JP2012213928A - Decorative sheet for three-dimensional molding, method for manufacturing the decorative sheet, decorative resin molded product, and method for manufacturing the decorative resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet for three-dimensional molding excellent in weatherability, scratch resistance, processability or the like, and to provide a method for manufacturing decorative resin molded products having the properties using the decorative sheet.SOLUTION: The decorative sheet for three-dimensional forming includes at least a pattern layer, a primer layer (a), a primer layer (b), and a surface protection layer which are sequentially formed on a base film. In the decorative sheet, the surface protection layer is composed of cured material of ionizing radiation-curable resin composition. The primer layer (b) is a layer containing polymer of hindered amine-based light stabilizer having a reactive functional group (A). The decorative resin molded product is manufactured using the decorative sheet by a simultaneous injection molding and decorating method or an insert molding method.

Description

  The present invention relates to a decorative sheet suitable for three-dimensional molding, a method for producing the decorative sheet, and a decorative resin molded product and a method for producing the decorative resin molded product using the decorative sheet. More specifically, a decorative sheet for three-dimensional molding having excellent weather resistance, scratch resistance, workability, and the like, a manufacturing method thereof, a decorative resin molded product using the decorative sheet, and the decorative for three-dimensional molding The present invention relates to a method for producing a decorated resin molded product by using an insert molding method or an injection molding simultaneous decorating method using a sheet.

  Decorated resin molded products decorated by laminating decorative sheets on the surface of molded products are 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 injects 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. There is an injection molding simultaneous decorating method for decorating the surface (for example, see Patent Document 1).

  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.
Further, although an ionizing radiation curable resin such as an ultraviolet curable resin is used as the surface protective layer, a method of making it a semi-cured state at the stage of the decorative sheet and completely curing it after the decorative molding has been tried (Patent Document 2). 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 3 and 4), 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. Although there is an example using a resin composition containing a small amount of oligomer (see Patent Document 5), 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 6).
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.

  On the other hand, automobile exterior materials such as automobile bumpers are often exposed to direct sunlight and wind and rain. Therefore, decorative sheets used for surface protection of exterior materials and the like are required to have extremely severe weather resistance. Yes. In order to improve the weather resistance, various sheets have been studied. For example, in Patent Document 7, weather resistance is improved by adding an additive such as a light stabilizer or an ultraviolet absorber to the protective layer. However, when the content of the additive in the protective layer is improved, due to compatibility with the binder resin forming the protective layer, these additives bleed out, causing stickiness. It was. On the other hand, if the content of the additive is such that it does not bleed out, sufficient performance of these additives cannot be obtained, and there is also a problem that satisfactory products cannot be obtained in terms of weather resistance.

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 JP 2009-66967 A

  The present invention relates to a decorative sheet for three-dimensional molding excellent in weather resistance, scratch resistance, workability, and the like, a method for producing the decorative sheet, and a decorative resin molding having excellent weather resistance and scratch resistance using the decorative sheet. It aims at providing goods and its manufacturing method.

As a result of intensive studies to achieve the above object, the present inventors have at least a pattern layer, a primer layer (a), a primer layer (b), and a surface protective layer in this order on the base film, The surface protective layer is a layer made of a cured product of an ionizing radiation curable resin composition, preferably a composition containing a specific compound, and the primer layer (b) has a reactive functional group as a weathering agent. It has been found that a decorative sheet, which is a layer containing a polymer of a hindered amine light stabilizer, is excellent in weather resistance, scratch resistance, processability, and the like, and that weathering bleed out is suppressed.
The present invention has been completed based on such findings.

That is, the present invention
(1) A three-dimensional decorative sheet having, in order, at least a pattern layer, a primer layer (a), a primer layer (b) and a surface protective layer on a base film, the surface protective layer being ionizing radiation curable A decorative sheet characterized in that it is a layer made of a cured product of a resin composition and the primer layer (b) is a layer containing a polymer of a hindered amine light stabilizer having a reactive functional group A,
(2) (a) a step of sequentially forming a primer layer (b) and a primer layer (a) on a release film, (b) a step of forming a picture layer on the primer layer (a), (c) the primer A step of transferring the layer (b), the primer layer (a) and the pattern layer onto the base film, (d) a step of peeling off the release film on the base film, (e) a primer layer (b) formed on the base film (b) A process for laminating an ionizing radiation curable resin composition thereon, and (f) a method for producing a decorative sheet comprising a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer, The method for producing a decorative sheet for three-dimensional molding, wherein the primer layer (b) is a layer containing a polymer of a hindered amine light stabilizer having a reactive functional group A,
(3) a decorative resin molded product using the decorative sheet for three-dimensional molding described in (1) above,
(4) The step of heating the decorative sheet from the protective layer side by a heating plate with the surface protective layer side of the decorative sheet for three-dimensional molding described in (1) above in the mold, the heated A process of preforming the decorative sheet so as to conform to the inner shape of the mold and tightly attaching the decorative sheet to the inner surface of the mold; a process of injecting the injection resin into the mold; A process for producing a decorative resin molded product, comprising a step of taking out a decorative resin molded product, and (5) the decorative sheet for three-dimensional molding according to (1) above is formed into a three-dimensional shape in advance by a vacuum forming die. Vacuum forming process to mold, process to trim the excess part to obtain a molded sheet, insert the molded sheet into the injection mold, close the injection mold and inject the fluid resin into the mold to mold with the resin A decorative resin molded product characterized by including a step of integrating sheets Manufacturing method,
Is to provide.

  According to the present invention, the three-dimensional decorative sheet having excellent weather resistance, scratch resistance, workability, and the like, and the decorative sheet, the properties described above by the insert molding method or the injection molding simultaneous decoration method. It is possible to provide a method for producing a decorated resin molded article having

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 decorative sheet for three-dimensional molding of the present invention is a decorative sheet having at least a pattern layer, a primer layer (a), a primer layer (b) and a surface protective layer in this order on a base film, the surface protective layer Is a layer made of a cured product of an ionizing radiation curable resin composition, and the primer layer (b) is a layer containing a polymer of a hindered amine light stabilizer having a reactive functional group A. To do.

  Drawing 1 is a mimetic diagram showing the section of one mode of decoration sheet 10 for three-dimensional fabrication of the present invention. In the example shown in FIG. 1, the three-dimensional decorative sheet 10 has a configuration having a pattern layer 12, a primer layer (a) 13, a primer layer (b) 14, and a surface protective layer 15 on the base film 11 in this order. It has become.

(Base film)
In the decorative sheet for three-dimensional molding 10 of the present invention, the base film 11 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 preferable, and polyolefin resins are particularly preferable when the decorative sheet is produced by transfer specifications.
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 said base film is selected according to a use, it is about 100-500 micrometers normally. When the thickness of the base film is 100 μm or more, the shape can be prevented from being distorted in vacuum forming. On the other hand, when the thickness is 500 μm or less, the decorative sheet becomes thick and the operability is prevented from being lowered. Can do. The thickness of the base film is more preferably 250 to 500 μm, and further preferably 300 to 500 μm.

  In addition, the base film is based on JIS K7127, uses Type B as a test piece, and has a tensile elastic modulus at room temperature measured in a range of 1000 to 4000 MPa (initial modulus) measured at a tensile speed of 50 m / min. Is preferred. If the tensile elastic modulus of the base film at room temperature is in the above range, high rigidity can be imparted to the base film, so that distortion of the shape during vacuum forming can be suppressed. A more preferable tensile elastic modulus is in the range of 2000 to 3000 MPa from the viewpoint of adjusting the tension when continuously producing with Roll To Roll.

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.

(Picture layer)
The pattern layer 12 shown in FIG. 1 gives a decorative property to a decorative resin molded product to be described later, and is formed by printing various patterns using ink and a printing machine. Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.

As the pattern ink used for the pattern layer 12, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., any one can be used alone or in combination of two or more. Of these, vinyl chloride / vinyl acetate copolymer resins are particularly preferred.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

In the three-dimensional decorative sheet 10 of the present invention, a concealing layer (not shown) may be provided between the base film 11 and the pattern layer 12 as desired. It is provided for the purpose of preventing the color of the pattern of the decorative sheet 10 from being affected by changes and variations in the color of the surface of the base film 11. Usually, it is often formed with an opaque color, and a so-called solid printing layer having a thickness of about 1 to 20 μm is preferably used.
Further, a polyolefin-based thermal adhesive layer having a melting point of about 70 to 130 ° C. may be provided between the base film 11 and the pattern layer 12.

(Primer layer (a))
In the decorative sheet 10 for three-dimensional molding of the present invention, a primer layer (a) 13 is disposed on the picture layer 12 described above. The primer layer (a) is a method for producing a decorative sheet by a transfer method, which will be described later, and functions as a release layer that facilitates release from the release film, and in relation to the primer layer (b) described later. It has a function as an interlayer adhesion layer that improves the interlayer adhesion of the base film, the pattern layer, both primer layers (a) and (b), and the surface protective layer.
Examples of the primer constituting the primer layer (a) include a two-component curable urethane resin having a polyol as a main component and a polyvalent isocyanate as a crosslinking agent (curing agent).

The polyol component has two or more hydroxyl groups in the molecule, and examples thereof include acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyethylene glycol, and polypropylene glycol. As the main agent, acrylic-urethane copolymers, vinyl chloride-vinyl acetate copolymers, polycarbonate-based urethane acrylates, and the like are also preferably used.
Examples of the polyvalent isocyanate 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.
Among these, an acrylic-urethane block copolymer is used as a main agent, and 100 parts by mass of the main agent is reacted with about 1 to 20 parts by mass of a polyvalent isocyanate compound as a curing agent, followed by thermosetting. A (meth) acryl-urethane copolymer primer is preferred.

(Primer layer (b))
The decorative sheet for three-dimensional molding 10 of the present invention has a primer layer (a) 13 and a surface in order to make fine cracks and whitening hardly occur in the stretched portion of the surface protective layer 15 and to improve interlayer adhesion. A primer layer (b) 14 is provided between the protective layer 15. Examples of the primer constituting the primer layer (b) 14 include the same ones as those constituting the primer layer (a) described above. Among them, a polycarbonate-based urethane acrylate is used as a main component, A (meth) polycarbonate urethane acrylate primer obtained by reacting and thermosetting a polyisocyanate compound of about 1 to 10 parts by mass as a curing agent with respect to 100 parts by mass of the main agent is suitable.

  In the decorative sheet for three-dimensional molding 10 of the present invention, the primer layer (b) 14 has a reactive functional group A as a weathering agent in order to impart excellent weather resistance to the decorative sheet. Containing a polymer of a hindered amine light stabilizer (hereinafter, the hindered amine light stabilizer is sometimes referred to as “HALS”, and HALS having the reactive functional group A is sometimes referred to as “reactive HALS”). Cost.

<Reactive HALS>
The reactive group A in the reactive HALS is not particularly limited as long as it can be polymerized by irradiation with ionizing radiation. For example, an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group may be used. Preferred examples include a functional group having at least one selected from these. Of these, a (meth) acryloyl group is preferable.

Examples of such reactive HALS include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6- Tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acrylo Examples include ru-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine and the like. It is done.
These reactive HALS may be used individually by 1 type, and may be used in combination of 2 or more type.
The reactive HALS is polymerized by irradiation with ionizing radiation to increase its molecular weight, or copolymerizes with the ionizing radiation curable resin at the interface between the primer layer (b) and the surface protective layer. As a result, bleed-out is suppressed.

  In the decorative sheet of the present invention, in the primer layer (b), from the viewpoint of the balance between weather resistance and bleed-out, the reactive HALS polymer is 100 parts by mass of the resin as the reactive HALS before polymerization. It is preferably included at a rate of 0.1 to 4.5 parts by mass (converted to a solid content) with respect to (in terms of solid content), more preferably 0.5 to 3.0 parts by mass. More preferably, it is contained at a ratio of 0.0 to 2.0 parts by mass.

  The primer layer (b) can contain an ultraviolet absorber or a light stabilizer having no reactive group as a weather resistance improver as long as the object of the present invention is not impaired. The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type etc. can be used, for example. Examples of the triazole group include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, and 3- [3 of polyethylene glycol. -(Benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester and the like.

  Examples of the triazine series include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- [4 -[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis [ 2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl)] Oki Ci] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferable, and examples of the benzophenone series include 2,4-dihydroxybenzophenone, 2 2, 2 ', 4-trihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like.

Moreover, the polymer of the reactive ultraviolet absorber which has polymerizable groups, such as a (meth) acryloyl group, can also be contained as a ultraviolet absorber.
In addition, the hindered amine light stabilizer or the ultraviolet absorber has a polymerizable group such as a (meth) acryloyl group in the molecule, so that it is polymerized by irradiation with ionizing radiation to increase its molecular weight or Bleed out is suppressed by copolymerizing with the ionizing radiation curable resin at the interface between the primer layer (b) and the surface protective layer, but the performance as a HALS of itself or the performance as an ultraviolet absorber is reduced. There is a fear.

On the other hand, examples of the light stabilizer having no reactive group 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.
In addition, the primer layer (a) described above includes a hindered amine light stabilizer not having a reactive group, an ultraviolet absorber, and a polymer of the reactive ultraviolet absorber within a range in which the object of the present invention is not impaired. And may be contained.

(Surface protective layer)
The surface protective layer 15 in the decorative sheet 10 of the present invention is a layer made of a cured product of an ionizing radiation curable resin composition, and the ionizing radiation curable resin composition (hereinafter simply referred to as “resin composition”). Is preferable from the viewpoints of scratch resistance, weather resistance, processability, and the like, as the ionizing radiation curable resin, those containing polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate, As the ionizing radiation curable compound, a polyfunctional (meth) acrylate can be included.
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. The ionizing radiation curable resin (compound) refers to a resin (compound) that crosslinks and cures when irradiated with the ionizing radiation.

<Polycarbonate (meth) acrylate>
In the present invention, polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate, or both are used as the ionizing radiation curable resin. From the viewpoint of effects, the use of polycarbonate (meth) acrylate is preferred. 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 using a polycondensation reaction from a diol compound (i), a trihydric or higher polyhydric alcohol (ii), and a compound (iii) which becomes a carbonyl component.
The diol compound (i) 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 (ii) 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 (iii) 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 (i), a trihydric or higher polyhydric alcohol (ii), and a compound (iii) to be a carbonyl component to polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (i) to the polyhydric alcohol (ii) is preferably in the range of 50:50 to 99: 1, and the diol compound (iii) of the compound (iii) serving as the carbonyl component ( The charging molar ratio of i) to polyhydric alcohol (ii) is preferably 0.2 to 2 equivalents relative to the hydroxyl groups 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.
In addition, the polyfunctional (meth) acrylate may be either an oligomer or a monomer, but from the viewpoint of improving the three-dimensional moldability of the sheet produced using the ionizing radiation curable resin composition, the polyfunctional (meth) acrylate oligomer Is preferred.

  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 ionizing radiation curable resin composition, 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 polycarbonate (meta). ) Acrylate: Polyfunctional (meth) acrylate = 98: 2-70: 30 is preferable.
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 is 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% by mass), the ionizing radiation curable resin composition. The three-dimensional formability of a sheet manufactured using a product will deteriorate. More preferably, the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is 95: 5 to 80:20.

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

<Acrylic silicone (meth) acrylate>
Next, acrylic silicone (meth) acrylate used as an 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. As long as it has two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal.
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 or more.
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 the three-dimensional formability, chemical resistance, and scratch resistance of a sheet produced using the resin composition, 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 of the sheet, and if it is 2500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance.

In the ionizing radiation curable resin composition, when the above-mentioned acrylic silicone (meth) acrylate is used as the ionizing radiation curable resin, the mass of the acrylic silicone (meth) acrylate and the above-described polyfunctional (meth) acrylate. The ratio is preferably 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 (that is, when the amount of acrylic silicone (meth) acrylate exceeds 95 mass%), the resin composition is used. The scratch resistance and three-dimensional formability of the manufactured sheet are reduced. 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 mass%), the chemical resistance of the sheet is reduced. And scratch resistance are reduced. More preferably, the mass ratio of acrylic silicone (meth) acrylate to multifunctional (meth) acrylate is 90:10 to 75:25.
In the ionizing radiation curable resin composition, the above-mentioned monofunctional (meth) acrylate is impaired together with the polyfunctional (meth) acrylate for the purpose of reducing the viscosity of the resin composition. In such a range, it can be contained as appropriate.

  The ionizing radiation curable resin composition is, as long as the purpose of the present invention is not impaired, optionally, a weathering agent such as a reactive HALS polymer as shown in the explanation of the primer layer (b), a reaction An appropriate amount of a weather resistance improver such as HALS or UV absorber having no functional functional group can be contained.

When an ultraviolet curable resin is used in the ionizing radiation curable resin composition, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect 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.

  Moreover, in the said ionizing radiation-curable resin composition, according to the desired physical property of the surface protection layer of the decorating sheet manufactured using the said resin composition, various additives are added in the range which does not impair the objective of this invention. Can be blended. Examples of the additive include 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, and an antifoaming agent. Agents, fillers, solvents, colorants and the like.

Here, 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.

The ionizing radiation curable resin composition is preferably electron beam curable as ionizing radiation curable. In the case of electron beam curable, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and stable curing characteristics can be obtained.
The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the primer layer (b) 14 by a coating method described later.
In the present invention, the resin composition is applied to the surface of the primer layer (b) 14 so that the thickness after curing is about 1 to 1000 μm, such as gravure coating, bar coating, roll coating, reverse roll coating, comma. It coats by well-known systems, such as a coat, preferably a gravure coat, and forms 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.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a material that deteriorates due to an electron beam is used as the base film 11, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the acceleration voltage so as to be equal to each other, it is possible to suppress the irradiation of the extra electron beam to the base film 11, and to minimize the deterioration of the base film 11 due to the excess electron beam. .
The irradiation dose is preferably such that the crosslink density of the resin 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).
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.

In this invention, it is preferable that the thickness after the hardening of the surface protective layer 15 is 1-1000 micrometers. If the thickness of the surface protective layer 15 after curing is 1 μm or more, sufficient physical properties as a protective layer such as scratch resistance and weather resistance can be obtained. On the other hand, if the thickness of the surface protective layer 15 after curing is 1000 μm or less, it is easy to irradiate ionizing radiation uniformly, it is easy to obtain uniform curing, and this is economically advantageous.
Further, the thickness of the surface protective layer 15 after curing is more preferably 1 to 50 μm, and further preferably 1 to 30 μm, so that the three-dimensional formability is improved, and a complicated three-dimensional shape such as an automobile interior use is obtained. High followability can be obtained. Therefore, in the decorative sheet of the present invention, even if a hard ionizing radiation curable resin is blended, excellent three-dimensional formability can be expressed, and the coating film is hardened without impairing the three-dimensional formability. Therefore, it is possible to provide excellent scratch resistance that is preferable in terms of processing and practical use.
Since the decorative sheet for three-dimensional molding of the present invention has a sufficiently high three-dimensional formability even when the thickness of the surface protective layer 15 is made thicker than the conventional one, the film thickness is particularly high for the surface protective layer. It is also useful as a decorative sheet for a member required for the vehicle, for example, a vehicle exterior part.

  Since the decorative sheet for three-dimensional molding 10 of the present invention improves the adhesion with the injection resin, an adhesive layer (illustrated) is provided on the back surface (surface opposite to the surface protective layer 15) of the decorative sheet 10 as desired. No.) can be provided. A thermoplastic resin or a curable resin is used for the adhesive layer depending on the injection resin. Examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. Can be used alone or in combination of two or more. Examples of the thermosetting resin include urethane resin and epoxy resin.

The pattern layer 12 is formed by a normal printing method such as gravure printing. The concealing layer is formed by a normal printing method such as gravure printing or a normal coating method such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating.
The primer layer (a) 13, primer layer (b) 14, adhesive layer, and thermal adhesive layer are gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip. It is formed by a normal coating method such as a coat, a silk screen solid coat, a wire bar coat, a flow coat, a comma coat, a pouring coat, a brush coating, a spray coating, or a transfer coating method. The transfer coating method is a method in which a primer layer, an adhesive layer, or a thermal adhesive layer is once formed on a thin sheet (film substrate), and then coated on the surface of the target layer in the decorative sheet 10. .

The thickness of the pattern layer 12 is appropriately selected depending on the pattern. The thickness of the masking layer is about 1 to 20 μm.
The thicknesses of the primer layer (a) 13 and the primer layer (b) 14 are each preferably about 0.1 to 10 μm. When it is 0.1 μm or more, the effect of preventing the surface protective layer from cracking, breaking, whitening, etc. can be sufficiently exerted. On the other hand, if the thicknesses of the primer layers (a) and (b) are 10 μm or less, the three-dimensional formability does not fluctuate when the primer layer is applied because the drying and curing of the coating is stable. preferable. From the above points, the thicknesses of the primer layers (a) and (b) are more preferably 1 to 10 μm. Similarly, the thickness of the adhesive layer and the thermal adhesive layer is preferably about 0.1 to 10 μm.

In the decorative sheet 10 of the present invention, a transparent film is provided between the pattern layer 12 and the primer layer (a) 13 for the purpose of improving the scratch resistance, weather resistance, chemical resistance, etc. of the decorative sheet. Layers can be interposed.
The transparent film layer is preferably a film layer made of a polyester resin from the viewpoint of the above effects, and specifically includes a polyethylene terephthalate film layer.

The thickness of the transparent film layer is preferably in the range of 10 to 80 μm. When this thickness is 10 μm or more, good printability can be imparted, and when it is 80 μm or less, the shrinkage force after vacuum forming does not become too strong, and the tensile modulus of the base film is increased. Also, distortion of the shape can be suppressed. The thickness of the transparent film layer is more preferably 20 to 75 μm, and further preferably 25 to 70 μm.
This transparent film layer may contain the above-mentioned weathering agent, weathering improving agent, and the like.

(Method for producing decorative sheet for three-dimensional molding)
As a manufacturing method of the decorating sheet of this invention mentioned above, the method of laminating | stacking each layer in order on a base film may be sufficient, and the transfer method shown below may be sufficient.
<Transfer method>
When producing the decorative sheet for three-dimensional molding of the present invention by the transfer method, for example, the following method can be employed.
(A) a step of sequentially forming a primer layer (b) and a primer layer (a) on a release film, (a) a step of forming a pattern layer on the primer layer (a), and (c) the primer layer (B) a step of transferring the primer layer (a) and the pattern layer onto the base film, (d) a step of peeling off the release film on the base film, and (e) a primer layer (b) formed on the base film. It is a method for producing a decorative sheet, including a step of laminating an ionizing radiation curable resin composition on the surface, and (f) a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer. In the present invention, the primer layer (b) is a layer containing a polymer of a hindered amine light stabilizer having a reactive functional group A.
The release film in the step (a) is preferably a release film having a smooth surface, and in the pattern layer forming step (b), a concealing layer can be combined as desired in addition to the pattern layer. . A layer combining the pattern layer and the design layer is hereinafter referred to as a “design layer”.

The base film, primer layer (a), primer layer (b), pattern layer, concealing layer and ionizing radiation curable resin composition in the above method are as described above.
If necessary, a thermal adhesive layer may be formed on the design layer in the step (a).
The thermal adhesive layer is as described above.

Moreover, when manufacturing the decorating sheet which interposes the transparent film layer mentioned above between a pattern layer and a primer layer (a), first, the said design layer is added to the transparent film which comprises a transparent film layer. Provide. The transparent film layer and the design layer are as described above. The transparent film may be subjected to an easy adhesion treatment, but the surface on which the design layer is provided is preferably not subjected to an easy adhesion treatment from the viewpoint of ensuring flatness, while the opposite surface is a surface protective layer. It is preferable that easy adhesion treatment is performed from the viewpoint of adhesiveness.
Next, a thermal adhesive layer is provided on the design layer as necessary.
After performing the step (a), a transparent film provided with the thermal adhesive layer is laminated on the primer layer (b) so that the surface opposite to the thermal adhesive layer is in contact therewith. Next, the primer layer (b), the primer layer (a), the design layer, and a transparent film layer having a thermal adhesive layer provided as necessary are transferred onto the base film. Next, a decorative sheet having a transparent film layer between the pattern layer and the primer layer (a) is obtained by sequentially performing the steps (e), (e) and (f).
The thermal adhesive layer may be directly formed on the base film.

In addition, in the manufacturing method of the decorating sheet mentioned above, that the surface of a peeling film is smooth means that surface roughness (Ra) is 0.5 micrometer or less, and it is preferable that it is 0.2 micrometer or less. Here, the surface roughness (Ra) refers to the arithmetic average roughness Ra defined in JIS B 0601: 2001.
The release film is not particularly limited as long as it is a film that can be peeled off after contact with the primer layer. Examples thereof include films and papers made of polyethylene terephthalate, polyethylene, polypropylene, etc., or films and papers coated with a release agent such as silicone (release treatment). The peeled film is preferably peeled and peeled easily.

The decorative sheet of the present invention can be used for various injection molding methods such as insert molding method, injection molding simultaneous decoration method, blow molding method, gas injection molding method, etc. Preferably used.
And the decorative resin molded product of the present invention using the decorative sheet for three-dimensional molding of the present invention is excellent in weather resistance and scratch resistance, and is an exterior material for automobiles, entrance doors and exterior materials for general residences, public It can be particularly suitably used for applications that are often exposed to direct sunlight or wind and rain, such as interior and exterior such as floor materials and outer walls of facilities, structures and structures installed outdoors.

Next, the manufacturing method of the decorative resin molded product of this invention is demonstrated.
[Method of manufacturing decorative resin molded product]
There are two aspects to the method for producing a decorated resin molded article of the present invention.
First, the first aspect is a step of heating the decorative sheet from the surface protective layer side by a hot plate with the surface protective layer side of the decorative sheet for three-dimensional molding of the present invention described above facing the mold, A step of preforming the heated decorative sheet so as to conform to the shape in the mold and closely contacting the inner surface of the mold and clamping, a step of injecting an injection resin into the mold, and after cooling the injection resin And a step of taking out the decorative resin molded product from the mold.

The manufacturing method (1st aspect) of the decorative resin molded product of this invention includes the following processes (1)-(4).
(1) First, the step of heating the decorative sheet from the surface protective layer side with a hot plate with the surface protective layer side of the decorative sheet for three-dimensional molding of the present invention facing the mold,
(2) A step of preforming the heated decorative sheet 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 said decorating sheet is about 160-190 degreeC normally.
In the step (3), the injection resin is melted and injected into the cavity to integrate the 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. Thereby, the said decoration sheet | seat integrates and bonds with the formed resin molding, and becomes 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.

Next, the second aspect is a vacuum forming step in which the decorative sheet of the present invention described above is formed into a three-dimensional shape in advance by a vacuum forming die, a step of trimming excess portions to obtain a formed sheet, and injecting the formed sheet It includes a step of inserting into a mold, closing the injection mold, and injecting a resin in a fluid state into the mold to integrate the resin and the molded sheet.
The difference from the first aspect described above is that it has a vacuum forming step corresponding to the preforming of the above-described method, and has a step of once removing from the vacuum forming mold and trimming excess portions to obtain a molded sheet. This is a method called so-called insert molding. The temperature for heating the decorative sheet and the heating temperature for the injection resin are the same as described above.
FIG. 2 is a schematic view showing a cross section of one embodiment of a decorative resin molded product obtained using the decorative sheet of the present invention. The decorative resin molded product 20 is formed on the base film 11 on the plastic substrate 16. , A pattern layer 12, a primer layer (a) 13, a primer layer (b) 14, and a surface protective layer 15 in this order. Reference numeral 10 denotes a decorative sheet.

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 obtained in each example were evaluated according to the following procedures.

<Evaluation of various characteristics of decorative sheet for three-dimensional molding>
(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: 100%) 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.
○: 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.
(Triangle | delta): The slight coating-film crack or whitening generate | occur | produced in a part of three-dimensional shape part or the largest extending | stretching part.
X: The coating film cracking and whitening were seen in the surface protective layer without being able to follow the shape of a type | mold.
(2) Weather resistance Weather resistance evaluation is performed with a weather resistance test apparatus “S-UV (with rain)”. In addition, time evaluates the color change at the time of implementing up to 500 hours.
○: No change Δ: slight change ×: slight change (3) Scratch resistance The appearance of the test piece after 5 reciprocations with a load of 1.5 kgf (14.7 N) was evaluated 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.
(4) Adhesion After the transfer, a cross-cut was made, and then a cellophane adhesive tape was affixed, and a peel test was conducted rapidly at 90 degrees. The evaluation criteria are as follows.
○: No peeling △: Slight peeling ×: Peeling

<Tensile modulus of base film>
The decorative sheet obtained in each Example and Comparative Example was cut into a “tensile No. 1 dumbbell” shape described in JIS K6251 to obtain a sample. Using an A & D Tensilon universal testing machine, the distance between chucks was 80 mm, and the test speed was 50 mm / min.

<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.

Example 1
An acrylic-urethane block, which is the main agent, as a resin composition for the primer layer (a) by gravure printing on a surface of a polyethylene terephthalate (hereinafter referred to as “PET”) film (thickness 25 μm) that has not been subjected to an easy adhesion treatment. A composition obtained by mixing 10 parts by mass of hexamethylene diisocyanate as a curing agent with respect to 100 parts by mass of the copolymer resin was applied to form a transparent primer layer (a) having a thickness of 2 μm.
Next, a pattern layer having a thickness of 3 μm was formed on the primer layer (a). On the pattern layer, polyethylene having a melting point of 110 ° C. was applied to form a heat bonding layer having a thickness of 2 μm.
A transparent polypropylene film (thickness: 380 μm, tensile elastic modulus: 2643 MPa), which is a base film, was laminated on the thermal adhesive layer, and the film was attached by heating at 150 ° C. for 10 minutes.

Next, after peeling off the PET film, a primer layer (b) resin composition having the following composition was applied to form a primer layer (b) having a thickness of 2 μm. Next, 5 g / m ² of a resin composition for a surface protective layer having the following composition was applied on the primer layer (b) by gravure printing to form a coating film.
Subsequently, the surface protection layer was formed by irradiating an electron beam on the conditions of 175 keV and 5 Mrad (50 kGy), and the said coating film was bridge-hardened, and the decorating sheet was obtained.
The decorative sheet was evaluated by the above method. The results are shown in Table 1.

(Resin composition for primer layer (b))
It is a composition obtained by mixing the following resin composition and curing agent in a ratio of 100: 5 (mass ratio).
Resin composition:
Polycarbonate urethane acrylate (mass ratio of urethane component and acrylic component in polycarbonate urethane acrylate: 70/30): 100 parts by mass-Hydroxyphenyltriazine ultraviolet absorber ("Tinuvin 479 (trade name)", Ciba Japan Co., Ltd. Manufactured, described as “UVA” in the table): 3.4 parts by mass. Light stabilizer having a reactive functional group (trade name “Sanol LS-3410”, 1,2,2,6,6-pentamethyl-4 -Piperidinyl methacrylate, manufactured by Ciba Japan Co., Ltd., described as “Reactive HALS” in the table): 1.7 parts by mass Curing agent: Hexamethylene diisocyanate

(Resin composition for surface protective layer)
-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)
(Component (A) of the present invention, described as “PC resin composition” in the table): 100 parts by mass / hydroxyphenyltriazine-based ultraviolet absorber (“Tinuvin 479 (trade name)”, manufactured by Ciba Japan Co., Ltd.) In the table, described as “UVA”): 4 parts by mass

Example 2
In the resin composition for a surface protective layer in Example 1, as component (A), acrylic silicone acrylate (weight average molecular weight: 20000, average molecular weight between crosslinking points 200) and hexafunctional urethane acrylate oligomer (weight average molecular weight: 5000) The decorative sheet was prepared in the same manner as in Example 1 except that the mixture (mass ratio 70:30) (component (A) of the present invention, described as “acrylic silicone resin composition” in the table)) was used. Obtained. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1
In Example 1, instead of the light stabilizer having a reactive functional group in the resin composition for the primer layer, a hindered amine light stabilizer having no reactive functional group (“Tinuvin 123 (trade name)”, Ciba A decorative sheet was obtained in the same manner as in Example 1 except that 2 parts by mass of “Non-Reactive HALS” in the table made by Japan Co., Ltd. was added. The results of evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 2
In Example 1, a decorative sheet was obtained in the same manner as in Example 1 except that the surface protective layer was formed on the primer layer (a) without forming the primer layer (b). The results of evaluation in the same manner as in Example 1 are shown in Table 1.

The decorative sheet for three-dimensional molding of the present invention is excellent in weather resistance, scratch resistance, workability, and the like, and is used for decorative applications such as automobile interior and exterior materials, building materials, and home appliance housings. In addition, a decorative resin molded product having excellent weather resistance and scratch resistance can be provided by insert molding or simultaneous injection molding.
[Explanation of symbols]

10 Three-dimensional decorative sheet 11 Base film 12 Picture layer 13 Primer layer (a)
14 Primer layer (b)
15 Surface protective layer 16 Plastic substrate 20 Decorative resin molded product

Claims (12)

  A decorative sheet having, in order, at least a pattern layer, a primer layer (a), a primer layer (b) and a surface protective layer on a base film, the surface protective layer being formed from a cured product of an ionizing radiation curable resin composition A decorative sheet for three-dimensional molding, wherein the primer layer (b) is a layer containing a polymer of a hindered amine light stabilizer having a reactive functional group A.   The decorative sheet for three-dimensional molding according to claim 1, wherein the ionizing radiation curable resin composition contains at least one selected from (A) polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate.   The decorative sheet for three-dimensional molding according to claim 1 or 2, wherein the ionizing radiation curable resin composition further comprises (B) a polyfunctional (meth) acrylate.   The decorative sheet for three-dimensional molding according to claim 3, wherein the polyfunctional (meth) acrylate is trifunctional or higher.   The decorative sheet for three-dimensional molding according to any one of claims 2 to 4, wherein the polycarbonate (meth) acrylate has a weight average molecular weight of more than 2000.   The decorative sheet for three-dimensional molding according to any one of claims 1 to 5, wherein the reactive functional group A is a functional group having an ethylenic double bond.   The decorative sheet for three-dimensional molding according to claim 6, wherein the functional group having an ethylenic double bond is a (meth) acryloyl group.   Resin constituting the primer layer with the polymer of the hindered amine light stabilizer having the reactive functional group A in the primer layer (b) as the hindered amine light stabilizer having the reactive functional group A before polymerization. The decorative sheet for three-dimensional molding according to any one of claims 1 to 7, which is contained at a ratio of 0.1 to 10 parts by mass with respect to 100 parts by mass (solid content).   (A) a step of sequentially forming a primer layer (b) and a primer layer (a) on a release film, (a) a step of forming a pattern layer on the primer layer (a), and (c) the primer layer (b) ), A step of transferring the primer layer (a) and the pattern layer onto the base film, (d) a step of peeling off the release film on the base film, (e) on the primer layer (b) formed on the base film A method for producing a decorative sheet, comprising: a step of laminating an ionizing radiation curable resin composition; and (f) a step of crosslinking and curing the ionizing radiation curable resin composition to form a surface protective layer. (B) is a layer containing the polymer of the hindered amine light stabilizer which has the reactive functional group A, The manufacturing method of the decorative sheet for three-dimensional shaping | molding characterized by the above-mentioned.   A decorative resin molded product using the decorative sheet for three-dimensional molding according to any one of claims 1 to 8.   A process of heating the decorative sheet 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 8 facing the mold, and heated The step of preforming the decorative sheet so as to conform to the inner shape of the mold, and closely clamping the mold to the inner surface of the mold, the step of injecting the injection resin into the mold, and after the injection resin has cooled, from the mold A method for producing a decorated resin molded product, comprising a step of taking out the decorated resin molded product.   A vacuum forming step in which the decorative sheet for three-dimensional forming according to any one of claims 1 to 8 is previously formed into a three-dimensional shape by a vacuum forming die, a step of trimming an excess portion 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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