JPH11277685A - Antibacterial decorative sheet and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain antibacterial capacity, to enhance abrasion resistance and to make feel extremely soft by forming an antibacterial protective layer to a surface by using an antibacterial agent and an ionization radiation curable resin containing a spherical filler made of polycarbonate. SOLUTION: An antibacterial decorative material is produced by forming a pattern layer 12 on a base material sheet comprising paper, plastic or the like by printing and forming an antibacterial protective layer 13 on the pattern layer 12 by gravure coater or the like using an ionizing radiation curable resin 14 containing an inorg. antibacterial agent and a spherical filler made of polycarbonate. Subsequently, the antibacterial protective layer 13 is irradiated with ionizing radiation to perfectly cure the ionizing radiation curable resin to produce an antibacterial decorative sheet 1 having antibacterial capacity, excellent in abrasion resistance or scratch resistance and having soft touch.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet for use in hot and humid places and hospitals and other places requiring a sanitary environment. Antibacterial properties, abrasion resistance and abrasion resistance are imparted to surface decoration materials for furniture and various cabinets, surface decoration of fittings, surface decoration sheets used for vehicle interiors and the like.

[0002]

2. Description of the Related Art Conventionally, interior decoration of buildings, surface decoration of fittings,
As a decorative sheet used for a vehicle interior or the like, a polyvinyl chloride film is used, and a decorative sheet decorated with printing, embossing, or the like has been used (Japanese Patent Publication No. 28-50).
No. 36, Japanese Patent Publication No. 58-14312, etc.). In addition, for indoor water supply (kitchens, bathrooms, washrooms, etc.) and various equipment (electric products, various appliances, etc.) in hot and humid places, hospitals and other places requiring a sanitary environment,
Attempts have been made to impart antibacterial performance to the above-mentioned equipment and the like by using wallpaper and decorative sheets having antifungal and antibacterial properties (disclosed in JP-A-1-313533).

As a method of improving abrasion resistance and abrasion resistance on the surface of a decorative sheet, there is a method of using a hard resin as a binder resin on the surface. However, as a base material, a thin paper or plastic sheet is used. When a substrate having such flexibility is used, there is a problem that the surface resin layer is broken or bent by bending. Therefore, as a method of improving abrasion resistance without lowering the flexibility of the surface resin layer, Japanese Patent Application Laid-Open No. 60-232642 discloses an average particle used as an abrasive such as a sand blast method or a brush polishing method. It is disclosed that a surface resin layer is formed using a paint containing a powder of a natural glass mainly composed of SiO ₂ and Al ₂ O ₃ having a diameter of 1 to 50 μm. In the case of a transfer sheet, an ionizing radiation-curable resin forming a surface protective layer has an average particle diameter of 1 to 5 μm for the purpose of improving abrasion resistance and abrasion resistance of the surface of a transferred body after transfer. It is disclosed that an alumina powder is added to form a protective layer of a transfer sheet.

[0004]

However, when a protective layer of a decorative material is formed using a coating material to which an inorganic filler such as alumina or natural glass powder is added, the resistance of the decorative material is higher than that of a material without the inorganic material. Although the abrasion property is improved, when the inorganic filler is hard and has a polygonal shape with sharp corners, the feeling of touch of the coating film is poor, and it cannot be used for those which emphasize soft feeling. In addition, when used as a flooring material, there is another problem that, when the decorative material comes into direct contact with the decorative material, such as footwear, the object is worn. In addition, when coating a substrate with a gravure roll coating method using an inorganic filler paint, the inorganic filler has a polygonal shape with sharp corners. This was a major problem in sheet processing.

The present invention solves the above problems by using a spherical resin made of a polycarbonate resin as a filler together with an antibacterial agent and an ionizing radiation-curable resin for forming a surface protective layer. The antibacterial performance was able to be given to. In other words, by using a spherical filler made of polycarbonate resin, during coating, without abrasion of the rolls and doctor blades, excellent abrasion resistance and abrasion resistance even on a flexible substrate,
In addition, a surface protective layer having antibacterial performance can be formed. Further, since a resin-made spherical filler is used as the filler, the surface of the decorative sheet has a very soft feel when touched as compared with the inorganic filler.

[0006]

Means for Solving the Problems In order to solve the above problems, the constitution of the antibacterial decorative sheet is as follows. In a decorative sheet having a pattern layer and an antibacterial protective layer formed on the surface of a substrate, the antibacterial protective layer is made of an ionizing radiation curable resin containing an antibacterial agent and a spherical filler. It was a decorative sheet. The antibacterial agent is an inorganic antibacterial agent, and the spherical filler is spherical particles made of polycarbonate, and the average particle size of the antibacterial agent is the highest frequency in the particle size distribution of the spherical filler. The content of the antibacterial agent is 0.25 to 2.5% by weight, and the content ratio of the antibacterial agent and the spherical filler is 1/100 to 15 / The antibacterial cosmetic sheet was characterized by being 100.

[0007] The method for producing the antibacterial cosmetic sheet is as follows. That is, a step of forming a pattern layer by printing on the surface of the substrate, a step of forming an ionizing radiation-curable resin layer containing an antibacterial agent and a spherical filler on the pattern layer, A step of irradiating the resin layer with ionizing radiation to cure the ionizing radiation-curable resin layer to form an antibacterial protective layer. Further, the step of forming an ionizing radiation-curable resin layer containing the antimicrobial agent and a spherical filler, the antimicrobial agent is an inorganic antimicrobial agent, the spherical filler is spherical particles made of polycarbonate, The average particle size of the antibacterial agent is within ± 30% of the most frequent particle size in the particle size distribution of the spherical filler, and the content of the antibacterial agent is 0.25 to 2.5% by weight. And the content ratio of the antibacterial agent and the spherical filler is from 1/100 to 15/10
A method for producing an antibacterial decorative sheet, which is a step of applying using an ionizing radiation-curable resin composition that is 0.

That is, when a pattern layer and an antibacterial protective layer are formed on the surface of a base material to produce an antibacterial decorative sheet, an ionizing radiation-curable resin is used as an antibacterial agent and an inorganic antibacterial agent and polycarbonate as a filler. Add spherical particles made of resin, form an antimicrobial protective layer using this resin composition, and irradiate this with ionizing radiation such as ultraviolet rays or electron beams to cure the coating film, thereby improving abrasion resistance. This is an antibacterial decorative sheet. Further, the average particle size of the antibacterial agent is set within ± 30% with respect to the most frequent particle size in the particle size distribution of the spherical filler, the content is set to 0.25 to 2.5% by weight, and the antibacterial property is protected. The ratio of the content of the antibacterial agent to the content of the spherical filler in the resin forming the layer is 1/100 to 15/100.
By doing so, it is possible to obtain a decorative sheet excellent in abrasion resistance and abrasion resistance and having antibacterial performance without impairing the soft touch.

In the step of forming the ionizing radiation-curable resin layer containing the antibacterial agent and the spherical filler during the production of the above antibacterial decorative sheet, the average particle size of the antibacterial agent is determined according to the particle size distribution of the spherical filler. Coating of the radiation-curable resin composition by adjusting the content ratio of the antibacterial agent and the spherical filler to 1/100 to 15/100 within ± 30% with respect to the particle size of the highest frequency in Can be stable over a long period of time.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is an exemplary antibacterial decorative sheet of the present invention, and is a schematic cross-sectional view when an antibacterial protective layer is formed using an ionizing radiation-curable resin containing an antibacterial agent and a spherical filler. FIG. 2 is a schematic cross-sectional view of another embodiment of the present invention in which an antibacterial decorative sheet is laminated on an adherend via an adhesive to form an antibacterial decorative sheet. FIG. 3 is an explanatory diagram for producing the antibacterial cosmetic sheet of the present invention.
FIG. 4 is an explanatory diagram for producing an antibacterial cosmetic sheet according to Example 1.

As shown in FIG. 1, the antibacterial decorative sheet 1 of the present invention basically comprises a base sheet 11, a picture layer 12,
And an antibacterial protective layer 13 made of an ionizing radiation curable resin 14 containing an antibacterial agent 15 and a spherical filler 16. Further, the antibacterial decorative sheet is manufactured using a thin sheet-like material, and this antibacterial decorative sheet is bonded to another sheet-like adherend 18 via an adhesive layer 17 as shown in FIG.
To the antibacterial decorative sheet 1 in some cases.

That is, a feature of the present invention is that an antimicrobial protective layer is formed from an ionizing radiation curable resin to which an antimicrobial agent and a spherical filler are added, and the ionizing radiation is irradiated to the protective layer to cure the ionizing radiation curable resin. Thus, a protective layer having excellent anti-abrasion and anti-microbial properties is formed on the surface. As the spherical filler, a spherical or elliptical spherical polycarbonate resin spherical filler is used, and the average particle size of the antibacterial agent is within ± 30% of the maximum frequency particle size distribution of the spherical filler. And then
The content ratio of the antibacterial agent and the spherical filler is 1/100 to 15 /
By setting it to 100, the surface protective layer is given a soft touch. Further, the average particle size of the antibacterial agent is set within ± 30% with respect to the most frequent particle size of the particle size distribution of the spherical filler, and the content ratio of the antibacterial agent and the spherical filler is 1/100.
By setting it to １５15/100, the coating liquid can be stably coated for a long time.

Hereinafter, a method for producing the antibacterial cosmetic sheet of the present invention will be described. First, as shown in FIG. 3 (a), using an impregnated paper or a plastic sheet as the base sheet 11, a woodgrain pattern or the like is printed on the base sheet 11 by gravure printing or the like to form a pattern layer 12. I do. next,
As shown in FIG. 3B, a base sheet 1 provided with a picture layer
An ultraviolet curable resin or an electron beam curable resin is used as the ionizing radiation curable resin 14 on the pattern layer 12, and an antibacterial agent 15 and a spherical filler 16 are added thereto. An ionizing radiation curable resin layer containing the antibacterial agent 15 and the spherical filler 16 (the antibacterial protective layer 13 before curing) is formed by coating by a coating method or the like. In the step of forming the ionizing radiation-curable resin layer containing the antibacterial agent and the spherical filler, the average particle size of the antibacterial agent in the ionizing radiation-curable resin composition (coating liquid) is the maximum frequency of the particle size distribution of the spherical filler. Within ± 30% of the particle size of
By setting the ratio to 100 to 15/100, a stable coating can be performed without causing aggregation of the antimicrobial agent during coating and without generating doctor streak. Further, the coating roll and the doctor are not worn.

Further, as shown in FIG. 3C, ionizing radiation 19 such as an ultraviolet ray or an electron beam is irradiated from above on the antibacterial protective layer 13 so that the ionizing radiation-curable resin 14 of the antibacterial protective layer 13 is irradiated. After curing, the antibacterial decorative sheet 1 is prepared as shown in FIG. Obtained antibacterial cosmetic sheet 1
Has antibacterial performance, and the spherical filler added to the ionizing radiation-curable resin is spherical or elliptical spherical particles made of polycarbonate resin, so the surface has a soft touch, abrasion resistance and abrasion resistance Will be excellent.

As the antibacterial agent used in the present invention, an inorganic silver-based antibacterial agent is preferable. The shape of the antibacterial agent is not particularly limited, but is preferably spherical, elliptical, or similar, and has a smooth curved surface. In particular, when emphasis is placed on the softness of the surface, it is desirable to use a spherical particle having few projections and corners and a smooth surface. Examples of inorganic antibacterial agents include zeolite, apatite, glass, silica gel, phosphate, zirconium phosphate and the like disclosed in JP-B-63-54013, JP-A-4-300975, and JP-A-2529574. There is an ion exchanger in which part or all of ion-exchangeable ions are replaced with ions of silver, copper, zinc, tin, lead, mercury, cobalt, ammonium, or the like. Above all, zeolite and zirconium phosphate in which some of the ion-exchangeable ions are replaced with silver ions are desirable from the viewpoint of safety and performance. The content of metal ions supported on zeolite and zirconium phosphate is preferably 0.1 to 15% by weight for silver ions and 0.1 to 8% by weight for copper or zinc ions. There is also an ion exchanger substituted with the above-mentioned metal ion, which is further substituted with an ammonium ion.

In the present invention, an antibacterial agent having an average particle size of 2 to 30 μm is used. The content in the ionizing radiation curable resin is 0.25 to 2.5% by weight.
Used in the range. When the average particle size is less than 2 μm, the proportion of the antibacterial agent exposed to the surface of the coating film of the surface protective layer decreases, and most of the antibacterial agent added to the resin layer does not exhibit the antibacterial effect, and the addition efficiency of the antibacterial agent is reduced become worse. Particle size is 30
If it exceeds μm, coating work becomes difficult,
Also, the flexibility of the coating film is impaired.

Further, in the present invention, when the antibacterial agent is added to the ionizing radiation-curable resin together with the spherical filler, the particle size of the antibacterial agent is ± 30% of the particle size of the spherical filler.
It is necessary to use those within. That is, by setting the average particle size of the antibacterial agent within ± 30% of the maximum particle size in the particle size distribution of the spherical filler, the coating suitability of the ionizing radiation-curable resin containing the antibacterial agent and the spherical filler is improved. And a stable coating can be obtained. If the average particle size of the antibacterial agent is out of the range of ± 30% with respect to the maximum frequency particle size in the particle size distribution of the spherical filler, coating suitability becomes unstable and abrasion of the coating roll and doctor occurs.

The amount of the antibacterial agent added to the ionizing radiation-curable resin is determined by curing the coating film of the ionizing radiation-curable resin by irradiation with ionizing radiation, and then adding the content to the cured coating film (antibacterial protective layer). Is 0.25 to 2.5% by weight.
When the content of the antibacterial agent in the antibacterial agent protective layer is less than 0.25% by weight, a sufficient antibacterial effect is not exhibited. When the content exceeds 2.5% by weight, the antimicrobial effect is not so good even if added more, and it is disadvantageous in cost to increase the antimicrobial agent content. On the other hand, if the content exceeds 2.5% by weight, the adhesiveness between the ionizing radiation-curable resin and the antibacterial agent becomes weak, and the suitability for coating becomes poor. Further, when the content is increased, the transparency of the surface layer becomes poor, and the pattern layer provided thereunder is not easily seen, so that the design effect as a decorative sheet cannot be sufficiently exhibited. Further, the content of the antibacterial agent is 1 to 15% by weight based on the content of the spherical filler.
And the softness of the decorative sheet is hardly impaired.

It is important that the spherical filler used in the present invention has a true spherical shape, an elliptical spherical shape obtained by flattening a sphere, or a shape similar to these, and has a smooth curved surface. The spherical filler can be used as long as it is higher than the hardness of the ionizing radiation-curable resin after curing. In the present invention, a polycarbonate spherical filler having high hardness is preferable. When using a spherical filler to improve the abrasion resistance of the decorative sheet, silica, chromium oxide, iron oxide, diamond, zirconia,
Inorganic spherical particles such as titania and graphite can also be used, but when emphasis is placed on the softness of the surface, organic particles are better.

In the present invention, a spherical filler having an average particle size of 2 to 30 μm and a particle size having a maximum frequency in the particle size distribution within ± 30% of the particle size of the antibacterial agent is used. You. When the particle size is less than 2 μm, the wear resistance and the scratch resistance are not improved. On the other hand, if the particle diameter exceeds 30 μm, it is difficult to coat the coating thinly, and the smoothness of the coating is impaired, which is not preferable.

The amount of the spherical filler added to the ionizing radiation-curable resin is, as in the case of the spherical antibacterial agent, such that the content of the ionizing radiation-curable resin in the cured coating film (antibacterial protective layer) is 50% by weight or less. And the content ratio of the antibacterial agent and the spherical filler must be 1/100 to 15/100. If the content of the spherical filler in the antibacterial protective layer exceeds 50% by weight, the coating operation becomes difficult.

Specific examples of the ionizing radiation-curable resin used in the present invention include radically polymerizable unsaturated groups such as (meth) acryloyl groups and (meth) acryloyloxy groups, and cationic groups such as epoxy groups in the molecule. A composition curable by ionizing radiation, which is obtained by appropriately mixing a monomer, a prepolymer, an oligomer, and / or a polymer having two or more polymerizable functional groups or thiols, is used. Here,
The (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and is used in the same meaning hereinafter. Here, the ionizing radiation means one having an energy quantum capable of polymerizing or crosslinking a molecule in an electromagnetic wave or a charged particle beam, and usually an electron beam or an ultraviolet ray is used. In the present invention, since an inorganic antibacterial agent and a spherical filler made of polycarbonate are added to the ionizing radiation-curable resin, the ultraviolet ray has insufficient transmission power, and the ionizing radiation-curable resin may not be sufficiently cured. An electron beam having a large transmission power is more preferable.

Examples of the prepolymer and oligomer include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, and the like.
Examples include methacrylates such as polyether methacrylate, polyol methacrylate and melamine methacrylate, acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate and melamine acrylate, and cationic polymerization type epoxy compounds. A molecular weight of about 250 to 10,000 is usually used. As the polymer having a radical polymerizable unsaturated group, the degree of polymerization of the polymer is 10,000.
Those having a degree or higher are used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolak type epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, dipentaerythritol tetrathioglycolate, and the like.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate and the like.

Examples of the polyfunctional monomer having a radically polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the monomer used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, Acrylates such as butoxyethyl acrylate, butyl acrylate, methoxy butyl acrylate and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and methacrylic Methacrylic esters such as lauryl acrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzyl acrylate) Amino) ethyl, methacrylic acid (N, N Dimethylamino) methyl, acrylate-2-(N, N-di-diethylamino) substituted amino alcohol esters of unsaturated acids such as propyl, acrylamide, unsaturated carboxylic acid amides such as methacrylamide,
Compounds such as ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate,
Polyfunctional compounds such as propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or
Alternatively, there are polythiol compounds having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol, and the like.

If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 95% by weight or less in order to impart ordinary coating suitability to the ionizing radiation-curable resin. Is preferred.

In selecting a monomer, if the flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not impair coating suitability, or a monofunctional or bifunctional acrylate monomer may be used. A structure having a relatively low crosslink density is used. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of the monomer may be increased within a range that does not hinder coating suitability,
It is preferable to use a tri- or more functional acrylate-based monomer to obtain a structure having a high crosslinking density. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing a monofunctional or difunctional monomer and a trifunctional or higher functional monomer.

Examples of the monofunctional acrylate monomer as described above include 2-hydroxyacrylate, 2-hexyl acrylate, phenoxyethyl acrylate and the like. Examples of the bifunctional acrylate monomer include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate monomer include trimethylolpropane triacrylate,
Pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and the like can be mentioned.

When the ionizing radiation-curable resin is cured by ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

As the material of the base sheet used in the present invention, paper, plastic, metal foil, plate and the like are used.
For example, paper, plastic sheets, sheet-like materials such as non-woven fabric, those having flexibility, in the manufacturing process,
This is preferable because continuous production is possible in a wound state. Normal,
When a sheet is used, the thickness of the sheet is 5 to 2
00 μm is preferred.

As the paper used as the base sheet,
Thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, so-called vinyl wallpaper raw paper in which polyvinyl chloride resin is sol- or dry-laminated with paper, fine paper, coated paper, sulfuric acid paper, glassine paper, parchment paper, Examples include paraffin paper and Japanese paper. Examples of paper-like sheets include nonwoven fabrics and woven fabrics made of inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber; and fibers of synthetic resin such as polyester and vinylon. There is.

Examples of the plastic sheet used as the base sheet include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate. Copolymer, ethylene-vinyl alcohol copolymer, vinyl resin such as vinylon, polyethylene terephthalate, polybutylene terephthalate, polyester resin such as polyethylene naphthalate-isophthalate copolymer, polymethyl methacrylate, polyethyl methacrylate, Acrylic resin such as polyethyl acrylate, polybutyl acrylate, polyamide resin such as nylon 6, nylon 66,
Cellulose resins such as cellulose triacetate and cellophane; synthetic resin sheets such as polystyrene, polycarbonate, polyarylate, and polyimide; and single or laminated films. Also, as the metal foil, aluminum,
Metal foils or sheets of iron, copper, stainless steel, etc .; and composites of the above materials.

On the surface of the substrate sheet used in the present invention, a printing ink, a protective layer (ionizing radiation curable resin layer),
Corona discharge treatment to improve adhesive strength with adhesive,
An easy adhesion treatment such as a plasma treatment and formation of an easy adhesion layer is performed. As the easily adhesive layer (also referred to as a primer layer or an anchor layer), resins such as acrylic resin, urethane resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyurethane resin, chlorinated polyethylene and chlorinated polypropylene are used. Although a coating solution dissolved in a solvent is used, it is particularly preferable to use a polyurethane resin. A coating solution obtained by dissolving the resin in a solvent is applied by a known method and dried to form an easily adhesive layer.

A pattern layer is formed on one side of the base sheet by printing or the like. As the pattern layer, there are a printed pattern by printing, an embossed pattern by embossing, and a concavo-convex pattern by hairline processing.Furthermore, the concave portion of the concavo-convex pattern may be filled with a coloring ink by a known wiping method to form a picture layer. it can. The print pattern layer is wood grain pattern,
Stone pattern, cloth pattern, leather pattern, geometric figure, character, symbol,
There are various abstract patterns or solid printing on the entire surface. The concealing layer of the full solid printing may be omitted depending on the surface condition of the adherend to which the decorative sheet is to be attached.

The ink used for pattern printing varies depending on the material and form of the base sheet. In general, however, it is generally possible to use nitrified cotton, cellulose acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, urethane resin, acrylic resin, or the like. A homopolymer such as a polyester resin or a polymer with another monomer is used as a vehicle, and an ink including a pigment, a coloring agent such as a dye, an extender pigment, a curing agent, an additive, and a solvent is used. .

As the printing of the picture, a normal printing method such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, and ink jet printing can be used. Alternatively, a transfer pattern may be formed by forming a pattern once on a release sheet, and transferring the pattern printing by a transfer printing method from the transfer sheet obtained. In addition, instead of printing patterns, aluminum, chromium, gold, silver, copper and other metals are vacuum deposited,
The pattern layer can also be formed by forming a metal thin film on the base sheet entirely or partially by sputtering or the like.

After the pattern layer is formed on the surface of the base sheet as described above, an antibacterial protective layer is formed by a known coating method using an ionizing radiation-curable resin containing an antibacterial agent and a spherical filler. To form To the ionizing radiation-curable resin to which an antimicrobial agent and a spherical filler are added, a coating composition is prepared by adding a thermoplastic resin, a filler, a photopolymerization initiator, a solvent, and the like, if necessary. The surface of the substrate sheet is coated with the composition by a direct coating method or a transfer coating method. In general, when a material that does not penetrate the coating composition is used as the material of the base sheet, any of a direct coating method or a transfer coating method may be used, but the base material through which the coating composition penetrates may be used. The transfer coating method is more preferable when the sheet or the base sheet having irregularities on the surface, or when it is necessary to provide uniformity in the coating thickness or when it is necessary to make the wear resistance of the protective layer uniform. .

Examples of the direct coating method include gravure coat, gravure reverse coat, gravure reverse offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, dip coat, solid coat by silk screen coat, wire bar coat,
Comma coat, spray coat, float coat, pouring coat, brush coating, spray coat, and the like can be used. Among them, a gravure coat is preferable.

In the transfer coating method, a coating film is once formed on a thin sheet (film) using the above-mentioned coating composition, and the coating film is cured by ionizing radiation such as electron beam or ultraviolet light. Later, the cured coating film is transferred to the surface of the base sheet.

As the ionizing radiation irradiating device for curing the ionizing radiation curable resin, an ultraviolet irradiating device or an electron beam irradiating device is used. As the ultraviolet irradiation device, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used. As the electron beam irradiator, various electron beam accelerators such as Cockloft-Wald type, Bande graph type, Resonant transformer type, Insulated core transformer type or linear type, Dynamitron type and high frequency type can be used.

When the electron beam is applied, the acceleration voltage is 100 to 1000 KeV, preferably 100 to 300 KV.
Irradiation at eV, the absorbed dose is usually 1 to 300 k
It is about Gy. When the absorbed dose is less than 1 kGy, curing of the coating film becomes insufficient, and when the irradiation amount exceeds 300 kGy, the cured coating film and the base sheet are yellowed or damaged. In the case of ultraviolet irradiation, the irradiation amount is 50.
The range is preferably from 1000 mJ / cm ^{2 to} 1000 mJ / cm ² . When the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing of the coating film becomes insufficient, and when the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film turns yellow. As a method of irradiating ionizing radiation, a method of first irradiating ultraviolet rays to cure the ionizing radiation-curable resin to at least the extent that the surface is dry to the touch, and then irradiating with an electron beam to completely cure the coating film There is also.

The abrasion-resistant decorative sheet of the present invention can be laminated on another adherend (or backing material). The object to be adhered is a sheet or film of various materials. The antibacterial decorative sheet of the present invention is used for various applications by laminating on various adherends and performing a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings, floors, etc., household equipment used in bathrooms, washrooms, kitchens, etc., surface makeup of window fittings such as window frames, doors, handrails, furniture such as desks, dining tables, wardrobes, etc. -Can be used for surface decoration of cabinets of OA equipment, interior of vehicles such as automobiles and trains, interior of aircraft, makeup of window glass, etc. Therefore, if the antibacterial decorative sheet cannot be directly adhered to the adherend, it is adhered to the adherend via a suitable easy-adhesion layer or an adhesive layer. However, when the antibacterial cosmetic material can be adhered to the adherend by heat fusion or the like, the easy-adhesion layer or the adhesive layer may be omitted.

As a material to be used as an adherend, either a plate material or a sheet (film), a wood veneer,
Wood plywood, particle board, medium density fiberboard (MD
F), such as wood board, woody board such as wood fiber board, metal such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS,
Phenolic resin, polyvinyl chloride, cellulosic resin,
Resins such as rubber are exemplified.

[0047]

The present invention will be described below in more detail with reference to examples. (Example 1) First, as the base sheet 11, a basis weight of 60 g was used.
/ M ² impregnated paper (“GF-601” manufactured by Kojin Co., Ltd.)
The woodgrain pattern was printed by gravure printing, and the picture layer 12 was formed on the base sheet 11 as shown in FIG. Next, as shown in FIG. 4 (b), the electron beam-curable resin 14 is placed on the pattern layer 12 side of the base sheet 11 provided with the pattern layer.
a) was coated with a coating resin composition (A) having the following composition in which a silver-based antibacterial agent 15 and a spherical filler 16 made of polycarbonate (hereinafter, referred to as PC) were added by a gravure reverse method. An m ² antibacterial protective layer 13 was formed.

Composition of coating resin composition (A) 100 parts by weight of electron beam-curable resin (based mainly on polyether-based urethane acrylate) 2 parts by weight of silicone resin Diameter 3.2μ) 1 part by weight Spherical filler (manufactured by PC; average particle size 2.8μ) 10 parts by weight In addition, “Zeomix AJ-10D” manufactured by Sinanen New Ceramics Co., Ltd. was used as a silver-based antibacterial agent.

In the coating using the coating resin composition (A), the particle size distribution of the particles in the coating liquid is stable over time, and the coating is free from uneven coating and doctor streaks. Could be coated. In addition, since the antibacterial agent and the spherical filler are applied in the same ratio (1:10) even after the elapse of time, the particle size distribution in the coating solution does not change with time, so that even when the long-run coating is performed, a stable high quality is obtained. An antibacterial cosmetic sheet was obtained.

Next, as shown in FIG. 4C, the absorbed dose was reduced on the antimicrobial protective layer 13 made of the above-mentioned electron beam curable resin by using an electron beam irradiation device at an acceleration voltage of 175 keV. Electron beam 20 so that it becomes 50 kGy (kilo gray)
To cure the electron beam curable resin 14a completely to form an antibacterial protective layer 13 on the surface, thereby producing an antibacterial decorative sheet 1 as shown in FIG. 4 (d). In the obtained antibacterial cosmetic sheet, the spherical filler added to the electron beam-curable resin is spherical particles made of polycarbonate, so that the surface has a soft touch and is excellent in abrasion resistance and scratch resistance. Was.

(Example 2) As the base sheet 11, a sheet-reinforced paper having a basis weight of 30 g / m ² (“FLEX-30” manufactured by Sanko Co., Ltd.)
4), a pattern layer 12 was formed on a substrate sheet 11 as shown in FIG. Next, as shown in FIG. 4 (b), a coating resin composition (B) having the following composition was used on the pattern layer 12 side of the base sheet 11 provided with the pattern layer, as in Example 1. Was coated by a gravure reverse method to form an antibacterial protective layer 13 having a coating amount of 25 g / m ² .

Composition of coating resin composition (B) 100 parts by weight of electron beam-curable resin (based on polyether-based urethane acrylate) 2 parts by weight of silicone resin Diameter 7μ) 3 parts by weight Spherical filler (manufactured by PC; average particle size 10μ) 30 parts by weight “Zeomix AJ-10D” manufactured by Sinanen New Ceramics Co., Ltd. was used as the silver-based antibacterial agent. Again,
As in Example 1, the coating was stable and a good-quality antibacterial cosmetic sheet was obtained. Moreover, the surface of the obtained antibacterial cosmetic sheet had a soft touch on the surface and was excellent in abrasion resistance and scratch resistance.

Example 3 A 100 μm-thick colored polyolefin-based resin sheet (“TUFPER” manufactured by Tatsuno Chemical Co., Ltd.) was used as the base sheet 11, and a urethane-based ink (Showa Ink Industries, Ltd.) was used. 4), and a pattern layer 12 was formed on the base sheet 11 as shown in FIG. Next, as shown in FIG. 4B, a gravure reverse method was performed using the same coating resin composition (A) as in Example 1 on the pattern layer 12 side of the base sheet 11 provided with the pattern layer. 20g
/ M ² of the protective layer 13 was formed. Further, similarly to Example 1, the electron beam is irradiated to cure the electron beam curable resin,
An antibacterial decorative sheet 1 as shown in FIG. Next, as shown in FIG.
On the base sheet 11 side, a urethane-based adhesive is applied to form an adhesive layer 17, and an adhesive sheet 18 is laminated on the ABS sheet having a thickness of 100 μm as an adherend 18 via the adhesive layer 17,
An antibacterial decorative sheet 1 as shown in FIG. 2 was produced.

Comparative Example 1 A wear-resistant decorative sheet was prepared in the same manner as in Example 1 except that the following coating resin composition (C) was used as the coating resin composition. And Composition of coating resin composition (C) ・ Electron beam-curable resin 100 parts by weight (based mainly on polyether-based urethane acrylate) ・ 2 parts by weight of silicone resin ・ Spherical filler (average particle diameter of 10 μm made of PC) 10 parts by weight In this case, since no antimicrobial agent was added, stable coating could be performed.

Comparative Example 2 An antibacterial decorative sheet was prepared in the same manner as in Example 1 except that the following coating resin composition (D) was used as the coating resin composition. did. Composition of coating resin composition (D) ・ Electron beam-curable resin 100 parts by weight (based mainly on polyether-based urethane acrylate) ・ 2 parts by weight of silicone resin ・ Silver-based antibacterial agent (average particle size: 1. 5 μ) 2 parts by weight Spherical filler (manufactured by PC; average particle size 2.8 μ) 10 parts by weight Particles aggregated and the coating was not stable. In this case, since the average particle size of the antibacterial agent was less than 2.0 and less than 30% of the particle size of the spherical filler, the particles of the antibacterial agent aggregated to generate a large particle size. That is, at the time of coating, it is applied from small particles in the coating liquid, and with the passage of time, the particle size distribution in the coating liquid changes,
The gloss of the decorative sheet greatly fluctuated, and a high-quality decorative sheet could not be obtained. In addition, stable coating could not be performed due to generation of doctor muscle.

Comparative Example 3 An antibacterial decorative sheet was prepared in the same manner as in Example 1 except that the following coating resin composition (E) was used as the coating resin composition. did. Composition of coating resin composition (E) ・ Electron beam curable resin 100 parts by weight (based mainly on polyether-based urethane acrylate) ・ 2 parts by weight of silicone resin ・ Silver-based antibacterial agent (average particle size of 4. 7 μ) 3 parts by weight Spherical filler (manufactured by PC; average particle size 2.8 μ) 10 parts by weight In this case, similarly to Comparative Example 2, doctor streaks were generated and stable coating could not be performed. In addition, the obtained decorative sheet had reduced scratch resistance.

(Antibacterial test) The antibacterial decorative sheets prepared in Examples 1, 2, and 3 and the abrasion-resistant decorative sheets and antibacterial decorative sheets prepared in Comparative Examples 1, 2, and 3 were subjected to the following method. Was tested for its inhibitory effect. Test strainEscherichia coli IFO 3301
(Escherichia coli, hereafter referred to as E.coli) ・ Methicillin Resistant Staphylococcus aurus (Methicillin Resistant Staphylococcus aurus)
eus) (Methicillin-resistant Staphylococcus aureus; hereinafter referred to as MRSA) Preparation of test bacterial solution In a normal broth medium (manufactured by Eiken Chemical Co., Ltd.) at 35 ° C and 16 ° C.
The culture solution of the test bacterium cultured with shaking for ２０20 hours was diluted 20,000-fold with a sterile phosphate buffer to obtain a bacterial solution. The number of viable bacteria was separately measured for the bacterial solution. Antibacterial test 1 ml of a bacterial solution was dropped on the surface of the antibacterial resin layer of the specimen (antibacterial decorative sheet and decorative sheet), and after storing at 25 ° C for 24 hours, the number of bacteria was measured to determine the antibacterial performance of the specimen. In addition, 1 ml of a bacterial solution was dropped on a petri dish as a control sample, and the same test was performed. Measurement of viable cell count Samples and control samples stored for 24 hours were subjected to SCDLP (Soy
Casein Digest Lecithin Polysorbate) Washed out with 10 ml of medium (manufactured by Nippon Pharmaceutical Co., Ltd.). The viable cell count is measured by
The number of bacteria per specimen and control sample was calculated.

The test results are shown in Table 1. All the samples prepared in the examples had excellent bactericidal effects, and the antibacterial performance of the decorative sheet having the antibacterial performance of the present invention could be demonstrated. That is, the antibacterial cosmetic sheets prepared in Examples 1, 2, and 3 gave E. coli after 24 hours. In E. coli, the initial number of bacteria decreased from 1.2 × 10 ⁵ to 30. In MRSA, the initial number of bacteria decreased from 2.4 × 10 ⁵ to 10 or less.
E. FIG. The sterilization rate of the antibacterial cosmetic sheet against E. coli and MRSA is 99.99% or more. On the other hand, in Comparative Example 1 in which no antibacterial agent was added, E. coli coli and MRS
The number of remaining bacteria 24 hours after A was still 10 ⁴ to 10 ⁵ . In Comparative Example 2 in which the average particle size of the antibacterial agent was 1.5 μm, the bactericidal rate was 99%, but the bactericidal effect was insufficient. That is, in the sterilization of microorganisms, when an object is contaminated with microorganisms, usually, 10 ⁵
Since about 10 ⁶ cells / cm ² of microorganisms are attached, if the sterilization rate is about 99%, it is still 10 ³ to 10 ⁴ cells / cm ^2.
Will remain, and the bactericidal effect is insufficient, and a bactericidal rate of at least 99.99% is required. Therefore, the antibacterial cosmetic sheet of the present invention has an excellent bactericidal effect and can be an effective means for preventing bacterial contamination if used for various equipment in hospitals and other places requiring a sanitary environment. Can be expected.

[0059]

[Table 1] * E.coli: Escherichia coli IFO 3301 * MRSA: Methicillin Resistant Staphylococcus aureus

[0060]

The antibacterial decorative sheet of the present invention has an antibacterial protective layer formed on its surface using an ionizing radiation-curable resin containing an antibacterial agent and a spherical filler made of polycarbonate. Compared to those using a polygonal powder, the antimicrobial performance is imparted, the abrasion resistance and the abrasion resistance are improved, and the feel is very soft. Therefore, even when the decorative material using the decorative sheet comes into direct contact with the object, the object does not wear out,
It can also be used when high wear resistance is required, such as flooring. Further, in the step of manufacturing the antibacterial cosmetic sheet, when coating the substrate sheet with an ionizing radiation curable resin containing an antibacterial agent and a spherical filler by a gravure roll coating method or the like, spherical polycarbonate particles as a filler. The average particle size of the antibacterial agent used is ± 3 with respect to the particle size that is used most frequently in the particle size distribution of the spherical filler.
Since it is within 0%, the coating can always be coated with a constant composition without a change in the particle size distribution in the coating liquid over time, so that coating can be performed in a stable state for a long time. Therefore, a stable and good-quality antibacterial cosmetic sheet can be always obtained. Further, since the gravure roll and the doctor blade are not worn or damaged, the working efficiency can be improved.
When the antibacterial cosmetic sheet of the present invention is used in a place where humans can touch, such as a handrail in a hospital or the like, it is possible to prevent bacteria and mold from being contaminated, and the handrail has a soft touch and a good touch.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an antibacterial decorative sheet according to the present invention, in which an antibacterial protective layer is formed using an ionizing radiation-curable resin containing an antibacterial agent and a spherical filler.

FIG. 2 is a schematic cross-sectional view of another embodiment of the antibacterial decorative sheet of the present invention, in which the antibacterial decorative sheet is laminated on an adherend via an adhesive to form an antibacterial decorative sheet.

FIG. 3 is an explanatory diagram for producing an antibacterial decorative sheet of the present invention.

FIG. 4 is an explanatory view when producing an antibacterial decorative sheet according to Example 1.

[Explanation of symbols]

 Reference Signs List 1 antibacterial decorative sheet 11 base sheet 12 picture layer 13 antibacterial protective layer 14 ionizing radiation curable resin 14a electron beam curable resin 15 antibacterial agent 16 spherical filler 17 adhesive layer 18 adherend 19 ionizing radiation 20 electron beam

Claims (4)

[Claims] 1. A decorative sheet having a pattern layer and an antibacterial protective layer formed on the surface of a substrate, wherein the antibacterial protective layer comprises:
An antibacterial decorative sheet comprising an ionizing radiation-curable resin containing an antibacterial agent and a spherical filler. 2. The antibacterial agent is an inorganic antibacterial agent, the spherical filler is spherical particles made of polycarbonate, and the average particle size of the antibacterial agent is within the particle size distribution of the spherical filler. Within ± 30% of the maximum frequency particle size, the content of the antibacterial agent is 0.25 to 2.5% by weight, and the content ratio of the antibacterial agent and the spherical filler is 1 /
2. The method according to claim 1, wherein the ratio is 100 to 15/100.
The antibacterial cosmetic sheet according to item 1. 3. A step of forming a pattern layer on the surface of the base material by printing, a step of forming an ionizing radiation-curable resin layer containing an antimicrobial agent and a spherical filler on the pattern layer, A step of irradiating the radiation-curable resin layer with ionizing radiation to cure the ionizing radiation-curable resin layer to form an antibacterial protective layer. 4. The step of forming an ionizing radiation-curable resin layer containing the antibacterial agent and a spherical filler, wherein the antibacterial agent is an inorganic antibacterial agent and the spherical filler is a spherical particle comprising polycarbonate. The average particle size of the antibacterial agent is within ± 30% of the most frequent particle size in the particle size distribution of the spherical filler, and the content of the antibacterial agent is 0.25 to 2. The step of applying using an ionizing radiation-curable resin composition which is 5% by weight and has a content ratio of the antibacterial agent and the spherical filler of 1/100 to 15/100. 4. The method for producing the antibacterial decorative sheet according to 3.