JP5861414B2 - Film for injection-molding simultaneous lamination and molded article, and production method thereof - Google Patents

Description

  The present invention relates to a film for injection-molding simultaneous lamination used for a molded product by injection molding and a molded product, and a method for producing them.

  Conventionally, inorganic glass has been used for a lens of an illuminator such as a lamp lens of an automobile. However, since the weight is heavy, it is not preferable from the viewpoint of saving fuel in recent years, and the weight is more forward than the front wheel of the vehicle. The provision of objects may adversely affect the exercise performance, and further has the disadvantage of being easily broken. Therefore, after obtaining a molded body by injection molding or the like using a light and highly transparent synthetic resin, a method for applying a hard coat layer by coating the surface has been studied, but the coating process is complicated. And there is a problem that it is very difficult to remove foreign matter.

On the other hand, when a resin molded body having a complicated surface shape such as a three-dimensional curved surface is decorated or a protective layer is laminated, an injection molding simultaneous lamination method is used. In the injection molding simultaneous lamination method, the film for lamination inserted in the mold at the time of injection molding is integrated with the molten injection resin injected into the cavity, and the surface of the resin molding is decorated. In general, a method of laminating a protective layer is roughly classified into an injection molding simultaneous laminating method and an injection molding simultaneous transfer method depending on the difference in the structure of a laminating film integrated with a resin molded body.
In the injection molding simultaneous transfer method, the transfer layer side of the lamination film for injection molding simultaneous transfer is directed into the mold and heated from the transfer layer side with a hot platen so that the lamination film follows the shape in the mold. After being molded into a mold and intimately attached to the inner surface of the mold, the molten injection resin is injected into the cavity to integrate the laminated film and the injection resin, and then the molded product is cooled and removed from the mold Then, by peeling off the substrate of the laminating film, a molded product to which the transfer layer is transferred is obtained.

  Therefore, as a method for producing a synthetic resin illumination lens without performing the above-described coating process, a method of obtaining a molded body with a highly transparent injection molding resin and simultaneously providing a hard coat layer on the surface of the molded body has been studied. (See Patent Documents 1 and 2).

JP-A-7-108560 JP-A-8-187748

The technologies described in Patent Documents 1 and 2 are such that a transfer film having a hard coat layer and a base material layer is supplied by a roll-to-roll and mounted in a mold, and the mold is closed and closely attached to the mold by vacuum suction. The molten resin is then injected and filled into the mold. However, when only vacuum suction is performed, the transfer film cannot be sufficiently conformed to the shape in the mold, and when the injection molding is performed as it is, the transfer film may be locally stretched by the injection resin. Yes, the decorative pattern may be deformed or the film may be torn.
Therefore, in order to efficiently perform preforming of a more complicated shape, a laminating film is supplied from a roll between a mold and a film clamp, and the entire circumference including the region where the laminating film is preliminarily molded is made of gold. A method is preferred in which the film is sandwiched between a mold and a film clamp, and the film for laminating is heated by a hot plate if necessary, and then preliminarily molded by vacuum suction from the mold side. However, when the laminating film has a cured product layer of an ionizing radiation curable resin composition, the film may shrink or curl due to curing shrinkage of this layer, etc., and it is laminated when sandwiched between a film clamp and a mold. There was a problem that the film for use was broken, air leaked from there, and defective preforming occurred.

  The present invention is good in the injection molding simultaneous laminating method having a step of pre-molding by sandwiching the entire circumference including the region to be preformed of the laminating film between the film clamp and the mold under such circumstances. An object of the present invention is to provide a laminating film having excellent curl resistance and scratch resistance, a molded article using the same, and a method for producing them.

  As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be solved by selecting a base material and a protective layer having a specific thickness and tensile elastic modulus. . The present invention has been completed based on such findings.

That is, the present invention
[1] Used in an injection molding simultaneous laminating method including a step of preliminarily forming by sandwiching the entire circumference including a region to be preformed of a laminating film with a film clamp and a mold, and vacuuming from the mold side. A laminate film, wherein the laminate film is formed by laminating a release layer and a protective layer on a substrate in this order, and the protective layer is a cured product of an ionizing radiation curable resin composition, The thickness of the base material is 40 to 300 μm, the thickness of the protective layer is 50 μm or less, the tensile elastic modulus of the base material is higher than the tensile elastic modulus of the protective layer, and is 3000 MPa or less. A film for simultaneous injection molding, characterized by
[2] The film for simultaneous injection-molding according to [1], wherein the ionizing radiation curable resin composition contains a polyfunctional (meth) acrylate,
[3] Laminating a release layer on a substrate, laminating an ionizing radiation curable resin composition layer on the release layer, and irradiating the ionizing radiation curable resin composition layer with ionizing radiation A method for producing a film for simultaneous injection-molding according to [1] or [2], comprising a step of curing the ionizing radiation-curable resin composition layer to form a protective layer;
[4] A step of supplying the injection-molding simultaneous laminating film according to [1] or [2] while directing the base material side into the mold, and a periphery including a region where the injection-molding simultaneous laminating film is preformed A step of clamping the entire circumference with a film clamp and a mold, a step of pre-molding the film for simultaneous injection molding so as to conform to the inner shape of the mold, and closely contacting the inner surface of the mold, and clamping the injection resin A method for producing a molded article with a base material, comprising a step of injecting the mold into the mold, and a step of taking out the molded article with the base material from the mold after the injection resin has cooled,
[5] A molded article having a resin molded body, a protective layer, a release layer, and a substrate in this order, wherein the protective layer is a cured product of an ionizing radiation curable resin composition, and the thickness of the substrate is 40 to 300 μm, the thickness of the protective layer is 50 μm or less, the tensile elastic modulus of the substrate is higher than the tensile elastic modulus of the protective layer, and is 3000 MPa or less. Molded products with materials,
[6] A molded article with a base material according to [5], which is for window material or resin cover,
[7] A method for producing a molded article comprising a step of peeling the substrate and the release layer from the molded article with a substrate obtained by the production method according to [4],
Is to provide.

  According to the present invention, in the injection molding simultaneous laminating method including a step of preliminarily forming a film for laminating, the entire circumference including the region to be preformed is sandwiched between a film clamp and a mold, and good curl resistance and It is possible to provide a laminated film having scratch resistance, a molded product using the same, and a method for producing them.

It is a schematic diagram which shows the cross section of an example of the film for lamination | stacking of this invention. It is a schematic diagram which shows the cross section of an example of the molded article of this invention. It is a schematic diagram which shows each process of the manufacturing method of the molded article of this invention.

[Laminating film]
The film for laminating of the present invention is an injection molding having a step of preliminarily molding by sandwiching the entire circumference including a region to be preformed of the laminating film with a film clamp and a mold, and vacuuming from the mold side. A film for lamination used in a simultaneous lamination method, comprising a release layer and a protective layer laminated in this order on a substrate, the protective layer being a cured product of an ionizing radiation curable resin composition, The thickness of the base material is 40 to 300 μm, the thickness of the protective layer is 50 μm or less, the tensile elastic modulus of the base material is higher than the tensile elastic modulus of the protective layer, and is 3000 MPa or less. It is characterized by that. Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing a cross section of an example of a preferred embodiment of the laminating film of the present invention.
The laminating film 10 of the present invention shown in FIG. 1 has a release layer 12 and a protective layer 13 on a substrate 11, and more preferably a primer layer 14, a decoration layer 15 and an adhesive layer 16. They are stacked in this order.

≪Base material≫
The substrate 11 is not particularly limited as long as it has a higher tensile elastic modulus than that of the protective layer 13 and a tensile elastic modulus of 3000 MPa or less. Polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polychlorinated Vinyl resins such as vinylidene, polyvinyl alcohol, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; methyl poly (meth) acrylate, Acrylic resins such as poly (meth) ethyl acrylate; styrene resins such as polystyrene, acrylonitrile / butadiene / styrene copolymers, cellulose triacetate, cellophane, polycarbonate, polyurethane-based elastomers Mainly due to fat it is used. Among these, acrylic resin, polycarbonate resin, and polyester resin (particularly polyethylene terephthalate) are preferable from the viewpoint of good moldability and peelability.
The tensile elastic modulus of the base material 11 needs to be higher than the tensile elastic modulus of the protective layer 13 and not more than 3000 MPa as described above, but the tensile elastic modulus of the base material 11 and the tensile strength of the protective layer 13 are required. A difference in elastic modulus of 50 MPa or more is preferable because a film for lamination with less curl is obtained, and the difference in tensile elastic modulus is more preferably 500 MPa or more.

The thickness of the substrate 11 is usually 40 to 300 μm, preferably 40 to 250 μm, and more preferably 50 to 200 μm, from the viewpoints of moldability, shape followability, and easy handling.
Moreover, the base material 11 can use the single layer sheet | seat of these resin, or the multilayer sheet | seat by the same kind or different resin.

The base material 11 can be subjected to a physical or chemical surface treatment by an oxidation method, an unevenness method, or the like on one side or both sides as desired for the purpose of improving adhesion to the release layer 12 described later.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the substrate 11, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  The base material 11 may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing interlayer adhesion between the base material 11 and a layer provided thereon. In addition, when using a commercially available polyester sheet, the commercially available product that has been subjected to the surface treatment as described above or that is provided with an easy-adhesive layer can be used.

≪Release layer≫
The release layer 12 is preferably provided so that the transfer layer 17 having the protective layer 13 and the primer layer 14, the decorative layer 15, and the adhesive layer 16 provided in order can be easily peeled from the substrate 11. Is a layer. By having the release layer 12, the transfer layer 17 is reliably and easily transferred from the lamination film of the present invention to the transfer target, and the release layer 18 composed of the base material 11 and the release layer 12 is reliably transferred. Can be peeled off. As shown in FIG. 1, the release layer 12 may be a solid release layer covering the entire surface (entirely solid), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability.

The release layer 12 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth) acrylic acid or urethane It can be formed by using a single or a plurality of mixed resin compositions. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer 12 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.
The thickness of the release layer 12 is usually about 0.01 to 5 μm, and preferably 0.05 to 3 μm.

≪Protective layer≫
The protective layer 13 is a cured product of an ionizing radiation curable resin composition, and the ionizing radiation curable resin used in the ionizing radiation curable resin composition crosslinks and polymerizes molecules in electromagnetic waves or charged particle beams. It refers to a resin having an energy quantum to be obtained, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable oligomers and polymerizable monomers conventionally used as ionizing radiation curable resins.

  As the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, acrylic (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, poly Preferred examples include ether (meth) acrylate-based, polycarbonate (meth) acrylate-based, and acrylic silicone (meth) acrylate-based oligomers. Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group. These polymerizable oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and in particular, a polyfunctionality having two or more ethylenically unsaturated bonds in the molecule ( (Meth) acrylate is preferred, and one kind may be used alone, or two or more kinds may be used in combination. As a functional group number, 2-8 are preferable, 2-6 are more preferable, and 3-4 are more preferable.

  In the present invention, together with the polyfunctional (meth) acrylate, for the purpose of adjusting the viscosity, methyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc. A monofunctional (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ionizing radiation curable resin composition in the present invention contains at least polycarbonate (meth) acrylate or acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate among the above various ionizing radiation curable resins. Since it satisfies both excellent chemical resistance and scratch resistance and good three-dimensional formability at the same time, there is no crack in the protective layer, it is easy to form in three dimensions and has high chemical resistance. It is preferable at the point which can obtain the film for lamination | stacking.

When using an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and polyfunctional (meth) acrylate, the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is preferably 98: It is 2-50: 50, More preferably, it is 95: 5-60: 40. 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 50:50 (that is, when the amount of the polycarbonate (meth) acrylate is less than 70% by mass), the three-dimensional moldability is lowered. End up.
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. The polycarbonate (meth) acrylate preferably has two or more functions, more preferably 2 to 5 functions, from the viewpoint of crosslinking and curing. If it is bifunctional or higher, the crosslinking density becomes sufficient, so that the protective layer 13 after curing is hardly damaged. If it is pentafunctional or lower, the crosslinking density is not too high. Even if it is a case where it uses for original shaping | molding, it can fully follow a shape.
The polycarbonate (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and 2,000 or more. More preferably, it is particularly preferably 5,000 or more. 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, 2,000 to 50,000 are preferable, and 5,000 to 20,000 are more preferable.

When using an ionizing radiation curable resin composition containing acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate, the mass ratio of acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is preferably It is 50: 50-95: 5, More preferably, it is 80: 20-95: 5.
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.
The acrylic silicone (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 1,000 or more, and more preferably 2,000 or more. 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 establishing three-dimensional formability, chemical resistance, and scratch resistance, it is particularly preferably 2,000 to 100,000.

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, trifunctional or higher functional (meth) acrylates are preferred from the viewpoint of curability. 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.
The polyfunctional (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and 2,000 or more. More preferably, it is more preferably 5,000 or more. The upper limit of the weight average molecular weight of the polyfunctional (meth) acrylate is not particularly limited, but is preferably 100,000 or less, more preferably 50,000 or less, and more preferably 20,000 or less from the viewpoint of controlling the viscosity not to be too high. Particularly preferred. From the viewpoint of achieving both scratch resistance and three-dimensional formability, it is more preferably 2,000 to 50,000, and particularly preferably 5,000 to 20,000.

  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.

Moreover, when using ultraviolet curable resin as ionizing radiation curable resin, it is desirable to add about 0.1-5 mass parts of photopolymerization initiators with respect to 100 mass parts of ultraviolet curable resin. The initiator for photopolymerization can be appropriately selected from those conventionally used. For example, benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; acetophenone, 2,2′-diethoxyacetophenone , Acetophenones such as p-dimethylacetophenone and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; 2-methyl-1- [4- (methylthio) [Alpha] -aminoalkylphenones such as phenyl] -2-monforinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; benzyldimethyl ketal, thioxa Sulfur compounds such as Nson, 2-chlorothioxanthone and 2,4-diethylthioxanthone are preferred.
As the photosensitizer, for example, p-dimethylbenzoate, tertiary amines, thiol sensitizers, and the like can be used.

  In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin 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.

In the said ionizing radiation curable resin composition, other resin can be contained in the range with the effect of this invention. For example, when it is desired to impart high curling resistance to the film for lamination 10 of the present invention or when flexibility is desired, a thermoplastic resin can be added. On the other hand, when resistance to a solvent is required, it is preferable not to contain a thermoplastic resin.
Thermoplastic resins include (meth) acrylic resins such as (meth) acrylic acid esters, polyvinyl acetals (butyral resin) such as polyvinyl butyral, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resins, urethane resins, Polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene and α-methylstyrene, acetal resins such as polyamide, polycarbonate and polyoxymethylene, fluororesins such as ethylene-tetrafluoroethylene copolymer, polyimide, polylactic acid, A polyvinyl acetal resin, liquid crystalline polyester resin, etc. are mentioned, These may be used individually by 1 type or in combination of 2 or more types. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.

Among the above thermoplastic resins, those having a (meth) acrylic resin as a main component are preferred in the present invention, and in particular, those obtained by polymerizing a monomer containing at least a (meth) acrylic acid ester as a monomer component. preferable.
More specifically, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and other monomers Is preferred.

The thermoplastic resin preferably has a weight average molecular weight of 10,000 to 250,000, and more preferably 100,000 to 250,000. When the weight average molecular weight is within this range, it is possible to obtain at a high level all of moldability, surface wear resistance, and scratch resistance after crosslinking and curing to form a protective layer.
In addition, it is a thing of polystyrene conversion measured here. The solvent used here can be appropriately selected from those usually used, and examples thereof include tetrahydrofuran (THF) and N-methyl-2-pyrrolidinone (NMP).

  The polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the thermoplastic resin is preferably in the range of 1.1 to 3.0. If the polydispersity is within this range, it is possible to obtain a high level of moldability, surface abrasion resistance, and scratch resistance after crosslinking and curing to form a protective layer. From the above points, the polydispersity of the (meth) acrylic resin is preferably in the range of 1.5 to 2.5.

  The protective layer 13 thus formed has various functions by adding various additives, for example, a so-called hard coat function, antifogging function, antifouling function, antifouling, having high hardness and scratch resistance. A glare function, an antireflection function, an ultraviolet shielding function, an infrared shielding function, and the like can also be imparted.

  Examples of additives include a weather 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 antifoaming agent, Examples thereof include fillers, solvents, colorants, and wear resistance improvers.

  In the present invention, the thickness of the protective layer 13 after curing needs to be 50 μm or less, and preferably 1 to 50 μm. When the thickness of the protective layer 13 after curing is 1 μm or more, excellent design properties such as transparency and gloss can be obtained, and furthermore, sufficient physical properties as a protective layer such as contamination resistance, scratch resistance, and weather resistance. Is obtained. On the other hand, when the thickness is 50 μm or less, it becomes easy to control the thickness of the coating film, and there is no cracking or whitening of the protective layer at the time of molding. It can have good design properties, and further, the solvent does not remain in the layer and does not cause curing failure. From this viewpoint, the thickness of the protective layer 13 after curing is preferably in the range of 2 to 20 μm, and more preferably in the range of 5 to 15 μm.

  Further, the surface of the protective layer 13 can be subjected to corona discharge treatment or plasma treatment as necessary for the purpose of improving the adhesion with the primer layer 14 provided thereon.

≪Primer layer≫
In the laminating film of the present invention, it is preferable that a primer layer 14 is further laminated between the protective layer 13 and the decorative layer 15. By providing the primer layer 14, the adhesion between the protective layer 13 and the decorative layer 15 can be further improved. The primer layer 14 is preferably a transparent or translucent layer, such as polyurethane resin, polyester resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, chlorinated resin. One kind of resin such as polyethylene and chlorinated polypropylene, or a mixture of two or more kinds is used, and those using a polyurethane two-component curable resin are particularly preferable.

As a polyurethane type two-component curable resin, for example, a polymer polyol such as a vinyl chloride-vinyl acetate copolymer system, a polyester system, a urethane system, an acrylic system, a polyether system, a polycarbonate system or the like, or a mixture thereof is used. What added the hardening | curing agent just before is used.
As the polymer polyol, an acrylic polymer polyol or a polyester polymer polyol is preferable, and an acrylic polymer polyol is more preferable. As the acrylic polymer polyol, (meth) acrylic acid alkyl ester such as ethyl (meth) acrylate is copolymerized with hydroxy acrylate such as 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like. The thing which introduce | transduced the hydroxyl group is mentioned preferably. Examples of the polyester polymer polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), and poly (butylene sebacate). Polycaprolactone is used.
Moreover, in this invention, the mixture of said acrylic polymer polyol and urethane resin is more preferable.

  As the curing agent, polyisocyanate is preferable, for example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or the like, or adducts of the above-mentioned various isocyanates. Alternatively, multimers such as adducts of tolylene diisocyanate, tolylene diisocyanate trimers, and the like can also be used.

  In the present invention, the polyurethane two-component curable resin preferably has a glass transition temperature Tg of 80 ° C. or higher when the polymer polyol is uncured, and the upper limit of the glass transition temperature Tg is not particularly limited. Usually, it is about 110 degreeC, and preferable Tg is the range of 80-100 degreeC. When the glass transition temperature Tg is within the above range, excellent adhesion is obtained, and the transition property of the decorative layer 15 is also good.

The primer layer can also be formed using a primer layer-forming resin composition containing the polyurethane-based two-component curable resin and a binder resin.
As this binder resin, a known binder resin having a glass transition temperature Tg of 77 ° C. or lower is preferably used, and either a compound having a hydroxyl group or a compound having no hydroxyl group may be used. A clear color can be expressed because the primer layer contains a binder resin having a low glass transition temperature Tg. Specifically, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, a polyester resin, or the like can be used as the binder resin. The weight average molecular weight in terms of standard polystyrene of a resin that can be used as the binder resin is preferably 10,000 to 300,000, and more preferably 5 to 200,000.
It is preferable that content of binder resin is 10-60 mass% with respect to the sum total of polymer polyol and binder resin.

  The primer layer 14 can be obtained by applying and drying a coating solution obtained by dissolving the above resin in a solvent by a known method. About the thickness of the primer layer 14, it is about 0.5-20 micrometers normally, Preferably, it is the range of 1-5 micrometers.

≪Decoration layer≫
The decorative layer 15 in the present invention is usually composed of a picture layer and / or a concealing layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is generally a solid surface weight average molecular weight determined by gel permeation chromatography (GPC). This is a layer provided to conceal the coloring of the injection resin or the like. In the concealing layer, a decorative layer may be formed alone in addition to the case of being provided inside the pattern layer in order to enhance the pattern of the pattern layer. Moreover, the said decoration layer may be transparent and may be colored.
The pattern layer in the present invention is a layer provided to express a pattern or a pattern such as a pattern or characters. Although the pattern of the pattern layer is arbitrary, for example, a pattern composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and the like can be mentioned.
The decorative layer 15 is formed on the primer layer 14 by using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing. 1 is formed between the primer layer 14 and the adhesive layer 16. The thickness of the decorative layer 15 is preferably 1 to 40 μm and more preferably 1 to 15 μm from the viewpoint of design.

  As the binder resin of the printing ink used for forming the decorative layer 15, polyester resins, polyurethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, cellulose resins, and the like are preferable. The main component is preferably an acrylic resin alone or a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin. Among these, when an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin or another acrylic resin is mixed, the printability and moldability are improved, which is preferable. Here, the acrylic resin includes polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer. Examples include acrylic resins such as polymers (where (meth) acrylate refers to acrylate or methacrylate), modified acrylic resins such as fluorine, and these can be used as one or a mixture of two or more. In addition, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and 2-hydroxyethyl ( Acrylic polyol obtained by copolymerizing (meth) acrylate ester having a hydroxyl group in the molecule such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Can also be used. As the vinyl chloride-vinyl acetate copolymer resin, those having a vinyl acetate content of about 5 to 20% by mass and an average degree of polymerization of about 350 to 900 are usually used. If necessary, the vinyl chloride-vinyl acetate copolymer resin may be further copolymerized with a carboxylic acid such as maleic acid or fumaric acid. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer resin is about acrylic resin / vinyl chloride-vinyl acetate copolymer resin = 1/9 to 9/1 (mass ratio). In addition, as a subcomponent resin, if necessary, other resins, for example, resins such as thermoplastic polyester resins, thermoplastic urethane resins, chlorinated polyethylene, chlorinated polypropylene, and other chlorinated polyolefin resins. May be mixed.

  Examples of the colorant used in the decorative layer 15 according to the present invention include aluminum, chromium, nickel, tin, titanium, iron phosphide, copper, gold, silver, brass and other metals, alloys, or scale-like foil powders of metal compounds. It consists of foil powder such as metallic pigment, mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, and basic lead carbonate. Pearlescent pigments, fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide, white inorganic pigments such as titanium dioxide, zinc white, antimony trioxide, zinc white, petal, Inorganic pigments such as vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone Be low, Hansa Yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, be mixed Indanthrene Blue RS, (including dyes) organic pigments such as aniline black one or more.

Although such a decoration layer 15 is a layer provided in order to provide the designability to the film for lamination of the present invention, a metal thin film layer or the like may be further formed for the purpose of improving the designability. The metal thin film layer can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. This metal thin film layer may be provided on the entire surface or may be partially provided in a pattern.
In addition to the above components, the printing ink used for forming the decorative layer 15 is appropriately added with an anti-settling agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like. be able to. The printing ink is provided in a form in which the above components are usually dissolved or dispersed in a solvent. Any solvent can be used as long as it dissolves or disperses the binder resin, and an organic solvent and / or water can be used. Examples of the organic solvent include hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, cellosolve acetate, and butyl cellosolve acetate, and alcohols.

≪Adhesive layer≫
The adhesive layer 16 according to the present invention transfers a transfer layer 17 having a protective layer 13, a primer layer 14, a decoration layer 15, and an adhesive layer 16, which are provided as necessary, to a molded product with good adhesiveness. It is formed for this purpose and is a layer provided as desired.

Examples of the adhesive layer 16 include those composed of a heat-sensitive adhesive, a pressure-sensitive adhesive, and the like. In the present invention, a heat that develops adhesion to a molded product by heating and pressurizing as necessary. A seal layer is preferred. Examples of the resin used for the adhesive constituting the adhesive layer 16 include an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, a styrene-acryl copolymer resin, Examples thereof include at least one resin selected from polyester resins and polyamide resins. One or two or more resins selected from the above resins are made into a form that can be applied such as a solution or an emulsion by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. It can be formed by coating and drying.
From the viewpoint that the laminating film can be efficiently transferred to a molded product with good adhesiveness, the laminating film of the present invention does not have the adhesive layer 16 or is provided with the adhesive layer 16 having a thickness of 30 μm or less. It is preferably about 0.1 to 20 μm, more preferably about 0.5 to 8 μm.

  The adhesive layer 16 includes organic UV absorbers such as benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, cyanoacrylate compounds, salicylate compounds, zinc, titanium, cerium, tin, iron, etc. It is possible to contain an additive of fine particles having an inorganic ultraviolet absorbing ability such as an oxide of the above. Further, as an additive, a coloring pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent whitening agent, and the like can be appropriately contained as necessary.

≪Method for manufacturing film for lamination≫
The laminating film of the present invention can be produced, for example, by the following steps [1] to [8].
[1] A step of laminating the release layer 12 on the substrate 11;
[2] A step of laminating an ionizing radiation curable resin composition layer on the release layer 12,
[3] A step of irradiating the ionizing radiation curable resin composition layer with ionizing radiation to cure or semi-cure the ionizing radiation curable resin composition layer to form the protective layer 13;
[4] Step of subjecting the surface of the protective layer 13 to corona discharge treatment or plasma treatment as desired [5] Step of laminating the primer layer 14 on the protective layer 13 as desired;
[6] If desired, a step of laminating the decorative layer 15 on the primer layer 14;
[7] A step of laminating the adhesive layer 16 on the decorative layer 15 as desired, and [8] a step of curing the semi-cured protective layer 13 as desired.
As a method for laminating the release layer 12, the protective layer 13, the primer layer 14, the decoration layer 15, and the adhesive layer 16 laminated on the substrate 11, known printing or coating means such as gravure printing or roll coating is used. .
When the decorative layer 15 is a combination of a pattern layer and a concealing layer as described above, for example, the first layer may be stacked and then dried, and then the next layer may be stacked.

In the step of forming the protective layer 13 in the present invention, the ionizing radiation curable resin composition layer laminated on the release layer 12 may be semi-cured or cured, but is a cured product. Since the surface performance is good and the resin composition is a predetermined one which will be described later, even a cured product has good moldability. When the ionizing radiation curable resin composition layer is cured, the resin composition layer can be cured by irradiating it with ionizing radiation such as an electron beam or ultraviolet rays. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer. It is preferable to cure.
In addition, in electron beam irradiation, since the transmission capability increases as the acceleration voltage is higher, when a base material that deteriorates due to an electron beam is used as the base material 11, the transmission depth of the electron beam and the thickness of the resin layer are By selecting the accelerating voltage so as to be substantially equal, it is possible to suppress irradiation of the extra electron beam to the base material 11 and to minimize the deterioration of the base material due to the excess electron beam. .
The irradiation dose is preferably such that the crosslinking density of the resin composition layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 70 kGy (1 to 7 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.

≪Use of laminating film≫
The film for lamination of the present invention can impart excellent stain resistance and moldability to a molded product. The film for laminating of the present invention makes use of this characteristic, the field of inorganic glass substitute materials such as automobile lighting equipment, the field of household appliances, the interior and exterior of automobiles, the field of personal computers, especially the housing of personal computers. It can use suitably, when decorating the member used in a wide field | area, etc., or laminating | stacking a protective layer.

[Production method of (with base material) molded product]
The laminating film of the present invention is suitably used for the injection molding simultaneous transfer laminating method. The molded article with a substrate of the present invention can be produced, for example, by an injection molding simultaneous transfer lamination method. More specifically, the molded article with a substrate of the present invention can be produced by, for example, the following steps (1) to (6), and the molded article of the present invention is, for example, the following step (1). It can manufacture by (8).
(1) supplying the substrate side of the laminating film while facing the mold,
(2) A step of sandwiching the entire circumference including a region to be preformed of the film for simultaneous injection molding with a film clamp and a mold,
(3) A step of heating a region to be preformed of the injection molding simultaneous laminating film by a hot plate provided as necessary,
(4) A step of pre-molding the injection molding simultaneous laminating film so as to conform to the shape in the mold and closely contacting the inner surface of the mold to clamp the mold;
(5) A step of injecting the injection resin into the mold,
(6) A step of taking out the molded article with the base material from the mold after the injection resin has cooled,
(7) The process of peeling a base material and a mold release layer from this molded article with a base material provided as needed,
(8) A step of curing the semi-cured protective layer 13 provided as necessary.

  In the step (1), as shown in FIG. 3A, the laminating film 10 is supplied so as to hang down between the film clamp 30 and the mold.

  In the above step (2), the end of the supplied laminating film 10 is suspended between the film clamp and the mold by the film feeding device, and this is sandwiched between the film clamp and the mold. It fixes (refer FIG.3 (b)). As a result, the region for pre-forming the laminating film and the space inside the mold are sealed, and pre-forming of the laminating film is possible by vacuum suction from the mold side.

  The step (3) is preferably provided when forming a deep-drawn shape, since the laminating film is softened by heating and the followability to the mold shape is improved.

In the above step (4), examples of the method for bringing the laminating film into close contact with the inner surface of the mold so as to conform to the inner shape of the mold include a method of evacuating. The state where the mold is clamped is shown in FIG.
When the laminating film in the mold is separated from the roll portion at the same time as or after the step (2) and before the step (6), the film can be cut with a heating wire or the like.

In the step (5), an injection resin, which will be described later, is melted and injected into a cavity to integrate the lamination film of the present invention 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 film for lamination is united with the formed resin molded body and adhered to form a molded product. The heating temperature of the injection resin depends on the injection resin, but is generally about 180 to 320 ° C.
After the molded product thus obtained is cooled and taken out from the mold, the base material 11 and the release layer 12 are peeled off to remove the protective layer 13, the primer layer 14, and the decoration provided as necessary. The transfer layer 17 composed of the layer 15 and the adhesive layer 16 is transferred to a molded product.

≪Injection resin≫
The injection resin used for the molded product is not particularly limited as long as it is a thermoplastic resin that can be injection-molded or a thermosetting resin (including one-component or two-component curable resin), and various resins may be used. it can. Examples of such thermoplastic resin materials include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; polystyrene, acrylonitrile-styrene copolymers, ABS resins (acrylonitrile-butadiene-styrene copolymer resins), and the like. Styrene resins; acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyacrylonitrile; polyolefin resins such as polyethylene, polypropylene, polybutene, polyethylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, Examples thereof include polyester resins such as polybutylene terephthalate; polycarbonate resins. Moreover, as a thermosetting resin, 1 liquid or 2 liquid reaction hardening type polyurethane-type resin, an epoxy-type resin, etc. are mentioned. These resins may be used alone or in combination of two or more.

These resins include various additives as required, such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, calcium carbonate, aluminum hydroxide, etc. Inorganic powders, wood powders, fillers such as glass fibers, lubricants, mold release agents, antistatic agents, colorants and the like can be added. Note that as the injection resin, a resin colored by adding a colorant may be used as appropriate according to the application. As the colorant, a known colorant similar to that which can be used for the above-mentioned substrate can be used.
There is no restriction | limiting in particular about the thickness of the injection resin molding which comprises a molded article, Although it selects according to the use of the said molded article, Usually, 1-5 mm, Preferably it is 2-3 mm.

[Molded product with substrate]
The molded article with a substrate of the present invention can be produced using the film for lamination of the present invention as described above, and the configuration thereof has a resin molded body, a protective layer, a release layer and a substrate in order. The protective layer is a cured product of an ionizing radiation curable resin composition, the thickness of the base material is 40 to 300 μm, the thickness of the protective layer is 50 μm or less, and the tensile elastic modulus of the base material Is higher than the tensile elastic modulus of the protective layer and not more than 3000 MPa. In addition, the molded article of the present invention may have an adhesive layer or a primer layer as desired between the resin molded body and the protective layer, and more specifically, the resin molded body and the adhesive. The layer structure which has a layer, a decoration layer, a primer layer, a protective layer, a mold release layer, and a base material in order may be sufficient. Here, the adhesive layer, the decorative layer, the primer layer, the protective layer, the release layer, and the substrate are the same as those described as the layers of the laminating film of the present invention.

FIG. 2 is a schematic view showing a cross section of an example of a preferred embodiment of the molded article of the present invention.
The molded product 20 includes a transfer layer 17 including a protective layer 13, a primer layer 14, a decoration layer 15, and an adhesive layer 16, and a base material 11 and a release layer 12 on the resin molded body 21. And has a laminated and integrated structure. Here, the base material 11, the release layer 12, the protective layer 13, the primer layer 14, the decoration layer 15, and the adhesive layer 16 are the same as those described as the layers of the laminating film of the present invention.
The molded article of the present invention has excellent stain resistance and is excellent in finish by using the film for laminating of the present invention that provides excellent moldability.
The molded article of the present invention makes use of these excellent characteristics to make use of the field of inorganic glass substitute materials such as automobile lighting equipment, the field of household electrical appliances, the interior and exterior of automobiles, or the field of personal computers. It can be suitably used in a wide range of fields such as a personal computer casing.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Evaluation method>
(1) Tensile modulus of protective layer The electron beam curable resin composition used for forming the protective layer was applied onto a biaxially stretched polyester film with a bar coater, and an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) ) Was irradiated and irradiated with an electron beam to form a protective layer (thickness: 20 μm). Using a sample obtained by peeling the protective layer from the polyester film, a sheet punched into a strip-shaped test piece conforming to JIS K7127 was prepared, and a tensile compression tester (Orientec) was used in a temperature environment of 25 ° C. From the first straight line portion of the tensile stress-strain curve obtained by using Tensilon RTC-1250A manufactured by Co., Ltd. and measuring under the conditions of a tensile speed of 50 mm / min, a distance between chucks of 80 mm, and a width of 25 mm, Calculated.
E = Δρ / Δε
E: Tensile modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points (2) Tensile modulus of the substrate A strip shape in accordance with JIS K7127 Prepare a sheet punched into the test piece and use a tensile and compression tester (Tensilon RTC-1250A manufactured by Orientec Co., Ltd.) under a temperature environment of 25 ° C., pulling speed 50 mm / min, chuck distance 80 mm, width From the first linear portion of the tensile stress-strain curve obtained by measurement under the condition of 25 mm, the calculation was performed according to the following formula.
E = Δρ / Δε
E: Tensile modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points (3) Formability Using the laminating film obtained in each Example and Comparative Example Then, a resin molded product was produced as shown below. Further, the obtained molded product was evaluated by the appearance after molding. The evaluation criteria are as follows.
<Production of resin molded product>
The laminating film obtained in each of the examples and comparative examples was heated at a hot platen temperature of 350 ° C. to set the temperature of the laminating film to 100 ° C., and vacuum formed so as to conform to the shape in the mold of injection molding. Adhered to the inner surface of the mold. The mold used had a shape of a tray with a size of 80 mm square, an aperture of 3 mm, and a corner portion of 11R. On the other hand, ABS resin (“Clarastic MTH-2 (trade name)”, manufactured by Nippon A & L Co., Ltd.) was used as the injection resin, and this was melted at 230 ° C. and then injected into the cavity. It was taken out from the mold at a temperature of 60 ° C., and a molded product 20 having the structure shown in FIG. 2 was obtained by transferring and forming a transfer layer comprising a base sheet, a picture layer, a concealing layer and an adhesive layer on the surface.
<Evaluation criteria>
A: Appearance defects such as cracking and whitening were not observed in the appearance of the molded product. (Maximum elongation 100%)
○: Although fine cracks, whitening, etc. are observed in the maximum extension portion, no appearance defects such as cracks, whitening, etc. were observed in the shallow drawn shape (elongation 50%).
Δ: Cracks, whitening and the like are observed in the maximum extension portion, but appearance defects such as cracks and whitening were not observed in the shallow drawn shape (an elongation of 25%).
X: Appearance defects such as cracking and whitening were remarkable.

(4) Curling resistance Using the laminating film obtained in each of the examples and comparative examples, a roll having a width of 400 mm was created, the laminating film was drawn out by 80 mm in the flow direction from this roll, and the film was suspended in the vertical direction. The curl width from the vertical direction was measured.
(Circle): The curl width was 50 mm or less x: The curl width was more than 50 mm (5) Scratch resistance About the film for lamination | stacking obtained by each Example and the comparative example, steel wool (made by Nippon Steel Wool Co., Ltd.,) Using a bonster # 0000), it was rubbed 5 times with a load of 1.5 kg, and the appearance was visually evaluated. The evaluation criteria are as follows.
○: Although fine scratches were observed on the surface, the coating film was not scraped or whitened.
Δ: Slight shaving or whitening of the coating film was observed.
X: There were significant scratches on the surface.

Example 1 (Manufacture of film for lamination)
As a base sheet, an acrylic-melamine resin is applied by a gravure method on an acrylic sheet (thickness: 100 μm, tensile elastic modulus: 2450 MPa) subjected to easy adhesion treatment, and a release layer (thickness: 3 μm) is applied. Formed.
Next, a resin component consisting of 94 parts by mass of a bifunctional polycarbonate-based urethane acrylate (weight average molecular weight: 10,000) and 6 parts by mass of a hexafunctional urethane acrylate (weight average molecular weight: 6,000), an ultraviolet absorber 1.1 mass An ionizing radiation curable resin composition containing 0.6 parts by weight, a light stabilizer and 0.2 parts by weight of a leveling agent is applied onto the release layer with a bar coater, and an acceleration voltage is 165 kV and an irradiation dose is 50 kGy. A protective layer (thickness: 10 μm) was formed by crosslinking and curing by irradiation with an electron beam of (5 Mrad).
Next, after the corona discharge treatment is applied to the surface of the protective layer, a polyurethane two-component curable resin (acrylic polymer polyol and xylylene diisocyanate as a curing agent, NCO equivalent and OH equivalent are the same. A primer layer (thickness of 1.5 μm) was formed by applying a composition containing the composition in an amount and a glass transition temperature Tg (when the polyol was uncured): 100 ° C. by gravure printing.
Next, a black printing ink (acrylic resin: 50% by mass, vinyl chloride-vinyl acetate copolymer) using an acrylic resin and a vinyl chloride-vinyl acetate copolymer resin as a binder resin on the primer layer. Resin: 50% by mass) was subjected to gravure printing at a coating amount of 3 g / m ² to form a decorative layer with a solid surface. Further, an acrylic resin (softening temperature: 125 ° C.) was subjected to gravure printing at a coating amount of 4 g / m ² to form an adhesive layer, and a laminated film having the configuration shown in FIG. 1 was produced.
The laminating film was evaluated by the above method. The evaluation results are shown in Table 1.

Examples 2-12 and Comparative Examples 1-3
In Example 1, laminate films were prepared in the same manner as in Example 1 except that the base material and ionizing radiation curable resin were those shown in Table 1, and each was evaluated by the above method. The evaluation results are shown in Table 1.

Comparative Example 4
The substrate sheet used in Example 1 was evaluated by the above method. The evaluation results are shown in Table 1.

Ionizing radiation curable resin composition A (resin component): difunctional polycarbonate-based urethane acrylate (weight average molecular weight: 10,000) 94 parts by mass, and hexafunctional urethane acrylate (weight average molecular weight: 6,000) 6 parts by mass ionization Radiation curable resin composition B (resin component): acrylic polymer (weight average molecular weight: 120,000) 60 parts by mass, and trifunctional acrylate monomer (molecular weight: 298) 40 parts by mass ionizing radiation curable resin composition C (resin Component): 3.9 functional urethane acrylate oligomer 30 parts by mass, and bifunctional acrylate monomer 70 parts by mass ionizing radiation curable resin composition D (resin component): bifunctional polycarbonate urethane acrylate (weight average molecular weight: 10,000) 50 parts by mass and tetrafunctional urethane acrylate (weight average Molecular weight 20,000) 50 parts by weight ionizing radiation-curable resin composition E (resin component): trifunctional acrylate monomer (weight average molecular weight: 296)

  The laminating film of the present invention is useful as a laminating film used in an injection molding simultaneous transfer laminating method for decorating a resin molded product or laminating a protective layer. In addition, since the film for lamination of the present invention imparts excellent stain resistance and moldability to the molded product, the molded product of the present invention has excellent stain resistance and excellent moldability. By using the obtained film for lamination of the present invention, the finish is excellent. Therefore, the molded product of the present invention has a wide range of fields, such as the field of inorganic glass substitute materials such as automobile lighting equipment, the field of household appliances, the interior and exterior of automobiles, the field of personal computers, especially the housing of personal computers. Can be suitably used. In addition, the molded product (with a base material) of the present invention is a vehicle window material or resin cover used for vehicles such as automobiles, trains, ships, and aircrafts, which are particularly required to prevent scattering of fragments generated by impacts and the like. It is also suitably used for such applications.

DESCRIPTION OF SYMBOLS 10 Laminating film 11 Base material 12 Release layer 13 Protective layer 14 Primer layer 15 Decoration layer 16 Adhesive layer 17 Transfer layer 18 Peeling layer 20 Molded product 21 Resin molding 30 Film clamp

Claims (7)

  For laminating used in the injection molding simultaneous laminating method including the step of preliminarily forming the film by sandwiching the entire circumference including the pre-molding area of the laminating film with a film clamp and a mold and vacuuming from the mold side A film for laminating, wherein a release layer and a protective layer are laminated in this order on a substrate, and the protective layer is a cured product of an ionizing radiation curable resin composition, The thickness is 40 to 300 μm, the thickness of the protective layer is 50 μm or less, and the tensile elastic modulus of the substrate is higher than the tensile elastic modulus of the protective layer and is 3000 MPa or less. A film for simultaneous injection molding.   The film for simultaneous injection-molding according to claim 1, wherein the ionizing radiation curable resin composition contains a polyfunctional (meth) acrylate.   The step of laminating a release layer on a substrate, the step of laminating an ionizing radiation curable resin composition layer on the release layer, and irradiating the ionizing radiation curable resin composition layer with ionizing radiation The method for producing a film for simultaneous injection molding according to claim 1 or 2, further comprising a step of curing the curable resin composition layer to form a protective layer.   A step of supplying the injection molding simultaneous laminating film according to claim 1 or 2 while directing the base material side into the mold, and a film clamp around the entire circumference including a region where the injection molding simultaneous laminating film is preformed A step of clamping between the mold and the mold, a step of pre-molding the film for simultaneous injection molding so as to conform to the inner shape of the mold, and tightly attaching the film to the inner surface of the mold, and injecting an injection resin into the mold The manufacturing method of the molded article with a base material including the process and the process of taking out the molded article with a base material from a metal mold | die after this injection resin cools.   A molded article having a resin molded body, a protective layer, a release layer and a substrate in this order, wherein the protective layer is a cured product of an ionizing radiation curable resin composition, and the thickness of the substrate is 40 to 300 μm The thickness of the protective layer is 50 μm or less, the tensile elastic modulus of the base material is higher than the tensile elastic modulus of the protective layer, and is 3000 MPa or less. Goods.   The molded article with a base material according to claim 5, which is used for a window material or a resin cover.   The manufacturing method of a molded article including the process of peeling a base material and a mold release layer from the molded article with a base material obtained with the manufacturing method of Claim 4.