JP2012201032A - Three-dimensional molding decorative sheet, method for manufacturing the same, decorative resin molded product using the decorative sheet, and method for manufacturing the same - Google Patents

Abstract

The present invention provides a decorative sheet for three-dimensional molding that has a metallic tone excellent in design and is excellent in moldability to give a decorated resin molded product excellent in scratch resistance.
A decorative sheet for three-dimensional molding having at least a metal thin film layer and a surface protective layer in this order on a base film, wherein the metal thin film layer and the surface protective layer are in direct contact with each other, or The surface protective layer is a layer made of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. This is a decorative sheet for three-dimensional molding.
[Selection] Figure 1

Description

  The present invention relates to a decorative sheet for three-dimensional molding, a manufacturing method thereof, a decorative resin molded product using the decorative sheet, and a manufacturing method thereof. More specifically, a decorative sheet for three-dimensional molding that gives a decorative resin molded product having a metallic tone with excellent design properties and excellent scratch resistance, a method for producing the same, and a decoration using the decorative sheet The present invention relates to a resin molded product and a manufacturing method thereof.

Plastic products with metal-like designs are used as substitutes for articles such as automobile grilles that have a chrome-plated appearance, and are superior to metals in terms of freedom of shape, strong corrosion resistance, light weight, low cost, etc. Since it is widely used mainly in the automobile industry. As a method of giving a metallic luster to the surface of such a resin molded product, particularly a molded product having a cubic surface and a three-dimensionality, plating or painting has been performed after molding, but these methods include waste water, solvent vapor, etc. Environmental measures were necessary, and there were also problems such as high costs.
In recent years, therefore, attempts have been made to use a metallic gloss sheet in combination and produce a molded product having a metallic gloss on the surface by insert molding (see, for example, Patent Documents 1 and 2).
However, the resin molded product having such a metallic luster has a problem that gloss reduction and whitening are conspicuous even with a slight scratch.
Moreover, when a polyester film is used as the support film, there is a limit to moldability (elongation) and shape stability after molding.

  On the other hand, a decorative resin molded product decorated by laminating a decorative sheet on the surface of the molded product is used in various applications such as vehicle interior parts. As a molding method of such a decorative resin molded product, the decorative sheet is formed into a three-dimensional shape in advance by a vacuum mold, the molded sheet is inserted into an injection mold, and the resin in a fluid state is placed in the mold. Insert molding method that integrates resin and molded sheet by injection, and decorative sheet inserted into the mold at the time of injection molding is integrated with molten resin injected and injected into the cavity, and the surface of the resin molded product There is an injection molding simultaneous decorating method (for example, refer to Patent Document 3).

  The decorative resin molded product is provided with a surface protective layer for the purpose of improving the scratch resistance of the surface. However, in the molding method of the decorative resin molded product described above, in the insert molding method, the decorative sheet is preliminarily formed into a three-dimensional (three-dimensional) shape by a vacuum mold, and in the simultaneous injection molding method, the decorative sheet is preliminarily used. During molding or injection of molten resin, in the process of drawing and adhering along the inner peripheral surface of the cavity, the decorative sheet is molded by vacuum / pneumatic action or by pulling of molten resin pressure or shear stress Since the film is stretched beyond the minimum necessary amount to conform to the shape, there has been a problem that the surface protective layer of the curved surface portion of the molded product is cracked.

For the above-mentioned problems, by using an ionizing radiation curable resin such as an ultraviolet curable resin as a surface protective layer and increasing the crosslink density of the resin forming the surface protective layer of the decorative sheet, Although attempts have been made to improve the wear resistance and scratch resistance of the surface, there is still a problem that cracks occur in the curved surface of the molded product during molding.
In addition, an attempt has been made to use an ionizing radiation curable resin such as an ultraviolet curable resin as a surface protective layer, to make a semi-cured state in the decorative sheet stage, and to completely cure after the decorative molding (Patent Document 4). The surface protective layer containing the uncured resin component is easily damaged and difficult to handle, and there is a problem of mold contamination due to the uncured resin component adhering to the mold. In order to solve this problem, there is a method of providing a protective film on the semi-cured surface protective layer. However, the manufacturing is complicated and the cost is increased.
Therefore, a surface protective layer that can achieve both scratch resistance and three-dimensional formability is desired.

  By the way, a polycarbonate (meth) acrylate-containing resin composition is known (see, for example, Patent Documents 5 and 6), and a yellowish polycarbonate urethane acrylate is used as an inner colored sheet on the back side of a surface transparent sheet of a decorative sheet for insert molding. There is an example using a resin composition containing a small amount of oligomer (see Patent Document 7), but there was no example using polycarbonate (meth) acrylate for the surface protective layer of the decorative sheet.

On the other hand, acrylic silicone resins have a structure in which acrylic polymer chains are strongly cross-linked by siloxane bonds, have excellent weather resistance, heat resistance, chemical resistance, and water resistance, and are widely used in exterior coatings. Yes. However, when it is used as a surface protective layer for the purpose of improving the scratch resistance of the surface of the resin molded product, the formed film may become hard and brittle and cracks may occur. In order to prevent this crack, when an acrylic silicone resin is used as the surface protective layer, the insert molding sheet after vacuum molding or the resin molded article after injection molding has been subjected to curing treatment such as ultraviolet curing (for example, (See Patent Document 8).
However, it is cumbersome and inferior in economic efficiency to the molded product after three-dimensional processing, and it is difficult to perform uniform curing.
Therefore, there is a demand for a surface protective layer that can achieve both three-dimensional formability and scratch resistance while maintaining the excellent chemical resistance of the acrylic silicone resin.

JP 2009-220318 A Japanese Patent No. 4542667 Japanese Patent Publication No. 50-19132 Japanese Patent Application Laid-Open No. 6-134859 JP-A-3-181517 JP 2000-351843 A JP 2003-145573 A Japanese Patent Application Laid-Open No. 6-100799

  The present invention has been made under such circumstances, and has a metallic tone that is excellent in design, and a decorative sheet for three-dimensional molding that gives a decorated resin molded article that is excellent in scratch resistance, and its manufacture It is an object of the present invention to provide a method, a decorative resin molded product having the above properties using the decorative sheet, and a method for producing the decorative resin molded product.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
An ionizing radiation curable resin composition comprising at least a metal thin film layer and a surface protective layer in this order on a base film, and the surface protective layer comprising polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. It has been found that a sheet made of a cured product of a product can be adapted to its purpose as a decorative sheet for three-dimensional molding. The present invention has been completed based on such findings.

That is, the present invention
(1) A decorative sheet for three-dimensional molding having at least a metal thin film layer and a surface protective layer in this order on a base film, wherein the metal thin film layer and the surface protective layer are in direct contact with each other or a primer. The surface protective layer is a layer made of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. Decorative sheet for three-dimensional molding,
(2) a decorative resin molded product using the decorative sheet for three-dimensional molding described in (1) above,
(3) A step of forming a design layer having a metal thin film layer on a release sheet, a step of transferring the design layer onto the base film, a step of peeling off the release sheet on the base film, and an ionizing radiation on the surface from which the base film has been peeled off A method for producing a decorative sheet, comprising a step of laminating a curable resin composition layer, a step of crosslinking and curing the ionizing radiation curable resin composition layer to form a surface protective layer,
(4) (a) a step of forming a primer layer on the release sheet, (b) a step of forming a design layer having a metal thin film layer on the primer layer, (c) the primer layer and the design layer on the base film (D) a step of peeling the release sheet on the base film, (e) a step of laminating an ionizing radiation curable resin composition layer on the primer layer formed on the base film, and (f ) A method for producing a decorative sheet having a step of forming a surface protective layer by crosslinking and curing the ionizing radiation curable resin composition layer,
(5) A step of heating the decorative sheet for three-dimensional molding from the protective layer side by means of a heating plate with the surface protective layer side of the decorative sheet for three-dimensional molding described in (1) above in a mold, A step of preforming the heated decorative sheet for three-dimensional molding so as to conform to the shape in the mold, and closely clamping the mold to the inner surface of the mold; a step of injecting an injection resin into the mold; the injection resin A method for producing a decorated resin molded product comprising the step of taking out a decorated resin molded product from a mold after cooling, and (6) the decorative sheet for three-dimensional molding described in (1) above A vacuum forming process in which a vacuum mold is formed into a three-dimensional shape in advance, a process in which an excess portion is trimmed to obtain a molded sheet, the molded sheet is inserted into an injection mold, the injection mold is closed, and a resin in a fluid state is molded Decorative tree having a process of injecting resin and molded sheet Method for producing a molded article,
Is to provide.

  According to the present invention, a three-dimensional molded decorative sheet having a metallic tone excellent in design and having a decorative resin molded article excellent in scratch resistance, a method for producing the same, and the decorative sheet using the decorative sheet A decorative resin molded product having properties and a method for producing the same can be provided.

It is a schematic diagram which shows the cross section of the one aspect | mode of the decorating sheet for three-dimensional shaping | molding of this invention. It is a schematic diagram which shows the cross section of the one aspect | mode of the decorative resin molded product obtained using the decorating sheet for three-dimensional shaping | molding of this invention.

First, the decorative sheet for three-dimensional molding of the present invention will be described.
[Decorative sheet for three-dimensional molding]
The three-dimensional decorative sheet of the present invention (hereinafter sometimes simply referred to as “decorative sheet”) has at least a metal thin film layer and a surface protective layer in this order on the base film. The metal thin film layer and the surface protective layer are in direct contact with each other or are in close contact with each other through a primer layer, and the surface protective layer is made of polycarbonate (meth) acrylate and / or acrylic. It is a layer made of a cured product of an ionizing radiation curable resin composition containing silicone (meth) acrylate.

(Base film)
In the decorative sheet of the present invention, a base film used as a base material is selected in consideration of suitability for vacuum forming, and typically a resin film made of a thermoplastic resin is used. As the thermoplastic resin, acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), polyolefin resin such as acrylic resin, polypropylene, polyethylene, polycarbonate resin, vinyl chloride resin, etc. are generally used. Of these, polyolefin resins, polycarbonate resins and ABS resins are preferred.
Moreover, the said base film can be used as a single layer film of these resin, or a multilayer film by the same kind or different resin.
Although the thickness of the base film is selected according to the use, it is usually about 200 to 800 μm, preferably 250 to 600 μm, more preferably 300 to 500 μm in consideration of cost and the like.

The base film can be subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides, if desired, in order to improve the adhesion to the layer provided thereon.
Examples of the oxidation method include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sand blast method and solvent treatment method. It is done. These surface treatments are appropriately selected according to the type of the base film, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, the base film may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

(Metal thin film layer)
The metal thin film layer in the decorative sheet of the present invention is a layer provided between the base film and the surface protective layer, and imparts high brightness similar to that of the metal surface and imparts design properties.
The metal that can be used in the present invention is not particularly limited as long as the effects of the present invention are achieved, and examples thereof include aluminum, nickel, copper, silver, gold, platinum, tin, brass, indium, chromium, and zinc. A metal can also be used in combination of 2 or more types.
Among these metals, indium, tin, chromium or aluminum is preferable, and tin and indium are particularly preferable from the viewpoint of high extensibility. A material having good extensibility has an advantage that cracks do not occur even when the sheet is stretched when three-dimensionally formed.

There are various methods for forming the metal thin film layer of the present invention, but using any of the above metals, it is possible to process any material by using a vapor deposition method such as vacuum vapor deposition, sputtering, or ion plating. It is preferable from the point that a film excellent in decorativeness can be applied.
In the present invention, the vacuum deposition method is particularly preferable in terms of low cost and less damage to the deposition target, and the deposition conditions are appropriately set according to the melting temperature or evaporation temperature of the metal used.
In addition to the above vapor deposition method, a method of applying a paste containing the metal can also be used.
As the thickness of the metal thin film layer, from the viewpoint of extensibility, the optical density O.D. The D value is preferably about 0.5 to 3, more preferably about 0.8 to 1.5. On the other hand, when applying a paste, about 0.1-30 micrometers is preferable and 0.5-20 micrometers is preferable.

The metal thin film layer may be provided directly on the base film, or a support film having a metal thin film layer provided on one side is joined so that the metal thin film layer faces the base film surface, and then the support film. It is also possible to use a method of peeling off and providing the metal thin film layer on the base film.
In addition, the metal thin film layer is in close contact with the surface protective layer described in detail below, and does not have other resin layers such as a transparent film layer typified by polyethylene terephthalate (PET) between the layers. Features. By this, the outstanding moldability as a three-dimensional decorating sheet can be provided. Here, the other resin layer does not exclude a primer layer having a thickness of about 10 μm or less used for the purpose of improving the adhesion between the metal thin film layer and the surface protective layer.

(Surface protective layer)
The surface protective layer in the decorative sheet of the present invention is a layer made of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate.
The ionizing radiation curable resin composition may further contain a polyfunctional (meth) acrylate.
Here, the ionizing radiation curable resin composition refers to a composition containing an ionizing radiation curable resin. The ionizing radiation means an electromagnetic wave or 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. The ionizing radiation curable resin refers to a resin that crosslinks and cures when irradiated with the ionizing radiation.

<Polycarbonate (meth) acrylate>
In the present invention, polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, or both are used as the ionizing radiation curable resin. First, polycarbonate (meth) acrylate will be described.
In the present invention, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning.

The polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and has (meth) acrylate in the terminal or side chain. This (meth) acrylate preferably has two or more functional groups from the viewpoint of crosslinking and curing.
Said polycarbonate (meth) acrylate is obtained by converting a part or all of the hydroxyl group of polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester), for example. This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) the method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups at the terminal or side chain. A typical method for producing this polycarbonate polyol is a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.
The diol compound (A) used as a raw material is represented by the general formula HO—R ₁ —OH. Here, R ₁ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in admixture of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. Furthermore, alcohols having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide are added to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or in combination of two or more.

  The compound (C) serving as the carbonyl component is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formates such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Etc. These may be used alone or in admixture of two or more.

  The polycarbonate polyol is synthesized by subjecting the above-described diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound (C) as the carbonyl component ( The charged molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents with respect to the hydroxyl group of the diol compound and polyhydric alcohol.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charge ratio is 3 or more on average in one molecule, preferably 3 to 50, more preferably 3 to 20. Within this range, a necessary amount of (meth) acrylate groups are formed by the esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.
The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

  The molecular weight of the polycarbonate (meth) acrylate used in the present invention is preferably 500 or more, more preferably 1000 or more, as measured by GPC analysis and converted to standard polystyrene. More preferably, The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less and more preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably more than 2000 and 50000 or less, and particularly preferably 5000 to 20000.

<Multifunctional (meth) acrylate>
The polyfunctional (meth) acrylate used for this invention should just be bifunctional or more (meth) acrylate, and there is no restriction | limiting in particular. However, when it is necessary to improve curability, trifunctional or higher functional (meth) acrylate is preferable. Here, bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule.
The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.

  Examples of the polyfunctional (meth) acrylate oligomer include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meta-methacrylate) having polysiloxane bonds in the main chain. ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules.

The polyfunctional (meth) acrylate monomers are specifically ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified di Cyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol proppant (Meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylol Propane tri (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 Examples include dipentaerythritol hexa (meth) acrylate.
The polyfunctional (meth) acrylate oligomer and polyfunctional (meth) acrylate monomer described above may be used alone or in combination of two or more.

In the present invention, when the above-described polycarbonate (meth) acrylate is used as the ionizing radiation curable resin, the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is the polycarbonate (meth) acrylate as the surface protective layer. ) Acrylate: Polyfunctional (meth) acrylate = Preferably made of a cured product of ionizing radiation curable resin composition of 98: 2 to 70:30.
When the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is larger than 98: 2 (that is, when the amount of the polycarbonate (meth) acrylate exceeds 98 mass%), the scratch resistance may be lowered. . On the other hand, when the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is smaller than 70:30 (that is, when the amount of the polycarbonate (meth) acrylate is less than 70 mass%), the three-dimensional moldability is lowered. There is a case. More preferably, the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is 95: 5 to 80:20.

<Monofunctional (meth) acrylate>
In the present invention, together with the polyfunctional (meth) acrylate, for the purpose of reducing the viscosity of the ionizing radiation curable resin composition, the monofunctional (meth) acrylate is within a range that does not impair the purpose of the present invention. It can be used together as appropriate. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

<Acrylic silicone (meth) acrylate>
Next, the acrylic silicone (meth) acrylate used as the ionizing radiation curable resin will be described.
The acrylic silicone (meth) acrylate used in the present invention is not particularly limited, and a part of the acrylic resin structure is substituted with a siloxane bond (Si—O) in one molecule, and the acrylic resin is a functional group. Any of those having two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the above.
As an example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned preferably, for example.

The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator.
Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These (meth) acrylate monomers are used alone or in combination of two.
The silicone macromonomer is synthesized, for example, by living anionic polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator and capping with a radically polymerizable unsaturated group-containing silane. As a silicone macromonomer, following formula (1);

Is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a methyl group or an n- butyl group are preferable. R ² represents a monovalent organic group, —CH═CH ₂ , —C ₆ H ₄ —CH═CH ₂ , — (CH ₂ ) ₃ O (CO) CH═CH ₂ or — (CH ₂ ) _3. O (CO) C (CH ₃ ) ═CH ₂ is preferred. R ^{3 s} may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group. Moreover, the numerical value of n is not specifically limited, For example, as for the number average molecular weight of a silicone macromonomer, 1000-30000 are preferable, More preferably, it is 1000-20000.

  The acrylic silicone (meth) acrylate obtained using the above-mentioned raw materials has structural units represented by the following formulas (2), (3) and (4), for example.

In formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the (meth) acrylate. An alkyl group or glycidyl group in the monomer, or an alkyl group which may have a functional group such as an alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ is an organic compound having a (meth) acryloyloxy group. Indicates a group.
The above-mentioned acrylic silicone (meth) acrylates are used alone or in combination of two.

The molecular weight of the acrylic silicone (meth) acrylate is preferably 1000 or more, more preferably 2000 or more, as measured by GPC analysis and converted to standard polystyrene. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both three-dimensional formability, chemical resistance, and scratch resistance, 2000 to 100,000 is particularly preferable.
Moreover, it is preferable that the average molecular weight between crosslinking points of acrylic silicone (meth) acrylate is 100-2500. If the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional formability, and if it is 2500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance.

In the present invention, when the above-mentioned acrylic silicone (meth) acrylate is used as the ionizing radiation curable resin, the surface protective layer is a mass of the acrylic silicone (meth) acrylate and the above-mentioned polyfunctional (meth) acrylate. The ratio is preferably a cured product of an ionizing radiation curable resin composition having an acrylic silicone (meth) acrylate: polyfunctional (meth) acrylate = 95: 5 to 50:50.
When the mass ratio of acrylic silicone (meth) acrylate to polyfunctional (meth) acrylate is greater than 95: 5 (ie, the amount of acrylic silicone (meth) acrylate exceeds 95 mass%), scratch resistance and three-dimensional molding May decrease. On the other hand, when the mass ratio of acrylic silicone (meth) acrylate to polyfunctional (meth) acrylate is smaller than 50:50 (that is, when the amount of acrylic silicone (meth) acrylate is less than 50% by mass), chemical resistance and scratch resistance are obtained. Adhesion may be reduced. More preferably, the mass ratio of acrylic silicone (meth) acrylate to multifunctional (meth) acrylate is 90:10 to 75:25.
In the present invention, the above-mentioned monofunctional (meth) acrylate is impaired together with the above-mentioned monofunctional (meth) acrylate for the purpose of reducing the viscosity of the ionizing radiation curable resin composition. It can be contained as appropriate within the range.

When using an ultraviolet curable resin composition as the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator to 100 parts by mass of the ultraviolet curable resin. . The initiator for photopolymerization can be appropriately selected from those conventionally used, and is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin Isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, Nzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, Examples include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal and the like.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the present invention, it is preferable to use an electron beam curable resin composition as the ionizing radiation curable resin composition. This is because the electron beam curable resin composition can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

Moreover, various additives can be mix | blended with the ionizing radiation curable resin composition which comprises the surface protective layer in this invention according to the desired physical property of the cured resin layer obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
Here, as the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. The ultraviolet absorber may be either inorganic or organic. As the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle size of about 5 to 120 nm can be preferably used. Examples of the organic ultraviolet absorber include benzotriazole-based compounds, specifically 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-). Amylphenyl) benzotriazole, 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol, and the like. On the other hand, examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1,2,2). , 6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate and the like. 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 be used. Moreover, it can also be copolymerized and used to such an extent that the performance (scratch resistance and three-dimensional moldability) as a surface protective layer of the polymer of this invention is not impaired.

Examples of the wear resistance improver include particles of α-alumina, silica, kaolinite, iron oxide, diamond, silicon carbide and the like as inorganic materials. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Organic materials include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 30 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles.
Examples of the polymerization inhibitor include hydroquinone, p-benzoquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Examples of the crosslinking agent include a polyisocyanate compound, an epoxy compound, a metal chelate compound, an aziridine compound, and an oxazoline compound. Used.
As the filler, for example, barium sulfate, talc, clay, calcium carbonate, aluminum hydroxide and the like are used.
Examples of the colorant include known coloring pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black.
As the infrared absorber, for example, a dithiol metal complex, a phthalocyanine compound, a diimmonium compound, or the like is used.

(Configuration of decorative sheet for three-dimensional molding)
Next, the structure of the decorative sheet for three-dimensional molding of the present invention will be described with reference to FIG.
Drawing 1 is a mimetic diagram showing the section of one mode of the decoration sheet for three-dimensional fabrication of the present invention. The decorative sheet for three-dimensional molding 10 of the present invention has a configuration in which a metal thin film layer 2 and a surface protective layer 3 are sequentially provided on a base film 1, and the metal thin film layer 2 and the surface protective layer 3 are in direct contact with each other. In close contact with each other or through a primer layer. In the embodiment shown in FIG. 1, a case where adhesion is made through the primer layer 5 is shown. The primer layer 5 is a layer provided as necessary, for example, when the adhesion between the metal thin film layer 2 and the surface protective layer 3 is low.
Moreover, it is preferable to have the adhesive layer 4 containing an acrylic resin and / or a vinyl chloride-vinyl acetate copolymer between the base film 1 and the metal thin film layer 2.
The base film 1, the metal thin film layer 2 and the surface protective layer 3 in the above configuration are as described above.

(Adhesive layer formed between the metal thin film layer and the base film)
The adhesive layer 4 in the decorative sheet for three-dimensional molding of the present invention is for improving the adhesiveness between the base film 1 and the metal thin film layer 2 and is made of a resin that can improve the adhesiveness. There is no restriction | limiting in particular, The adhesive layer by a dry lamination method may be sufficient, and a heat bonding layer (heat seal layer) may be sufficient.
Specific examples of the resin constituting the adhesive layer 4 include acrylic resin; polyester resin; cellulosic resin; vinyl chloride resin, vinyl acetate resin, or vinyl chloride / vinyl acetate copolymer resin (hereinafter collectively referred to as “ And so on). These resins can be used singly or in combination of two or more.
Further, the adhesive layer 4 may be multilayered if the adhesion required for a single layer cannot be obtained. For example, a strong adhesive force can be obtained by forming the adhesive layer 4A made of a resin that is in close contact with the metal thin film layer 2 and the adhesive layer 4B made of a resin that is easily in close contact with the base film 1 into two layers.
The thickness of the adhesive layer 4 (the whole layer in the case of the multilayer described above) is usually about 0.5 to 20 μm, preferably 1 to 5 μm.

When the adhesive layer 4 has a two-layer structure, the resin used for the layer (adhesive layer 4A) formed on the side in contact with the metal thin film layer is the above-mentioned resin by heating in a later step as long as it is the vinyl resin. In order to prevent the metal thin film layer 2 from becoming transparent, it is preferable to adjust the average acid value of the resin. For example, when the metal thin film layer 2 is a vacuum deposited film of tin, a resin having an average acid value of 1 to 6 mgKOH / g (low acid value vinyl resin) is preferably exemplified. Regarding the vinyl resin, an average acid value of 1 mgKOH / g or more is preferable because sufficient adhesion between the metal thin film layer, the base film, the injection molding resin, and the like can be obtained. On the other hand, it is preferable that it is 6 mgKOH / g or less because the above-mentioned metal thin film layer is not made transparent by heating in a subsequent step. From the above viewpoint, the average acid value of the vinyl resin is more preferably 2 to 5 mgKOH / g.
As a specific example of the resin of the adhesive layer (adhesive layer 4B) on the side to be bonded to the base film when the adhesive layer 4 has two or more layers, from the viewpoint of adhesion to the base film, an acrylic resin and / or A vinyl chloride-vinyl acetate copolymer resin is preferred.

Note that a colorant may be mixed in the adhesive layer 4 in order to impart concealability and the like. Moreover, by using the same colorant as the injection resin as the colorant, it is difficult to see the boundary between the injection resin and the decorative sheet, and the design can be improved.
Further, a separate colored layer may be provided between the adhesive layer 4 and the base film 1. The colored layer may be a pattern layer, a solid print layer, or a colored layer having a concealing property. In addition, by coloring the colored layer in the same color as the base film layer, it is difficult to see the boundary between the base film layer and the colored layer in the cross section of the decorative molded sheet, and the design property can be improved. In addition, as a binder used for a colored layer, the thing similar to the said adhesive layer 4 is used.
The colorant that can be used for the adhesive layer 4 and the colored layer is not particularly limited, and is carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine blue, cobalt blue. Inorganic pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue and other organic pigments or dyes, metal pigments made of scaly foils such as aluminum and brass, scaly foils such as titanium dioxide-coated mica and basic lead carbonate A piece of pearlescent pigment is used.

(Primer layer formed between the metal thin film layer and the surface protective layer)
The primer layer 5 provided as needed between the metal thin film layer 2 and the surface protective layer 3 is not particularly limited as long as it can improve the adhesion between the layers, and acrylic resin, chloride Examples thereof include vinyl-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, and chlorinated polyethylene. Of these, a primer layer obtained by reacting an acrylic polyol with a polyvalent isocyanate compound and thermally curing the primer layer is preferable.
Examples of the polyvalent isocyanate compound include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and 4,4′-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2,2, Aliphatic (or alicyclic) isocyanates such as 4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate; or adducts or multimers of the above various isocyanates. For example, an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer, and the like can also be used.
In addition, the thickness of the said primer layer 5 is about 0.5-20 micrometers normally, Preferably it is 1-5 micrometers.
In addition, the primer layer 5 can be mixed with a colorant to adjust the color and improve the design, and further, a pattern from a design viewpoint can be formed.
In addition, in the manufacturing process, the primer layer 5 may be temporarily wound into a roll shape after forming the primer layer 5 and before forming the surface protective layer. In that case, in order to prevent blocking, A known blocking agent such as silica can be contained.

<Formation of surface protective layer 3>
The formation of the surface protective layer 3 can be obtained, for example, by preparing a coating liquid containing the above-mentioned ionizing radiation curable resin composition, applying it on the primer layer 5 and crosslinking and curing it. In addition, the viscosity of a coating liquid should just be a viscosity which can form a non-hardened resin layer on the surface of the primer layer 5 by the below-mentioned coating system, and there is no restriction | limiting in particular.
In the present invention, the prepared coating liquid is applied to the surface of the primer layer 5 so that the thickness after curing is 1-1000 μm, such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. The known method, preferably gravure coating, is applied to form an uncured resin layer.

In the present invention, 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. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.
The irradiation dose is preferably such that the crosslinking density of the resin layer constituting the surface protective layer 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). Is done.
Further, the electron beam source is not particularly limited. 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. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

Next, the manufacturing method of the decorative sheet for three-dimensional molding of this invention is demonstrated.
[Method for producing decorative sheet for three-dimensional molding]
As a method for producing the above-described decorative sheet for three-dimensional molding of the present invention (hereinafter sometimes simply referred to as “decorative sheet production method”), a method of laminating each layer directly on a base film in order. , And a transfer method can be used.

  In the case of the transfer method, the step of forming a design layer having a metal thin film layer on the release sheet, the step of transferring the design layer onto the base film, the step of peeling off the release sheet on the base film, the base film was peeled off A step of laminating an ionizing radiation curable resin composition layer on the surface, and a step of crosslinking and curing the ionizing radiation curable resin composition layer to form a surface protective layer. Moreover, in the said method, the aspect which provides a primer layer on a peeling sheet and provides a design layer on it is especially preferable. Hereinafter, an embodiment in which a primer layer is provided will be described in detail. That is, a step of forming a primer layer on the release sheet [step (a)], a step of forming a design layer having a metal thin film layer on the primer layer [step (b)], and the primer layer and the design described above A step of transferring the layer onto the base film [step (c)], a step of peeling the release sheet on the base film [step (d)], and ionizing radiation curing on the primer layer formed on the base film A step of laminating the conductive resin composition layer (step (e)) and a step of crosslinking and curing the ionizing radiation curable resin composition layer to form a surface protective layer (step (f)). .

((A) Process)
(A) process in the manufacturing method of the decorating sheet of this invention is an acrylic polyol, polyvalent | monohydric, as demonstrated as the primer layer 5 in the structure of the decorating sheet | seat of this invention mentioned above on the peeling process surface of a peeling sheet. It is a step of forming a primer layer formed by reacting with an isocyanate compound and thermosetting.

((B) Process)
The step (b) is a step of forming a design layer having a metal thin film layer on the primer layer formed in the step (a). Specifically, on the primer layer, a vapor deposition method or the like is used. A metal thin film layer is formed by vapor-depositing a metal such as indium, tin, chromium, and aluminum, and further, the adhesive layer described as the adhesive layer 4 is provided on the metal thin film layer. Thus, a design layer can be formed.

((C) step and (d) step)
Step (c) in the method for producing a decorative sheet of the present invention is a step of transferring the primer layer and the design layer onto the base film so that the adhesive layer constituting the design layer is in contact with the base film, (D) A process is a process of peeling a peeling sheet on a base film.
In addition, you may provide the said contact bonding layer beforehand on a base film, without providing on a metal thin film layer.

(Step (e))
The step (e) is a step of laminating the ionizing radiation curable resin composition layer on the primer layer formed on the base film.
The ionizing radiation curable resin composition is as described in the description of the “surface protective layer in the decorative sheet for insert molding of the present invention” described above.

((F) Process)
The step (f) is a step of forming a surface protective layer by crosslinking and curing the ionizing radiation curable resin composition layer formed in the step (e).
The method for forming a surface protective layer by crosslinking and curing the ionizing radiation curable resin composition layer is shown in “Formation of the surface protective layer 3 in the configuration of the decorative sheet for insert molding of the present invention” described above. It is as follows.
Thus, the decorative sheet for insert molding of the present invention can be produced effectively.

Next, in the method of directly laminating, first, the adhesive layer 4 is formed on the base film 1. The adhesive layer 4 is as described above. A resin composition for forming the adhesive layer 4 is prepared and applied on the base film 1 using a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, and the adhesive layer 4 is formed. In addition, before forming the adhesive layer 4, the above-mentioned colored layer can be formed.
Next, a metal thin film layer is formed on the adhesive layer 4. The material and method for forming the metal thin film layer are as described above. Next, a primer layer formed between the metal thin film layer and the surface protective layer is formed to form a surface protective layer.

Next, the decorative resin molded product of the present invention will be described.
[Decorative resin molded product]
The decorative resin molded product of the present invention is characterized by having the above-described decorative sheet for three-dimensional molding of the present invention on a plastic substrate in a state where the base film of the decorative sheet is in contact.
The decorative resin molded product of the present invention will be described with reference to FIG. FIG. 2 is a schematic diagram showing a cross section of one embodiment of the decorative resin molded product of the present invention. The decorative resin molded product 20 is formed on the plastic substrate 6 and the decorative sheet 10 for three-dimensional molding of the present invention. (On the base film 1, the base film 1 is in contact with the adhesive layer 4, the metal thin film layer 2, the primer layer 5 and the surface protective layer 3 that are provided if necessary). It shows having in a state.

Next, the manufacturing method of the decorative resin molded product of this invention is demonstrated.
[Method of manufacturing decorative resin molded product]
The method for producing a decorative resin molded product of the present invention is a method for three-dimensional molding from the surface protective layer side of the decorative sheet for three-dimensional molding of the present invention to the mold with the surface protective layer side facing the mold. The process of heating the decorative sheet, the process of preforming the heated decorative sheet for three-dimensional molding so as to conform to the inner shape of the mold, and closely clamping the mold to the inner surface of the mold, the injection resin in the mold It includes a step of injecting, and a step of taking out the decorative resin molded product from the mold after cooling the injection resin.

The manufacturing method of the decorative resin molded product of the present invention includes the following steps (1) to (4).
(1) First, the process of heating the 3D-shaped decorative sheet from the surface protective layer side with a hot plate with the surface protective layer side of the decorative sheet for 3D molding facing into the mold,
(2) A step of preforming the heated decorative sheet for three-dimensional molding so as to conform to the shape in the mold and closely contacting the inner surface of the mold to clamp the mold,
(3) a step of injecting the injection resin into the mold, and (4) a step of taking out the decorative resin molded product from the mold after the injection resin has cooled,
In said (1) and (2), the temperature which heats the decoration sheet for three-dimensional shaping | molding is about 160-190 degreeC normally.
In the step (3), the injection resin is melted and injected into the cavity to integrate the three-dimensional decorative sheet and the injection resin. When the injection resin is a thermoplastic resin, it is made into a fluid state by heating and melting, and when the injection resin is a thermosetting resin, the uncured liquid composition is injected in a fluid state at room temperature or appropriately heated. Cool and solidify. As a result, the decorative sheet for three-dimensional molding is integrated with the formed resin molded body and adhered to form a decorative resin molded product. The heating temperature of the injection resin depends on the injection resin, but is generally about 180 to 320 ° C.

Moreover, as another aspect of the manufacturing method of the decorative resin molded product of the present invention, a vacuum forming step for forming the above-described decorative sheet for three-dimensional molding of the present invention into a three-dimensional shape in advance by a vacuum forming die, an extra portion To obtain a molded sheet by inserting the molded sheet into an injection mold, close the injection mold, and inject a resin in a fluid state into the mold to integrate the resin and the molded sheet. It is characterized by.
The difference from the above method is that it has a vacuum forming step corresponding to the preforming of the above method, and has a step of removing the mold once from the vacuum forming mold and trimming the excess part to obtain a molded sheet. This is a so-called insert molding method. The temperature for heating the decorative sheet for three-dimensional molding and the heating temperature for the injection resin are the same as described above.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics of the decorative sheet for three-dimensional molding obtained in each example were evaluated according to the following procedures.

<Evaluation of various characteristics of decorative sheet>
(1) Formability The decorative sheet is heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming is performed using a vacuum forming die (maximum draw ratio: 130%) to form the internal shape of the die. After the sheet is cooled, the decorative sheet is released from the mold. The evaluation criteria are as follows.
(Double-circle); It followed the three-dimensional shape well and the shape retainability was also good.
○: Although a fine coating crack or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, there was no practical problem.
X: The three-dimensional shape was satisfactorily followed, but warpage and distortion occurred.
XX: Coating film cracking or whitening occurred in a part of the three-dimensional shape portion or the maximum stretched portion.
(2) Scratch resistance The appearance of the test piece after 5 reciprocations was evaluated with a load of 1.5 kgf (14.7 N) using # 0000 steel wool. The evaluation criteria are as follows.
A: There was no scratch.
○: Although fine scratches were observed on the surface, the coating film was not cracked or whitened.
Δ: Minor scratches on the surface.
X: There were significant scratches on the surface.
(3) Chemical resistance Ethanol was dropped on each sheet piece 10 cm × 10 cm, and the appearance after standing at room temperature for 1 hour in a state covered with a watch glass was confirmed.
A: No change in appearance.
○: Extremely slight whitening and swelling were observed on the surface, but no significant whitening, swelling or dissolution was observed.
Δ: Extremely slight whitening, swelling, and dissolution were observed on the surface.
X: There was remarkable whitening, swelling, and dissolution on the surface.

<Weight average molecular weight and number average molecular weight of electron beam curable resin>
A high-speed GPC apparatus manufactured by Tosoh Corporation was used. The column used is a product name “TSKgel αM” manufactured by Tosoh Corporation, the solvent is N-methyl-2-pyrrolidinone (NMP), and the column temperature is 40 ° C. and the flow rate is 0.5 cm ³ / min. It was. The weight average molecular weight and number average molecular weight in the present invention are values in terms of standard polystyrene.
<Average molecular weight between crosslinking points after curing of electron beam curable resin>
The value obtained by dividing the number average molecular weight obtained above by the number of functional groups was defined as the average molecular weight between crosslinking points.

  Further, as the electron beam curable resin EB1, a mixture of a bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) and a hexafunctional urethane acrylate oligomer (weight average molecular weight: 6000) in a mass ratio of 80:20 was used, and EB2 A mixture of 70:30 mass ratio of acrylic silicone acrylate (weight average molecular weight: 20000, average molecular weight between cross-linking points after curing: 200) and hexafunctional urethane acrylate oligomer (weight average molecular weight: 5000) was used.

Example 1
As a release sheet, an acrylic / urethane block copolymer resin is coated on a release layer of biaxially stretched PET (thickness 25 μm, arithmetic average roughness Ra: 0.01 μm) having a silicone release layer on the surface layer. Thus, a transparent primer layer 5 having a thickness of 2 μm was formed.
Subsequently, after depositing tin on the primer layer 5 to form the metal thin film layer 2, a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 5.6 is formed on the metal thin film layer by a reverse coating method. Is applied to provide a heat-adhesive layer (adhesive layer 4A), on which an adhesive composed of an acrylic resin and a vinyl chloride / vinyl acetate copolymer resin (mass ratio 2: 8) is applied. The adhesive layer 4 was obtained by forming a layer (adhesive layer 4B). The thus obtained sheet provided with the primer layer 5, the metal thin film layer 2 and the adhesive layer 4 on the release sheet is brought into contact with the base film 1 made of ABS resin having a thickness of 300 μm on the adhesive layer 4 side. After that, a stainless steel mirror plate with an arithmetic average roughness Ra of 0.05 μm is provided on the primer layer side (front side), and a satin finish with an arithmetic average roughness Ra of 4.0 μm and a ten-point average roughness RzJIS of 16 μm on the base film side (back side). Using a hot press machine using a stainless steel metal plate with a handle, hot pressing was performed at 150 ° C. under a pressure of 0.5 MPa for 10 minutes. After the hot pressing, the release sheet was peeled off, and the primer layer 5, the metal thin film layer 2, and the adhesive layer 4 were transferred to the base film 1.
Next, an ionizing radiation curable resin of the type shown in Table 1 was applied to the surface of the primer layer after the release sheet was peeled off by gravure reverse so that the thickness after hardening was 10 μm. 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. A decorative sheet was obtained. Table 1 shows various characteristics of each decorative sheet.

Example 2
In Example 1, as the electron beam curable resin composition for forming the surface protective layer, the decorative sheet for three-dimensional molding of the present invention was used in the same manner as in Example 1 except that those shown in Table 1 were used. Got. Table 1 shows various characteristics of each decorative sheet.

Comparative Example 1
A transparent film, polyethylene terephthalate (hereinafter referred to as “PET”) film (thickness 25 μm, single-sided easy adhesion treatment) was prepared. Tin was vapor-deposited on the surface of the PET film that was not subjected to easy adhesion treatment, and a metal thin film layer was provided. The metal thin film layer had an optical density OD value of 0.7 to 1.4.
Next, a vinyl chloride / vinyl acetate copolymer resin having an average acid value of 5.6 is applied on the metal thin film layer by a reverse coating method to provide a thermal adhesive layer (corresponding to the adhesive layer 4A). An adhesive layer (corresponding to the adhesive layer 4B) is formed by applying an adhesive made of acrylic resin and vinyl chloride / vinyl acetate copolymer resin (mass ratio 2: 8) to form an adhesive layer. It was.
Next, a two-component curable urethane resin (the main component is polyester-based and the curing agent is hexamethylene diisocyanate) was applied to the easy-adhesion treated surface of the PET film by a reverse coating method to obtain a primer layer. On the primer layer, an electron beam curable resin composition of the type shown in Table 1 was applied by gravure reverse so that the thickness after curing was 10 μm. This uncured resin layer was 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.
Then, it stuck on the base film which consists of ABS resin of thickness 300 micrometers through the said contact bonding layer, and obtained the decorative sheet for three-dimensional shaping | molding. Table 1 shows various characteristics of each decorative sheet.

Comparative Example 2
In Comparative Example 1, a decorative sheet for three-dimensional molding was obtained in the same manner as in Comparative Example 1 except that the electron beam curable resin composition for forming the surface protective layer was used as shown in Table 1. . Table 1 shows various characteristics of the decorative sheet.

Comparative Example 3
In Comparative Example 1, a decorative sheet for three-dimensional molding was produced in the same manner as Comparative Example 1 except that the surface protective layer was not formed. The various characteristics of this decorative sheet are shown in Table 1.

Comparative Example 4
In Comparative Example 3, a decorative sheet for three-dimensional molding was produced in the same manner as Comparative Example 3, except that a transparent acrylic film having a thickness of 100 μm was used instead of the transparent PET film. The various characteristics of this decorative sheet are shown in Table 1.

EB1: Mixture of bifunctional polycarbonate acrylate (weight average molecular weight: 10,000) and hexafunctional urethane acrylate oligomer (weight average molecular weight: 6000) (mass ratio 80:20)
EB2: Mixture of acrylic silicone acrylate (weight average molecular weight: 20000, molecular weight between crosslinking points 200) and hexafunctional urethane acrylate oligomer (weight average molecular weight: 5000) (mass ratio 70:30)
EB3; hexafunctional urethane acrylate oligomer (weight average molecular weight: 2000)

Examples 3 and 4
Each of the two decorative sheets obtained in Examples 1 and 2 was used, and each decorative sheet was heated at a hot platen temperature of 170 ° C. so as to conform to the shape in the mold of injection molding, thereby protecting the surface. The layer side was adhered to the inner surface of the mold. The mold used was a 80 mm square size, 10 mm rising and 2R tray shape with a high deep drawing degree. On the other hand, an ABS resin [manufactured by Nippon A & L Co., Ltd., trade name “Clarastic MTH-2”] was used as an injection resin, which was melted at 230 ° C. and then injected into the cavity. After the injection resin was solidified, the decorative resin molded product was taken out from the mold to obtain a decorative resin molded product having the configuration shown in FIG.

The decorative sheet for three-dimensional molding of the present invention is excellent in moldability, is used for three-dimensional molding, has a metallic tone excellent in design, and gives a decorative resin molded article excellent in scratch resistance Can do. This decorative resin molded product is used as an alternative to an article such as an automobile grill.
[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Base film 2 Metal thin film layer 3 Surface protective layer 4 Adhesive layer 5 Primer layer 6 Plastic substrate 10 Decorating sheet 20 for three-dimensional molding Decorating resin molded product

Claims (10)

  A decorative sheet for three-dimensional molding having at least a metal thin film layer and a surface protective layer in this order on a base film, wherein the metal thin film layer and the surface protective layer are in direct contact with each other or through a primer layer. And the surface protective layer is a layer made of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate. Original decorative sheet.   The decorative sheet for three-dimensional molding according to claim 1, wherein the ionizing radiation curable resin composition further contains a polyfunctional (meth) acrylate.   The decorative sheet for three-dimensional molding according to claim 2, wherein the polyfunctional (meth) acrylate is trifunctional or higher.   The decorative sheet for three-dimensional molding according to any one of claims 1 to 3, wherein the metal thin film layer is an indium, tin, chromium, or aluminum thin film layer.   The decorative sheet for three-dimensional molding according to any one of claims 1 to 4, further comprising an adhesive layer containing an acrylic resin and / or a vinyl chloride-vinyl acetate copolymer between the metal thin film layer and the base film. .   A decorative molded product using the decorative sheet for three-dimensional molding according to any one of claims 1 to 5.   A step of forming a design layer having a metal thin film layer on the release sheet, a step of transferring the design layer onto the base film, a step of peeling off the release sheet on the base film, an ionizing radiation curable resin on the surface from which the base film has been peeled off A method for producing a decorative sheet, comprising a step of laminating a composition layer, and a step of crosslinking and curing the ionizing radiation curable resin composition layer to form a surface protective layer.   (A) a step of forming a primer layer on the release sheet, (b) a step of forming a design layer having a metal thin film layer on the primer layer, and (c) transferring the primer layer and the design layer onto the base film. A step, (d) a step of peeling the release sheet on the base film, (e) a step of laminating an ionizing radiation curable resin composition layer on the primer layer formed on the base film, and (f) the ionization A method for producing a decorative sheet, comprising a step of crosslinking and curing a radiation-curable resin composition layer to form a surface protective layer.   A step of heating the decorative sheet for three-dimensional molding from the protective layer side by a heating plate with the surface protective layer side of the decorative sheet for three-dimensional molding according to any one of claims 1 to 5 facing into the mold. , A step of preforming the heated decorative sheet for three-dimensional molding so as to conform to the shape in the mold, and closely clamping the mold to the inner surface of the mold, a step of injecting an injection resin into the mold, the injection A method for producing a decorated resin molded product comprising the step of taking out a decorated resin molded product from a mold after the resin has cooled.   A vacuum forming step in which the decorative sheet for three-dimensional forming according to any one of claims 1 to 5 is previously formed into a three-dimensional shape by a vacuum forming die, a step of trimming excess portions to obtain a formed sheet, A method for producing a decorative resin molded article, comprising the steps of inserting into an injection mold, closing the injection mold, injecting a fluid resin into the mold, and integrating the resin and the molded sheet.

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