剤は有機系抗菌剤に比べ一般に安全性が高く、耐久性、及び耐熱性にも優れているため望ましい。無機系抗菌剤とは、銀をはじめとする銅、亜鉛等の抗菌性金属を各種の無機物担体に担持したものである。抗菌剤の含有量は、硬化物100質量部に対して0.1~10質量部が好ましいが、詳細は抗菌剤の種類に応じて適宜調整することができる。
抗アレルゲン剤は、無機化合物又は有機化合物のいずれか一方を含むものであり、各々単体で用いても良いし、異なる2種以上を混合させても良い。無機化合物としては金属を担持してなる材料であることが好ましい。抗アレルゲン剤の含有量は、硬化物100質量部に対して0.1~10質量部が好ましいが、詳細は抗アレルゲン剤の種類に応じて適宜調整することができる。
硬化物層の厚みは、加工特性及び耐擦傷性のバランスの観点から、1.5μm以上30μm以下が好ましく、2μm以上20μm以下がより好ましく、3μm以上15μm以下がさらに好ましい。
硬化物層は、例えば、硬化物層を構成する材料(硬化性樹脂組成物、抗ウイルス性粒子等)、必要に応じて添加する溶剤等を含む硬化物層用インキを、基材上に塗布、乾燥、硬化することにより形成することができる。離型性を有する基材上に、硬化物層用インキを塗布、乾燥、硬化して硬化物層を形成し、当該硬化物層を別の基材等に転写することによって、硬化物層を形成することもできる。
本発明の抗ウイルス性物品は、硬化物層の単層でもよいし、硬化物層以外の層を有していてもよい。
(1)硬化物層
(2)基材/硬化物層
(3)基材/プライマー層/硬化物層
(4)基材/装飾層/硬化物層
(5)基材/透明性樹脂層/硬化物層
(6)基材/接着剤層/透明性樹脂層/硬化物層
(7)基材/接着剤層/装飾層/透明性樹脂層/硬化物層
(8)基材/装飾層/接着剤層/透明性樹脂層/硬化物層
(9)基材/透明性樹脂層/プライマー層/硬化物層
(10)基材/接着剤層/透明性樹脂層/プライマー層/硬化物層
(11)基材/接着剤層/装飾層/透明性樹脂層/プライマー層/硬化物層
(12)基材/装飾層/接着剤層/透明性樹脂層/プライマー層/硬化物層
なお、上記積層構成のうち、接着剤層は任意の粘着剤層であってもよい。また、基材の裏面に接着剤層又は粘着剤層を更に設けてもよい。
基材の形態は、フィルム、シート及び板等の平板状のもの、並びに、多面体、多角柱、円柱、球面及び回転楕円体面等の三次元形状のもの等が挙げられ、特に制限はない。
(A)樹脂/木質系材料
(B)樹脂/金属
(C)樹脂/繊維質材料
(D)樹脂/非金属無機材料
(E)樹脂1/樹脂2
(F)金属/木質系材料
(G)金属/非金属無機材料
(H)金属/繊維質材料
(I)金属1/金属2
(J)非金属無機材料/繊維質材料
抗ウイルス性物品は、硬化物層の基材側の面に接してプライマー層を有することが好ましい。プライマー層によって、基材と硬化物層との密着性が向上し、紫外線に暴露した際の長期的な層間密着性の確保(いわゆる耐候密着性)及び耐擦傷性を良好にしやすくできる。
抗ウイルス性物品は、強度を高めるなどの観点から、基材と硬化物層との間に透明性樹脂層を有していてもよい。特に、基材が樹脂基材の場合、透明性樹脂層を有することが好ましい。
抗ウイルス性物品は、意匠性を向上させる観点から、抗ウイルス性物品の任意の箇所に装飾層を有することが好ましい。
抗ウイルス性物品は、接着剤層を有していてもよい。
抗ウイルス性物品は、エンボス加工等の賦形処理で所望の凹凸形状(凹凸模様とも言う)を付与してもよい。
本発明の抗ウイルス性物品は、各種用途に用いることができる。具体的な用途としては、下記(1)~(12)のものが挙げられる。
(1)住宅、事務所、店舗、病院、診療所等の建築物の壁、床、天井等の内装部分の表面材。
(2)住宅、事務所、店舗、病院、診療所等の建築物の外壁、屋根、軒天井、戸袋等の外装部分の表面材。
(3)窓、窓枠、扉、扉枠等の建具の表面材(内装部分又は外装部分);建具の付随備品(取っ手等)の表面材;建具の治具の表面材。
(4)手すり、腰壁、廻り縁、敷居、鴨井、笠木の造作部材の表面材。
(5)塀、門扉、物干台の柱や手すり等の屋外(外装)部分の表面材。
(6)箪笥、机、椅子、食器棚、厨房の流し台等の家具の表面材;家具の付随備品(取っ手等)の表面材;家具の治具の表面材。
(7)テレビジョン受像機、ラジオ受信機、冷蔵庫、電子レンジ、洗濯機、扇風機、空調機等の各種家電製品の筐体等の表面材;家電製品の付随備品(取っ手、スイッチ、タッチパネル等)の表面材;家電製品の治具の表面材。
(8)電子複写機、ファクシミリ、プリンタ、パーソナルコンピュータ等の各種電算機器等のOA機器の表面材;銀行、郵便局等の金融機関のATM装置の各種OA機器類の筐体の表面材;各種OA機器類の付随備品(キーボード鍵盤、タッチパネル等)の表面材;各種OA機器類の治具の表面材。
(9)自動車、鉄道車両等の車輛、船舶、航空機等の乗物の内装又は外装部分(壁、床、天井、手すり、支柱、操作盤、レバー、ハンドル、舵輪等の操縦機器類)の表面材。
(10)各種建築物の間仕切;店舗、事務所、官公庁等の窓口、会計精算場所等におけるウイルスの飛沫感染防止のための遮蔽板又は遮蔽カーテン;保護面(フェイスガード)、保護眼鏡(ゴーグル)等の顔面保護具;あるいはこれらの表面材。
(11)伝票類等のビジネスフォーム;預金通帳;金融機関のキャッシュカード、クレジットカード、ポイントカード等のカード類;あるいはこれらの表面材。
(12)硝子、樹脂等の瓶;金属缶;樹脂レトルト容器等の樹脂軟包装材;各種チューブ類等の包装材料;あるいはこれらの表面材。
本発明の抗ウイルス性物品は、前述の通り硬化物層の単層でもよいし、硬化物層以外の層を有していてもよいが、各層に添加される各種添加剤はベシクル化されていることが好ましい。各種添加剤をベシクル化する方法としては特に限定されず、公知の方法によりベシクル化することができ、中でも超臨界逆相蒸発法が好ましい。
本発明の抗ウイルス性樹脂組成物は、硬化性樹脂組成物、及び、抗ウイルス性粒子を含むものである。
本発明の抗ウイルス性樹脂組成物は、溶剤を含むことが好ましい。抗ウイルス性樹脂組成物が溶剤を含むことにより、溶剤が揮発する際に抗ウイルス性粒子を硬化物層の表面に浮かび上がりやすくすることができ、硬化物層の表面付近に抗ウイルス性粒子の粒子を偏在させやすくできる。
実施例及び比較例の硬化物層用インキ(抗ウイルス性樹脂組成物)、並びに、実施例及び比較例の抗ウイルス性物品に関して、下記の評価を実施した。評価の雰囲気は、温度は23℃±5℃、湿度40~65%RHとした。
外光を遮った状態の部屋で、実施例及び比較例の硬化物層用インキ(抗ウイルス性樹脂組成物)をガラス製の瓶(アズワン社製、品番:ラボランスクリュー管瓶50ml)に30g入れ、蓋を閉め、評価用のサンプルを作製した。この段階において、サンプル内の硬化物層用インキ(抗ウイルス性樹脂組成物)の色は、何れも抗ウイルス剤未添加の組成物(実施例及び比較例の硬化物層用インキ(抗ウイルス性樹脂組成物)から抗ウイルス剤を除いた組成物)の色との差異はみられず、白色であった。
実施例及び比較例の抗ウイルス性物品に関して、製造直後のL*a*b*値を測定した。測定装置は、分光測色計(「Spectrolino」(型番)、GretagMacbeth社製)を用いた。
ΔE*ab=〔(L*2-L*1)2+(a*2-a*1)2+(b*2-a*2)2〕1/2
ダイプラ・ウィンテス社製の商品名「ダイプラ・メタルウェザー」
<照射条件>
照度:65mW/cm2、ブラックパネル温度:63℃、槽内湿度:50%RH、時間:20時間
<結露条件>
照度:0mW/cm2、槽内湿度:98%RH、時間:4時間
[実施例1]
下記の組成を混合及び攪拌してなる、実施例1の硬化物層用インキa(抗ウイルス性樹脂組成物a)を調製した。
・電離放射線硬化性樹脂組成物 100質量部
(多官能ウレタンオリゴマー 70重量部及び2官能オリゴマー30重量部からなる合計100重量部のウレタンアクリレート樹脂)
・抗ウイルス性粒子A 5質量部(下記の粒子A1と粒子A2とを質量比1:1で含む)
(スチレンポリマー誘導体化合物を含有する粒子(粒子A1):島貿易株式会社製のポリスチレンスルホン酸誘導体、商品名「VERSA-TL3」)
(不飽和カルボン酸誘導体化合物を含有する粒子(粒子A2):BYK製の溶剤系不飽和ポリカルボン酸ポリマー、商品名「BYK-P104」を乾燥させて成形した粒子
実施例1で用いた硬化物層用インキa(抗ウイルス性樹脂組成物a)から抗ウイルス性粒子Aを除き、代わりに、ゼオライトに銀イオンを担持させてなる抗ウイルス性粒子B(シナネンゼオミック製の品番「AJ10N」、平均粒子径2.5μm)3質量部を添加してなる、比較例1の硬化物層用インキb(抗ウイルス性樹脂組成物b)を調製した。
[実施例2]
実施例1で用いた硬化物層用インキaにおいて、抗ウイルス性粒子Aを、スチレン樹脂を含有する粒子(粒子A3)(polysciences社製スチレン樹脂粒子、商品名「ミクロスフェア(粒子径4.5μm)」に変更した以外は、実施例1と同様にして抗ウイルス性物品を得た。
実施例1の硬化物層用インキaに対して、抗アレルゲン性を有するアニオン性フェノール系材料(DIC社製「EXP20530A」)及び抗アレルゲン性を有する亜鉛系材料(DIC社製「EXP20530B」)を配合したこと以外は、実施例1と同様にして抗ウイルス性物品を得た。上記アニオン性フェノール系材料及び上記亜鉛系材料は、配合後の硬化物層用インキa100質量%中、それぞれ固形分割合で23質量%となるように配合した。
実施例1の硬化物層用インキaにおいて、抗ウイルス性粒子Aを前記粒子A1、前記粒子A2及び前記粒子A3の混合物とし、更に抗ウイルス性添加剤:Kao Chemicals製ポリオキシエチレンアルキルエーテル、商品名「エマルゲン 707」を配合した以外は、実施例1と同様にして抗ウイルス性物品を得た。
実施例1の硬化物層用インキaにおいて、抗ウイルス性粒子Aを前記粒子A3とし、更に抗ウイルス性添加剤:Kao Chemicals製ポリオキシエチレンアルキルエーテル、商品名「エマルゲン 707」を配合した以外は、実施例1と同様にして抗ウイルス性物品を得た。
実施例1の硬化物層用インキaにおいて、更に抗ウイルス性添加剤:Kao Chemicals製ポリオキシエチレンアルキルエーテル、商品名「エマルゲン 707」を配合した以外は、実施例1と同様にして抗ウイルス性物品を得た。
実施例1,2,4~6及び比較例1で作製した抗ウイルス性物品について、抗ウイルス試験方法(ISO21702)に準拠した方法で抗ウイルス性能試験を行い、下記のウイルス種に対する抗ウイルス活性値を下記評価基準に基づいて評価した。評価基準は下記の通りである。
ウイルス種:エンベロープウイルス(インフルエンザウイルス)、ノンエンベロープウイルス(ネコカリシウイルス)
++ :2ウイルス種に対する抗ウイルス活性値が共に2.0以上
+ :1ウイルス種に対する抗ウイルス活性値が2.0以上
- :2ウイルス種に対する抗ウイルス活性値が共に2.0未満
実施例1及び3で作製した抗ウイルス性物品について、アレルゲン性能を評価した。具体的には、実施例1及び実施例3で作製した抗ウイルス性物品を細かく切断し、ダニアレルゲン水溶液中に1日間浸した後のアレルゲン量を水平展開クロマト法(マイティチェッカー)で目視にて確認し、下記評価基準に従って評価した。評価基準は下記の通りである。
+:アレルゲン量の減少が確認できた(ダニアレルゲンレベル判定が+判定以下(すなわち100匹程度/m2以下)
-:アレルゲン量の減少が確認できなかった(ダニアレルゲンレベル判定が+判定超過)
10:硬化物層
11:硬化性樹脂組成物の硬化物
12:抗ウイルス性粒子
20:基材
Claims (13)
- 硬化物層を有する物品であって、
前記硬化物層は、硬化性樹脂組成物の硬化物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする、抗ウイルス性物品。 - 前記硬化物100質量部に対して、前記抗ウイルス性粒子Aを0.5~20.0質量部含む、請求項1に記載の抗ウイルス性物品。
- 基材上に前記硬化物層を有してなる、請求項1又は2に記載の抗ウイルス性物品。
- 前記1)及び/又は2)の抗ウイルス性粒子Aは、その構成成分がスチレン、スルホン酸ナトリウム、アクリル酸、マレイン酸及びフマル酸からなる群から選択される少なくとも一種の構造を有する、請求項1~3のいずれかに記載の抗ウイルス性物品。
- 前記硬化物層は、更にフェニルエーテル誘導体化合物を含有する、請求項1~4のいずれかに記載の抗ウイルス性物品。
- 前記硬化物層は、更に抗菌剤及び抗アレルゲン剤からなる群から選択される少なくとも一種を含有する、請求項1~5のいずれかに記載の抗ウイルス性物品。
- 前記抗ウイルス性粒子は、前記抗ウイルス性粒子Aとは異なる抗ウイルス性粒子Bを更に含有する、請求項1~6のいずれかに記載の抗ウイルス性物品。
- 前記抗ウイルス性粒子は、異なる2つの粒子径ピークを有する、請求項1~7のいずれかに記載の抗ウイルス性物品。
- 硬化性樹脂組成物、及び、抗ウイルス性粒子を含み、前記抗ウイルス性粒子は、1)スチレンポリマー誘導体化合物と不飽和カルボン酸誘導体化合物とを含有する粒子、2)スチレンポリマー誘導体化合物を含有する粒子と不飽和カルボン酸誘導体化合物を含有する粒子との混合粒子、及び3)スチレン樹脂を含有する粒子、からなる群から選択される少なくとも一種の抗ウイルス性粒子Aを含有することを特徴とする、抗ウイルス性樹脂組成物。
- 更にフェニルエーテル誘導体化合物を含有する、請求項9に記載の抗ウイルス性樹脂組成物。
- 更に抗菌剤及び抗アレルゲン剤からなる群から選択される少なくとも一種を含有する、請求項9又は10に記載の抗ウイルス性樹脂組成物。
- 前記抗ウイルス性粒子は、前記抗ウイルス性粒子Aとは異なる抗ウイルス性粒子Bを更に含有する、請求項9~11のいずれかに記載の抗ウイルス性樹脂組成物。
- 前記抗ウイルス性粒子は、異なる2つの粒子径ピークを有する、請求項9~12のいずれかに記載の抗ウイルス性樹脂組成物。
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