WO2018235816A1 - Composition de résine photodurcissable, film de revêtement durci, substrat comprenant un film de revêtement durci, procédé pour sa production, et méthode d'inactivation de virus - Google Patents

Composition de résine photodurcissable, film de revêtement durci, substrat comprenant un film de revêtement durci, procédé pour sa production, et méthode d'inactivation de virus Download PDF

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Publication number
WO2018235816A1
WO2018235816A1 PCT/JP2018/023307 JP2018023307W WO2018235816A1 WO 2018235816 A1 WO2018235816 A1 WO 2018235816A1 JP 2018023307 W JP2018023307 W JP 2018023307W WO 2018235816 A1 WO2018235816 A1 WO 2018235816A1
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meth
acrylate
cured film
photocurable resin
resin composition
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PCT/JP2018/023307
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English (en)
Japanese (ja)
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保紀 米
佳憲 亀田
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中国塗料株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a photocurable resin composition, a cured film, a substrate with a cured film, a method for producing them and a method for virus inactivation.
  • influenza virus has become a problem, and since influenza infectious diseases prevail in facilities where many people such as stations, airports, hospitals, and schools come and go, countermeasures are needed. Thus, there is a need for materials that inactivate viruses applicable to these locations.
  • Patent Document 1 discloses an antiviral composition containing silica-coated titanium oxide on which bismuth vanadate is supported and a divalent copper compound.
  • Patent Document 2 discloses an antiviral coating film having a copper-supported oxide, barium sulfate and a water-repellent resin binder.
  • the outstanding antiviral property is called for also in the dark place where light does not reach for a long time.
  • the conventional antiviral compositions and coating films described in Patent Documents 1 and 2 have a problem that antiviral properties are not exhibited in a place where light does not strike for a long time.
  • they since they have heavy metal components that cause metal allergy, they may cause metal allergy when they are in contact with the human body.
  • One embodiment of the present invention provides a photocurable resin composition and the like that can form a cured film having excellent antiviral properties even in a dark place.
  • a substrate with a cured film comprising the substrate and the cured film according to [4] or [5].
  • a method for producing a cured film comprising a curing step of curing the photocurable resin composition according to any one of [1] to [3] by light irradiation. [8] a coating step of coating the photocurable resin composition according to any one of [1] to [3] on at least a part of a substrate; After the application step, a curing step of curing the photocurable resin composition by light irradiation to form a cured film;
  • a method of producing a coated substrate having:
  • a composition having excellent dispersibility of an antiviral agent can be easily obtained, and further, a cured film having excellent antiviral properties can be easily obtained even in a dark place.
  • the photocurable resin composition according to an embodiment of the present invention is selected from polymers containing an alkali metal salt of an acidic group-containing compound and an alkali metal salt of an acidic group-containing compound. Containing an antiviral agent (A) containing at least one of the following, a photocurable resin (B), an unsaturated monomer (C), a pigment (D), and a photopolymerization initiator (E) Do. Since the composition contains such components, it can form a cured film having excellent physical properties, and since it contains the pigment (D), the dispersibility of the antiviral agent (A) is excellent. . Therefore, according to the composition, a cured film excellent in antiviral property can be easily obtained over a long period of time. In addition, since the present composition does not cause metal allergy, a cured film excellent in safety can be easily obtained.
  • the antiviral agent (A) contains at least one selected from polymers containing an alkali metal salt of an acid group-containing compound and an alkali metal salt of an acid group-containing compound. Such an antiviral agent (A) does not cause metal allergy even when in contact with the human body, and is excellent in antiviral properties even in the dark. Moreover, the dispersibility of the antiviral agent (A) in a composition improves by using it with a pigment (D) especially, and the cured film which is more excellent in antiviral property can be obtained.
  • the antiviral agent (A) used in the present composition may be one kind or two or more kinds.
  • the term "antiviral" as used in the present invention means that RNA viruses such as influenza virus have an effect of suppressing infection of a host cell, or suppresses proliferation of the virus in cells after infection of a host cell. Point to the effect.
  • the antiviral agent (A) has antiviral properties against various RNA viruses including influenza virus, but in particular, against influenza virus.
  • the acidic group examples include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. From the viewpoint of excellent antiviral property against influenza virus etc., a sulfonic acid group and a carboxyl group are preferable, and a sulfonic acid group is particularly preferable. preferable.
  • the alkali metal is not particularly limited, but is preferably sodium.
  • the alkali metal salt of the acidic group-containing compound has an acidic group capable of binding to the surface protein of the virus or is ionized to have the acidic group.
  • the surface protein of the virus has a role of binding to a sugar chain receptor of the host cell to infect the host, or the virus liberates from the infected cell and spreads the infection to the next cell. By binding to this surface protein, it is believed that these functions are inhibited to exert antiviral properties.
  • the acidic group-containing compound is not particularly limited, and, for example, Sulfonic acids such as alkane sulfonic acid, alkyl benzene sulfonic acid, alkyl phenyl sulfonic acid, alkyl diphenyl ether sulfonic acid, alkyl naphthalene sulfonic acid, modified products of these such as polyoxyethylene; Unsaturated sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid and styrene sulfonic acid; fatty acid; Aromatic carboxylic acid; (Meth) acrylic acid, (meth) acrylic acid dimer, maleic acid, fumaric acid, vinylbenzoic acid, crotonic acid, itaconic acid, unsaturated carboxylic acids such as citraconic acid; Unsaturated bond-containing phosphoric acids such as 2-hydroxyethyl methacrylate acid phosphate,
  • alkali metal salt of the acidic group-containing compound examples include sodium styrene sulfonate and sodium alkylphenyl sulfonate.
  • the polymer containing the alkali metal salt of the acidic group-containing compound is a homopolymer of a compound having an unsaturated bond among alkali metal salts of the acid group-containing compound, or an alkali metal salt of the acid group-containing compound.
  • Examples thereof include copolymers of a compound having an unsaturated bond and other copolymerizable compounds. These can be obtained by polymerizing by a known method.
  • alkali metals of acid group of homopolymer of acid group-containing compound having unsaturated bond, or copolymer of acid group-containing compound having unsaturated bond and other copolymerizable compound are alkali metal chloride (co (Co) polymer obtained by introducing the above-mentioned acidic group into a polymer or a (co) polymer of the following other copolymerizable compound by a conventionally known method, and further introducing the introduced acidic group into an alkali metal It may be
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the weight average molecular weight (Mw) of the polymer gives a composition excellent in handleability, and the antiviral property From the viewpoint of being able to easily obtain an excellent cured film, etc., it is preferably at least 5,000, more preferably at least 20,000, further preferably at least 50,000, particularly preferably at least 100,000, preferably at least 5,000,000. More preferably, it is 2 million or less, more preferably 1 million or less.
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the content of the alkali metal salt of the acidic group-containing compound (alkali metal salt structure of the acidic group-containing compound) is 20 mol% or more is preferable with respect to the said whole polymer from the point that the cured film which is excellent by property can be obtained easily.
  • the acid group is a sulfonic acid group
  • the content of the alkali metal salt of the sulfonic acid group-containing compound (alkali metal salt structure of the sulfonic acid group-containing compound) falls within the above range, the cured film becomes moisture Even in the case of contact with the above, whitening of the film can be suppressed.
  • the antiviral agent (A) is a polymer containing an alkali metal salt of an acidic group-containing compound
  • the acidic group in the molecule (acidic group in the molecule and the salt group of the acidic group (salt)
  • the ratio of the acid group regarded as a salt among the total of the acid groups) maintains the acidity of the present composition in an appropriate range, and from the viewpoint of being able to easily obtain a composition which is more excellent in stability, etc. It is preferably 50 mol% or more, more preferably 70 to 100 mol%, and particularly preferably 85 to 100 mol%.
  • the polymer containing the alkali metal salt of the acid group-containing compound and the alkali metal salt of the acid group-containing compound is further crosslinked by a crosslinking agent from the viewpoint that an antiviral agent (A) excellent in water resistance can be obtained.
  • a crosslinking agent include epoxy compounds, glycidyl compounds, aziridine compounds, oxazoline compounds, amine compounds, polyaminoamide compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, heat latent cationic polymerization catalysts, and photolattices.
  • the antiviral agent (A) is a particulate antiviral agent immobilized on an inorganic carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermiculite, perlite, or an organic polymer carrier such as polyethylene or polypropylene. May be
  • an inorganic carrier such as talc, bentonite, clay, kaolin, diatomaceous earth, silica, vermiculite, perlite, or an organic polymer carrier such as polyethylene or polypropylene.
  • the average particle diameter of the particulate antiviral agent (A) measured by the laser diffraction particle size distribution measuring device is preferably 0.5, from the viewpoint of easily obtaining a cured film which is more excellent in antiviral property. It is -30 ⁇ m, more preferably 1-25 ⁇ m. In addition, the said average particle diameter points out the particle size (what is called median diameter D50) of 50% of accumulation in the particle size distribution on a volume basis.
  • the antiviral agent (A) having an average particle diameter in the above range is unlikely to be detached from the cured film, and therefore, a cured film can be obtained which is more excellent in antiviral persistence.
  • the antiviral agent (A) when an antiviral agent (A) having an average particle diameter larger than that of the pigment (D) is used, the antiviral agent (A) is oriented on the surface of the cured film to obtain a cured film having more excellent antiviral properties. it can.
  • the antiviral agent (A) may be used in the form of a dispersion dispersed by a dispersion medium.
  • the dispersion medium is not particularly limited, and conventionally known dispersion media such as water and organic solvents can be used, and as the organic solvent, aromatic hydrocarbons (eg, xylene, toluene), ketones (eg, ketones) Examples: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, esters (eg: ethyl acetate, butyl acetate, isobutyl acetate), alcohols (eg: isopropyl alcohol, butanol), glycol ethers (eg: propylene glycol monomethyl ether), etc. It can be mentioned.
  • the compounding quantity of the antiviral agent (A) with respect to solid content of 100% by mass of the present composition is preferably 0 in terms of being able to obtain a cured film which is more excellent in antiviral property and further excellent in hardness and water resistance.
  • the content is preferably 5 to 15% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass. If the compounding amount is less than the above range, the resulting cured film may not exhibit sufficient antiviral properties, and if the compounding amount exceeds the above range, the hardness or water resistance of the cured film may be reduced. .
  • the photocurable resin (B) is not particularly limited as long as it is a photocurable resin other than a polymer containing an alkali metal salt of an acidic group-containing compound, but as the photocurable resin (B), for example, And oligomers and polymers having at least one unsaturated double bond.
  • the resin (B) used in the present composition may be one kind or two or more kinds.
  • Examples of the unsaturated double bond include a (meth) acryloyl group, a vinyl group, an allyl group and a styryl group, and a (meth) acryloyl group is preferable from the viewpoint of reactivity at the time of active energy ray irradiation.
  • Examples of the resin (B) include polyester (meth) acrylate resins, epoxy (meth) acrylate resins, polyether (meth) acrylate resins and urethane (meth) acrylate resins.
  • polyester (meth) acrylate resin for example, polyester (meth) acrylate resin obtained by reacting (meth) acrylic acid with polyester synthesized from polybasic acid or its anhydride and polyhydric alcohol It can be mentioned.
  • the polybasic acids include phthalic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, isoecebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, trimellitic acid, pyromellitic acid, pimelic acid, And azelaic acid.
  • polyhydric alcohol examples include 1,6-hexanediol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol.
  • epoxy (meth) acrylate resins examples include (meth) acrylic acid-modified epoxy resins obtained by adding (meth) acrylic acid to epoxy resins.
  • the epoxy resin to be subjected to modification for example, a resin obtained by reacting bisphenol A, bisphenol F, bisphenol S or phenol novolac with epichlorohydrin, cyclopentadiene oxide or cyclohexene oxide and epichlorohydrin are reacted with each other. The obtained resin is mentioned.
  • polyether (meth) acrylate resins examples include polyether (meth) acrylate resins obtained by transesterification of polyether and (meth) acrylic acid ester such as ethyl (meth) acrylate.
  • polyether examples include polyethers obtained by ethoxylation or propoxylation of trimethylolpropane and pentaerythritol and the like, and polyethers obtained by polyetherifying 1,4-butanediol and the like. Can be mentioned.
  • urethane (meth) acrylate resins include urethane (meth) acrylate resins obtained by reacting an isocyanate compound, a hydroxy group-containing (meth) acrylate compound, and optionally a polyol compound.
  • the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
  • Examples of the hydroxy group-containing (meth) acrylate compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Examples thereof include hydroxyl group-containing alkyl esters of (meth) acrylic acid such as hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • Examples of the polyol compound include an adduct of hydrogenated bisphenol A and ethylene oxide, hydrogenated bisphenol A, neopentyl glycol, 1,6-hexanediol, and trimethylolpropane.
  • the compounding amount of the resin (B) relative to 100% by mass of the solid content of the present composition can easily obtain a cured film excellent in hardness and scratch resistance, and can suppress curing shrinkage when forming the cured film, etc. It is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass. If the amount is less than the above range, the hardness and the scratch resistance of the resulting cured film may be reduced. If the amount is more than the range, the cure shrinkage upon forming the cured film may be too large. There is.
  • Unsaturated Monomer (C)> As unsaturated monomer (C), monofunctional monomer having one unsaturated double bond, bifunctional monomer having two unsaturated double bonds, trifunctional or more having three or more unsaturated double bonds And polyfunctional monomers. Among these monomers, (meth) acrylate monomers are preferable from the viewpoint of being able to easily obtain a cured film which is more excellent in photocurability and excellent in antiviral property.
  • the unsaturated monomer (C) used in the present composition may be of one type or two or more types, and using at least one of a monofunctional monomer and a bifunctional monomer is low in viscosity and excellent in coating workability. It is preferable from the point that this composition can be obtained easily.
  • Examples of monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) Acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, al
  • bifunctional monomer for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, PEG200 # di (meth) acrylate (EO part is n ⁇ 4), tetraethylene glycol di (meth) acrylate, PEG300 # Di (meth) acrylate (EO part n 6 6), PEG 400 # di (meth) acrylate (EO part n 9 9), PEG 600 # di (meth) acrylate (EO part n 13 14), polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, PO-added neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) Acrylate, hydroxide Pivalate neopentyl glycol di (meth) acrylate, polytet
  • the compounding quantity of the unsaturated monomer (C) with respect to solid content 100 mass% of this composition can obtain easily the composition which is excellent in coating property, and can suppress the curing defect at the time of forming a cured film.
  • the amount is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and particularly preferably 50 to 80% by mass from the viewpoint that a cured film having a desired hardness can be easily obtained. If the compounding amount is less than the above range, the viscosity of the composition obtained may be increased and the coatability may be reduced, and if the compounding amount exceeds the above range, the hardness of the cured film is reduced or a cured film is formed. Poor curing may occur.
  • the blending ratio of the photocurable resin (B) to the unsaturated monomer (C) is 20% by mass or less of the component (B) based on 100% by mass in total of the component (B) and the component (C) It is preferable from the point that the cured film which is more excellent in antiviral property is obtained.
  • the pigment (D) As the pigment (D), conventionally known pigments can be used.
  • the pigment (D) is particles other than the components (A) to (C) and (E). Since this composition uses a pigment (D), a cured film having irregularities on the surface can be obtained, and it is considered that the area in which the antiviral agent (A) and the virus are in contact is increased. Furthermore, it is considered that the dispersibility of the antiviral agent (A) can be improved and it can be uniformly oriented on the surface of the cured film. For this reason, the cured film which is excellent in antiviral property can be obtained easily.
  • the pigment (D) used in the present composition may be one kind or two or more kinds.
  • organic resin particles such as acrylic particles, polystyrene particles, polyethylene wax particles, polypropylene wax particles, PTFE particles, urethane particles, silicone particles, metal oxide particles (eg, silica particles, Inorganic fine particles such as aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles) can be mentioned.
  • metal oxide particles eg, silica particles, Inorganic fine particles such as aluminum oxide fine particles, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles
  • inorganic fine particles are preferable, silica Microparticles are more preferred.
  • the average particle size of the pigment (D) is not particularly limited, but preferably 1 to 10 ⁇ m, more preferably 2 to 8 ⁇ m.
  • the average particle diameter refers to the cumulative 50% particle diameter (so-called median diameter D50) in the volume-based particle size distribution, and can be measured by a laser diffraction particle size distribution measuring device.
  • the lower limit of the pigment volume concentration (hereinafter also referred to as "PVC") of the pigment (D) is preferably 2%, more preferably 3%, particularly preferably 5%.
  • the upper limit is preferably 25%, more preferably 20%, particularly preferably 15%.
  • Said PVC refers to the total volume concentration of the pigment (D) with respect to the volume of solids in the present composition. Specifically, it can be obtained from the following equation.
  • PVC volume of pigment (D) ⁇ 100 / volume of solid content in the composition
  • the solid content is a component obtained by removing volatile components such as an organic solvent from the composition, and curing The component which remains as a cured film is shown.
  • the volume of solid content in the present composition can be calculated from the mass and the true density of the solid content of the composition.
  • the mass and the true density of the solid content may be measured values or values calculated from raw materials used.
  • the volume of the pigment (D) can be calculated from the mass and the true density of the pigment (D) used.
  • the mass and the true density of the pigment (D) may be measured values or values calculated from the raw materials used. For example, it can be calculated by separating the pigment (D) and the other components from the solid content of the present composition, and measuring the mass and true density of the separated pigment (D).
  • the photopolymerization initiator (E) is not particularly limited as long as it is a compound that can generate a radical or a cation upon irradiation with light and react the above components (B) and (C) to cure the present composition.
  • the initiator (E) used in the present composition may be one kind or two or more kinds.
  • an alkyl phenone type initiator As an initiator (E), an alkyl phenone type initiator, an acyl phosphine oxide type initiator, and a hydrogen abstraction type initiator are mentioned, for example.
  • alkyl phenone type initiator for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone.
  • acylphosphine oxide initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • hydrogen abstraction initiators examples include benzophenone, 2,4,6-trimethylbenzophenone, methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-ethylanthraquinone, camphorquinone, oxy-phenyl-acetic acid 2- Mixtures of [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, including phenylglyoxylic acid methyl ester .
  • 1-hydroxy-cyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferable.
  • the content of the initiator (E) based on 100% by mass of the solid content of the present composition can easily obtain a cured film which is excellent in curability, hardness and adhesion with a substrate, and further yellowing due to ultraviolet light etc.
  • the content is 0.1 to 10% by mass, more preferably 3 to 9% by mass, and particularly preferably 4 to 8% by mass, from the viewpoint of easily obtaining a cured film capable of suppressing the above. If the compounding amount is less than the above range, the curability at the time of forming a cured film may be insufficient, and the hardness of the obtained cured film may be reduced.
  • the compounding amount exceeds the above range, the unreacted initiator (E) tends to remain in the cured film, the hardness of the obtained cured film tends to decrease, and the cured film is easily yellowed by ultraviolet light and the like. In addition, the adhesion to the substrate may be reduced.
  • additives other than the components described above may be added to the composition.
  • additives generally used in the field of the present invention can be used in the range not to impair the effects of the present invention, for example, organic solvents, leveling agents, antifoaming agents, polymerization inhibitors, Non-reactive diluents, matting agents, anti-settling agents, dispersing agents, heat stabilizers, UV absorbers may be mentioned. These compounding quantities can be suitably adjusted in the range which does not impair the effect of this invention.
  • the other additives may be used alone or in combination of two or more.
  • the composition may contain an organic solvent from the viewpoint of adjusting the viscosity to a predetermined range.
  • organic solvent conventionally known solvents can be used.
  • aromatic hydrocarbons eg: xylene, toluene
  • ketones eg: methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone
  • esters eg: ethyl acetate, butyl acetate, isobutyl acetate
  • alcohols eg: isopropyl Alcohol, butanol
  • glycol ethers eg, propylene glycol monomethyl ether
  • a leveling agent is blended from the viewpoint of improving the repelling of the composition, improving the wettability to the substrate surface, and easily forming a cured film having a uniform film thickness.
  • a leveling agent various leveling agents, such as fluorine type, an acryl type, and silicon type, are mentioned, for example.
  • the compounding amount of the leveling agent with respect to 100% by mass of the solid content of the present composition is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 1.0% by mass.
  • an antifoaming agent it is preferable to add an antifoaming agent to the present composition from the viewpoint of suppressing the generation of air bubbles in the composition and easily forming a cured film having a good appearance.
  • an antifoamer various antifoamers, such as an acryl type and a silicon type, are mentioned, for example.
  • the compounding amount of the antifoaming agent with respect to 100% by mass of the solid content of the present composition is preferably 0.0001 to 1.0% by mass.
  • a dispersing agent may be added to the present composition from the viewpoint of improving the dispersibility of the pigment (D) in the composition and easily forming a cured film having a good appearance.
  • the dispersant is not particularly limited, and, for example, a copolymer having a pigment-adsorbing group such as carboxylic acid, phosphoric acid or amine, a copolymer having a compatible chain such as fatty acid, polyamino, polyether, polyester, polyurethane or polyacrylate Various dispersants such as copolymers may be mentioned.
  • the compounding amount of the dispersant based on 100% by mass of the solid content of the present composition is preferably 0.1 to 10% by mass.
  • the cured film formed using this composition is excellent in antiviral property and does not cause metal allergy, so it is in contact with human beings (eg, portable) Devices equipped with image display devices such as telephones, smartphones and tablets, electrical appliances such as home appliances, protective films for image display devices, furniture, doorknobs, handrails, handlebars of automobiles, toys)
  • image display devices such as telephones, smartphones and tablets
  • electrical appliances such as home appliances
  • protective films for image display devices furniture, doorknobs, handrails, handlebars of automobiles, toys
  • the cured film (hereinafter also referred to as "the main cured film") according to an embodiment of the present invention is a film formed from the present composition, and specifically, the step of curing the present composition by light irradiation It can manufacture by including (hardening process).
  • the base material with a cured film which concerns on one Embodiment of this invention contains a base material and the said main cured film.
  • the present cured film and the substrate with the present cured film specifically apply the present composition to at least a part of the substrate (coating step) and then apply the present composition by light irradiation. It can manufacture by including the process (hardening process) made to harden
  • the substrate is not particularly limited as long as it is a substrate on which the main cured film is to be formed, and examples thereof include plastics, woods, metals, glasses, ceramics, and concrete.
  • the plastic include various plastic substrates (eg, triacetyl cellulose, polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic, polyurethane, polyester, polycarbonate, polysulfone, polyether, Films and molded articles formed from polymethylpentene, polyether ketone, (meth) acrylonitrile and the like can be mentioned.
  • PET polyethylene terephthalate
  • diacetyl cellulose acetate butyrate cellulose
  • polyether sulfone polyacrylic, polyurethane
  • polyester polycarbonate
  • polysulfone polyether
  • the application (coating) method in the application step may be appropriately selected according to the composition of the present composition to be used, the type of the substrate, etc.
  • spray coating, dip coating, air knife coating, curtain Coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method, dipping method can be mentioned.
  • a drying step may be provided to dry the applied composition before the curing step. This drying step may be performed under heating at about 5 to 120 ° C. to shorten the drying time.
  • the light irradiated in the curing step is preferably an active energy ray
  • the active energy ray include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, rays such as infrared rays, electromagnetic waves such as X rays and ⁇ rays, and electron rays And a proton beam and a neutron beam.
  • ultraviolet rays are preferable in view of curing speed, availability of an irradiation apparatus, cost and the like.
  • the irradiation dose of ultraviolet light is 100 to 3, using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode lamp, an LED lamp or the like that emits light in a wavelength range of 200 to 500 nm.
  • the method etc. which are irradiated by about 000 mJ / cm ⁇ 2 > etc. are mentioned.
  • heating may be performed at about 5 to 120 ° C. in order to shorten the curing time after or during the light irradiation.
  • the thickness of the cured film is not particularly limited as long as it can protect the substrate, but it is preferably 1 to 10 ⁇ m, more preferably 2 to 7 ⁇ m, and particularly preferably 2 to 5 ⁇ m.
  • the average length (RSm) of the roughness curvilinear element measured based on JIS B 0601: 2013 of the main cured film surface is preferably 300 ⁇ m or less. If the RSm is 300 ⁇ m or less, a cured film which is more excellent in antiviral property tends to be obtained.
  • the virus inactivation method according to an embodiment of the present invention is a method of inactivating a virus at least in a dark place using the main cured film or the substrate with the main cured film. It is. Specifically, the virus is inactivated by bringing the cured film into contact with the virus. The contact is usually performed at normal temperature, but may be performed under heating in some cases. Specifically, for articles such as housings of home appliances, image display devices such as displays of smartphones and protective films, interiors of automobiles, window films of automobiles, interior materials such as walls, floors and ceilings, surfaces of furniture, etc.
  • the method of forming this cured film and inactivating the virus which contacted the cured film is mentioned.
  • the virus can be inactivated even when these articles are in a dark place such as in a room, in a garage, in storage furniture and in a bag or at night.
  • This method can be used for inactivation of various RNA viruses including influenza virus, and in particular, can be preferably used for inactivation of influenza virus. Whether or not the virus has been inactivated can be confirmed by the value of the virus activity value in accordance with JIS L 1922: 2016.
  • the "dark place" refers to a place where no light exists, including ultraviolet light.
  • a photocurable resin composition was prepared by mixing the following materials in the composition shown in Table 1.
  • the numerical value of the column of the photocurable resin composition in Table 1 shows a mass part, and the density of solid content and solid content is the value computed from the used raw material.
  • ⁇ Antiviral agent (A)> Water dispersion containing sodium salt of acid group-containing polymer and sodium alkylphenyl sulfonate (solid content 35%)
  • ⁇ Preparation of a substrate with a cured film> The photocurable resin composition prepared above is applied once to a PET film “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd. so that the dry film thickness is about 3 ⁇ m, and the ultraviolet light is irradiated with a high pressure mercury lamp. (Irradiation dose: 400 mJ / cm 2 ), the coating was cured to obtain a substrate with a cured coating.
  • Virus activity value of the substrate with a cured film obtained (antiviral) in accordance with JIS L 1922: 2016 except that the following concentration of influenza virus solution was used to wash out on a petri dish and recovery of the washout solution was performed was evaluated. Specifically, a substrate with a cured film and a substrate without a cured film (control sample) are cut into 6 cm square and used as a sample, and the sample is placed in a petri dish, and influenza virus liquid (concentration: 10 5 to 10) on the surface 6 PFU / mL) was added dropwise (reaction area 4 cm square), and allowed to stand in the dark (25 ° C.) for 2 hours.
  • influenza virus liquid concentration: 10 5 to 10
  • the virus solution was washed out on a petri dish and recovered by the solution to prepare a dilution series.
  • Epithelial cells dog kidney-derived cells
  • the virus infectivity titer was measured by TCID 50 assay to determine the antiviral activity value. Those having an antiviral activity value of 2.0 or more were taken as pass, and those having 3.0 or more were evaluated as particularly excellent. The results are shown in Table 1.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

La présente invention concerne une composition de résine photodurcissable, un film de revêtement durci, un substrat comprenant un film de revêtement durci, un procédé pour sa production et une méthode d'inactivation de virus. La composition de résine photodurcissable comprend : (A) un agent antiviral contenant au moins un sel d'un métal alcalin d'un composé contenant un groupe acide et/ou un polymère contenant un sel d'un métal alcalin d'un composé contenant un groupe acide ; (B) une résine photodurcissable, (C) un monomère insaturé, (D) un pigment, et (E) un amorceur de photopolymérisation.
PCT/JP2018/023307 2017-06-21 2018-06-19 Composition de résine photodurcissable, film de revêtement durci, substrat comprenant un film de revêtement durci, procédé pour sa production, et méthode d'inactivation de virus WO2018235816A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020203069A1 (fr) * 2019-04-04 2020-10-08 リケンテクノス株式会社 Peinture pour la formation d'un film de revêtement antiviral, film de revêtement et film stratifié
JP7338768B1 (ja) 2022-09-29 2023-09-05 大日本印刷株式会社 化粧シート
WO2023171557A1 (fr) * 2022-03-10 2023-09-14 積水化学工業株式会社 Élément d'inhibition d'infection virale
WO2023171555A1 (fr) * 2022-03-10 2023-09-14 積水化学工業株式会社 Agent inhibiteur d'infection virale, particules inhibitrices d'infection virale, et matériau de revêtement inhibiteur d'infection virale

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011256357A (ja) * 2010-05-12 2011-12-22 Nagase Chemtex Corp ハードコート用組成物、ハードコートフィルム及び表示デバイス
JP2012036363A (ja) * 2010-07-13 2012-02-23 Sekisui Chem Co Ltd 塗料及び化粧シート
JP2012140613A (ja) * 2010-12-15 2012-07-26 Sekisui Chem Co Ltd 水性フロアーポリッシュ及びインフルエンザウイルス感染阻止製品
JP2013193966A (ja) * 2012-03-16 2013-09-30 Sekisui Chem Co Ltd 樹脂組成物、樹脂溶液、積層体及び樹脂シート
JP2016102072A (ja) * 2014-11-27 2016-06-02 ロンシール工業株式会社 抗ウイルス性を有する表面処理剤及び表面処理剤が塗布されている抗ウイルス性シート状物
JP2016128395A (ja) * 2015-01-09 2016-07-14 ロンシール工業株式会社 抗ウイルス性合成樹脂組成物及びその製造方法
JP2017210566A (ja) * 2016-05-26 2017-11-30 ロンシール工業株式会社 抗ウイルス性を有する表面処理剤及び表面処理剤が塗布されている抗ウイルス性シート状物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011256357A (ja) * 2010-05-12 2011-12-22 Nagase Chemtex Corp ハードコート用組成物、ハードコートフィルム及び表示デバイス
JP2012036363A (ja) * 2010-07-13 2012-02-23 Sekisui Chem Co Ltd 塗料及び化粧シート
JP2012140613A (ja) * 2010-12-15 2012-07-26 Sekisui Chem Co Ltd 水性フロアーポリッシュ及びインフルエンザウイルス感染阻止製品
JP2013193966A (ja) * 2012-03-16 2013-09-30 Sekisui Chem Co Ltd 樹脂組成物、樹脂溶液、積層体及び樹脂シート
JP2016102072A (ja) * 2014-11-27 2016-06-02 ロンシール工業株式会社 抗ウイルス性を有する表面処理剤及び表面処理剤が塗布されている抗ウイルス性シート状物
JP2016128395A (ja) * 2015-01-09 2016-07-14 ロンシール工業株式会社 抗ウイルス性合成樹脂組成物及びその製造方法
JP2017210566A (ja) * 2016-05-26 2017-11-30 ロンシール工業株式会社 抗ウイルス性を有する表面処理剤及び表面処理剤が塗布されている抗ウイルス性シート状物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020203069A1 (fr) * 2019-04-04 2020-10-08 リケンテクノス株式会社 Peinture pour la formation d'un film de revêtement antiviral, film de revêtement et film stratifié
JP6799200B1 (ja) * 2019-04-04 2020-12-09 リケンテクノス株式会社 抗ウイルス性塗膜形成用塗料、塗膜、及び積層フィルム
WO2023171557A1 (fr) * 2022-03-10 2023-09-14 積水化学工業株式会社 Élément d'inhibition d'infection virale
WO2023171555A1 (fr) * 2022-03-10 2023-09-14 積水化学工業株式会社 Agent inhibiteur d'infection virale, particules inhibitrices d'infection virale, et matériau de revêtement inhibiteur d'infection virale
JP7338768B1 (ja) 2022-09-29 2023-09-05 大日本印刷株式会社 化粧シート
WO2024070900A1 (fr) * 2022-09-29 2024-04-04 大日本印刷株式会社 Feuille décorative
JP2024049531A (ja) * 2022-09-29 2024-04-10 大日本印刷株式会社 化粧シート

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