阅读说明：本技术 透明性树脂膜、装饰板和装饰板的制造方法 (Transparent resin film, decorative sheet, and method for producing decorative sheet ) 是由 古田哲 藤井亮 中岛智美 根津义昭 茅原利成 住田阳亮 于 2019-09-30 设计创作，主要内容包括：本发明提供在基材所设置的图案层上叠层时能够目视确认密合状态的透明性树脂膜、以及使用该透明性树脂膜得到的装饰板以及该装饰板的制造方法。本发明涉及用于保护在基材的一侧叠层的图案层的透明性树脂膜,上述透明性树脂膜的特征在于,至少具有热塑性树脂层、和在上述图案层上叠层的一侧的外部雾度层。(The invention provides a transparent resin film which can visually confirm the close state when being laminated on a pattern layer arranged on a base material, a decorative plate obtained by using the transparent resin film and a manufacturing method of the decorative plate. The present invention relates to a transparent resin film for protecting a pattern layer laminated on one side of a substrate, the transparent resin film being characterized by comprising at least a thermoplastic resin layer and an outer haze layer laminated on one side of the pattern layer.)

1. A transparent resin film for protecting a pattern layer laminated on one side of a substrate, characterized in that,

the transparent resin film has at least a thermoplastic resin layer and an outer haze layer on the side laminated with the pattern layer.

2. The transparent resin film according to claim 1,

the haze value of the outer haze layer is 4% or more and less than 100%.

3. The transparent resin film according to claim 1 or 2,

a polyethylene terephthalate film having a haze value of 0.1% or less is bonded to the side of the outer haze layer opposite to the thermoplastic resin layer side through a pure water layer, and the haze value in a state in which the back surface is wet, as measured from the thermoplastic resin layer side, is 90% or less.

4. The transparent resin film according to claim 1, 2 or 3,

the outer haze layer has a thickness of 0.5 μm to 20 μm.

5. The transparent resin film according to claim 1,

the transparent resin film has a concavo-convex shape on the side opposite to the side laminated on the pattern layer,

a haze value (1) of 70% or more, the haze value (1) being a haze value obtained by removing a surface haze on a side opposite to a side laminated on the pattern layer,

a haze value (2) is 70% or less, and the haze value (2) is a haze value obtained by removing a surface haze on a side laminated on the pattern layer and a surface haze on a side opposite to the side laminated on the pattern layer.

6. The transparent resin film according to claim 1, 2, 3, 4 or 5,

the thermoplastic resin layer has a surface protective layer on the side opposite to the side laminated on the pattern layer.

7. A decorative plate is characterized in that a decorative plate is provided,

the transparent resin film according to claim 1, 2, 3, 4, 5 or 6, which comprises a substrate, a pattern layer and the transparent resin film in this order in the thickness direction.

8. A method for manufacturing a decorative panel according to claim 7, the method comprising:

forming an adhesive layer on a surface of the transparent resin film on which the pattern layer is to be laminated; and

and a step of bonding the transparent resin film to the pattern layer via the adhesive layer.

Technical Field

The present invention relates to a transparent resin film, a decorative sheet obtained using the transparent resin film, and a method for producing the decorative sheet.

Background

In recent years, due to the widespread use of an ink jet printing method using an ink jet printer, decorative sheets used for building materials, decorative molded articles, and the like can be produced in many types and in small batches, and complicated patterns (characters, numerals, figures, and the like) can be printed as a pattern layer. The inkjet printing method has an advantage that the substrate to be printed is not limited to a film, and can be printed on a flat plate or a substrate having an uneven or curved surface.

However, since the pattern layer printed by the inkjet printing method is usually located on the outermost surface of the substrate, surface properties such as scratch resistance, stain resistance, and weather resistance are insufficient, and a transparent resin film needs to be laminated on the surface of the pattern layer in order to protect the pattern layer.

As such a transparent resin film, for example, patent document 1 discloses a cover film in which a protective layer is provided on one surface of a transparent polypropylene containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer, and an adhesive layer is provided on the other surface.

However, in the case where the conventional transparent resin film is laminated with the pattern layer provided on the base material, even when air is interposed between the pattern layer provided on the base material and the transparent resin film, the amount of change in gloss of the surface of the transparent resin film is small, and it is difficult to visually determine whether or not air is interposed, and when air is interposed, there is a problem that the adhesion force between the pattern layer and the transparent resin film is reduced.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-120255

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a transparent resin film which can visually confirm the close state when being laminated on a pattern layer arranged on a base material, a decorative plate obtained by using the transparent resin film and a manufacturing method of the decorative plate.

Means for solving the problems

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that a transparent resin film which can easily be produced into a product having excellent adhesion to a pattern layer can be obtained by providing an external haze layer on the surface of the side laminated with the pattern layer of a substrate in the transparent resin film and easily judging whether air is interposed or not when the transparent resin film is laminated on the surface of the pattern layer of the substrate, and excluding the product in which adhesion to the pattern layer is decreased by the air interposed, and have completed the present invention.

The present invention is a transparent resin film for protecting a pattern layer laminated on one side of a substrate, the transparent resin film being characterized by comprising at least a thermoplastic resin layer and an outer haze layer laminated on the pattern layer on one side.

The haze value of the outer haze layer is preferably 4% or more and less than 100%.

Preferably, a polyethylene terephthalate film having a haze value of 0.1% or less is attached to the side of the outer haze layer opposite to the thermoplastic resin layer side through a pure water layer, and the haze value in a wet state from the back surface measured from the thermoplastic resin layer side is 90% or less.

The thickness of the outer haze layer is preferably 0.5 μm to 20 μm.

Preferably, the transparent resin film has an uneven shape on a side opposite to a side on which the pattern layer is laminated, and has a haze value (1) of 70% or more and a haze value (2) of 70% or less, the haze value (1) being a haze value obtained by removing a surface haze on a side opposite to the side on which the pattern layer is laminated, and the haze value (2) being a haze value obtained by removing a surface haze on a side on which the pattern layer is laminated and a surface haze on a side opposite to the side on which the pattern layer is laminated.

Preferably, the thermoplastic resin layer has a surface protective layer on a side opposite to a side laminated on the pattern layer.

The present invention also provides a decorative sheet comprising a base material, a pattern layer and the transparent resin film of the present invention in this order in a thickness direction.

The present invention is also a method for manufacturing a decorative sheet according to the present invention, including: forming an adhesive layer on a surface of the transparent resin film on which the pattern layer is to be laminated; and a step of bonding the transparent resin film to the pattern layer via the adhesive layer.

The present invention is also a method for manufacturing a decorative sheet, characterized by comprising: forming an adhesive layer on one surface of the transparent resin film on which the pattern layer is laminated; and a step of bonding the transparent resin film to the pattern layer via the adhesive layer.

Effects of the invention

Since the transparent resin film of the present invention has the external haze layer on the surface of the side laminated on the pattern layer of the base material, when the transparent resin film is laminated on the surface of the pattern layer of the base material, whether or not air is sandwiched can be easily determined by visual observation, and a product whose adhesion force with the pattern layer is lowered by the sandwiched air is excluded, whereby a product having excellent adhesion with the pattern layer can be easily produced.

The decorative sheet of the present invention obtained by laminating such a transparent resin film of the present invention on the surface of the pattern layer of the substrate is easy to form a state in which air is not sandwiched between the pattern layer and the transparent resin film, and is easy to produce a product having excellent adhesion force.

Drawings

Fig. 1 is a schematic cross-sectional view showing a preferred example of the transparent resin film of the present invention.

Fig. 2 is a schematic view showing a cross section of another preferred example of the transparent resin film of the present invention.

Fig. 3 is a schematic cross-sectional view showing a preferred example of the decorative sheet of the present invention.

Detailed Description

< transparent resin film >

The transparent resin film of the present invention will be explained.

In the following description, the upper limit of the lower limit of the numerical range indicated by "-" means "not less than" and (for example, α to β are not less than α and not more than β).

A preferred example of the transparent resin film of the present invention will be described with reference to the drawings.

As shown in fig. 1, the transparent resin film 10 of the present invention has at least a thermoplastic resin layer 11 and an outer haze layer 12.

(thermoplastic resin layer)

The thermoplastic resin constituting the thermoplastic resin layer includes 1 or more of the following resins, and examples thereof include: olefin resins such as polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene), ethylene- α -olefin copolymers, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymers, propylene-butene copolymers, ethylene-vinyl acetate copolymer saponified products, olefin-based thermoplastic elastomers, or mixtures thereof; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1, 4-cyclohexanedimethanol copolymer, and polyester thermoplastic elastomers; acrylic resins such as polymethyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymers, and methyl (meth) acrylate-styrene copolymers; polyamide-based thermoplastic resins such as nylon-6 and nylon-66; polycarbonate resins, polyvinyl chloride, polystyrene, ionomers, and the like. Among them, polypropylene is preferably used from the viewpoint of high tensile strength, excellent chemical resistance and excellent production process.

Wherein, in the present specification, (meth) acrylate means acrylate or methacrylate.

The thermoplastic resin layer may be an unstretched layer, or may be uniaxially or biaxially stretched as necessary.

The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 20 μm at the lower limit, more preferably 500 μm at the upper limit, even more preferably 60 μm at the lower limit, and even more preferably 420 μm or less at the upper limit.

When the thickness of the thermoplastic resin layer is less than 20 μm, the tensile strength may be insufficient to protect the surface of the pattern layer, and when it exceeds 500 μm, the transmittance of the transparent resin film of the present invention may be reduced, which may result in a reduction in the visibility of the pattern layer.

The thermoplastic resin layer is not particularly limited as long as the pattern layer provided on the substrate is visible, and may be colored. In this case, a colorant may be added to the non-halogen thermoplastic resin. As the colorant, a pigment or a dye used in a pattern layer described later can be used.

The thermoplastic resin layer may contain various additives such as a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component (for example, rubber).

When the thermoplastic resin layer has a structure of 2 or more layers, it may be laminated via a transparent adhesive layer or may be heat laminated.

Lamination by a thermal lamination method is preferable from the viewpoint that an adhesive is not required and problems such as peeling due to deterioration of the adhesive are not caused.

As the heat lamination method, a known method such as a melt coextrusion method using a T die can be used.

As the transparent adhesive layer, a known adhesive can be used. Examples thereof include polyurethane, acrylic, polyolefin, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, and the like, and further include butadiene-acrylonitrile rubber, chloroprene rubber, natural rubber, and the like. These adhesives may be used alone, or 2 or more kinds may be used in combination.

The thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 μm, and more preferably about 1 to 5 μm.

After laminating 2 or more thermoplastic resin layers by the thermal lamination method, the haze value can be adjusted by quenching.

The quenching as used herein means that the transparent resin film is cooled at a rate of 200 ℃/sec or more.

As a method for quenching, there is a method of contacting a metal roll cooled to 10 ℃ or lower for several seconds immediately after lamination by a thermal lamination method.

The cooling rate is preferably 230 ℃/sec, more preferably 250 ℃/sec.

The surface (hereinafter also referred to as front surface) of the thermoplastic resin layer opposite to the surface (hereinafter also referred to as back surface) on which the external haze layer is provided may be a smooth surface or may have an uneven shape.

By making the surface smooth, the pattern layer laminated on one surface of the base material can be more clearly displayed.

The smooth surface is a surface having a center line average roughness Ra of 2.0 μm or less as defined in JIS B0601 (1982).

The "surface" means the outermost surface (the side opposite to the side laminated on the pattern layer) of the transparent resin film, and when the transparent resin film has a surface protection layer described later, means the outermost surface on the side having the surface protection layer.

Further, since the surface has the uneven shape, the transparent resin film of the present invention can exhibit a design feeling, and the decorative sheet obtained using the transparent resin film of the present invention can be further excellent in design.

The depth of the formed uneven shape is not particularly limited, but is preferably adjusted so that the center line average roughness Ra, as defined in JIS B0601 (1982), falls within the range of 5 to 20 μm, for example.

The maximum height Rz defined in JIS B0601 (2001) is preferably 20 to 200 μm.

The transparent resin film of the present invention has the above-described uneven shape, and thus the design can be more appropriately improved.

On the other hand, when the maximum height Rz is less than 20 μm, the design may not be sufficiently provided, and when it exceeds 200 μm, the forming property of the uneven shape may be lowered.

The maximum height Rz is preferably 50 μm to 180 μm, more preferably 70 μm to 150 μm.

In the present specification, the center line average roughness Ra defined in JIS B0601 (1982) and the maximum height Rz defined in JIS B0601 (2001) can be obtained by measuring under the following conditions using a surface roughness measuring instrument ("SURFCOM-FLEX-50A", manufactured by tokyo precision corporation).

(measurement conditions)

The number of times of measurement: n-5 (optional 5 dots)

Calculating a standard: JIS' 01

Measurement types are as follows: roughness measurement

Evaluation length: 12.5mm

Cutoff value: 2.5mm

Measuring speed: 0.60mm/s

Filtering type: gaussian

Removing the shape: straight line

λ s value: 8.0 μm

In the case of a wood grain duct or a hairline pattern having a directional uneven shape, the flow direction and the vertical direction thereof are measured, and the maximum height (Rz) is determined as the value of the both.

At this time, the measurement site is measured by selecting a position having a concave-convex shape.

The method for forming the uneven shape on the surface of the thermoplastic resin layer is not particularly limited, and examples thereof include embossing by heat, and a method of transferring the uneven shape on the thermoplastic resin layer by a shaping sheet.

As the embossing by heat, for example, a known method of embossing by a single sheet or a rotary embossing machine can be mentioned.

Examples of the pattern to be embossed include sand grain, hair grain, pear peel pattern, wood grain board guide groove, stone board surface unevenness, cloth surface texture, and ruled line groove.

The temperature at which the embossing is performed is not particularly limited, but a temperature at which so-called embossing recovery reduction in which the uneven pattern disappears at the time of the heat pressure bonding molding is preferable, and the uneven pattern can be transferred at a sheet temperature of 120 to 160 ℃ and 1.0 to 4.0MPa, for example.

In the case where the transparent resin film is subjected to embossing, the embossing may be performed after the formation of a surface protective layer described later, or may be performed before the formation of the surface protective layer.

For example, as a specific embodiment, 1) after forming the thermoplastic resin layer, a surface protective layer is formed, and finally, embossing processing is performed. In another specific embodiment, 2) the surface protective layer may be formed by forming a thermoplastic resin layer, then embossing the thermoplastic resin layer. In another specific embodiment, 3) the surface protective layer may be formed after the thermoplastic resin layer is formed and embossed.

(surface protective layer)

As shown in fig. 2, the transparent resin film 10 of the present invention may be provided with a surface protection layer 14 on the surface of the thermoplastic resin layer 11 opposite to the external haze layer 12, with a primer layer 13 for surface protection layer interposed therebetween.

By having the surface protective layer, the transparent resin film of the present invention has more excellent durability (scratch resistance, stain resistance, weather resistance, and the like), and the surface of the pattern layer can be protected more appropriately, and a decrease in design properties due to damage of the transparent resin film itself of the present invention can be prevented appropriately.

The surface protection layer may have a single-layer structure or may have a multi-layer structure formed of the same or different materials.

The surface protective layer is not particularly limited, and examples thereof include a protective layer composed of a crosslinked cured product of a two-liquid curable resin or an ionizing radiation curable resin composition, and the crosslinked cured product is preferably transparent, may be translucent, and may be colored within a range in which a pattern layer described later can be seen.

Examples of the two-liquid curable resin include a two-liquid curable polyurethane resin, a two-liquid curable polyester resin, and a two-liquid curable epoxy resin.

As the ionizing radiation curable resin composition, for example, an oligomer having a radical polymerizable unsaturated bond or a cation polymerizable functional group in a molecule (hereinafter, also referred to as a prepolymer, a macromer, and the like) and/or a monomer having a radical polymerizable unsaturated bond or a cation polymerizable functional group in a molecule are preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle having energy capable of polymerizing or crosslinking molecules, and is generally an Electron Beam (EB) or ultraviolet ray (UV).

Examples of the oligomer or monomer include compounds having a (meth) acryloyl group, a radical polymerizable unsaturated group such as a (meth) acryloyloxy group, and a cation polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers may be used alone or in combination. Wherein, in the present specification, the above (meth) acryloyl group means an acryloyl group or a methacryloyl group.

As the oligomer having a radical polymerizable unsaturated group in the molecule, for example, an oligomer such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, or triazine (meth) acrylate is preferably used, and a urethane (meth) acrylate oligomer is more preferably used. As the molecular weight, a polymer having a molecular weight of about 250 to 10 ten thousand is usually used.

The monomer having a radical polymerizable unsaturated group in the molecule is preferably a polyfunctional monomer, and more preferably a polyfunctional (meth) acrylate.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, bisphenol a ethylene oxide-modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate { 5-functional (meth) acrylate }, dipentaerythritol hexa (meth) acrylate { 6-functional (meth) acrylate }, and the like. Here, the polyfunctional monomer means a monomer having a plurality of radical polymerizable unsaturated groups.

In the present invention, the ionizing radiation-curable resin composition more preferably contains an ionizing radiation-curable resin component composed of a urethane acrylate oligomer and a polyfunctional monomer, and the ionizing radiation-curable resin component is particularly preferably a urethane acrylate oligomer/polyfunctional monomer (mass ratio) of 6/4 to 9/1. Within the range of the mass ratio, the scratch resistance is more excellent.

Further, if necessary, a monofunctional monomer may be suitably used in addition to the ionizing radiation-curable resin component described above within a range not departing from the object of the present invention.

Examples of the monofunctional monomer include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

When the ionizing radiation-curable resin composition is crosslinked by ultraviolet rays, a photopolymerization initiator is preferably added to the ionizing radiation-curable resin composition.

When the ionizing radiation curable resin composition is a resin system having a radical polymerizable unsaturated group, the photopolymerization initiator may be acetophenone, benzophenone, thioxanthone, benzoin, or benzoin methyl ether, alone or in combination.

In the case where the ionizing radiation-curable resin composition is a resin system having a cationically polymerizable unsaturated group, the photopolymerization initiator may be an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, or the like, used alone or as a mixture. The amount of the photopolymerization initiator is about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation-curable resin component.

Further, various additives may be further added to the ionizing radiation-curable resin composition as needed. Examples of such additives include: thermoplastic resins such as polyurethane resins, polyvinyl acetal resins, polyester resins, polyolefin resins, styrene resins, polyamide resins, polycarbonate resins, acetal resins, vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, acrylic resins, and cellulose resins; lubricants such as silicone resins, waxes, fluorine-containing resins, and the like; ultraviolet absorbers such as benzotriazole and benzophenone; light stabilizers such as hindered amine radical scavengers; colorants such as dyes and pigments.

Further, as the electron beam source of the ionizing radiation, for example, a source which irradiates electrons having an energy of 70 to 1000keV with various electron beam accelerators of the kochrowatt-walton type, van der graaff type, resonance transformer type, insulation core transformer type, linear type, high frequency high voltage type, high frequency type, and the like is used. The dose of the electron beam irradiation is preferably about 1 to 10Mrad, for example.

As the ultraviolet source of the ionizing radiation, for example, a light source such as an ultra-high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light lamp, or a metal halide lamp can be used, and as the wavelength of the ultraviolet, a wavelength region of 190 to 380nm is mainly used.

(undercoat layer for surface protective layer)

The primer layer for surface protection layer preferably contains a binder resin.

The surface protective layer primer layer is preferably transparent, and may be translucent or colored within a range where the pattern layer can be recognized.

Examples of the binder resin include a polyurethane resin, an acrylic-polyurethane resin (acrylic-modified polyurethane resin), an acrylic-polyurethane copolymer resin (block copolymer), a cellulose resin, a polyurethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of polyurethane and nitrocellulose), a polyester resin, and a vinyl chloride-vinyl acetate copolymer resin. When the urethane acrylate oligomer is blended in the ionizing radiation curable resin composition for the surface protective layer, a urethane resin is preferable in view of adhesion to the surface protective layer and efficiency in production.

The thickness of the primer layer for surface protection layer is preferably 0.5 μm to 10 μm. When the thickness is 0.5 μm or more, the adhesion between the transparent resin film of the present invention and a pattern layer described later can be suitably ensured, and when the thickness is 10 μm or less, the transparent resin film of the present invention does not become excessively thick, sufficient transparency can be obtained, and the design of the decorative sheet can be suitably ensured. And also can inhibit adhesion during film formation.

The blocking refers to a phenomenon in which films are not easily separated from each other when a transparent resin film is formed or an adhesive primer is applied and wound into a roll shape and then unwound. The surface protective layer primer layer may contain inorganic fine particles such as silica.

Further, an additive may be added to the surface protective layer primer layer as needed. Examples of the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

(outer haze layer)

The transparent resin film of the present invention has an outer haze layer.

The external haze laminated layer is provided on the back surface of the thermoplastic resin layer to protect the surface of the pattern layer laminated on one surface of the substrate described later.

In the transparent resin film of the present invention, the haze value of the outer haze layer is preferably 4% or more and less than 100%. If the haze value is less than 4%, when the transparent resin film of the present invention is laminated on the surface of the pattern layer, the biting gas may not be visually recognized, and the adhesion may be insufficient. A more preferable lower limit of the haze value of the outer haze layer is 5%, and a further preferable lower limit is 6%.

The haze value of the outer haze layer is a value obtained by subtracting the haze value in a state where the back surface is wet from the haze value of the entire transparent resin film.

The haze of the entire transparent resin film can be measured, for example, by irradiating light from the front side of the external haze layer or the front side of the transparent resin film with a known haze meter.

The haze of the wet back surface can be measured by irradiating the transparent resin film with light from the front side thereof in a state where PET having a haze value of 0.1% or less is adhered to the back surface of the transparent resin film through pure water, and using a known haze meter. This is because the haze value of the transparent resin film from which the haze value of the outer haze layer has been removed can be calculated.

In the transparent resin film of the present invention, a polyethylene terephthalate film having a haze of 0.1% or less is preferably bonded to the side of the outer haze layer opposite to the thermoplastic resin layer side through a pure water layer, and the haze value in a wet state from the back surface measured from the thermoplastic resin layer side is preferably 90% or less.

When the haze value in a wet back surface state measured from the thermoplastic resin layer side exceeds 90%, the transparency of the transparent resin film of the present invention is lowered, and the visibility of the pattern layer may be deteriorated when the decorative sheet is produced.

A more preferable upper limit of the haze value in the state where the back surface is wet is 80%, and a further more preferable upper limit is 60%.

The material constituting the outer haze layer is used for improving adhesion to the pattern layer, and examples thereof include a urethane resin, an acrylic resin, a urethane-acrylic copolymer resin, a cellulose resin, a polyester resin, a vinyl chloride-vinyl acetate copolymer, and the like.

The thickness of the outer haze layer is preferably 0.5 μm to 20 μm. When the thickness is less than 0.5 μm, the adhesion between the substrate and the transparent resin film is insufficient, and when the thickness exceeds 20 μm, the surface and the back of the film come into contact with each other when the transparent resin film is formed into a roll shape, and the adhesion may occur. A more preferable lower limit of the thickness of the outer haze layer is 0.8 μm, a more preferable upper limit is 15 μm, a further preferable lower limit is 1 μm, and a further preferable upper limit is 10 μm.

As a method for making the haze value in the wet state of the back surface within the above range, for example, a method of adjusting the amount of the additive contained in the thermoplastic resin layer, a method of making the thickness of the thermoplastic resin layer thin, or the like can be considered.

In order to further enhance the adhesion between the external haze layer and the thermoplastic resin layer, the surface of the thermoplastic resin layer on which the external haze layer is provided may be subjected to a surface treatment such as corona discharge treatment or plasma treatment. The method and conditions for the surface treatment may be performed by a known method.

Further, an undercoat layer or the like may be formed between the outer haze layer and the base material layer to improve adhesion.

The outer haze layer may have a function as an undercoat layer for improving adhesion to the base material layer or the thermoplastic resin layer. As the primer layer, the same primer layer as the primer layer for the surface protective layer is suitably used.

The outer haze layer may have a single layer or a plurality of layers similar to the thermoplastic resin layer on the surface opposite to the thermoplastic resin layer side.

The external haze layer may contain additives as needed. Examples of the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set according to the product characteristics.

(haze value of transparent resin film)

The haze value (hereinafter also referred to as haze value (1)) of the transparent resin film of the present invention after removing the surface haze on the side opposite to the side laminated on the substrate is preferably 70% or more.

The transparent resin film of the present invention has such a haze, and therefore, the heat absorption rate can be improved, and the formability of the uneven shape is excellent.

In general, the uneven shape formed by embossing or the like disappears due to heat, time, or the like, but the haze value (1) is in a predetermined range, and thus the disappearance of the uneven shape can be suppressed.

The haze value (1) is more preferably 75% or more, and still more preferably 80% or more.

In the present specification, the HAZE is a value measured using DIRECT READING HAZE METER (manufactured by toyoyo seiki).

The haze value (1) can be measured by the following method.

That is, a sheet was prepared by sequentially laminating a transparent resin film, pure water, and a PET film (haze value of 3% or less).

In this case, the pure water is laminated on the side of the transparent resin film having the uneven shape.

The obtained sheet was obtained by measuring a HAZE value from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, using DIRECT READING HAZE METER (manufactured by toyoyo seiki corporation), removing the HAZE value of the PET film, more specifically, subtracting the HAZE value (for example, 3%) of the PET film.

The haze value (hereinafter also referred to as haze value (2)) of the transparent resin film of the present invention, which is obtained by removing the surface haze of the side laminated on the substrate and the surface haze of the side opposite to the side laminated on the substrate, is preferably 70% or less.

The transparent resin film of the present invention has such a haze that a pattern formed on a pattern layer described later is clearly visible, and thus has excellent design properties.

The haze value (2) is more preferably 65% or less, and still more preferably 60% or less.

The haze value (2) can be measured by the following method.

That is, a sheet was prepared by sequentially laminating a PET film (having a haze value of 3% or less), pure water, a transparent resin film, pure water, and a PET film (having a haze value of 3% or less).

The obtained sheet was obtained by measuring a HAZE value from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, using DIRECT READING HAZE METER (manufactured by toyo seiki corporation), and removing the HAZE value of the PET film, specifically, subtracting the individual PET films (for example, the HAZE values of the PET films are 3% and 6% in total), respectively.

(method for producing transparent resin film)

The method for producing the transparent resin film of the present invention is not particularly limited, and examples thereof include a method of laminating the above layers with the transparent adhesive layer or the primer layer for a surface protective layer interposed therebetween, a method of laminating the layers by a heat lamination method, and the like.

As the heat lamination method, a known method such as melt coextrusion using a T die can be used.

< decorative panel >

The transparent resin film of the present invention is used for protecting the pattern layer, and has an external haze layer on the surface of the substrate on the side where the pattern layer is laminated, so that when the transparent resin film is laminated on the surface of the pattern layer of the substrate, whether air is interposed can be easily determined by visual observation, and the adhesion to the pattern layer can be easily made excellent.

Such a decorative sheet having a substrate, a pattern layer, and the transparent resin film of the present invention in this order in the thickness direction is also one embodiment of the present invention.

Next, a preferred example of the decorative sheet of the present invention will be described with reference to fig. 3.

The decorative sheet 20 of the present invention is formed by laminating a pattern layer 24 on one surface of a base material 25 and laminating a transparent resin film 10 of the present invention on the side of the pattern layer 24 opposite to the side having the base material 25.

In addition, the adhesive layer 23 is preferably provided in order to further secure the adhesion between the pattern layer 24 and the transparent resin film 10 of the present invention.

The following describes the respective configurations of the decorative sheet of the present invention.

(substrate)

The material constituting the base material is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, and metal materials. And may also be a composite thereof.

The resin material preferably contains a thermoplastic resin, for example.

As the thermoplastic resin, preferred are: examples of the thermoplastic resin include monomers and copolymers of a polyvinyl resin such as a polyvinyl chloride resin, a polyvinyl acetate resin, or a polyvinyl alcohol resin, a polyolefin resin such as polyethylene, polypropylene, polystyrene, an ethylene-vinyl acetate copolymer resin (EVA), or an ethylene- (meth) acrylic resin, a polyester resin such as a polyethylene terephthalate resin (PET resin), an acrylic resin, a polycarbonate resin, a polyurethane resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), or an acrylonitrile-styrene copolymer, or a mixed resin thereof. Among them, polyolefin resins, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, ionomers, and the like are preferable. The resin material may be foamed.

Examples of the woody material include various raw materials such as fir, cypress, beech, pine, eucalyptus, teak, and horse chest wood. The core material may be any of a flat cut veneer, a wood plywood (including LVL), a particle board, a Medium Density Fiberboard (MDF), a High Density Fiberboard (HDF), a laminated material, and the like, which are made of these raw materials, and a laminated material obtained by laminating them.

Examples of the metal material include iron.

The base material may contain an inorganic compound.

In the case where the substrate has a plurality of thermoplastic resin layers, the types of resins forming the plurality of thermoplastic resin layers may be the same or different, and the thicknesses of the plurality of thermoplastic resin layers may be the same or different.

In the present invention, the base material may have a hollow structure, a slit groove or a through hole may be formed in a part of the base material, or a frame-like structure in which the above materials are combined.

The thickness of the substrate is not particularly limited, and is preferably 0.01mm or more, and more preferably 0.1mm or more and 50mm or less, for example.

The substrate also includes a substantially plate-shaped substrate other than a flat plate, and also includes a substrate having irregularities or a curved surface.

(Pattern layer)

The pattern layer of the substrate is a layer for imparting decorativeness to the decorative sheet of the present invention obtained using the transparent resin film of the present invention, and may be, for example, a masking layer (entire surface printing layer) uniformly colored, a pattern layer formed by printing various patterns using ink and a printing machine, or a layer formed by combining a masking layer and a pattern layer (hereinafter referred to as a pattern layer).

By providing the masking layer, when the base material is colored or uneven in color, the color of the surface can be adjusted by giving an intended hue.

Further, by providing the pattern layer, it is possible to impart a decorative sheet with a grain pattern, a stone pattern simulating the surface of a rock such as a marble pattern (for example, a travertine marble pattern), a cloth pattern imitating a cloth pattern or a cloth-like pattern, a tiled pattern, a bricklaying pattern, or a pattern such as a parquet, or the like obtained by combining and maintaining these patterns. These patterns can be formed by multicolor printing using ordinary process pigments of yellow, red, blue and black colors, or by multicolor printing of special colors by preparing plates of the respective colors constituting the patterns.

As the ink composition used for the pattern layer, a binder resin may be used in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed. The binder resin is not particularly limited, and examples thereof include a polyurethane resin, a vinyl chloride/vinyl acetate copolymer resin, a vinyl chloride/vinyl acetate/acrylic copolymer resin, an acrylic resin, a polyester resin, and a nitrocellulose resin. As the binder resin, any 1 of them may be used alone or 2 or more may be used in combination.

Further, as the colorant, carbon black (ink), inorganic pigments such as iron black, titanium white, antimony white, chrome yellow, titanium yellow, iron oxide red, cadmium red, ultramarine blue, cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, metal pigments composed of scaly foils such as aluminum and brass, and pearl (pearl) pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate are preferably cited.

The thickness of the pattern layer is not particularly limited, and is, for example, preferably 0.1 μm or more, and more preferably 0.5 μm or more and 600 μm or less. When the thickness of the pattern layer is within the above range, the decorative sheet of the present invention can be provided with excellent design properties and can also be provided with a masking property.

However, when the base material itself is designed to have design properties in advance, such as a flat cut veneer, and the base material itself is intended to be used for the design, the base material itself also serves as the pattern layer, and thus the pattern layer does not have to be separately provided.

The external haze layer of the transparent resin film of the present invention is laminated on the surface of the pattern layer laminated on one surface of the substrate to protect the surface of the pattern layer.

Such a decorative sheet comprising a base material, a pattern layer and the transparent resin film of the present invention in this order in the thickness direction is also one aspect of the present invention.

The thickness of the decorative sheet of the present invention is not particularly limited, and is preferably 0.05mm or more, and more preferably 1mm or more and 50mm or less, for example.

The decorative sheet of the present invention may further have a support layer and the like as required. In this case, the coating material may be provided on the back side of the transparent adhesive layer, the primer layer, the support layer, and the like.

The transparent adhesive layer and the primer layer are preferably the same layers as those described in the transparent resin film.

(support layer)

The support layer may be a synthetic resin support layer or a foamed resin support layer, and is preferably present in the lowermost layer of the substrate (on the side opposite to the side on which the transparent resin film is laminated).

The substrate having the support layer further improves the scratch resistance and impact resistance of the decorative sheet.

Examples of the resin constituting the synthetic resin support layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, polyalkylene terephthalate having high heat resistance [ for example, polyethylene terephthalate in which a part of ethylene glycol is substituted with 1, 4-cyclohexanedimethanol, diethylene glycol, or the like, so-called trade name PET-G (manufactured by Eastman Chemical Company) ], polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, amorphous polyester (a-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, and the like. These resins may be used alone or in combination of 2 or more.

The synthetic resin support layer may contain hollow beads.

The kind, particle size, content and the like of the hollow beads are as described in Japanese patent application laid-open No. 2014-188941.

The thickness of the synthetic resin support layer is not particularly limited, but is, for example, preferably 100 to 600 μm, and more preferably 150 to 450 μm.

Examples of the method for forming the synthetic resin support layer include calendering, and molten resin extrusion. Among them, the molten resin extrusion molding is preferable, and for example, the extrusion molding using a T die is more preferable.

The foamed resin support layer may be present in a layer (opposite to the side having the uneven shape) below the synthetic resin support layer.

The foamed resin support layer can be applied to the one described in Japanese patent laid-open publication No. 2014-188941.

(support body)

The substrate may be a support.

The support is not particularly limited, and various kinds of paper, plastic film, wood-based board such as wood, ceramic-based material, and the like can be appropriately selected according to the application. These materials may be used alone, but may be a laminate of any combination of a composite of papers, a composite of papers and a plastic film, or the like.

The paper may be thin paper, kraft paper, titanium paper, or the like. These paper base materials can enhance the interlayer strength between the fibers of the paper base material and between other layers and the paper base material, and in order to prevent fluffing, a resin such as an acrylic resin, styrene butadiene rubber, melamine resin, or urethane resin (impregnation of the resin after paper making or internal filling during paper making) may be further added to these paper base materials. Examples of the paper include inter-paper reinforced paper and resin-impregnated paper.

In addition to these, various papers often used in the field of building materials, such as a pile paper, a paperboard, a base paper for a gypsum board, and a vinyl-based wall paper tube having a vinyl chloride resin layer provided on the surface of the paper, can be cited.

Further, coated paper, double coated paper, parchment paper, cellophane paper, parchment paper, wax paper, japanese paper, and the like, which are used in the business field, general printing, packaging, and the like, may also be used. In addition, woven or nonwoven fabrics of various fibers having an appearance and properties similar to those of paper can also be used as the base material, unlike these papers. Examples of the various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, and synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

In the case where the paper is impregnated with a thermosetting resin, conventionally known thermosetting resins can be widely used. Examples of the thermosetting resin include unsaturated polyester resins, polyurethane resins (including two-pack curable polyurethane), epoxy resins, aminoalkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, silicone resins, and polysiloxane resins.

The layer obtained by impregnating the paper with the thermosetting resin in this manner is also referred to as a thermosetting resin layer. Further, the thermosetting resin may eventually function as a surface protective layer.

As a method for forming the thermosetting resin layer, for example, when the support has a porous base material, a method for impregnating the porous base material with the thermosetting resin can be mentioned.

Impregnation can be performed by supplying the thermosetting resin from either or both of the front surface side and the back surface side of the porous base material. The method is not particularly limited, and examples thereof include: a method of immersing the porous base material in a bath containing a thermosetting resin from the surface on which the release layer is formed or the opposite surface thereof; a method of coating a thermosetting resin on the surface of the porous base material on which the release layer is formed, the opposite surface thereof, or both surfaces thereof by a coating machine such as a kiss coater or a comma coater; a method of ejecting a thermosetting resin onto the surface of the porous base material on which the release layer is formed, the opposite surface thereof, or both surfaces thereof by a spray device, a shower device, or the like.

Specific examples of the resin constituting the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, phenol resins, polyvinyl alcohol, vinyl resins such as ethylene-vinyl alcohol copolymers, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymers (ABS resins), cellulose triacetate, and polycarbonates. Among these, polyolefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable from the viewpoints of various physical properties such as weather resistance and water resistance, printability, suitability for molding, cost, and the like.

The thickness of the support is not particularly limited, and when the support is a plastic film, the thickness is preferably 20 to 200 μm, more preferably 40 to 160 μm, and still more preferably 40 to 100 μm.

When the support is paper, the grammage is preferably 20 to 150g/m²More preferably 30 to 100g/m²。

The shape of the support is not limited to a flat plate shape, and may be a special shape such as a three-dimensional shape.

The support may be subjected to an easy adhesion treatment such as a physical treatment or a chemical surface treatment on one or both sides thereof in order to improve adhesion to the layer provided on the support.

(paper impregnated with phenolic resin)

The decorative sheet may be laminated with a phenol resin impregnated paper as required.

The phenol resin-impregnated paper may be laminated on the surface of the porous base opposite to the side on which the abrasion-resistant layer and the release layer are formed.

The phenolic resin impregnated paper is usually obtained by impregnating a core paper with a phenolic resin at an impregnation rate of about 45 to 60% and a grammage of 150～250g/m²And (3) drying the kraft paper at about 100-140 ℃ to obtain the paper. Commercially available phenol resin-impregnated paper can be used. When the phenol resin-impregnated paper is laminated, the back surface of the porous base material may be subjected to corona discharge treatment or the above-mentioned undercoat layer may be applied to form a back surface undercoat layer, as required.

(sealing layer)

When a base material having an impregnation property such as paper is used as the support, a sealing layer may be provided between the support and the pattern layer.

The sealing layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation-curable resin composition, and more preferably contains a cured product of a thermosetting resin composition.

The content of the cured product of the curable resin composition is preferably 50% by mass or more, more preferably 65 to 95% by mass, of the total solid content of the sealant layer.

Examples of the thermosetting resin composition and the ionizing radiation-curable resin composition of the sealing layer include the same compositions as exemplified for the surface protective layer. The thermosetting resin composition is preferably a two-liquid curable resin of a polyol and an isocyanate, and more preferably a two-liquid curable resin of an acrylic polyol and hexamethylene diisocyanate.

In the sealing layer, particles are preferably contained from the viewpoint of drying suitability and viscosity adjustment. The content of the particles is preferably 5 to 50 mass%, more preferably 5 to 35 mass% of the total solid content of the sealant layer.

The particles of the sealing layer are preferably inorganic particles, and among them, silica is preferable.

The average particle diameter of the particles is preferably 0.1 to 2.0 μm, more preferably 0.2 to 1.5 μm.

< coating Material >

The decorative sheet of the present invention can be used by being laminated on a coating material so as to be in contact with the side opposite to the side having the uneven shape.

On the other hand, when the coating material having the pattern layer is used, the decorative sheet of the present invention can be obtained by laminating the transparent resin film on the coating material having the pattern layer.

Among them, the pattern layer is preferably used.

Examples of the material of the coating material include: wood boards such as wood veneers, crushed aggregate hot pressboards, MDF (medium density fiberboard) and the like; gypsum boards such as gypsum boards and gypsum particle boards; cement boards such as calcium silicate boards, asbestos rock boards, lightweight foamed concrete boards, hollow extruded cement boards, and the like; fiber cement boards such as pulp cement boards, asbestos cement boards, and wood cement boards; ceramic plates such as pottery, porcelain, tile, glass, enamel, etc.; metal plates such as iron plates, galvanized steel plates, polyvinyl chloride sol-coated steel plates, aluminum plates, copper plates, and the like; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, and polycarbonate plates; thermosetting resin plates such as phenol resin plates, urea resin plates, unsaturated polyester resin plates, polyurethane resin plates, epoxy resin plates, and melamine resin plates; a so-called FRP panel obtained by impregnating a resin such as a phenol resin, a urea resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, a melamine resin, or a diallyl phthalate resin with a glass fiber nonwoven fabric, a cloth, a paper, or other various fibrous substrates, curing the impregnated resin, and compounding the cured resin. These may be used alone, or 2 or more kinds thereof may be laminated to form a composite substrate.

The thickness of the coating material is not particularly limited.

The method of laminating the coating material is not particularly limited, and examples thereof include laminating the coating material with the primer layer interposed therebetween, and laminating the coating material with an adhesive.

The adhesive may be appropriately selected from known adhesives according to the type of the coating material and the like. Examples thereof include polyvinyl acetate, polyurethane, acrylic acid, urethane acrylic acid (including copolymers) polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ionomers, and further include butadiene-acrylonitrile rubber, chloroprene rubber, and natural rubber.

< method for manufacturing decorative panel >

Examples of the method for producing the decorative sheet of the present invention include a heat-melting method or a heat-laminating method, and a method for laminating the base material, the pattern layer, and the transparent resin film by using an aqueous adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot-melt adhesive, an adhesive for forming the transparent adhesive layer, or the like.

Preferably, the method for manufacturing the decorative sheet includes a step of forming an adhesive layer on a surface of the transparent resin film on the side where the pattern layer is laminated; and a step of bonding the transparent resin film to the pattern layer via the adhesive layer.

Such a method for manufacturing the decorative sheet of the present invention is also one embodiment of the present invention.

In the transparent resin film, when the uneven shape is provided on the surface on the side opposite to the side on which the pattern layer is laminated, the uneven shape is formed by embossing or the like, but the surface on the side opposite to the surface on which the embossing is performed (the surface on the side on which the pattern layer is laminated) follows the uneven shape on the side on which the embossing is performed, and the uneven shape is slightly provided on the surface on the side opposite to the surface on which the embossing is performed. In this case, air enters the uneven shape on the side where the pattern layer is laminated, which is formed by the transparent resin film, so that so-called gas-trapping occurs, and the design may be degraded.

In the method for manufacturing a decorative sheet according to the present invention, since the step of forming the adhesive layer on the surface of the transparent resin film having the pattern layer is included, the adhesive layer can be made to enter the concave portion having the uneven shape on the surface having the pattern layer, and the occurrence of the biting can be prevented, and the deterioration of the design can be suppressed.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

(example 1)

A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-pack type curable polyurethane resin (thickness: 1 μm) containing isocyanate as a curing agent and silica was applied to one surface of the transparent polypropylene film to form a primer layer for a surface protective layer.

A transparent polypropylene resin (200 μm thick) was laminated on the other surface (the surface not coated with the primer layer for surface protection layer) of the transparent polypropylene film by extrusion heat lamination. After the surface was corona-treated, a two-pack type curable polyurethane resin (thickness: 2 μm) containing isocyanate as a curing agent was applied as an outer haze layer. A urethane (meth) acrylate as an electron beam-curable resin was applied to the surface of the surface protective layer undercoat layer by gravure coating at a coating weight of 15 μm, and then an electron beam was irradiated using an electron irradiation apparatus at an accelerating voltage of 165keV and 5Mrad to form a surface protective layer. Then, heat-absorbing embossing is performed so that the surface comes into contact with an embossing plate to impart a concavo-convex shape, thereby producing a transparent resin film.

Then, the haze value of the entire transparent resin film and the haze in a wet back surface were measured by a haze measuring instrument in accordance with the method described later.

On the other hand, HDF (thickness 3mm) was prepared. A pattern layer was formed on one surface of the HDF using an ink jet printer to a thickness of 2 μm, thereby preparing a substrate.

The surface of the obtained transparent resin film on the side opposite to the side having the uneven shape was coated with a two-pack curable polyester resin (thickness: 50 μm) using isocyanate as a curing agent to form an adhesive layer, and the surface of the obtained transparent resin film on the side opposite to the side having the uneven shape and the surface of the substrate on the side having the pattern layer were laminated via the adhesive layer. Thereafter, 10kg/m of²The pressure of (3) is maintained for 3 days in a normal temperature environment.

(method of measuring haze value)

As a measuring apparatus, DIRECT HAZE Meter (manufactured by Toyo Seiko Co., Ltd.) was used.

Haze value of the entire sheet: the transparent resin film was irradiated with light from the side having the surface with the uneven shape, specifically, from the side of the surface protection layer provided with the uneven shape in example 1, and the haze value was measured.

Haze value in a state of back surface wet: pure water was dropped on the surface of the transparent resin film having the external haze layer, and a PET film (a thickness of lumiror T6050 μm, a haze value of 0.1% by tomi corporation) was laminated without sandwiching air, and in this state, light was irradiated from the surface of the transparent resin film having the uneven shape, specifically, from the surface of the surface protection layer having the uneven shape in example 1, and the haze value was measured.

Haze value of outer haze layer: a haze value in a state where the back surface is wet is subtracted from a haze value of the entire sheet is calculated.

(whether or not biting of breath can be confirmed by visual observation)

Can clearly judge the biting of qi

Can determine qi occlusion by oblique light confirmation

Failure to determine the nature of biting

(design of appearance at the time of sealing)

The laminated design looks very clear

The laminated design looked slightly hazy

The laminated design looked very blurred

The design after lamination was hardly visible (examples 2 to 4, reference example 1)

A transparent resin film was produced in the same manner as in example 1, except that samples having different haze values of the outer haze layer were used as shown in table 1. Thereafter, the same evaluation as in example 1 was performed.

[ Table 1]

In the transparent resin films obtained in examples 1 to 4, the biting gas was easily visually confirmed.

On the other hand, in the transparent resin film obtained in reference example 1, the biting gas was not visually confirmed.

(example 5)

A polypropylene resin (60 μm thick) was prepared, and a primer was applied to one surface (the side laminated on the substrate having the pattern layer) to form an outer haze layer (a two-pack type curable polyurethane resin having 2 μm thick and using isocyanate as a curing agent). A polypropylene resin (60 μm thick) was laminated on the other surface of the polypropylene resin by extrusion heat lamination. Immediately thereafter, the sheet was brought into contact with a metal roll set at 10 ℃ for 0.5 second and cooled (quenched) at 200 ℃/second to obtain a transparent resin layer having an external haze layer formed thereon.

Next, the surface of the transparent resin layer opposite to the surface having the external haze layer was subjected to corona treatment, and then a primer (thickness 2 μm) was applied to form a primer layer for a surface protective layer. After an ionizing radiation-curable resin (coating amount 15 μm) was applied to the surface by gravure coating, an electron irradiation apparatus was used to irradiate an electron beam at an acceleration voltage of 165keV and 5Mrad, thereby forming a surface protective layer.

Then, the side having the surface protective layer was heated by an infrared non-contact heater, and then embossed by hot pressing to obtain a transparent resin film having an uneven shape.

A decorative sheet was obtained by applying a two-pack curable polyester (thickness: 50 μm) to the surface of a transparent resin film having an outer haze layer to form an adhesive layer, and laminating the adhesive layer on a base material (MDF (medium density fiberboard) having a thickness: 3mm) having a pattern layer of 2 μm provided by an ink jet printer.

(example 6)

A decorative sheet was produced in the same manner as in example 5, except that the thickness of the outer haze layer was changed to 1 μm.

(example 7)

A decorative sheet was produced in the same manner as in example 5, except that the thickness of the outer haze layer was changed to 5 μm.

(reference example 2)

A decorative sheet was produced in the same manner as in example 5, except that the thickness of the outer haze layer was changed to 0.5 μm.

(reference example 3)

A polypropylene resin (thickness: 60 μm) was prepared, and a primer (two-pack curable polyurethane resin having a thickness of 2 μm and using isocyanate as a curing agent) was applied to one surface of the polypropylene resin to form an outer haze layer. A polypropylene resin (60 μm thick) was laminated on the other surface of the polypropylene resin by extrusion heat lamination. Immediately thereafter, the sheet was brought into contact with a metal roll at 50 ℃ for 0.5 second, and then left to stand at 25 ℃ and cooled at 50 ℃/second (slow cooling) to obtain a transparent resin layer having an external haze layer formed thereon.

A decorative sheet was produced in the same manner as in example 5, except for the above.

< haze value >

The haze values (1) of the transparent resin films obtained in examples 5 to 7 and reference examples 2 to 3, from which the surface haze on the side opposite to the side laminated on the substrate was removed, and the haze values (2) of the transparent resin films from which the surface haze on the side laminated on the substrate and the surface haze on the side opposite to the side laminated on the substrate were removed were measured by the following methods.

< haze value (1) >

A sheet was prepared by laminating a transparent resin film, pure water and a PET film (Lumiror T60100. mu.m thick, haze value 1.5%, manufactured by Toray corporation) in this order.

In this case, the pure water is laminated on the side of the transparent resin film having the uneven shape.

The HAZE value of the obtained sheet was measured from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, using DIRECT READING HAZE METER (manufactured by toyoyo seiki corporation), and the HAZE value of the PET film was removed, specifically, the HAZE value of the PET film was 1.5% by subtraction, to obtain a HAZE value (1).

< haze value (2) >

A sheet was prepared by laminating a PET film (Lumiror T60100. mu.m thick and haze value of 1.5% manufactured by Toray corporation), pure water, a transparent resin film, pure water, and a PET film (Lumiror T60, 100. mu.m thick and haze value of 1.5% manufactured by Toray corporation) in this order.

The HAZE value of the obtained sheet was measured from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, using DIRECT READING HAZE METER (manufactured by toyoyo seiki corporation), and the HAZE value of the PET film was removed, specifically, by subtracting the HAZE values of the PET films from 1.5% each and 3% in total, to obtain a HAZE value (2).

(shaping Property of concave-convex shape)

The transparent resin films obtained in examples 5 to 7 and reference examples 2 to 3 were measured for the gloss value (G) on the side where the uneven shape was formed (the side having the surface protection layer)_A)。

Subsequently, the transparent resin film was immersed in glycerin at 100 ℃ for 30 seconds, cooled with cold water, and the gloss value (G) of the side on which the uneven shape was formed was measured again_B)。

The formability of the uneven shape was evaluated according to the following evaluation criteria. (G)_A) And (G)_B) The closer the value of (b) is, the less the relief pattern disappears.

The gloss value was measured using a gloss meter (GMX-202 (angle 60 ℃ C.) manufactured by color technical research institute, village) in accordance with JIS Z8741.

++：(G_B)/(G_A) Is more than 80%.

+：(G_B)/(G_A) Is 60% or more and less than 80%.

-：(G_B)/(G_A) Less than 60%.

(design Property)

The decorative sheets obtained in examples 5 to 7 and reference examples 2 to 3 were visually observed and evaluated according to the following criteria.

++: the printed pattern formed on the pattern layer appeared clear.

+: the printed pattern formed on the pattern layer looks slightly discolored (blurred).

-: the printed pattern formed on the pattern layer does not look sharp.

[ Table 2]

	Example 5	Example 6	Example 7	Reference example 2	Reference example 3
						Cooling method	Quenching	Quenching	Quenching	Quenching	Slow cooling
Thickness of outer haze layer (μm)	2	1	5	0.5	2
						Haze value (1) (%)	82	75	86	68	89
Haze value (2) (%)	59	52	66	49	73
						Shaping property of concave-convex shape	++	+	++	-	++
Design of appearance	++	++	+	++	-

It was confirmed that the transparent resin films obtained in examples 5 to 7 were excellent in the shaping property of the uneven shape, and the decorative sheets obtained in the examples were also excellent in the design property.

On the other hand, in reference example 2 in which the haze value (1) was less than 70%, the formability of the uneven shape was poor, and in reference example 3 in which the haze value (2) was more than 70%, the design property was poor.

Industrial applicability

According to the present invention, it is possible to provide a transparent resin film in which whether or not a pattern layer of a base material and the transparent resin film are bonded can be visually confirmed. The decorative sheet of the present invention is suitably used for doors such as partition doors and sliding doors, flooring materials, walls, patios, and various decorative molded articles as building materials for interior decoration.

Description of the symbols

10: the transparent resin film of the present invention; 11: a thermoplastic resin layer; 12: an outer haze layer; 13: a primer layer for a surface protective layer; 14: a surface protection layer; 20: a decorative plate; 23: an adhesive layer; 24: a pattern layer; 25: a substrate.