JP7032473B2 - Antibacterial hard coat and its manufacturing method - Google Patents

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 cabinets, storage shelves, cupboards, and desks; home appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; or wood, plywood as building materials such as floors, walls, and bathrooms. , On the surface of a base material made of wood-based materials such as laminated lumber, particle board, and hard board; or on the surface of a base material made of metal-based materials such as iron and aluminum, and decorate / cosmetic The one that has been used is 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. In order to impart the above-mentioned characteristics to the decorative sheet, it is widely practiced to form a hard coat made of an active energy ray-curable resin composition on the surface thereof.

In recent years, contamination by various bacteria, especially contamination by strong bacteria such as Staphylococcus aureus, has been highlighted as a serious problem, and in-hospital and in-house infections in hospitals, elderly homes, nurseries, etc. have become a social problem. There is. Therefore, it is strongly required to impart antibacterial properties to articles such as furniture, home appliances, and building materials used in these facilities. However, there is a problem that the hard coat obtained by impregnating the active energy ray-curable resin composition with an antibacterial agent, applying the antibacterial agent, and curing the mixture by irradiation with the active energy ray has almost no antibacterial property. At present, no hard coat made of an active energy ray-curable resin composition has antibacterial properties and sufficient hard coat properties.

Japanese Unexamined Patent Publication No. 59-136166

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

As a result of diligent research, the present inventor has found that the above-mentioned 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) an organic nitrogen-sulfur-based antibacterial agent; , A hard coat having an antibacterial activity value of 2 or more measured at a temperature of 23 ° C.

In the second invention, the above component (B) is used, and the above component (B) is 2-methyl-4-isothiazolin-3-one, 1,2-benzoisothiazolin-3-one, 5-chloro-2-methyl. A first containing one or more selected from the group consisting of -4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 1-hydroxypyridine-2 (1H) -thione. The hard coat described in the invention.

The 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.

The fourth invention is the hard coat according to the third invention, wherein the component (C) contains (C1) an acylphosphine oxide-based photopolymerization initiator.

In the fifth invention, the component (C) is composed of (C1) 20 to 60% by mass of an acylphosphine oxide-based photopolymerization initiator and 80 to 20% by mass of (C2) an acetophenone-based photopolymerization initiator. The hard coat according to the fourth invention, wherein the sum of the above component (C1) and the above component (C2) is 100% by mass.

The 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.

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

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

The ninth invention is an article containing 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 substrate;
(2) A step of pre-drying the wet coating film obtained in the above step (1) to form a dry coating film;
(3) A step of superimposing an active energy ray-permeable film on the surface of the dry coating film obtained in the above step (2) and temporarily attaching the film;
(4) A step of irradiating the laminate obtained in the above step (3) with active energy rays to cure the dry coating film;
including,
Consisting of an active energy ray-curable resin composition,
It is a method for producing a hard coat having an antibacterial activity value of 2 or more measured at a temperature of 23 ° C. for Staphylococcus aureus according to JIS Z2801: 2010.

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 the surface can be suitably used for decoration and makeup of articles such as furniture, home appliances, and building members. Further, articles such as furniture, home appliances, and building materials decorated and decorated with a decorative sheet having a hard coat on the surface of the present invention can be suitably used in hospitals, elderly homes, nurseries, and the like.

The hard coat of the present invention comprises an active energy ray-curable resin composition containing (A) a polyfunctional (meth) acrylate; and (B) an organic nitrogen-sulfur-based antibacterial agent. The hard coat of the present invention is preferably from an active energy ray-curable resin composition containing (A) polyfunctional (meth) acrylate; (B) organic nitrogen-sulfur-based antibacterial agent; and (C) photopolymerization initiator; Become.

(A) Polyfunctional (meth) acrylate:
The 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, so that it can be used for ultraviolet rays, electron beams, etc. It polymerizes and cures with active energy rays to form a hard coat.

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, and 2, Bifunctional reaction containing (meth) acryloyl group such as 2'-bis (4- (meth) acryloyloxypolyethylene oxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropylene oxyphenyl) propane. Sexual monomer; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate. (Meta) acryloyl group-containing tetrafunctional reactive monomer such as (meth) acryloyl group-containing tetrafunctional reactive monomer; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group-containing octafunctional reactive monomer such as tripentaerythritol acrylate; And polymers (oligomers and prepolymers) having one or more of these as constituent monomers can be mentioned. In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

The polyfunctional (meth) acrylate is preferably an ethanolamine-modified polyether (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule, with the total of the components (A) being 100% by mass. % Or more, more preferably 30% by mass or more, still more 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 decorating the article by using the 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. It may be:

As the ethanolamine-modified polyether (meth) acrylate having three or more (meth) acryloyl groups in one molecule, for example, those disclosed as the component (A) of JP2013-064098 should be used. Can be done.

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

(B) Organic nitrogen sulfur antibacterial agent:
The component (B) is an organic nitrogen-sulfur-based antibacterial agent, and is an organic compound having one or more nitrogen atoms and one or more sulfur atoms in one molecule. A preferable typical example of the component (B) is a heterocyclic compound containing one or more nitrogen atoms as a hetero atom, which may have one or more sulfur atoms in one molecule.

Examples of the organic nitrogen-sulfur-based antibacterial agent include 2-methyl-4-isothiazolin-3-one (CAS number 2682-20-4) and 1,2-benzoisothiazolin-3-one (CAS number 2634-33-). 5) 5-Chloro-2-methyl-4-isothiazolin-3-one (CAS number 26472-55-4) and 2-n-octyl-4-isothiazolin-3-one (CAS number 26530-20-1). ) And the like; and a pyrithione-based compound such as 1-hydroxypyridin-2 (1H) -thione; and the like. As the component (B), one kind or a mixture of two or more kinds of these can be used.

The blending amount of the component (B) is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0. It may be 01 parts by mass or more. On the other hand, from the viewpoint of legal regulation, self-regulation of the industry, and economic efficiency, it may be usually 1 part by mass or less, preferably 0.5 part by mass or less, and more preferably 0.1 part by mass or less.

(C) Photopolymerization initiator:
From the viewpoint of improving the curability by the active energy ray, it is preferable that the active energy ray-curable resin composition further contains the above-mentioned 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, and 4-benzoyl. Benzophenone-based photopolymerization initiators such as -4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone; benzoin, benzoin. Benzophenone-based photopolymerization initiators such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzylmethyl ketal; acetophenone-based photopolymerization such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenylketone. 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-based photopolymerization initiators such as acetophenone dimethylketal; Triazine-based photopolymerization initiators; Bisimidazole photopolymerization initiators; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis (2,4,6) -Trimethylbenzoyl) -Acylphosphinoxide-based photopolymerization initiators such as phenylphosphinoxide; Titanocene-based photopolymerization initiators; Oxymuester-based photopolymerization initiators; Oxymuphenyl acetate ester-based photopolymerization initiators; Hydroxyketone-based light Examples thereof include a polymerization initiator; and an aminobenzoate-based photopolymerization initiator.

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

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

The blending amount of the component (C) is usually 10 parts by mass or less, preferably 7 from the viewpoint of preventing the hard coat formed from being yellowed and colored with respect to 100 parts by mass of the component (A). It may be 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 arbitrary component, but from the viewpoint of surely obtaining the effect of using the above 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, more preferably 3 parts by mass or more.

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

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

The blending amount of the component (D) is usually 10 parts by mass from the viewpoint of preventing the hard coat formed from becoming yellowish and colored with respect to 100 parts by mass of the component (A) and from the viewpoint of the curing rate. It may be 10 parts or less, preferably 7 parts by mass or less, and 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 arbitrary component, but from the viewpoint of surely obtaining the effect of using 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 contains two or more isocyanate groups (-N = C = O) in one molecule from the viewpoint of toughness of the formed hard coat and adhesion to the film substrate. The compound to be contained can be further contained. Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexylisocyanate; trimethylolpropaneadductate of tolylene diisocyanate, trimethylolpropaneadductate of hexamethylenediisocyanate, and trimethylol of isophorone diisocyanate. Polyisocyanate 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 type isocyanate of the above polyisocyanate. A cross-linking agent or the like can be given. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more of these can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as needed.

The blending 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. It may be 10 parts by mass 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 surely obtaining the effect of using the compound having two or more isocyanate groups in one molecule, it is usually 0.1 part by mass or more, preferably 0.1 part by mass or more. It may be 0.3 parts by mass or more, more preferably 0.5 parts by mass or more.

The active energy ray-curable resin composition may contain, if desired, an antistatic agent, a surfactant, a leveling agent, a tincture-imparting agent, a contamination inhibitor, a printability improver, an antioxidant, and a weather resistance stabilizer. , A light-resistant stabilizer, a heat stabilizer, an inorganic fine particle, an organic fine particle, an inorganic colorant, and an additive such as an organic colorant can be contained in one or more kinds.

Since the active energy ray-curable resin composition is diluted to a concentration that is easy to apply, it may contain a solvent, if desired. The solvent is particularly limited as long as it does not react with the components (A) to (D) and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like. As the solvent, one kind or a mixture of two or more kinds of these 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 2 or more, preferably 2.5 or more, more preferably 3 or more, still more preferably 3.5, measured at a temperature of 23 ° C. for Staphylococcus aureus according to JIS Z2801: 2010. The above is most preferably 4 or more. The higher the antibacterial activity value, the more preferable. Here, the antibacterial activity value is a value measured according to (a) antibacterial property 1 of the following Example.

Similarly, the hard coat of the present invention has an antibacterial activity value of 2 or more, preferably 2.5 or more, more preferably 3 or more, still more preferably 3 or more, as measured at a temperature of 23 ° C. for methicillin-resistant Staphylococcus aureus according to JIS Z2801: 2010. Is 3.5 or more, most preferably 4 or more. The higher the antibacterial activity value, the more preferable. Here, the antibacterial activity value is a value measured according to (b) antibacterial property 2 of the following Example.

The hard coat of the present invention has the above-mentioned antibacterial property, and any active energy ray-curable resin composition containing an antibacterial agent is used, preferably the above-mentioned active energy ray-curable resin composition. (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 substrate using a material;
(2) A step of pre-drying the wet coating film obtained in the above step (1) to form a dry coating film;
(3) A step of superimposing an active energy ray-permeable film on the surface of the dry coating film obtained in the above step (2) and temporarily attaching the film;
(4) A step of irradiating the laminate obtained in the above step (3) with active energy rays to cure the dry coating film;
Can be obtained by a method including.

The film base material used in the above step (1) is not particularly limited, and any resin film can be used as the film base material. Examples of the resin film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylicimide resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene. Resins; Cellulosic resins 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- Ethylene / propylene / styrene copolymer and styrene resin such as styrene / ethylene / ethylene / propylene / styrene copolymer; polyvinyl chloride resin; polyvinylidene chloride resin; fluororesin containing polyvinylidene fluoride; In addition, resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulphon, and polyethersulphon; can be mentioned. These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, it includes a laminated film in which two or more layers of one or more of these are laminated.

When the film base material is one of the constituent layers of the decorative sheet, the wet coating film forming surface of the film base material is corona discharged from the viewpoint of improving the adhesion between the film base material and the hard coat. It may be one that has been subjected to an easy adhesion treatment such as treatment or formation of an anchor coat.

When the film base material is one of the constituent layers of the decorative sheet, the thickness of the film base material is not particularly limited, but may be usually 20 μm or more, preferably 30 μm or more from the viewpoint of handleability. From the viewpoint of design, 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, and more preferably 300 μm or less.

When the hard coat formed on the surface of the film substrate is transferred to another film substrate and used, the wet coating film-forming surface of the film substrate is easily peeled off. It's okay.

When the hard coat formed on the surface of the film substrate is transferred to another film substrate and used, the thickness of the film substrate is not particularly limited, but from the viewpoint of handleability, it is usually 20 μm or more. 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 for forming the wet coating film of the active energy ray-curable resin composition in the step (1) is not particularly limited. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

In the above step (2), the wet coating film obtained in the above step (1) is pre-dried to become a dry coating film. In the pre-drying, for example, it takes about 0.5 to 10 minutes to pass the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150 ° C, preferably a temperature of 50 to 120 ° C. This can be done by passing at a line speed, preferably 1 to 5 minutes.

In the above step (3), the active energy ray permeable film is superposed on the surface of the dry coating film obtained in the above step (2) and temporarily attached. As a result, oxygen damage in the curing reaction due to irradiation with the active energy ray of the active energy ray-curable resin composition is suppressed.

Although not bound by the theory, the hard coat of the present invention has the above-mentioned antibacterial and anti-viral properties and has sufficient hard coat properties by being temporarily pasted on the surface of the above-mentioned dry coating film. By blocking oxygen from the active energy ray-permeable film, the oxygen damage in 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 of temporarily adhering 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 above step (2) is placed on a rotating heating drum 3 preheated to a desired temperature on the opposite side of the above-mentioned dry coating film of the laminate 1 obtained in the above step (2). The surface of the film is placed so as to be on the heating drum 3 side, and the active energy ray permeable film 2 is placed on the surface of the dry coating film and crimped by the crimping roll 4. The laminated body 6 in which the active energy ray-permeable film is laminated and temporarily attached on the surface of the dry coating film is released from the heating drum 3 by the guide roll 5 and sent to the step (4).

The active energy ray-permeable film is a film having an active energy ray transmittance 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 nanometers with respect to the integrated area of the transmission spectrum assuming that the transmittance of the active energy rays in the entire range of wavelengths of 200 to 600 nanometers is 100%. It is a ratio of the integrated area of the transmission spectrum of a line, and is a value measured by incident light on a film at an incident angle of 0 ° using a spectrophotometer "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation.

Preferred examples of the active energy ray-permeable film include a biaxially stretched polyethylene terephthalate resin film, a biaxially stretched polypropylene resin film, and a fluororesin-containing resin film.

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

In the step (4), the laminated body obtained in the step (3) is usually irradiated with active energy rays from the surface on the side of the active energy ray permeable film, 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 an electron beam. Examples of the active energy ray used in the above step (4) include a white active energy ray using a high-pressure mercury lamp, a metal halide lamp, or the like as a light source. Further, the white active energy ray may be monochromaticized by using a filter such as a 365 filter (short wave cut filter), a 254 filter (long wave cut filter), and a 300 filter.

The irradiation amount of the active energy ray in the step (4) is appropriately adjusted depending on the curing characteristics, the hard coat thickness, the line speed, and the like of the active energy ray-curable resin composition. The irradiation amount may be usually 10 to 10000 mJ / cm ² , preferably 50 to 1000 mJ / 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 an active energy ray-curable resin composition on at least one surface of an active energy ray-permeable film;
(2') A step of pre-drying the wet coating film obtained in the above step (1') to form a dry coating film;
(3') A step of superimposing a film base material on the surface of the dry coating film obtained in the above step (2') and temporarily pasting it;
(4') A step of irradiating the laminate obtained in the above step (3') with active energy rays to cure the dry 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. Compared with the method described later, the above-mentioned method has an advantage that it is easy to improve 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. Have.

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

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

In the above step (3'), the film base material is superposed on the surface of the dry coating film obtained in the above step (2') and temporarily attached. As a result, oxygen damage in the curing reaction due to irradiation with the active energy ray of the active energy ray-curable resin composition is suppressed. Moreover, although it is not intended to be bound by theory, it is considered that the inactivation of the above 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 laminated body obtained in the step (3') is usually irradiated with active energy rays from the surface on the side of the active energy ray permeable film, and the dry coating film is cured and hardened. A coat is formed. The active energy rays and the irradiation amount thereof have been described in the description of the step (4) of the above-mentioned 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 cosmetic sheet using Staphylococcus aureus (NBRC12732) under the conditions of a temperature of 23 ° C., a viable cell count of 1.4 × 10 ⁴ / mL of the test bacterial solution, and an inoculation amount of 0.4 mL. The hard-coated surface of the test piece having a size of 50 mm in length and 50 mm in width was measured. The blank was a hard coat forming surface having a size of 50 mm in length and 50 mm in width collected from a film base material (hereinafter referred to as (α-1)) of a decorative sheet. 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. The cleaning was carried out by lightly wiping the entire surface of the test piece with a Japanese gauze having absorbed ethanol having a purity of 99% or more, and then sufficiently drying the test piece.

(B) Antibacterial property 2:
Using methicillin-resistant Staphylococcus aureus (IID1677), the measurement was performed in the same manner as in (a) antibacterial property 1 above, except that the viable cell count of the test bacterial solution was 1.0 × 10 ⁴ / mL. ..

(C) Scratch resistance:
The decorative sheet was placed on a JIS L0849: 2013 Gakushin type tester (friction tester type 2) so that the hardcourt surface was on the surface. Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type tester, a load of 500 g was applied and the surface of the test piece was rubbed 10 times. The friction points were visually observed and evaluated according to the following criteria.
◎: No scratches ○: 1 to 5 scratches △: 6 to 10 scratches ×: 11 or more scratches

(D) Contamination resistance:
After spot-contaminating the hard-coated surface of the decorative sheet with Pilot's red fountain pen bottle ink "INK-30 (trade name)", the contaminated part was covered with a watch glass and left at room temperature for 24 hours. Next, the contaminated part was wiped and washed with a paper wiper "Kim Wipe (trade name)" of Nippon Paper Crecia Co., Ltd., which was sufficiently impregnated with distilled water, until the paper wiper was not newly soiled. Was visually observed and evaluated according to the following criteria.
◎: No contamination ○: Slight contamination remains △: Contamination remains considerably ×: Contamination remains remarkably

(E) Color difference:
In accordance with JIS Z 8722: 2009, the XYZ coordinates were measured using the spectrocolorimeter "CM600d" of Konita Minolta Japan Co., Ltd. under the conditions of geometric condition c and the condition including the component that becomes mirror surface reflection, and this was measured as L * a * b. * By converting to coordinates, the color when light was incident from the hard coat forming surface side of the film substrate (α-1) below 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.

(F) Minimum bending radius (crack resistance):
Bending at a bending temperature of 23 ° C ± 2 ° C for a test piece whose condition was adjusted for 24 hours at a temperature of 23 ° C ± 2 ° C and a relative humidity of 50 ± 5% with reference to the bending formability (method B) of JIS-K6902: 2007. The line was set at a right angle 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. Among the molded jigs in which cracks did not occur, the radius of the front part of the molded jig having the smallest radius of the front part was set as the minimum bending radius. This "front portion" means the same term for a molded jig in method B as defined in JIS K6902: 2007, paragraph 18.2. The minimum bending radius may be preferably 50 mm or less, more preferably 40 mm or less, still more preferably 35 mm or less.

(G) Surface smoothness: (Surface appearance):
While applying the hard-coated surface of the decorative sheet at various angles of incidence of the light of the fluorescent lamp, the reflection of the fluorescent tube, the unevenness of the surface, and the feeling of cloudiness were visually observed and evaluated according to the following criteria.
⊚: There are no waviness or scratches on the surface. There is no cloudiness, and the reflection of the fluorescent tube is clear.
◯: There is a slight swell. The reflection of the fluorescent tube is clear.
Δ: The reflection of the fluorescent tube becomes a little unclear.
X: There are many irregularities on the surface, and the fluorescent tube of the fluorescent lamp becomes unclear.

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

(B) Antibacterial agent:
(B-1) As active ingredients, 2-methyl-4-isothiazolin-3-one is 2.5% by mass, 1,2-benzoisothiazolin-3-one is 2.5% by mass, and 1-one in the solvent. An antibacterial agent containing 4.0% by mass of hydroxypyridine-2 (1H) -thione. Therefore, 1 part by mass of the above component (B-1) means that 0.09 part by mass of the above (B) antibacterial agent is added.

(C) Photopolymerization initiator:
(C-1) BASF's acylphosphine oxide-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) "IRGACURE TPO (trade name)".
(C-2) BASF's acetophenone-based photopolymerization initiator (1-hydroxy-cyclohexyl-phenylketone) "IRGACURE184 (trade name)".
(C-3) BASF's acetophenone-based photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropane-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-diphenylacrylate.

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

(Α) Film substrate:
(Α-1) White polyester resin film "HR (WHT) (trade name)" of RIKEN TECHNOS CORPORATION. Thickness 250 μm.

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

Example 1
(1) 50 parts by mass of the above component (A-1), 50 parts by mass of the above component (A-2), 2 parts by mass of the above component (B-1), 2 parts by mass of the above component (C-1), the above component ( C-2) Active energy ray-curable resin composition containing 3 parts by mass of the above component (D-1), 2 parts by mass of the above component (E-1), and 150 parts by mass of the above 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 thickness after curing was 10 μm.
(2) Next, the inside of the drying furnace set to 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 and dried. It was made into a coating film.
(3) Next, using the apparatus shown in the conceptual diagram in FIG. 1, a rotating heating drum 3 in which the laminate 1 of the film substrate (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 placed 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-permeable film (β-1) was overlaid on the surface of the dry coating film and temporarily attached by crimping the film on the surface of the dry coating film. Next, the laminate 6 having the film base material (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, the active energy rays are irradiated from the surface side of the active energy ray-transmitting film (β-1) of the laminated body 6 under the condition of an integrated 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 off 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 2-10
The procedure was the same 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 11
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 of the above component (D-1), 2 parts by mass of the above component (E-1), and 150 parts by mass of the above component (E-2). A film Mayer bar type coating device was used on one surface of the film substrate (α-1) to form a wet coating film so that the thickness after curing was 10 μm. Next, the wet coating film was pre-dried in a drying oven set to a temperature of 90 ° C. at a line speed such that the time required to pass from the inlet to the outlet was 1 minute, and the wet coating film was pre-dried to form a dry coating film. did. Next, the dry coating film was cured by irradiating the dry coating film with active energy rays under the condition of an integrated light amount of 240 mJ / cm ² using a high-pressure mercury lamp type ultraviolet irradiation device to form a hard coat. In this way, a decorative sheet having a hard coat on one side of the film base material (α-1) was obtained. The above tests (a) to (g) were performed. The results are shown in Table 2.

Example 12
The procedure was the same as in Example 11 except that the composition 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. Further, the preferable 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 stacking apparatus used in an 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: Crimping roll 5: Guide roll 6: Film substrate, pre-dried coating film, and active energy Laminated body having a line-transmitting film in this order

Claims (11)

(A) Polyfunctional (meth) acrylate; and
(B) Organic nitrogen-sulfur antibacterial agent;
Consists of an active energy ray-curable resin composition containing
For Staphylococcus aureus, the antibacterial activity value measured at a temperature of 23 ° C. is 2 or more according to JIS Z2801: 2010; and the CIELAB color difference is 1.2 or less .
Here, for the CIELAB color difference, the XYZ coordinates are measured using the spectrocolorimeter "CM600d (trade name)" of Konita Minolta Japan Co., Ltd. under the conditions including the geometric condition c and the component that becomes the mirror surface reflection in accordance with JIS Z8722: 2009. , The color of the hard coat forming surface of the white polyester resin film "HR (WHT) (trade name)" with a thickness of 250 μm of Riken Technos Co., Ltd. calculated by converting this into L * a * b * coordinates, and the above white color. It is calculated from the color of the hard coat surface formed on the surface of the polyester resin film so that the thickness after curing is 10 μm, in accordance with the 4.3 color difference of JIS Z8781-4: 2013.
The hard coat according to claim 1, wherein the active energy ray-curable resin composition further contains (C) a photopolymerization initiator.
100 parts by mass of the above component (A) polyfunctional (meth) acrylate;
The above component (B) organic nitrogen sulfur-based antibacterial agent 0.001 to 1 part by mass; and
The hard coat according to claim 2, which contains 0.1 to 10 parts by mass of the component (C) photopolymerization initiator.
The hard coat according to claim 2 or 3, wherein the component (C) contains (C1) an acylphosphine oxide-based photopolymerization initiator.
The above component (C) is
It is composed of 20 to 60% by mass of (C1) acylphosphine oxide-based photopolymerization initiator and 80 to 20% by mass of (C2) acetophenone-based photopolymerization initiator.
The hard coat according to any one of claims 2 to 4, wherein the sum of the above component (C1) and the above component (C2) is 100% by mass.
The hard coat according to any one of claims 1 to 5, wherein the active energy ray-curable resin composition further contains (D) an ultraviolet absorber.
The hard coat according to claim 6, wherein the component (D) ultraviolet absorber contains a cyanoacrylate-based ultraviolet absorber.
The above component (B) organic nitrogen-sulfur antibacterial agent is 2-methyl-4-isothiazolin-3-one, 1,2-benzoisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one. One of claims 1 to 7, which comprises one or more selected from the group consisting of on, 2-n-octyl-4-isothiazolin-3-one, and 1-hydroxypyridin-2 (1H) -thione. The hard coat described in.
An article containing the hard coat according to any one of claims 1 to 8.
A decorative sheet containing the hard coat according to any one of claims 1 to 8.
An article containing the decorative sheet according to claim 10.

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