JP5949181B2 - Laminated sheet, decorative resin molded product, decorative resin molded product manufacturing method, and decorative sheet manufacturing method - Google Patents

Description

  The present invention relates to a laminated sheet, a decorative resin molded product using the laminated sheet, a method for manufacturing the decorative resin molded product, and a method for manufacturing the decorative sheet.

A decorative resin molded product in which a laminated sheet is provided on the surface of the molded product is used in various applications such as vehicle interior parts. As a molding method for such a decorative resin molded product, a laminated sheet is molded into a three-dimensional shape in advance by vacuum molding to produce a decorative sheet, and a decorative sheet inserted into a mold at the time of injection molding is used. For example, an injection molding simultaneous decorating method that integrates with the molten resin injected and injected into the cavity and decorates the surface of the resin molded body. In this simultaneous injection molding decoration method, an emboss is formed on the inner surface of a mold by etching or engraving, and the emboss is formed on the surface of the molded product at the same time as the molded product is manufactured.
As a method for producing a molded product using this simultaneous injection molding method, for example, a release layer, a pattern layer, and an adhesive layer are formed on one surface of a base film, and an embossed sheet such as a nonwoven fabric is pasted on the other surface. A method is described in which the combined transfer material is fixed to an injection mold, and then a molten resin is injected, the resin is cooled and solidified, a molded product is taken out, and the base film is peeled off together with the embossed sheet (Patent Document) 1).

JP-A-2-63807

In the general method for manufacturing a molded article described in Patent Document 1, when vacuum forming is performed, the laminated films are integrally pressed against a mold to form as shown in FIG. It becomes possible to do. However, there is a case where the films are peeled off during vacuum forming, and there is a problem that causes molding defects in the concave portion (deep drawing portion) of the mold as shown in FIG.
This invention makes it a subject to provide the lamination sheet which can prevent the molding defect which generate | occur | produces in the recessed part of a metal mold | die at the time of vacuum forming. Moreover, let it be a subject to provide the manufacturing method of the decorating resin molded product using the said laminated sheet, the decorating resin molded product, and the decorating sheet.

  As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by the following invention. That is, the gist of the present invention is as follows.

[1] A laminated sheet for vacuum forming in which the embossed film and the base film body are attached with an adhesive force P, and the adhesive force P is 1.5 times or more the suction pressure at the time of vacuum forming, A laminated sheet, wherein the tensile stress of the base film body at 100 to 130 ° C and a tensile rate of 130% is equal to or lower than the tensile stress of the embossed film.
[2] A decorative resin molded product using the laminated sheet.
[3] A method for manufacturing a decorative resin molded product in which the laminated sheet is placed in a mold and preformed of the laminated sheet, and then the resin is filled in the mold.
[4] A method of manufacturing a decorative sheet by vacuum forming a laminated sheet in which an embossed film and a base film body are attached with an adhesive force P, wherein the adhesive force P is a suction during vacuum forming. A method for producing a decorative sheet, wherein the tensile stress of the base film body is 1.5 times or more of the pressure, the tensile stress of the base film body at 100 to 130 ° C and a tensile rate of 130% is equal to or less than the tensile stress of the embossed film.

  ADVANTAGE OF THE INVENTION According to this invention, the lamination sheet which can prevent the molding defect which generate | occur | produces in the recessed part of a metal mold | die at the time of vacuum forming can be provided. Moreover, the manufacturing method of the decorating resin molded product using the said laminated sheet, the decorating resin molded product, and the manufacturing method of a decorating sheet can be provided.

It is a schematic diagram which shows the cross section of the metal mold | die at the time of vacuum forming, and a lamination sheet. It is a figure which shows the tensile stress in 100 degreeC of the embossed film and base film body which were used for the Example. It is a figure which shows the tensile stress in 110 degreeC of the embossed film used for the Example, and a base film body. It is a figure which shows the tensile stress in 120 degreeC of the embossed film and base film body which were used for the Example. It is a figure which shows the tensile stress in 130 degreeC of the embossed film and base film body which were used for the Example.

[Laminated sheet]
The laminated sheet of the present invention is a laminated sheet for vacuum forming in which an embossed film and a substrate film body are adhered with an adhesion force P, and the adhesion force P is 1.5 times the suction pressure at the time of vacuum molding. It is above, The tensile stress of the base film body in 100-130 degreeC and the tensile rate of 130% is below the tensile stress of an embossed film, It is characterized by the above-mentioned.
According to the present invention, in the laminated sheet adhered with the specific adhesion force P, the tensile stress of the base film body at 100 to 130 ° C. and the tensile rate of 130% is set to be equal to or lower than the tensile stress of the embossed film. In this case, since the base film body flexibly follows the embossed film in the concave portion of the molding die, molding defects hardly occur between the base film body and the embossed film.
Hereinafter, when there is no description about the conditions of a tensile stress, the tensile stress in 100-130 degreeC and the tensile rate of 130% is pointed out.

<Embossed film>
The embossed film that can be used in the present invention is not particularly limited, but a polyethylene terephthalate film (PET film), an acrylonitrile-butadiene-styrene copolymer film (ABS film), a polypropylene film (PP film), an acrylic film, and the like. Among these, a polyethylene terephthalate film (PET film) is preferable.
10-200 micrometers is preferable, as for the thickness of an embossed film, 20-150 micrometers is more preferable, and 30-100 micrometers is still more preferable.

<Base film body>
The base film body in the present invention is a laminated film of the base film and each layer described later, and is not particularly limited as long as it has the predetermined tensile stress.
The tensile stress of the base film body is preferably 5 to 70% of the tensile stress of the embossed film, and more preferably 5 to 65% from the viewpoint of followability to the embossed film and the prevention of molding defects. Preferably, 5 to 25% is more preferable, and 5 to 15% is still more preferable.

The adhesive force P in the present invention is 1.5 times or more the suction pressure at the time of vacuum forming. If this adhesive force P is less than 1.5 times the suction pressure at the time of vacuum forming, there arises a problem that the films are separated, that is, separated. This adhesion force P is preferably 1.6 times or more, more preferably 3 times or more of the suction pressure at the time of vacuum molding, from the viewpoint of further suppressing molding defects.
This adhesive force P is preferably 20 times or less, more preferably 10 times or less, from the viewpoint of production efficiency. Examples of the adhesive force include an adhesive force due to static electricity, an adhesive force due to an adhesive, and an adhesive force due to fusion bonding such as thermal lamination. Among these, an adhesive force due to static electricity is preferable.
The suction pressure at the time of vacuum forming is preferably from 0.1 to 1 kPa, more preferably from 0.2 to 0.9 kPa, and still more preferably from 0.3 to 0.8 kPa, from the viewpoint of mold followability of the film.

≪Base film≫
The base film is not particularly limited as long as it does not exceed the tensile stress of the embossed film. However, the transfer polyethylene terephthalate film (transfer PET film), acrylonitrile-butadiene-styrene copolymer resin film (ABS resin film), acrylic A resin film, a polypropylene film (PP film), and the like are preferable. Among these, a transfer polyethylene terephthalate film, an acrylonitrile-butadiene-styrene copolymer resin film, and an acrylic resin film are preferable.
As thickness of this base film, 25-450 micrometers is preferable, 30-300 micrometers is more preferable, 50-150 micrometers is still more preferable.

  In this invention, what laminated | stacked the mold release layer, the peeling layer, the pattern layer, the concealing layer, the adhesive bond layer, the surface protective layer, etc. on the said base film is good also as a base film body. Even if these layers are laminated on the base film, the tensile stress of the base film can be regarded as the tensile stress of the base film because the influence on the tensile stress of the base film is small. In addition, it is preferable that the adhesive force P between each layer formed on a base film is 1.5 times or more of the suction pressure at the time of vacuum forming, and each layer is formed by forming each layer by a general method. Can be adhered with a force 1.5 times or more that of vacuum molding.

≪Release layer≫
The release layer is provided to improve peelability. The release layer may be a solid release layer covering the entire surface, or may be provided in a part. Usually, it is preferable to use a solid release layer in consideration of releasability.

The release layer is made of one or more acrylic resins, polyester resins, polyolefin resins, polystyrene resins, polyurethane resins, cellulose selected from fluorine resins, acrylic-melamine resins, and acrylic-polyethylene resins. Resins, vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers forming the thermoplastic resins, and these resins were modified with (meth) acrylic acid or urethane Things can be used. These may be used alone or in combination of two or more. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and those obtained by urethane modification thereof are preferable. More specifically, an acrylic-melamine resin, an acrylic-melamine resin-containing composition, a resin composition in which a polyester resin and a copolymer of ethylene and acrylic acid are modified with urethane, an acrylic resin and styrene And a resin composition in which an emulsion of a copolymer with acrylic is mixed. Furthermore, it is particularly preferable that the release layer is composed of a composition containing 50% by mass or more of an acrylic-melamine resin.
The thickness of the release layer is usually about 0.01 to 5 μm, and preferably in the range of 0.05 to 3 μm.

≪Release layer≫
The release layer is also for improving the peelability. Release layer is, for example, microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, part Waxes such as modified wax, fatty acid ester, fatty acid amide, silicone wax, silicone resin, fluorine resin, acrylic resin, polyester resin, polyurethane resin, cellulose resin, vinyl resin, vinyl chloride-vinyl acetate It can be formed of a thermoplastic resin such as a copolymer resin or nitrified cotton. These may be used alone or in combination of two or more.
It is important to select the resin composition used for the release layer from the viewpoint of adjusting the peel strength between the release layer and the release layer within a preferable range due to a synergistic effect with the resin composition used in the release layer. Particularly preferred are acrylic resins and polyester resins.

The release layer can also be formed using a binder resin and a releasable material. As the binder resin, thermoplastic resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, and other acrylic resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl alcohol, Vinyl resins such as polyvinyl butyral, cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, or unsaturated polyester resins that are thermosetting resins, polyester resins, polyurethane resins, aminoalkyd resins, and the like can be used. As the releasable material, waxes, silicone waxes, silicone resins, melamine resins, fluorine resins, fine powders of talc and silica, surfactants and metal soaps can be used.
1-10 mass parts is preferable and, as for the compounding quantity of the mold release material with respect to 100 mass parts of binder resin, 3-5 mass parts is more preferable. The release layer is prepared by dissolving or dispersing the necessary materials in an appropriate solvent to prepare a release layer coating solution, and using this on the substrate, a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate It can be formed by coating and drying by means such as. The thickness after the drying is usually 0.1 to 10 μm, and preferably 1 to 5 μm.
In addition, when a decorative resin molded product is manufactured using the laminated sheet of the present invention, the base film and the release layer may be removed at the final stage of manufacturing, and in this case, the release layer is a decorative resin. Since it becomes a layer constituting the outermost surface of the molded product, this release layer may have the same function as a surface protective layer described later.

≪Picture layer≫
The pattern layer is a layer provided as necessary to express a pattern such as a pattern or characters. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone pattern, cloth pattern, sand pattern, geometric pattern, character, and the like can be mentioned. In addition, the pattern layer can be provided with a pattern pattern layer that expresses the above pattern and an entire solid layer, alone or in combination. The entire solid layer is usually used as a concealing layer. The pattern layer is usually formed on the release layer by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing. it can. The thickness of the pattern layer is preferably 5 to 40 μm and more preferably 20 to 30 μm from the viewpoint of design.

The binder resin of the printing ink used for forming the pattern layer includes polyester resin, polyurethane resin, acrylic resin, acrylic-urethane resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, poly Examples thereof include butyl methacrylate-vinyl chloride-vinyl acetate copolymer resins, cellulose resins, and the like, and resins mainly composed of acrylic resins, and mixtures of acrylic resins and vinyl chloride-vinyl acetate copolymer resins. Is more preferable. Among these, from the viewpoint of printability and moldability, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, or a mixture of another acrylic resin is more preferable.
Here, the acrylic resin includes polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer. Examples thereof include acrylic resins such as polymers, and modified acrylic resins such as fluorine. These may be used alone or in combination of two or more.
In addition, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl (meth) ) Acrylic polyol obtained by copolymerizing (meth) acrylic acid ester having a hydroxyl group in the molecule such as acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. You can also

  As a colorant used in the pattern layer, a metallic pigment made of a scaly foil powder of a metal such as aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass, an alloy, or a metal compound, Pearl luster made of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, and basic lead carbonate Pigments, fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, zinc white, petal, vermilion, ultramarine, cobalt Inorganic pigments such as blue, titanium yellow, yellow lead, carbon black, isoindolinone yellow, Hansa Yellow A, Na quinacridone red, mention may be made permanent red 4R, phthalocyanine blue, indanthrene blue RS, organic pigments such as aniline black (including dyes). These may be used individually by 1 type, and may mix and use 2 or more types.

≪Hidden layer≫
In the present invention, a concealing layer may be provided as necessary. It is provided for the purpose of preventing the pattern color of the decorative sheet from being affected by changes and variations in the color of the base film body surface. The concealing layer is a normal printing method such as gravure printing, offset printing, silk screen printing, printing from a transfer sheet, inkjet printing, gravure coating, gravure reverse coating, gravure offset coating, spin coating, roll coating, reverse roll coating. It is formed by the usual coating method such as.
The hiding layer is usually formed with an opaque color, and the thickness is preferably about 1 to 20 μm. The ink composition for forming the concealing layer can be appropriately selected from those used for the pattern layer and employed.

≪Adhesive layer≫
Examples of the adhesive that can be used as the adhesive layer in the present invention include acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyester-urethane resin, styrene resin, chlorinated polypropylene resin, polyamide resin, and urethane resin. And epoxy resins. These resins can be laminated using a known method such as gravure printing, offset printing, roll coating, screen printing and the like. The coating amount of the adhesive layer is preferably in the range of 0.5~25g / m ^2. Moreover, as thickness at the time of drying of an adhesive bond layer, it is the range of 0.5-25 micrometers normally, and the range of 1-5 micrometers is preferable.

《Primer layer》
As the ink used for forming the primer layer, an ink in which an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed with the binder is used. There is no restriction | limiting in this binder, For example, ester resin, urethane resin, acrylic resin, urethane-acrylic copolymer resin, polycarbonate resin, urethane acrylic copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose Resin etc. can be mentioned, These resin may be used individually by 1 type, and may use 2 or more types together. There is no limitation on the method for applying the primer layer. For example, one or two or more resins are used as a coating composition or ink composition using a solvent or the like, and an appropriate application means such as a roll coating method or a gravure printing method is used. Can be formed.

  It is preferable to add a weather resistance improving agent to the resin composition constituting the primer layer. Examples of the weather resistance improver include an ultraviolet absorber (UVA) and a light stabilizer. The ultraviolet absorber (UVA) absorbs harmful ultraviolet rays and improves long-term weather resistance and stability. In addition, the light stabilizer itself absorbs little ultraviolet light, but stabilizes by efficiently capturing harmful free radicals generated by ultraviolet energy.

  The ultraviolet absorber can be blended easily by kneading into a resin or the like constituting the primer layer, or by dissolving or dispersing the ultraviolet absorber in a solvent or the like and applying it to the primer layer. It is preferable to contain this ultraviolet absorber in the range of 6-15 mass% in the solid content of a primer layer. When the amount is 6% by mass or more, a sufficient ultraviolet ray absorbing effect is obtained, and adhesion deterioration between the primer layer and other layers does not occur even in a weathering accelerated test or the like. Further, when the content is 15% by mass or less, the ultraviolet absorber does not bleed out. From the above points, the content of the ultraviolet absorber is preferably in the range of 8 to 13% by mass.

  The thickness of the primer layer is preferably 0.5 to 20 μm. When the thickness of the primer layer is within the above range, sufficient adhesion and weather resistance can be obtained, and further, cracking hardly occurs during processing. From the above points, the thickness of the primer layer is more preferably 1 to 20 μm, more preferably 1 to 10 μm, and still more preferably 1 to 6 μm.

≪Surface protective layer≫
The surface protective layer is preferably a layer formed by applying a coating agent composition containing a curable resin such as an ionizing radiation curable resin or a thermosetting resin, which will be described later, and a thermoplastic resin as a binder resin.
Examples of the curable resin include ionizing radiation curable resin, thermosetting resin, etc. Among these, solvent-free is possible, environmental and health points, and a photopolymerization initiator is required. However, an ionizing radiation curable resin is preferable because stable curing characteristics can be obtained. That is, a surface protective layer formed by applying an ionizing radiation curable resin composition containing an ionizing radiation curable resin as the coating agent composition is preferable.
In addition, as a coating agent composition in this invention, the coating agent composition containing at least 1 sort (s) of ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin, and the various additives mentioned later is preferable.

(Ionizing radiation curable resin)
The ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with ionizing radiation, and conventionally used polymerizable monomers and polymerizable oligomers can be used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

  As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

Examples of the polymerizable oligomer include oligomers having radically polymerizable unsaturated groups in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.
In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate and the like as long as the purpose of the present invention is not impaired for the purpose of reducing the viscosity. . These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  The weight average molecular weight of the polymerizable oligomer used in the present invention (polystyrene equivalent weight average molecular weight measured by GPC method) is preferably 1,000 to 10,000, and more preferably 2,000 to 10,000. . When the weight average molecular weight is within the above range (oligomer), the processability is excellent, and the coating agent composition has appropriate thixotropy, so that the surface protective layer can be easily formed.

When an electron beam curable resin composition is used as the coating agent composition, an uncured resin layer formed as described below is irradiated with an electron beam to cure the uncured resin layer. The acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably an amount that saturates the crosslink density of the resin layer, and is usually selected in the range of 5 to 300 kGy.

  The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

(Thermosetting resin)
As the thermosetting resin, either a two-component reaction curable resin or a single curable resin may be used. Specifically, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane Resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like.
As the thermosetting resin composition, a resin to which a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender pigment, or the like is added to the resin as necessary. Is preferred.
The curing agent is usually an unsaturated polyester resin, polyurethane resin, an amine epoxy resin, a peroxide such as methyl ethyl ketone peroxide, a radical initiator such as azoisobutyl nitrile, an unsaturated polyester resin, etc. Often used. Further, as the isocyanate, a divalent or higher aliphatic isocyanate or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of preventing thermal discoloration and weather resistance.

(Thermoplastic resin)
Examples of thermoplastic resins include fluorine resins, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, and nitrified cotton. be able to.
A copolymer of monomers forming these thermoplastic resins, or those obtained by modifying these resins with (meth) acrylic or urethane can be used alone or in admixture of two or more.
Among these, polyester resins, polyolefin resins, polystyrene resins, acrylic resins, copolymers of monomers forming these resins, and those obtained by urethane modification thereof are preferable. More specifically, a resin composition obtained by mixing a polyester resin and a urethane-modified copolymer of ethylene and acrylic acid, and a resin composition obtained by mixing an acrylic resin and an emulsion of a copolymer of styrene and acrylic. Thing etc. are mentioned.

(Method for preparing coating agent composition)
In the present invention, the coating liquid is prepared by uniformly mixing the curable resin, the thermoplastic resin, and various additives at a predetermined ratio. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.

(Application method of coating agent composition)
The coating composition is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating so that the thickness after curing is usually about 1 to 20 μm. Do. Moreover, it is preferably 2 to 20 μm from the viewpoint of obtaining excellent weather resistance and its durability, and further transparency and antifouling properties.

<Laminated structure>
As a laminated sheet in the present invention, a base film, a release layer, a release layer, a picture layer, a concealing layer, an adhesive layer in this order, a base film, a picture layer, a concealing layer, and an adhesive layer in this order. What has it, a base film, a pattern layer, and a surface protective layer in this order are preferable.

[Decorative resin molded product, decorative resin molded product manufacturing method, and decorative sheet manufacturing method]
The decorative resin molded product of the present invention is preferably produced using the laminated sheet of the present invention. In addition, this decorative resin molded product is preferably produced by the injection molding simultaneous decorating method and the insert molding method using the laminated sheet. For example, the laminated sheet is placed in a mold to form a laminated sheet. It is preferable to manufacture the decorative resin molded product according to the present invention by filling the mold with a resin after preforming.

In the simultaneous injection molding decoration method, the laminated sheet of the present invention is placed in a female mold that is also used as a vacuum molding die provided with an injection molding suction hole, and pre-molding (in-line pre-molding) is performed with this female mold. After making the decorative sheet, the mold is clamped, the resin in a fluid state is injected and filled in the mold, solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding, Manufactures decorative resin molded products.
In the injection molding simultaneous decorating method, the decorative sheet receives heat pressure from the injection resin. Therefore, if the decorative sheet is close to a flat plate and the aperture of the decorative sheet is small, the decorative sheet may or may not be preheated. .

  As the injection resin, a resin corresponding to the application is used, and a thermoplastic resin such as a polyolefin resin such as polyethylene or polypropylene, an ABS resin, a styrene resin, a polycarbonate resin, an acrylic resin, or a vinyl chloride resin is representative. In addition, thermosetting resins such as urethane resins and epoxy resins can be used depending on applications.

In the insert molding method, in the vacuum molding process, the laminated sheet of the present invention is vacuum-formed into a molded product surface shape in advance (off-line pre-molding) using a vacuum molding die, and then trimmed as necessary to decorate. Get a sheet. This decorative sheet is inserted into an injection mold, the mold is clamped, a resin in a fluid state is injected into the mold, solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. To produce decorative resin molded products.
As the injection resin in the insert molding method, the same resin as that used in the simultaneous injection molding method can be used.

  The decorative sheet is preferably manufactured by the method for manufacturing a decorative sheet of the present invention. That is, the embossed film and the base film body are attached at 1.5 times or more of the suction pressure at the time of vacuum forming, and the tensile stress of the base film body at 100 to 130 ° C. and a tensile rate of 130% is the tensile strength of the embossed film. By producing a decorative sheet so as to be less than the stress, it is possible to prevent defective molding that occurs in the concave portion of the mold, and thus the decorative sheet can be efficiently produced.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
The films used in Examples and Comparative Examples are as follows.
<Embossed film (A)>
Polyethylene terephthalate film (PET film) (thickness 50μm)
<Base film body (B-1)>
The base film body (B-1) is obtained by forming a release layer, a release layer, a pattern layer, a concealing layer, and an adhesive layer on a transfer PET film (thickness 50 μm) according to the following procedure ( Thickness 60 μm).
That is, a release layer composed of an acrylic-polyethylene resin was formed on one side (surface) of a transfer PET film having a thickness of 50 μm as a base film by gravure printing. Next, a release layer made of an acrylic resin was provided on the release layer, and a pattern layer was provided thereon. The pattern layer was formed by gravure printing using a printing ink having an acrylic-urethane resin as a binder resin and a metallic pigment (trade name “7600”, average particle size 20 μm, manufactured by Toyo Aluminum Co., Ltd.) as a colorant. . Next, a concealing layer is formed by gravure printing of the same composition as the composition forming the pattern layer and containing a high concealing pigment (titanium white and coloring pigment), and further a polyester-urethane resin as a main component. The base material film body (B-1) was manufactured by applying the adhesive layer to be a gravure printing method.

<Base film body (B-2)>
The base film (B-2) is obtained by forming a picture layer, a concealing layer, and an adhesive layer on an acrylic resin film (thickness 125 μm) according to the following procedure (thickness 135 μm).
That is, a resin film made of an acrylic resin (methyl methacrylate resin) is used as a base film, and a polybutyl methacrylate-vinyl chloride-vinyl acetate copolymer (mass ratio: 2/1) composition is formed on one surface (surface). Gravure printing was performed on the pattern layer. Next, a concealing layer is formed by gravure printing of the same composition as the composition forming the pattern layer and containing a high concealing pigment (titanium white and colored pigment), and an adhesive comprising an acrylic resin A layer was formed by gravure printing to obtain a laminated sheet.

<Base film body (B-3)>
The base film (B-3) is obtained by forming a pattern layer and a surface protective layer on an ABS resin film (thickness: 100 μm) according to the following procedure (thickness: 110 μm).
That is, an ABS resin film was used as a base film, and a woodgrain pattern layer was formed on one surface (surface) of the film by gravure printing using an acrylic resin composition. Subsequently, a primer layer made of an acrylic resin (acrylic ester homopolymer) was gravure-printed on the surface of the pattern layer. Next, an electron beam curable resin (urethane acrylic oligomer) having the following composition was applied to the surface of the primer layer by gravure coating. The uncured resin layer is irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin composition, thereby forming a surface protective layer. 3) was produced.

<Measurement method of tensile stress>
The embossed film and the base film body used in each example were cut into 50 mm × 80 mm, respectively, at a temperature of 100 ° C., 110 ° C., 120 ° C., and 130 ° C., respectively, with a gripping interval of 50 mm and a tensile speed of 200 mm / min It measured using the Tensilon tensile tester with a heating oven. The results are shown in FIGS.
In each of the base film bodies (B-1) to (B-3) used in the examples, the tensile stress at a tensile rate of 130% (when pulled by 65 mm) is smaller than the tensile stress of the embossed film. In addition, the tensile stress of the base material (A) and the base film bodies (B-1) to (B-3) shown in Table 1 is a value at 110 ° C. and a tensile rate of 130%, respectively.

Examples 1-3
The embossed film (A) and the base film body (B) were combined as shown in Table 1, and both were laminated by electrostatic force. Table 1 shows the results of measuring the adhesive force between the embossed film (A) and the base film body (B) at this time. Next, the laminated film was heated with a far-infrared heater inside the mold, and vacuum molding was performed when the film temperature reached 110 ° C., and then injection molding was performed to produce a decorative resin molded product.
Each manufactured decorative resin molded product was evaluated according to the following criteria. The test method B is a test in which the processing conditions are stricter than the test method A. The results are shown in Table 1.

<Evaluation method>
Test method A: Formability when processing into a shape with a corner R of 10 and an aperture of 10 mm
Evaluation was performed according to the criteria described above.
Test method B: Formability when processed into a shape with a corner R of 1 and an aperture of 10 mm
Evaluation was performed according to the criteria.
<Evaluation criteria>
○: Good molded products were obtained in both test methods A and B.
(Triangle | delta): Although it was able to shape | mold by the test method a, in the test method b, some molding defects were seen.
X: Molding defects were observed in both test methods A and B.

  As described above, the adhesive force P between the embossed film and the base film body is 1.5 times or more the suction pressure at the time of vacuum forming, and the tensile stress of the base film body at 100 to 130 ° C. and a tensile rate of 130% is embossed. In Examples 1 to 3 below the tensile stress of the film, molding defects do not occur in the recesses of the mold.

1 Mold 2 Embossed film 3 Base film body

Claims (2)

The base film body and the embossed film having a tensile stress at 100 to 130 ° C. and a tensile rate of 130% below the tensile stress of the embossed film are used. Adhering by static electricity so that the adhesive force is 1.5 times or more of the suction pressure, producing a laminated sheet,
The manufacturing method of the decorating sheet which arrange | positions the obtained lamination sheet to a metal mold | die, and vacuum-forms the said lamination sheet with the suction pressure of 0.1-1 kPa . The base film body and the embossed film having a tensile stress at 100 to 130 ° C. and a tensile rate of 130% below the tensile stress of the embossed film are used. Adhering by static electricity so that the adhesive force is 1.5 times or more of the suction pressure, producing a laminated sheet,
The resulting laminated sheet was placed in a mold, after preliminary molding by vacuum molding suction pressure 0.1~1kPa the laminated sheet, the decorated resin molded article to fill the resin into the mold Production method.

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