JP2020128554A - Antibacterial hard coat, and method for producing the same - Google Patents

Abstract

To provide a hard coat that is composed of an active energy ray-curable resin composition and has both antibacterial properties and sufficient hard coat properties.SOLUTION: A hard coat has an active energy ray-curable resin composition containing (A) polyfunctional (meth) acrylate and (B) a halogen element-containing sulfone-based antibacterial agent, preferably further containing (C) a photopolymerization initiator and (D) an ultraviolet absorber. For Staphylococcus aureus, an antibacterial activity measured at 23°C in accordance with JIS Z2801:2010 is 2 or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a hard coat made of an active energy ray-curable resin composition having antibacterial properties, and a method for producing the same.

Traditionally, furniture such as display cabinets, storage chests, cupboards, and desks; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; or building materials such as floors, walls, and bathrooms, wood and plywood. , Decorative wood, particle board, and hardboard on the surface of a base material made of a wood-based material; or a surface of a base material made of a metal-based material such as iron and aluminum, a decorative sheet is attached to the surface for decoration and makeup. What has been done is being used. The decorative sheet is required to have not only decorativeness but also scratch resistance and stain resistance at a high level in a well-balanced manner. It is widely practiced to form a hard coat made of an active energy ray-curable resin composition on the surface of a decorative sheet in order to impart the above characteristics to the decorative sheet.

In recent years, pollution with various bacteria, especially with strong bacteria such as Staphylococcus aureus, has been highlighted as a serious problem, and nosocomial/nosocomial infections in hospitals, elderly homes, and nurseries have become a social problem. There is. Therefore, articles such as furniture, home electric appliances, and building members used in these facilities are strongly required to have antibacterial properties. However, there is a problem that a hard coat obtained by containing an antibacterial agent in an active energy ray-curable resin composition, applying the antibacterial agent, and curing the composition by irradiation with an active energy ray hardly exhibits antibacterial properties. The present situation is that a hard coat made of an active energy ray-curable resin composition, which has antibacterial properties and sufficient hard coat properties, has not yet been obtained.

JP-A-59-136166

An object of the present invention is to provide a hard coat made of an active energy ray-curable resin composition, which has antibacterial properties. A further object of the present invention is to provide a hard coat comprising an active energy ray-curable resin composition, which has antibacterial properties and sufficient hard coat properties.

As a result of earnest research, the present inventor has found that the above problems can be achieved by curing a specific active energy ray-curable resin composition by a specific method.

That is, the present invention comprises an active energy ray-curable resin composition containing (A) a polyfunctional (meth)acrylate; and (B) a halogen element-containing sulfone-based antibacterial agent, and for Staphylococcus aureus JIS Z2801: According to 2010, the hard coat has an antibacterial activity value of 2 or more measured at a temperature of 23°C.

A second invention is the first invention, wherein the component (B) contains at least one member selected from the group consisting of diiodomethyl-p-tolylsulfone and 2,3,5,6 tetrachloro-4-methylsulfonylpyridine. The hard coat according to the invention.

A third invention is the hard coat according to the first invention or the second invention, wherein the active energy ray-curable resin composition further contains (C) a photopolymerization initiator.

A fourth invention is the hard coat according to any one of the first to third inventions, wherein the component (C) contains (C1) an acylphosphine oxide-based photopolymerization initiator.

5th invention, the said component (C) consists of (C1) acylphosphine oxide type photoinitiator 20-60 mass% and (C2) acetophenone type photoinitiator 80-20 mass%, Here, The sum of the component (C1) and the component (C2) is 100% by mass, which is the hard coat according to the fourth invention.

A sixth invention is the hard coat according to any one of the first to fifth inventions, wherein the active energy ray-curable resin composition further contains (D) an ultraviolet absorber.

A seventh invention is an article including the hard coat according to any one of the first to sixth inventions.

An eighth invention is a decorative sheet including the hard coat according to any one of the first to sixth inventions.

A ninth invention is an article including the decorative sheet according to the eighth invention.

The tenth invention is
(1) A step of forming a wet coating film of an active energy ray-curable resin composition on at least one surface of a film base material;
(2) A step of predrying the wet coating film obtained in the above step (1) to form a dried coating film;
(3) a step of stacking an active energy ray transparent film on the surface of the dried coating film obtained in the above step (2) and temporarily pasting it; and
(4) A step of irradiating the laminate obtained in the step (3) with an active energy ray to cure the dried coating film;
including,
Consisting of an active energy ray curable resin composition,
This is a method for producing a hard coat in which the antibacterial activity value of Staphylococcus aureus according to JIS Z2801:2010 at a temperature of 23° C. is 2 or more.

The hard coat of the present invention has antibacterial properties. The preferred hard coat of the present invention has antibacterial properties and sufficient hard coat properties. Therefore, the decorative sheet having the hard coat of the present invention on its surface can be suitably used for decoration and makeup of articles such as furniture, home electric appliances, and building members. Further, articles such as furniture, home electric appliances, and building members, which are decorated and made up with a decorative sheet having the hard coat on the surface of the present invention, can be suitably used in hospitals, nursing homes, nurseries and the like.

The hard coat of the present invention comprises (A) a polyfunctional (meth)acrylate; and (B) a halogen element-containing sulfone-based antibacterial agent;
An active energy ray-curable resin composition containing The hard coat of the present invention preferably contains (A) a polyfunctional (meth)acrylate; (B) a halogen element-containing sulfone-based antibacterial agent; and (C) a photopolymerization initiator. Consists of.

(A) Polyfunctional (meth)acrylate:
The above component (A) is a (meth)acrylate having two or more (meth)acryloyl groups in one molecule, and has two or more (meth)acryloyl groups in one molecule, and therefore, it is possible to prevent ultraviolet rays, electron beams and the like. It functions to form a hard coat by being polymerized and cured by active energy rays.

Examples of the polyfunctional (meth)acrylate include diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2, (Meth)acryloyl group-containing bifunctional reaction such as 2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane and 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane Monomers; trifunctional reactive monomers containing (meth)acryloyl group such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate Etc. (meth)acryloyl group-containing tetrafunctional reactive monomer; dipentaerythritol hexaacrylate and other (meth)acryloyl group-containing hexafunctional reactive monomer; tripentaerythritol acrylate and other (meth)acryloyl group-containing octafunctional reactive monomer Further, a polymer (oligomer or prepolymer) containing one or more of these as constituent monomers can be used. In addition, in this specification, (meth)acrylate means an acrylate or a methacrylate.

The polyfunctional (meth)acrylate is preferably 20 mass% of an ethanolamine-modified polyether (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule, with the total amount of the component (A) being 100 mass %. % Or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. It is possible to improve the crack resistance of the hard coat and improve the workability when decorating and applying makeup to an article using a decorative sheet. On the other hand, from the viewpoint of surface hardness, the content of the ethanolamine-modified polyether (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule is preferably 90% by mass or less, more preferably 60% by mass. May be:

As the ethanolamine-modified polyether (meth)acrylate having three or more (meth)acryloyl groups in one molecule, for example, one disclosed as the component (A) in JP2013-064098A is used. You can

As the component (A), one kind or a mixture of two or more kinds thereof can be used.

(B) Sulfone-based antibacterial agent containing halogen element:
The component (B) is a halogen element-containing sulfone-based antibacterial agent, and is a sulfone compound having one or more halogen elements in one molecule.

Examples of the halogen element-containing sulfone-based antibacterial agent include diiodomethyl-p-tolylsulfone, 2,3,5,6 tetrachloro-4-methylsulfonylpyridine, and the like. As the component (B), one kind or a mixture of two or more kinds thereof can be used.

From the viewpoint of antibacterial properties, the compounding amount of the above component (B) is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0. The amount may be 01 parts by mass or more. On the other hand, from the viewpoint of laws and regulations, voluntary regulation of the industry, and economical efficiency, it is usually 1 part by mass or less, preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less, and further preferably 0.1 part by mass or less. It may be less than or equal to parts by mass.

(C) Photopolymerization initiator:
From the viewpoint of improving the curability due to active energy rays, the active energy ray-curable resin composition preferably further contains the component (C) photopolymerization initiator.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone-based photopolymerization initiators such as -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; benzoin, benzoin Benzoin-based photopolymerization initiators such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone-based photopolymerizations such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone Initiators: Anthraquinone-based photopolymerization initiators such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; Thioxanthone-based photopolymerization initiators such as thioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; Alkylphenone photopolymerization initiators such as acetophenone dimethyl ketal; triazine photopolymerization initiators; bisimidazole photopolymerization initiators; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6) -Trimethylbenzoyl)-phenylphosphine oxide and other acylphosphine oxide photopolymerization initiators; titanocene photopolymerization initiators; oxime ester photopolymerization initiators; oxime phenylacetate photopolymerization initiators; hydroxyketone photopolymerization initiators Examples thereof include a polymerization initiator; and an aminobenzoate-based photopolymerization initiator.

Among these, the component (C) preferably contains (C1) an acylphosphine oxide photopolymerization initiator from the viewpoint of scratch resistance and stain resistance; (C1) an acylphosphine oxide system. It is more preferable that the photopolymerization initiator and the (C2) acetophenone-based photopolymerization initiator be used; 20 to 60% by mass, preferably 30 to 50% by mass of the component (C1) and 80 to 20% by mass of the component (C2). %, preferably 70 to 50% by mass, and more preferably the sum of the above component (C1) and the above component (C2) is 100% by mass.

As the component (C), one kind or a mixture of two or more kinds thereof can be used.

The blending amount of the above component (C) is usually 10 parts by mass or less, preferably 7 parts by weight from the viewpoint of preventing the formed hard coat from being yellowed and colored with respect to 100 parts by mass of the above component (A). It may be not more than 5 parts by mass, more preferably not more than 5 parts by mass. On the other hand, the lower limit of the blending amount is not particularly limited because it is an optional component, but from the viewpoint of surely obtaining the effect of using the component (C), it is usually 0.1 part by mass or more, preferably 0.5 part by mass or more. It may be preferably 1 part by mass or more, and more preferably 3 parts by mass or more.

(D) UV absorber:
From the viewpoint of improving the weather resistance of the hard coat, the active energy ray-curable resin composition preferably further contains the component (D) ultraviolet absorber.

Examples of the ultraviolet absorber include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H -Benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, and 2-(5- Benzotriazole-based UV absorbers such as chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol; 2-(4,6-diphenyl-1,3,5-triazine-2- Yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenol)-1,3,5- A triazine-based UV absorber such as triazine; a cyanoacrylate-based UV absorber such as ethyl-2-cyano-3,3-diphenylacrylate, (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; and [ Examples thereof include benzophenone-based UV absorbers such as 2-hydroxy-4-(octyloxy)phenol](phenyl)methanone. As the above component (D), one kind or a mixture of two or more kinds thereof can be used.

The blending amount of the component (D) is usually 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of preventing the formed hard coat from yellowing and coloring, and from the viewpoint of curing speed. Parts or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less. On the other hand, the lower limit of the blending amount is not particularly limited because it is an optional component, but from the viewpoint of reliably obtaining the use effect of the component (D), it is usually 0.1 part by mass or more, preferably 0.5 part by mass or more, It may be preferably 1 part by mass or more.

The active energy ray-curable resin composition has two or more isocyanate groups (-N=C=O) in one molecule from the viewpoint of the toughness of the formed hard coat and the adhesion to the film substrate. The compound having can be further included. Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethane such as block isocyanate of polyisocyanate A crosslinking agent etc. can be mentioned. As the compound having two or more isocyanate groups in one molecule, one kind or a mixture of two or more kinds thereof can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added, if necessary.

The compounding amount of the compound having two or more isocyanate groups in one molecule is usually 40 parts by mass or less, preferably 20 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of curability by active energy rays. Parts or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. On the other hand, the lower limit of the blending amount is not particularly limited because it is an optional component, but from the viewpoint of reliably obtaining the use effect of the compound having two or more isocyanate groups in one molecule, it is usually 0.1 part by mass or more, preferably It may be 0.3 parts by mass or more, more preferably 0.5 parts by mass or more.

In the active energy ray-curable resin composition, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain inhibitor, a printability improving agent, an antioxidant, a weather resistance stabilizer. One or more additives such as a light resistance stabilizer, a heat stabilizer, an inorganic fine particle, an organic fine particle, an inorganic colorant, and an organic colorant may be contained.

The active energy ray-curable resin composition may contain a solvent, if desired, in order to dilute it to a concentration that facilitates coating. The solvent is not particularly limited as long as it does not react with the components (A) to (D) and other optional components or catalyze (promote) self-reaction (including deterioration reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the solvent, one kind or a mixture of two or more kinds can be used.

The active energy ray curable resin composition can be obtained by mixing and stirring these components.

The hard coat of the present invention has an antibacterial activity value of Staphylococcus aureus measured according to JIS Z2801:2010 at a temperature of 23° C. of 2 or more, preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5. As described above, it is most preferably 4 or more. The higher the antibacterial activity value, the more preferable. Here, the above-mentioned antibacterial activity value is a value measured according to (a) antibacterial property 1 in the following examples.

Similarly, the hard coat of the present invention has an antibacterial activity value of E. coli of 2 or more, preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5 according to JIS Z2801:2010 at a temperature of 23°C. As described above, it is most preferably 4 or more. The higher the antibacterial activity value, the more preferable. The above-mentioned antibacterial activity value is a value measured according to (b) antibacterial property 2 in the following examples.

The hard coat of the present invention has the above-mentioned antibacterial property, and using any active energy ray curable resin composition containing an antibacterial agent, preferably the above active energy ray curable resin composition. (1) forming a wet coating film of the active energy ray-curable resin composition on at least one surface of the film substrate using the product;
(2) A step of predrying the wet coating film obtained in the above step (1) to form a dried coating film;
(3) a step of stacking an active energy ray transparent film on the surface of the dried coating film obtained in the above step (2) and temporarily pasting it; and
(4) A step of irradiating the laminate obtained in the step (3) with an active energy ray to cure the dried coating film;
Can be obtained by a method including.

The film substrate used in the step (1) is not particularly limited, and any resin film can be used as the film substrate. Examples of the resin film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; polyethylene, polypropylene, and polyolefin resins such as polymethylpentene. Resin: Cellulosic resin such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile/butadiene/styrene copolymer resin (ABS resin), styrene/ethylene/butadiene/styrene copolymer, styrene/ Styrene resins such as ethylene/propylene/styrene copolymers and styrene/ethylene/ethylene/propylene/styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; Other examples include resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, and polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. It also includes a laminated film in which two or more layers of one or more of these are laminated.

When the film substrate is one of the constituent layers of the decorative sheet, from the viewpoint of enhancing the adhesion between the film substrate and the hard coat, the wet coating film forming surface of the film substrate is corona discharge. It may be subjected to a treatment or an easy adhesion treatment such as anchor coat formation.

When the film substrate is one of the constituent layers of the decorative sheet, the thickness of the film substrate is not particularly limited, but from the viewpoint of handleability, it may be usually 20 μm or more, preferably 30 μm or more. From the viewpoint of designability, it may be usually 50 μm or more, preferably 80 μm or more. On the other hand, from the viewpoint of thinning the decorative sheet, it may be usually 2000 μm or less, preferably 800 μm or less, more preferably 300 μm or less.

When the hard coat formed on the surface of the film base material is transferred to another film base material and used, the surface of the film base material on which the wet coating film has been formed is subjected to an easy peeling treatment. You may

When the hard coat formed on the surface of the film substrate is used by transferring it to another film substrate, the thickness of the film substrate is not particularly limited, but usually 20 μm or more from the viewpoint of handleability, It may be preferably 30 μm or more. On the other hand, from the viewpoint of economy, it may be usually 100 μm or less, preferably 75 μm or less.

The method of forming a wet coating film of the active energy ray-curable resin composition in the step (1) is not particularly limited. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

In the step (2), the wet coating film obtained in the step (1) is pre-dried to form a dry coating film. In the pre-drying, for example, the time required for passing the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150° C., preferably 50 to 120° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

In the step (3), the active energy ray-permeable film is superposed on the surface of the dried coating film obtained in the step (2) and temporarily attached. This suppresses oxygen damage in the curing reaction of the active energy ray-curable resin composition due to irradiation with active energy rays.

Although not intending to be bound by theory, the hard coat of the present invention has the above-mentioned antibacterial/antiviral property and sufficient hard coat property because it is laminated and temporarily attached on the surface of the dry coating film. By blocking the oxygen by the activated energy ray permeable film thus formed, the oxygen damage of the curing reaction is suppressed, and the inactivation of the component (B) due to the interaction between the active energy ray and oxygen is also suppressed. Is considered.

An example of a method for stacking and temporarily pasting the active energy ray-permeable film on the surface of the dry coating film will be described with reference to FIG. The laminate 1 obtained in the step (2) is provided on the rotating heating drum 3 preheated to a desired temperature on the side opposite to the dry coating film of the laminate 1 obtained in the step (2). Is placed so that the surface thereof faces the heating drum 3, and the active energy ray permeable film 2 is further placed on the surface of the dry coating film, and the surface is pressed by the pressing roll 4. The laminated body 6 in which the active energy ray transparent film is superposed and temporarily adhered on the surface of the dried coating film is released from the heating drum 3 by the guide roll 5 and sent to the step (4).

The active energy ray transmissive film is a film having an active energy ray transmissivity of usually 70% or more, preferably 80% or more. Here, the active energy ray transmittance is the active energy at a wavelength of 200 to 600 nm with respect to the integrated area of the transmission spectrum when the transmittance of the active energy ray in the entire wavelength range of 200 to 600 nm is assumed to be 100%. It is the ratio of the integrated area of the transmission spectrum of the line, and is the value measured by making light incident on the film at an incident angle of 0° using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

Preferable examples of the active energy ray transparent film include a biaxially stretched polyethylene terephthalate resin film, a biaxially stretched polypropylene resin film, and a fluorine-containing resin film.

The bonding surface of the active energy ray-permeable film with the dry coating film may be highly smooth when a high-gloss hard coat is desired. The surface of the active energy ray-permeable film that is attached to the dry coating film may be engraved with an embossed pattern if a hard coat having an embossed pattern is desired.

In the step (4), the laminate obtained in the step (3) is irradiated with an active energy ray, usually from the surface on the side of the active energy ray-permeable film, so that the dry coating film is cured and a hard coat is formed. It is formed.

Examples of the active energy ray used in the above step (4) include ultraviolet rays and ionizing radiation such as electron rays. As the active energy ray used in the step (4), for example, a white active energy ray using a high pressure mercury lamp, a metal halide lamp or the like as a light source can be mentioned. Further, the white active energy rays may be monochromaticized using a filter such as a 365 filter (short-wave cut filter), a 254 filter (long-wave cut filter), and a 300 filter to be used.

The irradiation amount of the active energy ray in the step (4) is appropriately adjusted depending on the curing characteristics of the active energy ray-curable resin composition, the hard coat thickness, the line speed and the like. The above dose is usually 10 to 10000 mJ / cm ^2, preferably from a 50~1000mJ / cm ^2.

The hard coat of the present invention uses any active energy ray-curable resin composition containing an antibacterial agent, preferably using the above-mentioned active energy ray-curable resin composition,
(1') a step of forming a wet coating film of the active energy ray-curable resin composition on at least one surface of the active energy ray transparent film;
(2') a step of predrying the wet coating film obtained in the above step (1') to form a dried coating film;
(3') a step of stacking a film substrate on the surface of the dried coating film obtained in the step (2') and temporarily attaching it; and
(4') a step of irradiating the laminate obtained in the step (3') with an active energy ray to cure the dried coating film;
Can be obtained by a method including.
The method described below has an advantage that it can be applied to a film substrate having low solvent resistance as compared with the method described above. The above-mentioned method has an advantage that it is easier to increase the adhesion between the film base material and the hard coat when the film base material is one of the constituent layers of the decorative sheet, as compared with the method described below. Have.

The method of forming a wet coating film of the active energy ray-curable resin composition in the step (1') is not particularly limited. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. The active energy ray transparent film has been described in the description of the step (3) of the above method.

In the step (2'), the wet coating film obtained in the step (1') is pre-dried to be a dried coating film. In the pre-drying, for example, the time required for passing the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150° C., preferably 50 to 120° C. is about 0.5 to 10 minutes. , Preferably by passing at a line speed of 1 to 5 minutes.

In the step (3'), the film base material is overlaid and temporarily attached onto the surface of the dried coating film obtained in the step (2'). This suppresses oxygen damage in the curing reaction of the active energy ray-curable resin composition due to irradiation with active energy rays. Although not intended to be bound by theory, it is considered that the inactivation of the component (B) due to the interaction between the active energy ray and oxygen is also suppressed. The film substrate has been described in the description of step (1) of the above method.

In the step (4′), the laminate obtained in the step (3′) is irradiated with an active energy ray, usually from the surface on the side of the active energy ray-permeable film, so that the dry coating film is cured and hardened. A coat is formed. The active energy ray and its irradiation dose have been explained in the explanation of the step (4) of the above method.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Measurement method (a) Antibacterial property 1:
According to JIS Z2801:2010, a makeup sheet is used using Staphylococcus aureus (NBRC12732) at a temperature of 23° C., a viable cell count of the test bacterial solution of 6.3×10 ⁵ /mL, and an inoculum of 0.4 mL. The measurement was performed on the hard coat surface of a test piece having a size of 50 mm in length and 50 mm in width taken from the above. The blank was a hard coat-formed surface having a size of 50 mm in length and 50 mm in width, which was sampled from the film base material of the decorative sheet ((α-1) below). As the cover film, a polyethylene film having a length of 40 mm, a width of 40 mm and a thickness of 0.09 mm was used. Further, the cleaning was carried out by lightly wiping the entire surface of the test piece with a pharmacopoeia gauze that had absorbed ethanol having a purity of 99% or more, and then sufficiently drying it.

(B) Antibacterial property 2:
Escherichia coli (NBRC3972, Escherichia coli) was used, and the measurement was performed in the same manner as in (a) Antibacterial activity 1 except that the viable cell count of the test bacterial solution was set to 5.2×10 ⁵ /mL.

(C) Scratch resistance:
The decorative sheet was placed on a Gakushin-type tester (friction tester type 2) according to JIS L0849:2013 so that the hard coat surface was the surface. Subsequently, #0000 steel wool was attached to the friction terminal of the Gakushin-type tester, a load of 500 g was placed thereon, and the surface of the test piece was rubbed back and forth 10 times. The rubbed portion was visually observed and evaluated according to the following criteria.
⊚: No scratches ○: 1 to 5 scratches Δ: 6 to 10 scratches ×: 11 or more scratches

(D) Contamination resistance:
The hard-coated surface of the decorative sheet was spot-contaminated with a red fountain pen bottle ink "INK-30 (trade name)" of Pilot Co., Ltd., and then the contaminated portion was covered with a watch glass and left at room temperature for 24 hours. Then, the contaminated part is wiped and washed with a paper wiper "Kimwipe (trade name)" of Nippon Paper Crecia Co., Ltd., which is sufficiently impregnated with distilled water, until the paper wiper does not get new dirt, Was visually observed and evaluated according to the following criteria.
⊚: No pollution ○: Slight contamination remains Δ: Contamination remains considerably ×: Contamination remains significantly

(E) Color difference:
According to JIS Z 8722:2009, a XYZ coordinate is measured using a spectrocolorimeter “CM600d” manufactured by Konita Minolta Japan Co., Ltd. under a geometric condition c and a condition including a component that causes specular reflection, and L*a*b. * By converting into coordinates, the color when light was incident from the hard coat forming surface side of the following film substrate (α-1) was measured. Similarly, the color when light was incident from the hard coat surface side of the decorative sheet was measured. The CIELAB color difference between the two was calculated based on the 4.3 color difference of JIS Z8781-4:2013. The CIELAB color difference may be preferably 1.6 or less, more preferably 1.2 or less, still more preferably 0.8 or less.

(To) Minimum bending radius (crack resistance):
With reference to the bending formability (method B) of JIS-K6902:2007, a test piece that was conditioned for 24 hours at a temperature of 23° C.±2° C. and a relative humidity of 50±5% was bent at a bending temperature of 23° C.±2° C. and bent. The line was perpendicular to the machine direction of the decorative sheet, and was bent so that the hard coat of the decorative sheet was on the outside so that a curved surface was formed. The minimum bending radius was defined as the radius of the front portion of the molding jig having the smallest radius of the front portion of the forming jigs in which no crack was generated. This "front surface part" means the same term regarding the molding jig in the B method defined in Section 18.2 of JIS K6902:2007. The minimum bend radius may be preferably 50 mm or less, more preferably 40 mm or less, even more preferably 35 mm or less.

(G) Surface smoothness: (Surface appearance):
The hard coat surface of the decorative sheet was applied to the hard coat surface while varying the incident angle of the light of the fluorescent lamp, and the reflection of the fluorescent tube, the surface irregularities and the feeling of cloudiness were visually observed and evaluated according to the following criteria.
A: There is no undulation or scratch on the surface. There is no cloudiness and the reflection of the fluorescent tube is clear.
◯: There is slight undulation. The reflection of the fluorescent tube is clear.
Δ: The reflection of the fluorescent tube is slightly unclear.
X: There are many irregularities on the surface, and the fluorescent tube of the fluorescent lamp becomes unclear.

Raw material (A) polyfunctional (meth)acrylate used:
(A-1) Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
(A-2) An ethanolamine-modified polyether acrylate having 4 acryloyl groups in one molecule, synthesized according to paragraph 0055 of JP2013-064098A.

(B) Antibacterial agent:
(B-1) An antibacterial agent "PBM-Obtain Joint (trade name)" containing diiodomethyl-p-tolylsulfone of MIC Co., Ltd. as an active ingredient. The active ingredient is 3% by mass. Therefore, 1 part by mass of the component (B-1) means that 0.03 parts by mass of the antibacterial agent (B) is mixed.
(B-2) An antibacterial agent containing 2,3,5,6 tetrachloro-4-methylsulfonylpyridine as an active ingredient. The active ingredient is 3% by mass. Therefore, 1 part by mass of the above component (B-2) means that 0.03 parts by mass of the above (B) antibacterial agent was mixed.

(C) Photopolymerization initiator:
(C-1) "IRGACURE TPO (trade name)", an acylphosphine oxide-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF.
(C-2) Acetophenone-based photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl ketone) “IRGACURE184 (trade name)” manufactured by BASF.
(C-3) BASF's acetophenone photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) "IRGACURE 1173 (trade name)".

(D) UV absorber:
(D-1) BASF's cyanoacrylate-based ultraviolet absorber "Ubinal 3039 (trade name)". (2-Ethylhexyl)-2-cyano-3,3-diphenyl acrylate.

(E) Other ingredients:
(E-1) Tosoh Corporation's compound "Coronate HX (trade name)" having two or more isocyanate groups in one molecule.
(E-2) Methyl ethyl ketone.

(Α) Film substrate:
(Α-1) White polyester resin film “HR (WHT) (trade name)” manufactured by RIKEN TECHNOS CORPORATION. Thickness 250 μm.

(Β) Active energy ray transparent film:
(Β-1) A biaxially stretched polyethylene terephthalate resin film having a thickness of 50 μm. Active energy ray transmittance of 82%.

Example 1
(1) 50 parts by mass of the component (A-1), 50 parts by mass of the component (A-2), 2 parts by mass of the component (B-1), 2 parts by mass of the component (C-1), and the component ( C-2) 3 parts by mass, component (D-1) 3 parts by mass, component (E-1) 2 parts by mass, and active energy ray-curable resin composition containing 150 parts by mass of the component (E-2). A wet coating film was formed on one surface of the film substrate (α-1) by using a film Mayer bar type coating device so that the cured product had a thickness of 10 μm.
(2) Next, pass through the drying furnace set at a temperature of 90° C. at a line speed such that the time required to pass from the inlet to the outlet is 1 minute, and the above wet coating film is pre-dried and dried. It was a coating film.
(3) Next, using the apparatus whose conceptual diagram is shown in FIG. 1, the rotating heating drum 3 in which the laminate 1 of the film base material (α-1) and the dry coating film is preheated to a temperature of 30° C. The surface of the laminate 1 opposite to the dry coating film is on the heating drum 3 side, and the active energy ray-permeable film (β-1) 2 is further applied to the dry coating film. The active energy ray transmissive film (β-1) was placed on the surface of the dried coating film and temporarily adhered to the surface of the dried coating film by placing it on the surface of No. 1 and press-bonding it with a press roll 4. Next, the laminate 6 having the film substrate (α-1), the dry coating film, and the active energy ray-permeable film (β-1) in this order was released from the heating drum 3 by the guide roll 5.
(4) Next, using a high-pressure mercury lamp type ultraviolet irradiation device, active energy rays are irradiated from the above-mentioned active energy ray transparent film (β-1) surface side of the laminate 6 under the condition of a cumulative light amount of 240 mJ/cm ^2. Then, the dry coating film was cured to form a hard coat.
(5) Subsequently, the active energy ray-permeable film (β-1) was peeled and removed to obtain a decorative sheet having a hard coat on one surface of the film substrate (α-1). The above tests (a) to (g) were performed. The results are shown in Table 1.

Examples 2-11
Example 1 was carried out in the same manner as in Example 1 except that the formulation of the active energy ray-curable resin composition used was changed as shown in Table 1 or 2. The results are shown in Table 1 or 2.

Example 12
50 parts by mass of the component (A-1), 50 parts by mass of the component (A-2), 2 parts by mass of the component (B-1), 2 parts by mass of the component (C-1), and the component (C-2). ) 3 parts by mass, 3 parts by mass of the component (D-1), 2 parts by mass of the component (E-1), and 150 parts by mass of the component (E-2), an active energy ray-curable resin composition, A wet coating film was formed on one surface of the film substrate (α-1) using a film Mayer bar type coating device so that the thickness after curing was 10 μm. Next, the inside of the drying furnace set at a temperature of 90° C. is passed at a line speed such that the time required to pass from the inlet to the outlet is 1 minute, and the wet coating film is pre-dried to form a dried coating film. did. Next, using a high-pressure mercury lamp type ultraviolet irradiation device, the dry coating film was cured by irradiating the dry coating film with an active energy ray under the condition of an integrated light amount of 240 mJ/cm ² , to form a hard coat. Thus, a decorative sheet having a hard coat on one surface of the film substrate (α-1) was obtained. The above tests (a) to (g) were performed. The results are shown in Table 2.

Examples 13 and 14
Example 12 was carried out in the same manner as in Example 12 except that the formulation of the active energy ray-curable resin composition used was changed as shown in Table 2. The results are shown in Table 2.

The hard coat of the present invention produced by the method of the present invention has an antibacterial activity value of 2 or more and exhibits antibacterial properties. The preferred hard coat of the present invention also has good scratch resistance, stain resistance, color tone, and surface smoothness.

It is a conceptual diagram of the lamination device used in the Example.

1: Laminate having a film substrate and a pre-dried coating film in this order 2: Active energy ray permeable film 3: Heating drum 4: Pressure roll 5: Guide roll 6: Film substrate, pre-dried coating film, and active energy Laminate having linearly transparent film in this order

Claims (10)

(A) polyfunctional (meth)acrylate; and
(B) a halogen element-containing sulfone-based antibacterial agent;
Consisting of an active energy ray-curable resin composition containing
A hard coat having an antibacterial activity value of 2 or more for Staphylococcus aureus measured at a temperature of 23° C. according to JIS Z2801:2010.
The hard coat according to claim 1, wherein the component (B) contains at least one member selected from the group consisting of diiodomethyl-p-tolylsulfone and 2,3,5,6 tetrachloro-4-methylsulfonylpyridine. ..
The hard coat according to claim 1 or 2, wherein the active energy ray-curable resin composition further contains (C) a photopolymerization initiator.
The hard coat according to any one of claims 1 to 3, wherein the component (C) contains (C1) an acylphosphine oxide-based photopolymerization initiator.
The above component (C) is
(C1) Acylphosphine oxide-based photopolymerization initiator 20 to 60 mass% and (C2) acetophenone-based photopolymerization initiator 80 to 20 mass%,
The hard coat according to claim 4, wherein the sum of the component (C1) and the component (C2) is 100% by mass.
The hard coat according to claim 1, wherein the active energy ray-curable resin composition further contains (D) an ultraviolet absorber.
An article comprising the hard coat according to claim 1.
A decorative sheet comprising the hard coat according to claim 1.
An article comprising the decorative sheet according to claim 8.
(1) A step of forming a wet coating film of an active energy ray-curable resin composition on at least one surface of a film base material;
(2) A step of predrying the wet coating film obtained in the above step (1) to form a dried coating film;
(3) a step of stacking an active energy ray transparent film on the surface of the dried coating film obtained in the above step (2) and temporarily pasting it; and
(4) A step of irradiating the laminate obtained in the step (3) with an active energy ray to cure the dried coating film;
including,
Consisting of an active energy ray curable resin composition,
A method for producing a hard coat, wherein the antibacterial activity value of Staphylococcus aureus measured according to JIS Z2801:2010 at a temperature of 23° C. is 2 or more.