JP6834315B2 - Decorative sheet, manufacturing method of decorative sheet, decorative resin molded product, and manufacturing method of decorative resin molded product - Google Patents

Description

The present invention relates to a decorative sheet, a method for producing a decorative sheet, a decorative resin molded product, and a method for producing a decorative resin molded product.

Conventionally, decorative resin molded products in which a decorative sheet is laminated on the surface of the resin molded product have been used for vehicle interior / exterior parts, building material interior materials, home appliance housings, and the like. In the production of such a decorative resin molded product, a molding method in which a decorative sheet to which a design has been given in advance is integrated with the resin by injection molding or the like is used. As a typical example of such a molding method, a decorative sheet is molded into a three-dimensional shape in advance by a vacuum forming mold, the decorative sheet is inserted into an injection molding mold, and a fluid resin is injected into the mold. This includes an insert molding method in which the resin and the decorative sheet are integrated.

In a decorative sheet used in such an insert molding method or the like, a base material layer may be provided as a support film on the innermost back surface in direct contact with the resin injected in injection molding. The base material layer exerts a function of imparting rigidity to the decorative sheet to maintain its shape.

Further, there is known a technique for manufacturing a decorative resin molded product having a smooth surface and a visual three-dimensional effect by providing an uneven shape on the back surface or the inside of such a decorative sheet. As a decorative sheet used for such a purpose, for example, a sheet having a transparent base film and a colored layer and embossing from the side of the colored layer to the side of the transparent base film is known. (Patent Document 1). However, in the decorative sheet, the uneven shape is exposed on the back surface of the sheet, and the injection resin is directly laminated on the uneven surface, so that there is a problem that the uneven shape is likely to disappear due to heat pressure during injection molding. ..

In Patent Document 1, as a countermeasure to the problem that the uneven shape is likely to disappear due to heat pressure during injection molding, the uneven surface is filled by further laminating a support film on the uneven surface, and the back surface of the decorative sheet is covered. A flattened configuration has also been proposed. However, in the case of a decorative sheet having such a configuration, a gap is likely to occur between the support film and the concave-convex concave portion (the portion convex on the front side of the decorative sheet). Then, such voids may expand during vacuum forming or injection molding, and the expansion may cause the transparent base film to protrude toward the surface side, impairing the surface smoothness of the decorative sheet.

Japanese Unexamined Patent Publication No. 2012-213929

A main object of the present invention is to provide a decorative sheet capable of imparting a visual three-dimensional effect to a resin molded product while having a smooth surface. A further object of the present invention is to provide a method for producing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for producing the decorative resin molded product.

The present inventors have made diligent studies to solve the above problems. As a result, it is composed of a laminate having at least a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order, and the transparent resin film is smooth on both sides and is on the intermediate layer side of the base material layer. The surface of the decorative sheet is provided with an uneven shape, and the concave portion of the uneven shape is filled with at least an intermediate layer. The decorative sheet has a smooth surface but gives a visual three-dimensional effect to the resin molded product. It was found that it can be preferably applied.

The present invention is an invention completed by further studying based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. It is composed of a laminate having at least a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
The intermediate layer is composed of a cured product of an ionizing radiation curable resin composition.
The transparent resin film has smooth surfaces on both sides.
The surface of the base material layer on the intermediate layer side is provided with an uneven shape.
A decorative sheet in which the uneven concave portion is filled with at least the intermediate layer.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface of the intermediate layer on the adhesive layer side is smooth.
Item 3. A colored layer is further provided between the base material layer and the intermediate layer.
Item 3. The decorative sheet according to Item 1 or 2, wherein a part of the recess is filled with the colored layer.
Item 4. A primer layer is further provided between the base material layer and the intermediate layer.
Item 3. The decorative sheet according to any one of Items 1 to 3, wherein a part of the recess is filled with the primer layer.
Item 5. Item 2. The decorative sheet according to any one of Items 1 to 4, wherein the base material layer has the uneven shape in which the depth of the recess is 5 μm or more and 100 μm or less.
Item 6. Item 2. The decorative sheet according to any one of Items 1 to 5, wherein the thickness of the intermediate layer located on the flat portion of the base material layer is 1 μm or more and 30 μm or less.
Item 7. It is composed of a laminate including at least a molding resin layer, a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
The intermediate layer is composed of a cured product of an ionizing radiation curable resin composition.
The transparent resin film has smooth surfaces on both sides.
The surface of the base material layer on the intermediate layer side is provided with an uneven shape.
A decorative resin molded product in which the uneven concave portion is filled with at least the intermediate layer.
Item 8. It is a method for producing a decorative sheet composed of a laminate including a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
At least step 1 of preparing a sheet having a base material layer,
Step 2 of forming an uneven shape on the surface of one side of the sheet,
Step 3 of applying the ionizing radiation curable resin composition so as to fill at least a part of the uneven concave portion.
Step 4 of curing the ionizing radiation curable resin composition to form an intermediate layer,
Step 5 of laminating an adhesive layer and a transparent resin film layer having smooth both sides on the intermediate layer.
A method of manufacturing a decorative sheet.
Item 9. Item 8. The method for producing a decorative sheet according to Item 8, further comprising a step of pressing the surface of the intermediate layer between the steps 4 and 5 to smooth the surface of the intermediate layer.
Item 10. A step of vacuum forming the decorative sheet according to any one of Items 1 to 6 with a vacuum forming mold to obtain a molded sheet.
The molding sheet is inserted into an injection molding mold, the injection molding mold is molded, and a fluid resin is injected into the mold from the base material layer side to be solidified, and the outer surface of the resin molded product is simultaneously injected. And the process of integrating the molded sheet into
A method for manufacturing a decorative resin molded product.

According to the present invention, it is possible to provide a decorative sheet capable of imparting a visual three-dimensional effect to a resin molded product while having a smooth surface. Further, according to the present invention, it is also possible to provide a method for producing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for producing the decorative resin molded product.

It is a schematic sectional view of an example of the decorative sheet of this invention. It is a schematic sectional view of an example of the decorative sheet of this invention. It is a schematic sectional view of an example of the decorative resin molded article manufactured by using the decorative sheet of this invention.

1. 1. Decorative sheet The decorative sheet of the present invention is composed of a laminate including at least a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order, and the intermediate layer is an ionizing radiation curable resin. It is composed of a cured product of the composition, the transparent resin film is smooth on both sides, the surface of the base material layer on the intermediate layer side is provided with an uneven shape, and the concave and convex concave portions are formed by at least the intermediate layer. It is characterized by being buried. By having such a structure, the decorative sheet of the present invention can suitably impart a visual three-dimensional effect to the resin molded product while having a smooth surface.

That is, in the decorative sheet of the present invention, both sides of the transparent resin film located on the front surface side are smooth, while an uneven shape is formed on the surface of the base material layer located on the back surface side (molding resin layer side). Further, the uneven concave portion of the base material layer is filled with at least an intermediate layer. The concave-convex concave portion of the base material layer is formed by an ionizing radiation-curable resin composition used for forming an intermediate layer, and further, a composition used for forming a colored layer or a primer layer provided as needed. It is easy to fill and it is difficult for voids to occur in the recess. Therefore, it is preferably suppressed that the voids expand during vacuum forming or injection molding such as an insert molding method, and the surface smoothness of the decorative sheet is impaired. Further, since the intermediate layer is a cured resin, it is less likely to be deformed by heat pressure during injection molding as compared with a thermoplastic resin. Therefore, the decorative sheet of the present invention effectively suppresses the disappearance of the uneven shape due to heat pressure during injection molding, and imparts a visual three-dimensional effect to the resin molded product while having a smooth surface. can do.

Hereinafter, the decorative sheet of the present invention will be described in detail. In addition, in this specification, the numerical range indicated by "~" means "greater than or equal to" and "less than or equal to", except for the parts specified as "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in the present specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

Laminated Structure of Decorative Sheets The decorative sheet of the present invention includes, for example, a base material layer 1, an intermediate layer 2, an adhesive layer 3, and a transparent resin film 4 in this order, as shown in FIG. It has a laminated structure. The surface of the base material layer 1 on the intermediate layer 2 side is provided with a concave-convex shape, and the concave-convex shape of the base material layer 1 is filled with at least the intermediate layer 2.

Further, as shown in FIG. 2, for example, in the decorative sheet of the present invention, a base is used for the purpose of imparting decorativeness to a decorative resin molded product manufactured by using the decorative sheet of the present invention. A colored layer 5 may be provided between the material layer 1 and the adhesive layer 3 if necessary. Further, a primer layer 6 may be provided as needed for the purpose of improving the adhesion between the intermediate layer 2 and the layer located below the intermediate layer 2. As shown in FIG. 2, when the decorative sheet of the present invention has the colored layer 5 and / or the primer layer 6, the concave-convex concave portion of the base material layer 1 is also formed by the colored layer 5 and / or the primer layer 6. It is buried.

As will be described later, when the decorative sheet of the present invention has the colored layer 5 and / or the primer layer 6, the surfaces of the colored layer 5 and the primer layer 6 on the adhesive layer 3 side each have an uneven shape. .. The uneven shape is formed by providing the colored layer 5 and / or the primer layer 6 on the surface of the base material layer 1 having the uneven shape. That is, the uneven shape of the colored layer 5 and the primer layer 6 and the uneven shape of the base material layer 1 have corresponding shapes.

In the decorative sheet of the present invention, one or more other layers may be further laminated depending on the function imparted to the decorative sheet or the decorative resin molded product.

As the laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / intermediate layer / adhesive layer / transparent resin film is laminated; a base material layer / colored layer / intermediate layer / adhesive layer / transparent resin film Laminated laminated structure; base material layer / primer layer / intermediate layer / adhesive layer / transparent resin film laminated laminated structure; base material layer / colored layer / primer layer / intermediate layer / adhesive layer / transparent resin film Examples thereof include a laminated structure in which is laminated. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / intermediate layer / adhesive layer / transparent resin film is laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. .. FIG. 2 shows an example of a decorative sheet in which a base material layer / colored layer / primer layer / intermediate layer / adhesive layer / transparent resin film is laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. A schematic cross-sectional view is shown.

Each layer forming a decorative sheet [base material layer 1]
The base material layer 1 is a layer provided to impart rigidity to the decorative sheet to retain its shape and to make the decorative sheet suitable for vacuum forming by an insert molding method or the like. Further, in the decorative sheet of the present invention, the base material layer 1 is provided in order to suitably impart a visual three-dimensional effect to the resin molded product while having a smooth surface.

The base material layer 1 is preferably formed of a thermoplastic resin from the viewpoint of suitably exhibiting a visual three-dimensional effect due to the uneven shape while making it suitable for an insert molding method or the like. The thermoplastic resin is not particularly limited, but is limited to acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin. ; Polyethylene terephthalate (PET) resin, acrylonitrile-butadiene-styrene resin; acrylonitrile-styrene-acrylic acid ester resin and the like. The base material layer 1 is preferably formed of the same resin as the molding resin layer 7 described later. For example, when the molding resin layer 7 is made of ABS resin, the base material layer 1 is also formed of ABS resin. When the molding resin layer 7 is made of acrylic resin, it is preferable that the base material layer 1 is also made of acrylic resin. The resin forming the base material layer 1 may be of one type or two or more types.

The thickness of the base material layer 1 is not particularly limited, but is preferably about 100 μm to 500 μm from the viewpoint of preferably exhibiting a visual three-dimensional effect due to the uneven shape while being suitable for an insert molding method or the like. .. When ABS resin is used as the base material layer 1, it is more preferably about 200 μm to 400 μm. Further, when an acrylic resin is used as the base material layer 1, it is more preferably about 100 μm to 200 μm.

The base material layer 1 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if necessary, in order to improve the adhesion to the adjacent layer. .. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Further, examples of the unevenness method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin constituting the base material layer 1, but from the viewpoint of effect and operability, a corona discharge treatment method is preferable.

Further, the base material layer 1 may be colored by blending a colorant or the like, painted to adjust the color, or formed a pattern to impart designability.

The surface of the base material layer 1 on the intermediate layer 2 side has an uneven shape. Since the base material layer 1 has the uneven shape, in the decorative sheet of the present invention, even if both sides of the transparent resin film 4 are smooth, the decorative resin molded product has the uneven shape. A visual three-dimensional effect can be preferably imparted. That is, as described above, the base material layer 1 has an uneven shape on the surface on the intermediate layer 2 side, and the concave portion having the uneven shape is filled with at least the intermediate layer 2. Further, when a colored layer 5 or a primer layer 6 is provided between the base material layer 1 and the intermediate layer 2, the recesses are also filled with these layers (see FIG. 2). Therefore, voids are unlikely to occur in the recess. Further, since the intermediate layer filling the recess is a cured resin (cured product of an ionizing radiation curable resin composition), it is harder than a thermoplastic resin and is less likely to be deformed by heat pressure during injection molding. Therefore, it is preferably suppressed that the voids expand during vacuum forming or injection molding such as the insert molding method, and the surface smoothness of the decorative sheet is impaired. As a result, the surface is smooth but uneven. It is possible to preferably exhibit a visual three-dimensional effect due to the shape.

From the viewpoint of preferably imparting a visual three-dimensional effect due to the concave-convex shape, as shown in FIG. 1, the base material layer 1 has a concave-convex shape having a concave depth d of 5 μm to 100 μm. Is preferable. That is, it is preferable that at least a part of the uneven shape formed on the base material layer 1 has a concave depth d of 5 μm to 100 μm. The depth d of the recess is more preferably 8 μm to 60 μm. The depth of the recess can be measured, for example, by observing a cross section with a microscope. The depth d of the recess is appropriately adjusted according to the thickness of the base material layer 1.

The uneven shape of the base material layer 1 can be suitably formed by, for example, embossing the surface of the base material layer 1. The embossing is a known method, in which the base material layer 1 whose surface is heated and softened is pressed by an embossing plate, and the uneven pattern formed on the embossed plate is formed on the surface of the base material layer 1 and cooled. , It is a method of fixing. A known single-wafer type or rotary type embossing machine can be used for embossing.

In the decorative sheet of the present invention, when the colored layer 5 and the primer layer 6 are provided, the surface of the base material layer 1 is provided with an uneven shape by embossing or the like, and then the colored layer 5 or the primer layer is provided by a printing method or the like. 6 may be formed, or a colored layer 5 or a primer layer 6 may be formed on the surface of the flat base material layer 1, and embossing may be performed on the colored layer 5 or the primer layer 6 to make the base material layer 1 uneven. The shape may be provided. In either case, the colored layer 5 and the primer layer 6 having an uneven surface on the intermediate layer 2 side can be provided. When the colored layer 5 or the primer layer is provided, as shown in FIG. 2, the colored layer 5 and the primer layer 6 are present without the intermediate layer 2 reaching the bottom of the recess of the base material layer 1. Alternatively, although not shown, the intermediate layer 2 may reach the bottom of the recess.

[Intermediate layer 2]
In the decorative sheet of the present invention, the intermediate layer 2 is a layer provided for filling at least a part of the concave-convex-shaped concave portion to prevent the concave-convex shape from disappearing due to heat pressure during injection molding. Is. The intermediate layer 2 is composed of a cured product of an ionizing radiation curable resin composition.

As shown in FIG. 1, when the base material layer 1 and the intermediate layer 2 are in direct contact with each other, in the present invention, all of the concave-convex-shaped individual recesses of the base material layer 1 are intermediate layers, respectively. It is preferably filled with 2. Further, as shown in FIG. 2, when the colored layer 5 and the primer layer 6 are provided, a part of each concave-convex concave portion of the base material layer 1 is filled with the colored layer 5 and the primer layer 6, respectively. Further, it is preferable that all of the recesses that are not filled with the colored layer 5 and the primer layer 6 are filled with the intermediate layer 2.

Further, the surface of the intermediate layer 2 on the adhesive layer 3 side is preferably smooth. As a result, when the adhesive layer 3 of the intermediate layer 2 is formed, it is effectively suppressed that voids are generated at the interface between the intermediate layer 2 and the adhesive layer 3, and the decorative sheet of the present invention has a surface surface. Although it is smooth, it is possible to preferably exhibit a visual three-dimensional effect due to the uneven shape. As a method of smoothing the surface of the intermediate layer 2 on the adhesive layer 3 side, for example, as described later, a method of pressing the surface of the intermediate layer 2 that fills the concave-convex concave portion of the base material layer 1 can be mentioned. ..

The fact that the surface of the intermediate layer 2 is smooth means that at least the uneven shape like the above-mentioned base material layer 1 is not provided on the surface, and it is preferable that the concave portion of the above-mentioned base material layer 1 is not provided. This means that there are no irregularities with a height difference of more than 1/10 times the depth d (μm) of the surface.

The ionizing radiation curable resin of the ionizing radiation curable resin composition used for forming the intermediate layer 2 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, it is polymerized in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer and the like having a sex unsaturated bond or an epoxy group. Here, ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, but in addition, X It also includes electromagnetic waves such as rays and γ-rays, and charged particle beams such as α-rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the intermediate layer 2 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. used.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propantri (meth) acrylate, ethylene oxide-modified trimethyl propanthry (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyisocyanate compound, and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate in which this epoxy (meth) acrylate is partially modified with a dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, it is preferable to use polycarbonate (meth) acrylate from the viewpoint of obtaining excellent three-dimensional moldability. It is also preferable to use a combination of polycarbonate (meth) acrylate and urethane (meth) acrylate.

(Other additive ingredients)
Various additives can be added to the intermediate layer 2 according to the desired physical properties to be provided in the intermediate layer 2. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

(Thickness of intermediate layer 2)
For example, as shown in FIG. 1, the thickness w of the intermediate layer 2 located on the flat portion of the base material layer 1 (the portion where the concave-convex concave portion of the base material layer 1 is not formed) is set as the thickness w. It is preferably about 1 to 30 μm, more preferably about 3 to 25 μm, and further preferably about 7 to 15 μm.

(Formation of intermediate layer 2)
The intermediate layer 2 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the composition, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer by the coating method described later.

In the present invention, the prepared coating liquid is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating so as to have the above thickness, and is uncured. A resin layer is formed.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the intermediate layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the intermediate layer 2, the electron beam transmission depth and the intermediate layer 2 are used. The acceleration voltage is selected so that the thicknesses of the are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the intermediate layer 2 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the intermediate layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, bandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

By adding various additives to the intermediate layer 2 thus formed, a hard coat function, an antifogging coat function, an antifouling coat function, an antiglare coat function, an antireflection coat function, an ultraviolet ray shielding coat function, and infrared rays are added. A process for imparting a function such as a shielding coat function may be performed.

[Adhesive layer 3]
The adhesive layer 3 is provided on the surface of the intermediate layer 2 and is provided to bond the intermediate layer 2 and the transparent resin film 3. The material constituting the adhesive layer 3 is not particularly limited, but preferably a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include (meth) acrylic resins such as (meth) acrylic acid ester, polyvinyl acetal (butyral resin) such as polyvinyl butyral, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resin, and acetic acid. Vinyl resin, urethane resin, polyolefin such as polyethylene and polypropylene, polystyrene and chlorinated polyolefin, styrene resin such as α-methylstyrene, acetal resin such as polyamide, polycarbonate and polyoxymethylene, ethylene-4 ethylene fluorinated weight Examples thereof include fluororesins such as coalescence, polyimides, polylactic acid, polyvinyl acetal resins, and liquid crystal polyester resins. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. When two or more kinds are combined, a copolymer of monomers constituting these resins may be used, or each resin may be mixed and used.

The thermosetting resin is not particularly limited, and examples thereof include a two-component curable urethane resin using a polyol and an isocyanate-based curing agent. Examples of the polyol include polyester polyols, polyurethane polyols, and polyether polyols.

As a material constituting the adhesive layer 3, a polyol and an isocyanate-based curing agent are used from the viewpoint of improving the adhesiveness between the base material layer 1 and the transparent resin film 4 and improving the designability due to the uneven shape even after vacuum forming. A two-component curable urethane resin using the above is preferable, and a polyester polyol is particularly preferable as the above-mentioned polyol.

The adhesive layer 3 can be formed by a known printing or coating method such as gravure printing or roll coating.

The thickness of the adhesive layer 3 located on the flat portion of the base material layer 1 (the portion of the base material layer 1 in which the concave-convex concave portion is not formed) is not particularly limited, but is preferably 5 μm or more. , More preferably about 10 μm to 15 μm.

[Transparent resin film 4]
The transparent resin film 4 is a layer provided to ensure the surface smoothness of the decorative sheet and to give a visual three-dimensional effect due to the uneven shape of the base material layer 1.

The material constituting the transparent resin film 4 is not particularly limited, but from the viewpoint of suitably molding the decorative sheet by an insert molding method or the like, a thermoplastic resin is preferable. As the thermoplastic resin, preferably, acrylic resin, vinyl chloride resin, ABS resin (acrylonitrile-styrene-butadiene copolymer), styrene resin, polycarbonate resin, polyester resin (for example, polyethylene terephthalate, moldable polyester resin, etc.), Examples thereof include polyolefin resins (polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymers, propylene-butene copolymers, olefin-based thermoplastic elastomers, etc.). Among these, acrylic resin, moldable polyester resin and the like are particularly preferable from the viewpoint of excellent transparency and moldability.

Examples of the acrylic resin include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer and the like. One type of acrylic resin may be used alone, or two or more types may be used in combination.

Examples of the moldable polyester resin include polyester-based thermoplastic elastomers and amorphous polyesters. As the polyester-based thermoplastic elastomer, a block polymer or the like using a highly crystalline and high melting point aromatic polyester for the hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or lower for the soft segment, etc. There is. Further, as the aromatic polyester having high crystallinity and high melting point, for example, polybutylene terephthalate is used, and as the amorphous polyether, polytetramethylene glycol or the like is used. Further, as the amorphous polyester, there is typically an ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer. The transparent resin film 4 may be made of one kind of thermoplastic resin, or may be made of two or more kinds of thermoplastic resins.

The transparent resin film 4 may be a single layer or may be composed of a plurality of layers. Further, the transparent resin film 4 may contain various additives such as a stabilizer, a plasticizer, an ultraviolet absorber, and a hindered amine-based light stabilizer, if necessary.

In the decorative sheet of the present invention, both sides of the transparent resin film 4 are smooth. As a result, it is possible to suitably impart a visual three-dimensional effect to the resin molded product while the surface is smooth. In the present invention, the fact that both sides of the transparent resin film 4 are smooth means that at least the uneven shape like the above-mentioned base material layer 1 is not provided on both sides of the transparent resin film 4. The arithmetic average roughness Ra of JISB0601: 2001 is preferably 1 μm or less, and more preferably 0.1 μm or less on both sides of the transparent resin film 4. The arithmetic mean roughness Ra can be measured using a contact type surface roughness meter (for example, Handy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.) or the like.

The thickness of the transparent resin film 4 is not particularly limited, but from the viewpoint of achieving a visual three-dimensional effect due to the uneven shape of the base material layer 1 while ensuring excellent moldability of the decorative sheet by an insert molding method or the like. Is preferably about 30 μm to 300 μm, preferably about 100 μm to 200 μm. When the transparent resin film 4 is composed of a plurality of layers, the thickness is the total thickness of the plurality of layers.

Corona on the front surface, back surface, or both front and back surfaces of the transparent resin film 4 is necessary for the purpose of improving the adhesion with other layers in contact with the transparent resin film 4 and modifying the surface such as adjusting the wettability. Discharge treatment, plasma treatment, etc. may be performed.

[Colored layer 5]
The colored layer 5 is a layer provided between the base material layer 1 and the intermediate layer 2 as needed for the purpose of imparting decorativeness to the decorative resin molded product. The colored layer 5 can be formed, for example, by printing an ink for forming a colored layer on the base material layer 1 by a conventionally known printing method such as gravure printing, silk screen printing, or offset printing. Further, the colored layer 5 may be formed on the base film having peelability and then formed on the base layer 1 by transfer.

The ink for forming a colored layer comprises a vehicle made of a binder or the like, a colorant such as a pigment or a dye, and various additives appropriately added thereto. As the resin of the binder, for example, one kind of resin selected from acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, cellulose resin, chlorinated polypropylene, urethane resin, polyamide resin and the like, or two kinds of resins. The above mixed resin is used.

The resin composition for forming a colored layer is a thermoplastic resin to which a coloring agent is added. As the thermoplastic resin, for example, the thermoplastic resin used for the transparent resin film 4 described above may be used. Can be done.

As the colorant, known ones exhibiting various colors can be used, but inorganic pigments such as carbon black and iron black are preferable, and the content of the colorant in the color layer 5 is 10% by mass to 50% by mass. preferable. By making the colored layer 5 black or substantially black, it is possible to obtain a design having a unique carbon-like three-dimensional depth that is not found in other colors.

The thickness of the colored layer 5 located on the flat portion of the base material layer 1 (the portion of the base material layer 1 in which the concave-convex concave portion is not formed) is not particularly limited, but is preferably 0.5 μm. As described above, more preferably about 1 μm to 10 μm can be mentioned.

Further, the colored layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of them. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metal. The thickness of the colored layer 5 (metal thin film layer) in this case is not particularly limited, but the optical density (OD value) is 0.6 to 1.8 from the viewpoint of enhancing the design and moldability of the decorative sheet. The degree, preferably about 0.8 to 1.5. Further, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Primer layer 6]
The primer layer 6 is a layer that is included as necessary for the purpose of enhancing the adhesion between the intermediate layer 2 and the layer located below the intermediate layer 2. The primer layer 6 can be formed of a resin.

The resin forming the primer layer 6 is not particularly limited, and examples thereof include urethane resin, acrylic resin, (meth) acrylic-urethane copolymer resin, polyester resin, butyral resin, and the like. Among these resins, urethane resin, acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable. These resins may be used alone or in combination of two or more.

As the urethane resin, polyurethane containing a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent) can be used. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, and polyether polyol. Specific examples of the isocyanate include polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanates, isophorone diisocyanates, and hydrogenated tolylene diisocyanates. Examples thereof include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

Among the above urethane resins, from the viewpoint of improving adhesion after cross-linking, a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking material is preferable; more preferably. Is a combination of an acrylic polyol and a hexamethylene diisocyanate.

The thickness of the primer layer 6 is not particularly limited, and examples thereof include about 0.1 to 10 μm, preferably about 1 to 10 μm. By satisfying such a thickness of the primer layer 6, cracking, breaking, whitening and the like of the intermediate layer 2 can be effectively suppressed. In the present invention, the thickness of the primer layer 6 is the thickness of the primer layer 6 located on the flat portion of the substrate layer 1 (the portion of the substrate layer 1 in which the concave-convex concave portion is not formed). To say.

The primer layer 6 uses a resin forming the primer layer 6 to form a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, and a solid coat with a silk screen. It is formed by a usual coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the surface of the target layer in the decorative sheet is coated.

(Manufacturing method of decorative sheet)
The decorative sheet of the present invention can be suitably produced by a method including the following steps 1 to 5.
At least step 1 of preparing a sheet having a base material layer
Step 2 of forming an uneven shape on the surface of one side of the sheet
Step 3 of applying the ionizing radiation curable resin composition so as to fill at least a part of the uneven concave portion.
Step 4 of curing the ionizing radiation curable resin composition to form an intermediate layer
Step 5 of laminating an adhesive layer and a transparent resin film layer having smooth both sides on the intermediate layer.

Details of the base material layer, the intermediate layer, the adhesive layer, the transparent resin film layer, the colored layer, the primer layer and the like provided as needed are as described above.

Further, the method for forming the concave-convex shape and the like are also as described above. For example, in the case of providing the coloring layer 5 and the primer layer 6 in the decorative sheet of the present invention, in step 2, the surface of the base material layer 1 is provided with an uneven shape by embossing or the like, and then by a printing method or the like. A sheet on which the colored layer 5 and the primer layer 6 are formed may be obtained. Further, in step 1, after obtaining a sheet in which the colored layer 5 and the primer layer 6 are formed on the surface of the flat base material layer 1, in step 2, embossing is performed on the colored layer 5 and the primer layer 6. An uneven shape may be formed on the base material layer 1.

In the method for producing a decorative sheet of the present invention, it is preferable to further include a step of pressing the surface of the intermediate layer 2 to smooth the surface of the intermediate layer 2 between the steps 4 and 5. .. As described above, since the surface of the intermediate layer 2 on the adhesive layer 3 side is smooth, when the adhesive layer 3 is formed on the surface of the intermediate layer 2, the interface between the intermediate layer 2 and the adhesive layer 3 is formed. The formation of voids is effectively suppressed, and the decorative sheet of the present invention can suitably exhibit a visual three-dimensional effect due to the uneven shape while having a smooth surface. Further, in the decorative sheet of the present invention, since the intermediate layer 2 is composed of a cured product of the ionizing radiation curable resin composition, it is hard and can effectively protect the uneven shape filled with the intermediate layer 2. it can. Therefore, the decorative sheet of the present invention does not easily lose its uneven shape even when the surface is pressed, and the visual three-dimensional effect of the uneven shape can be effectively exhibited.

The heating temperature at the time of pressing is not particularly limited as long as the surface of the intermediate layer becomes smooth, but is preferably about 90 to 100 ° C. The pressure at the time of pressing is not particularly limited, but is preferably about 4 to 5 kgf. The pressing time is preferably about 1 to 10 seconds.

2. 2. Decorative Resin Molded Product In the present invention, a decorative resin molded product can be suitably produced by using the above-mentioned decorative sheet of the present invention. Specifically, the decorative resin molded product is formed by integrating the molding resin layer 7 with the decorative sheet of the present invention. That is, as shown in FIG. 3, the decorative resin molded product of the present invention comprises the molding resin layer 7, the base material layer 1, the intermediate layer 2, the adhesive layer 3, and the transparent resin film 4. The intermediate layer is composed of a cured product of an ionizing radiation curable resin composition, and the transparent resin film 4 is smooth on both sides and is formed on the surface of the base material layer 1 on the intermediate layer 2 side. Is provided with an uneven shape, and the concave portion having the uneven shape is filled with at least the intermediate layer 2. The decorative resin molded product of the present invention has the above-mentioned colored layer 5, primer layer 6, and the like, if necessary.

The decorative resin molded product is produced by an injection molding method such as an insert molding method using the decorative sheet of the present invention. In the decorative sheet of the present invention, the problem that the injection resin flows between the decorative sheet and the injection molding mold during injection molding in these molding methods is unlikely to occur. Therefore, it is preferable to apply the decorative sheet of the present invention to the insert molding method to produce a decorative resin molded product.

In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. Obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, and a fluid resin is injected into the mold from the base material layer 1 side to be solidified, and the outer surface of the resin molded product is simultaneously injected. By integrating the molded sheet into the molded product, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is produced by an insert molding method including the following steps.
A vacuum molding step of molding the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum molding die, a trimming step of trimming an excess portion of the vacuum-molded decorative sheet to obtain a molded sheet, and an injection molding die of the molded sheet. A step of integrating the resin and the molding sheet by injecting the resin in a fluid state into the injection molding mold from the base material layer 1 side.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated for molding. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but is usually about 120 ° C. to 200 ° C. Further, in the integration step, the temperature of the resin in the flowing state is not particularly limited, but can usually be about 180 ° C. to 320 ° C.

In the decorative resin molded product of the present invention, the molding resin layer may be formed by selecting a resin according to the intended use. The molding resin that forms the molding resin layer may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate (PC) resins, acrylic resins, vinyl chloride resins and the like. Among these, ABS resin is preferable because it is excellent in adhesion to the base material layer 1 of the decorative sheet of the present invention. These thermoplastic resins may be used alone or in combination of two or more.

Further, examples of the thermosetting resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

The decorative resin molded product of the present invention has a smooth surface and preferably exhibits a visual three-dimensional effect due to its uneven shape. Therefore, for example, an interior or exterior material of a vehicle such as an automobile; a window frame, a door frame, etc. Such as fittings; interior materials for buildings such as walls, floors, and ceilings; housings for home appliances such as television receivers and air conditioners; can be used as containers and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Example 1>
A colored layer (thickness 1 μm, acrylic-vinyl chloride copolymer, solid black) was formed on one side of a colored ABS film (thickness 400 μm) as a base material layer by gravure printing. Next, a primer layer was formed on the colored layer (thickness 1 μm, acrylic urethane resin). Next, an uneven pattern (depth 50 μm, grid-like carbon pattern) was formed from above the primer layer using an embossed plate. Next, an ionizing radiation curable resin composition (a mixture of an acrylic polymer and a trifunctional monomer with a mass ratio of 7: 3) was applied over the uneven shape of the primer layer by gravure coating so as to fill the uneven shape. .. The uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to cure the ionizing radiation curable resin composition to form an intermediate layer. Next, the surface of the intermediate layer was smoothed by press working from above the intermediate layer under the conditions of a temperature of 90 ° C., a pressure of 5 kgf, and 1 second. At this time, the thickness of the intermediate layer located on the flat portion of the primer layer was set to 10 μm. Next, an adhesive composed of a polyester polyol and an isocyanate-based curing agent was applied and dried from above the intermediate layer to form an adhesive layer (thickness 10 μm). Further, a transparent acrylic film (thickness 125 μm) having smooth surfaces on both sides as a transparent resin film was laminated on the adhesive layer to obtain a decorative sheet.

<Comparative example 1>
In Example 1, the adhesive layer and the transparent acrylic film were laminated on the smoothed primer layer by performing the above-mentioned press working in a state where the primer layer was the uppermost surface without forming the intermediate layer. Obtained a decorative sheet in the same manner as in Example 1.

<Smoothness evaluation>
Each of the decorative sheets obtained above was heated to 180 ° C. and vacuum formed (pre-molded) using a vacuum forming mold having a portion having a draw ratio of 100 to 300%. The texture of the decorative sheet after molding and the surface of the decorative sheet before molding on the transparent resin film side was evaluated. Further, the surface of the decorative sheet on the transparent resin film side was observed from various angles (the direction directly above the decorative sheet was 90 ° and the horizontal direction was 0 °), and the smoothness before and after molding was evaluated. The evaluation criteria are as follows. The evaluation results are shown in Table 1.
A: No unevenness was felt to the touch, and the surface of the transparent acrylic film was felt flat at all angles by visual observation.
B: No unevenness was felt to the touch, but visual observation showed that the surface of the transparent acrylic film had unevenness.
C: Unevenness was felt to the touch, and even by visual observation, the surface of the transparent acrylic film was felt to be uneven.
D: The unevenness was clearly felt to the touch, and the surface of the transparent acrylic film was felt to be uneven even by visual observation.

<Design evaluation>
The surface of each decorative sheet molded in the above smoothness evaluation on the transparent resin film side was observed from various angles (the direction directly above the decorative sheet was 90 ° and the horizontal direction was 0 °), and the following was observed. The designability before and after molding was evaluated according to the criteria. The evaluation results are shown in Table 1.
A: I could feel the three-dimensional design of the carbon pattern at all angles, and I could feel the sharp design of the embossed plate shape.
B: I could feel the three-dimensional design of the carbon pattern at all angles, but the sharpness was slightly inferior to the design of the embossed plate shape.
C: When observed from the direction of 90 °, the three-dimensional effect of the carbon pattern was slightly low, but when observed from the directions of 45 ° and 60 °, a deep design was felt.
D: A flat design with a carbon pattern was felt at all angles, and no three-dimensional design was felt.

It is composed of a laminate including a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order, and the intermediate layer is composed of a cured product of an ionizing radiation curable resin composition, and is a transparent resin film. The decorative sheet of Example 1 has a smooth surface on both sides, a concave-convex shape is provided on the surface of the base material layer on the intermediate layer side, and the concave-convex-shaped recess is filled with at least the intermediate layer. Both before and after, it was excellent in smoothness and design.
On the other hand, in the decorative sheet of Comparative Example 1 in which such an intermediate layer is not provided, the uneven shape is not protected by the intermediate layer, so that the uneven shape collapses due to the press working performed from above the primer layer, and the decorative sheet Even before the molding of the above, the designability was deteriorated. Further, after the decorative sheet was molded, the uneven shape was almost eliminated due to the deformation during molding.

1 ... Base material layer 2 ... Intermediate layer 3 ... Adhesive layer 4 ... Transparent resin film 5 ... Colored layer 6 ... Primer layer 7 ... Molding resin

Claims (10)

A decorative sheet used for manufacturing a decorative resin molded product by integrating the molded resin layer.
The decorative sheet is composed of a laminate including at least a base material layer located on the molding resin layer side, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
The intermediate layer is composed of a cured product of an ionizing radiation curable resin composition.
The transparent resin film has smooth surfaces on both sides.
The surface of the base material layer on the intermediate layer side is provided with an uneven shape.
A decorative sheet in which the uneven concave portion is filled with at least the intermediate layer. The decorative sheet according to claim 1, wherein the surface of the intermediate layer on the adhesive layer side is smooth. A colored layer is further provided between the base material layer and the intermediate layer.
The decorative sheet according to claim 1 or 2, wherein a part of the recess is filled with the colored layer. A primer layer is further provided between the base material layer and the intermediate layer.
The decorative sheet according to any one of claims 1 to 3, wherein a part of the recess is filled with the primer layer. The decorative sheet according to any one of claims 1 to 4, wherein the base material layer has the uneven shape in which the depth of the recess is 5 μm or more and 100 μm or less. The decorative sheet according to any one of claims 1 to 5, wherein the thickness of the intermediate layer located on the flat portion of the base material layer is 1 μm or more and 30 μm or less. It is composed of a laminate including at least a molding resin layer, a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
The intermediate layer is composed of a cured product of an ionizing radiation curable resin composition.
The transparent resin film has smooth surfaces on both sides.
The surface of the base material layer on the intermediate layer side is provided with an uneven shape.
A decorative resin molded product in which the uneven concave portion is filled with at least the intermediate layer. The method for producing a decorative sheet according to any one of claims 1 to 6, further comprising a laminate comprising a base material layer, an intermediate layer, an adhesive layer, and a transparent resin film in this order.
At least step 1 of preparing a sheet having a base material layer,
Step 2 of forming an uneven shape on the surface of one side of the sheet,
Step 3 of applying the ionizing radiation curable resin composition so as to fill at least a part of the uneven concave portion.
Step 4 of curing the ionizing radiation curable resin composition to form an intermediate layer,
Step 5 of laminating an adhesive layer and a transparent resin film layer having smooth both sides on the intermediate layer.
A method of manufacturing a decorative sheet. The method for producing a decorative sheet according to claim 8, further comprising a step of pressing the surface of the intermediate layer between the steps 4 and 5 to smooth the surface of the intermediate layer. A step of vacuum forming the decorative sheet according to any one of claims 1 to 6 with a vacuum forming mold to obtain a molded sheet.
The molding sheet is inserted into an injection molding mold, the injection molding mold is molded, and a fluid resin is injected into the mold from the base material layer side to be solidified, and the outer surface of the resin molded product is simultaneously injected. And the process of integrating the molded sheet into
A method for manufacturing a decorative resin molded product.