JP6855956B2 - A decorative film and a method for manufacturing a decorative molded product using the decorative film. - Google Patents

Description

The present invention relates to a decorative film for attaching to a resin molded body by thermoforming, and a method for producing a decorative molded body using the decorative film. Specifically, a decorative film for attaching to a resin molded body by thermoforming, which can suppress wrinkles and rupture of the film during thermoforming and can exhibit sufficient adhesive strength to the resin molded body. The present invention relates to a method for producing a decorative molded product using the decorative film.

In recent years, there has been an increasing demand for decoration technology that replaces painting due to demands for VOC (volatile organic compound) reduction and the like, and various decoration technologies have been proposed.

In particular, a technique has been proposed in which a decorative sheet instead of a coating film is applied to a molded product by vacuum pressure air molding or vacuum forming to form a decorative molded product in which the decorative sheet and the molded product are integrated (see, for example, Patent Document 1). In recent years, it has been receiving particular attention.

Compared to other decorative moldings typified by insert molding, vacuum pressure air forming and decorative molding by vacuum forming have a greater degree of freedom in shape, and the end face of the decorative sheet is rolled up to the back side of the decorative object, resulting in seams. Since it does not occur, it has an excellent appearance, and since it can be thermoformed at a relatively low temperature and low pressure, by imparting textures or the like to the surface of the decorative sheet, the reproducibility of the textures or the like on the surface of the decorative molded body is excellent. It has the advantage of.

On the other hand, as automobile parts, household appliances parts, and building material parts, polarities such as polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, and polyphenylene ether resin. A resin molded body made of a resin material is often used. Since these polar resin materials are inferior in water resistance and chemical resistance, it is expected that the water resistance and chemical resistance will be improved by attaching a decorative sheet.

On the other hand, polyolefin-based resins have characteristics of low polarity and excellent water resistance and chemical resistance, and various decorative sheets made of polyolefin-based resins have been proposed. However, since the conventional decorative sheet made of a polyolefin resin material is inferior in thermoforming property and has poor adhesiveness to a resin material having polarity, its suitability for vacuum pressure air forming and decorative molding by vacuum forming is insufficient. Met.

JP-A-2002-67137

In the prior art, a decorative film made of a substrate having a polarity suitable for vacuum pressure air forming and decorative molding by vacuum forming and a polypropylene-based resin having good adhesiveness has not yet been developed. In view of the above problems, the subject of the present invention is a decorative film used for three-dimensional decorative thermoforming, which can be adhered to a polar substrate and has an excellent product appearance, and a decorative film using the same, which is excellent in water resistance and chemical resistance. The purpose of the present invention is to provide a method for producing a decorative molded product.

In order to attach the decorative film in the solid state to the resin molded body in the solid state having polarity, it is necessary that the adhesive layer of the film has polarity and the surface of the molded body and the film are sufficiently softened or melted. is there. That is, it is important to apply the amount of heat required for softening or melting the surface of the molded product and the film, or to use a molded product and film that are easily softened or melted, but when the film is sufficiently heated, the viscosity of the film decreases. We focused on the fact that the film breaks or rampages due to the push-up of the molded product in the three-dimensional decorative heat molding process and the inflow of air when the vacuum chamber is returned to atmospheric pressure, leading to poor appearance. As a result, they have found that a decorative film containing a layer made of a specific polypropylene-based resin and a layer made of a polar polyolefin resin can solve the above-mentioned problems, and have completed the present invention.

That is, the decorative film of the present invention has any of the following configurations (1) to (3).
(1) A decorative film for being adhered onto a resin molded body by thermal molding, wherein the decorative film is made of a polyolefin-adhesive resin (C) on a layer (I) made of a polypropylene-based resin (A). The polypropylene-based resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 minutes or less, and the polyolefin adhesive resin (C) has at least A decorative film which is a polyolefin resin having a polar functional group containing one kind of hetero atom and whose MFR (230 ° C., 2.16 kg load) is 100 g / 10 minutes or less.
(2) The decorative film has a surface decorative layer (II) made of a surface decorative layer resin on the side of the layer (I) opposite to the surface side of the adhesive layer (III). The decorative film according to (1) above.
(3) The surface decorative layer resin is made of a polypropylene-based resin (B), and the MFR (230 ° C., 2.16 kg load) of the polypropylene-based resin (B) exceeds 2 g / 10 minutes. The decorative film according to (2) above.

Further, the method for producing a decorative molded product of the present invention comprises any of the following configurations (4) to (6).
(4) The step of preparing the decorative film according to any one of (1) to (3), the step of preparing a resin molded body, and the resin molded body and the decorative film in a decompressable chamber box. The step of setting, the step of depressurizing the inside of the chamber, the step of heating and softening the decorative film, the step of pressing the decorative film against the resin molded body, and the step of returning or pressurizing the inside of the chamber to atmospheric pressure. A method for manufacturing a decorative molded product.
(5) The resin molded body is selected from polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, polyphenylene ether resin, and composite materials thereof. The method for producing a decorative molded body according to (4) above, wherein the decorative molded body is made of a polar resin material.
(6) The method for producing a decorative molded body according to (4) above, wherein the resin molded body is made of a propylene-based resin composition.

As a result of diligent research, the present inventors have made the decorative film include a layer (I) made of a polypropylene-based resin (A) having a specific MFR. From a polyolefin adhesive resin (C) that has excellent thermosetting properties during original decorative thermosetting, can sufficiently lengthen the heating time, and has a specific MFR and functional group on the adhesive surface between the decorative film and the substrate. Since the adhesive layer (III) is interposed, the decorative film can be attached to the polar substrate. Further, the decorative molded product obtained by the decorative film of the present invention and the substrate made of a polar resin material is particularly excellent in water resistance and chemical resistance.

According to the method for producing a decorative molded article of the present invention, it is possible to obtain a beautiful decorative molded article having no holes or wrinkles on its surface and no air entrainment between the decorative film and the resin molded article.

FIG. 5 is a schematic cross-sectional view illustrating an embodiment of a decorative molded body in which the decorative film of the present invention is attached to a molded body, and (a) to (c) are examples in which the layer configurations of the decorative films are different from each other. Is. It is a schematic cross-sectional view explaining the outline of the apparatus used in the manufacturing method of the decorative molded article of this invention. It is a schematic cross-sectional view explaining the state that the resin molded body and the decorative film are set in the apparatus of FIG. It is a schematic cross-sectional view explaining the state of heating and depressurizing the inside of the apparatus of FIG. FIG. 5 is a schematic cross-sectional view illustrating a state in which a decorative film is pressed against a resin molded body in the apparatus of FIG. It is a schematic cross-sectional view explaining how the inside of the apparatus of FIG. 2 returns to atmospheric pressure or pressurizes. It is a schematic cross-sectional view explaining how the edge of an unnecessary decorative film was trimmed in the obtained decorative molded body.

In the present specification, the decorative film means a film for decorating a molded product. Decorative molding refers to molding in which a decorative film and a molded body are attached to each other. The three-dimensional decorative thermoforming is a molding in which a decorative film and a molded body are attached to each other, and has a step of thermoforming the decorative film along the attachment surface of the molded body and at the same time attaching the decorative film. In this step, in order to prevent air from being entrained in the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is attached to the molded body, and pressure is released (applied). It refers to molding, which is a process of bringing them into close contact with each other by pressure). Hereinafter, embodiments for carrying out the present invention will be described in detail.

The decorative film in the present invention is a decorative film for being attached onto a resin molded body by thermal molding, and is composed of a layer (I) made of a polypropylene resin (A) and a polyolefin adhesive resin (C). The polypropylene resin (A) contains the seal layer (III) and has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 minutes or less, and the polyolefin adhesive resin (C) has an MFR (230 ° C., 2.16 kg). The load) exceeds 2 g / 10 minutes.

Polypropylene resin (A)
By including the layer (I) made of the polypropylene-based resin (A) in the decorative film, it is possible to suppress the occurrence of appearance defects due to the film breaking or violent during thermoforming. As a result, the thermoformability of the decorative film is improved, so that it is not necessary to include a thermosetting resin layer having excellent thermoformability. Further, by improving the moldability of the polypropylene-based resin (A), it is extremely simple that a single layer of the polypropylene-based resin (A) or a layer (I) made of the polypropylene-based resin (A) and a surface decorative layer are laminated. It can be used as a decorative film with various configurations, and with such a configuration, the decorative film can be molded by (co) extrusion.

The polypropylene-based resin (A) in the present invention is various types of propylene-based resins such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), and a propylene block copolymer (block polypropylene). Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of the propylene monomer.

The polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 minutes or less, preferably 1.5 g / 10 minutes or less, and more preferably 1 g / 10 minutes or less. By setting the MFR of the polypropylene-based resin (A) to the above value or less, a decorative molded product having a good appearance can be obtained.

The lower limit of the MFR of the polypropylene resin (A) is not particularly limited, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.3 g / 10 minutes or more. By setting the MFR to the above value or more, the moldability at the time of manufacturing the decorative film is improved, and it is possible to suppress the occurrence of appearance defects called sharkskin and interface roughness on the film surface.

In the present specification, the MFR of the polypropylene-based resin and the polypropylene-based resin composition described later was measured in accordance with ISO 1133: 1997 Connections M under the conditions of 230 ° C. and a 2.16 kg load. The unit is g / 10 minutes.

The polypropylene-based resin (A) in the present invention preferably has high crystallinity from the viewpoint of heat resistance, scratch resistance, and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene-based resin (A) is preferably 155 ° C. or higher, more preferably 158 to 170 ° C., and even more preferably 160 to 168 ° C. The polypropylene-based resin (A) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. Further, even if the melting point is high, if a low crystallinity component is contained, the scratch resistance and the solvent resistance are lowered. Therefore, the polypropylene-based resin (A) is an ethylene-α-olefin having an ethylene content of 50 to 70% by weight. It is preferable that it does not contain a copolymer.

The polypropylene-based resin (A) may contain additives, fillers, colorants, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) containing a propylene-based polymer, additives, fillers, colorants, other resin components, and the like. The total amount of additives, fillers, colorants, other resin components and the like is preferably 50% by weight or less based on the polypropylene resin composition.

When the polypropylene-based resin (A) is a polypropylene-based resin composition, it is preferable that the polypropylene-based resin composition has the characteristics of the polypropylene-based resin (A). That is, the MFR (230 ° C., 2.16 kg load) of the polypropylene-based resin composition is 2 g / 10 minutes or less.

When the decorative molded product of the present invention is molded as a colored molded product, a colorant needs to be used only for the decorative film, so that an expensive colorant is used as compared with the case where the entire resin molded product is colored. It is possible to suppress. In addition, changes in physical properties associated with the addition of a colorant can be suppressed.

As the additive, it can be used for polypropylene-based resins such as antioxidants, neutralizers, light stabilizers, ultraviolet absorbers, crystal nucleating agents, blocking inhibitors, lubricants, antistatic agents, and metal deactivators. Various known additives can be blended.

Examples of the antioxidant include a phenol-based antioxidant, a phosphite-based antioxidant, and a thio-based antioxidant. Examples of the neutralizing agent include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, benzotriazoles, benzophenones and the like.

Examples of the crystal nucleating agent include amide-based nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol-based derivatives, and rosin metal salts. Among these crystal nucleating agents are aluminum pt-butyl benzoate, 2,2'-methylenebis phosphate (4,6-di-t-butylphenyl) sodium, and 2,2′-methylenebis phosphate (4). , 6-di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Examples thereof include a complex of an aluminum hydroxide salt (thin-6-oxide) and an organic compound, p-methyl-benzylene sorbitol, p-ethyl-benzylidene sorbitol, and a sodium salt of rosin.

Examples of the lubricant include higher fatty acid amides such as stearic acid amide. Examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester. Examples of the metal deactivator include triazines, phosphons, epoxies, triazoles, hydrazides, oxamides and the like.

As the filler, various known fillers that can be used for polypropylene-based resins, such as inorganic fillers and organic fillers, can be blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, carbon fiber and the like. Further, examples of the organic filler include crosslinked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles.

Examples of other resin components include polyethylene-based resins, polyolefins such as ethylene-based elastomers, modified polyolefins, and other thermoplastic resins.

It is also possible to color the product in order to impart designability, and various colorants such as inorganic pigments, organic pigments, and dyes can be used for coloring. It is also possible to use bright materials such as aluminum flakes, titanium oxide flakes, and (synthetic) mica.

The polypropylene-based resin composition is prepared by a method of melt-kneading a propylene-based polymer with additives, fillers, other resin components, etc., and a method of melt-kneading a propylene-based polymer with additives, fillers, etc., and drying the other resin components. It can be produced by a method of blending, a method of dry blending a masterbatch in which additives, fillers and the like are dispersed in a carrier resin in addition to a propylene polymer and other resin components at a high concentration.

Polyolefin adhesive resin (C)
The decorative film of the present invention contains a bonding layer (III) made of a polyolefin adhesive resin (C) on a bonding surface with a resin molded body (base) to form a substrate made of a resin material having polarity. Can be firmly adhered.

The MFR (230 ° C., 2.16 kg load) of the polyolefin adhesive resin (C) in the present invention is 100 g / 10 minutes or less, preferably 50 g / 10 minutes or less, and more preferably 20 g / 10 minutes or less. By setting the MFR of the polyolefin adhesive resin (C) to the above value or less, the layer (I) made of the polypropylene-based resin composition (A) is attached to the layer (I) made of the polyolefin adhesive resin (C) by an extrusion molding method. (III) can be laminated. The lower limit of the MFR of the polyolefin adhesive resin (C) is not particularly limited, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.3 g / 10 minutes or more. By setting the MFR of the polyolefin adhesive resin (C) to the above value or more, roughening of the interface at the laminated interface occurs in the coextrusion molding of the polypropylene resin composition (A) and the polyolefin adhesive resin (C). However, it is possible to prevent problems such as the polyolefin adhesive resin (C) not being laminated to the edge of the film.

The polyolefin adhesive resin (C) in the present invention is a polyolefin resin having a polar functional group having at least one heteroatom from the viewpoint of improving the adhesiveness with the layer (I) made of the polypropylene resin (A). Is preferable.

Examples of the polar functional group having a hetero atom include an epoxy group, a carbonyl group, an ester group, an ether group, a hydroxy group, a carboxy group or a metal salt thereof, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, and an acid anhydride group. Examples thereof include an amino group, an imide group, an amide group, a nitrile group, a thiol group, a sulfo group, an isocyanate group and a halogen group. Specific examples of polyolefins having such polar functional groups include acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer and ethylene / vinylidene chloride copolymer. Combined, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer , Ethethylene / isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / Butyl methacrylate copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / Acrylic acid metal salt copolymer, ethylene / methacrylate metal salt copolymer, ethylene / vinyl acetate copolymer or its sacrifice, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, Ethylene or α-olefin / vinyl monomer copolymers such as ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer; chlorine such as chlorinated polypropylene and chlorinated polyethylene Examples include copolymerized polyolefins. Further, these resins may be used alone or may be mixed in two or more kinds. Further, if necessary, other resins or rubbers, tackifiers, various additives and the like may be mixed.

Examples of the other resin or rubber include polyα-olefins such as polypentene-1 and polymethylpentene-1, ethylene or α-olefin / α-olefin copolymers such as propylene / butene-1 copolymers. Ethylene or α-olefin / α-olefin / diene monomer copolymer such as ethylene / propylene / 5-ethylidene-2-norbornene copolymer, polydiene copolymer such as polybutadiene, polyisoprene, styrene / butadiene random co Single amount of vinyl such as polymer, vinyl monomer / diene monomer random copolymer such as styrene / isoprene random copolymer, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer Hydrogenation (vinyl monomer / diene) such as body / diene monomer / vinyl monomer block copolymer, hydrogenation (styrene / butadiene random copolymer), hydrogenation (styrene / isoprene random copolymer) Hydrogenation (vinyl monomer / diene monomer) such as monomer random copolymer), hydrogenation (styrene / butadiene / styrene block copolymer), hydrogenation (styrene / isoprene / styrene block copolymer) / Vinyl monomer block copolymer), acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer and other vinyl monomers / diene monomer / vinyl monomer grafts Polymers, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, ethyl polyacrylate, butyl polyacrylate, methyl polymethacrylate, vinyl polymers such as polystyrene, vinyl chloride / acrylonitrile copolymer, vinyl chloride / Vinyl acetate copolymer, acrylonitrile / styrene copolymer, vinyl copolymer such as methyl methacrylate / styrene copolymer and the like can be mentioned.

Examples of the tackifier include rosin-based resins (gam rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resin, and terpene resin ( Polymers of α-pinene, β-pinene, limonene, etc.), aromatic hydrocarbon-modified terpene resin, petroleum resin (aliphatic, alicyclic, aromatic, etc.), kumaron inden resin, styrene resin, Examples thereof include phenol resins (alkylphenols, phenolxylene formaldehyde, rosin-modified phenolic resins, etc.), xylene resins, and the like, and these can be used alone or in combination of two or more. Of these, rosin-based resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferable from the viewpoint of thermal stability, and are compatible with the modified polyolefin-based resin of the present invention. However, rosin-based resins and terpene phenol resins are particularly preferable because they can contribute to adhesion to polar resins.

Examples of the additive include antioxidants, metal deactivators, phosphorus-based processing stabilizers, ultraviolet absorbers, ultraviolet stabilizers, fluorescent whitening agents, metal soaps, stabilizers such as antioxidative adsorbents, and cross-linking agents. , Chain transfer agent, nucleating agent, lubricant, plasticizer, filler, reinforcing material, pigment, dye, flame retardant, antistatic agent and the like, and may be added within a range that does not impair the effects of the present invention.

Among the above-mentioned polyolefin resins having polar functional groups, from the viewpoint of adhesiveness to the layer (I), as commercial products, the product name "Admer" manufactured by Mitsui Chemicals Corporation, the product name "Modic" manufactured by Mitsubishi Chemical Corporation, and Sanyo Chemicals Co., Ltd. A company-made "Umex" or the like can be preferably used.

Decorative film The decorative film in the present invention includes a layer (I) made of a polypropylene-based resin (A) and a sticking layer (III) made of a polyolefin adhesive resin (C). The decorative film can have various configurations in addition to the layer (I) and the sticking layer (III). That is, even if the decorative film is a two-layer film composed of a layer (I) and a sticking layer (III), it is a multilayer film composed of a layer (I), a sticking layer (III) and another layer. May be good. The sticking layer (III) is arranged on the outermost surface of the decorative film to be stuck to the resin molded body (base). The outermost surface of the decorative film may be textured, embossed, printed, sandplasted, scratched, or the like.

The decorative film has a large degree of freedom in shape, and the end face of the decorative film is caught up to the back side of the object to be decorated, so that no seam is formed, so that the appearance is excellent. You can express various textures with. For example, when giving a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems in molding with a molded body mold to be embossed, that is, a molded body mold is required for each embossing pattern, and it is very difficult and expensive to apply complicated embossing to a curved mold. It is possible to solve the problem of being, and to obtain a decorative molded body easily embossed with various patterns.

The multilayer film can include a surface layer, a surface decoration layer, a printing layer, a light-shielding layer, a coloring layer, a base material layer, a sticking layer, a barrier layer, a tie layer layer that can be provided between these layers, and the like. .. The layer (I) made of the polypropylene-based resin (A) may be any layer other than the adhesive layer among the layers constituting the multilayer film.

In the multilayer film, the layers other than the layer (I) and the bonding layer (III) are preferably a layer made of a thermoplastic resin, and more preferably a layer made of a polypropylene resin. The layers other than the layer (I) and the sticking layer (III) can be distinguished from the layer (I) and the sticking layer (III) by the MFR (230 ° C., 2.16 kg load) of the polypropylene-based resin. ) Is not particularly limited. Each layer is preferably a layer that does not contain a thermosetting resin. By using the thermoplastic resin, the recyclability is improved, and by using the polypropylene-based resin, the complexity of the layer structure can be suppressed, and the recyclability is further improved.

When the decorative film is a two-layer film, the layer (I) made of the polypropylene-based resin (A) constitutes a surface layer opposite to the surface to be attached to the resin molded product, and the polyolefin adhesive resin (C) is formed. The sticking layer (III) made of the resin forms a sticking layer on the sticking surface to the resin molded product.

When the decorative film is a multilayer film having three or more layers, the layer (I) made of the polypropylene-based resin (A) is preferably the outermost layer of the decorative film in order to sufficiently exhibit solvent resistance. The layer structure is such that another layer (including a plurality of layers) is included between the layer (I) made of the polypropylene resin (A) and the adhesive layer (III) made of the polyolefin adhesive resin (C). preferable.

1 (a) to 1 (c) are explanatory views schematically illustrating a cross section of an embodiment of a decorative film attached to a resin molded body. In FIGS. 1 (a) to 1 (c), the arrangement of the layer (I) and the bonding layer (III) will be specified and described for ease of understanding, but the layer structure of the decorative film is limited to these examples. It is not interpreted as. In the present specification, reference numeral 1 in the drawing is a decorative film, reference numeral 2 is a layer (I), reference numeral 3 is a bonding layer (III), reference numeral 4 is a surface decoration layer (II), and reference numeral 5 is a resin molded product. Shown. FIG. 1A shows an example in which the decorative film is made of a two-layer film, and a sticking layer (III) made of a polyolefin adhesive resin (C) is stuck to the resin molded body 5, and the sticking layer (III) is stuck. ), A layer (I) made of a polypropylene resin (A) is laminated. The decorative film of FIG. 1B is composed of a sticking layer (III), a layer (I) and an intermediate layer, and the sticking layer (III) is stuck to the surface of the resin molded body 5 and the sticking layer (III) is stuck. ), The intermediate layer and the layer (I) are laminated in this order. The decorative film of FIG. 1 (c) is composed of a surface decorative layer (II) composed of a sticking layer (III), a layer (I) and a polypropylene-based resin (B), and is a sticking layer on the surface of the resin molded body 5. (III) is attached, and the layer (I) and the surface decoration layer (II) are laminated in this order on the attachment layer (III).

Another preferred embodiment of the decorative film is a multilayer film containing a surface decorative layer (II) made of a surface decorative layer resin on the outermost surface opposite to the surface to be attached to the resin molded body. The surface decorative layer resin is preferably a thermoplastic resin, and more preferably a polypropylene-based resin (B) having an MFR (230 ° C., 2.16 kg load) of more than 2 g / 10 minutes. That is, the layer (I) made of the polypropylene resin (A) having an MFR of 2 g / 10 minutes or less, which improves thermoforming property, generally has poor gloss and grain transferability due to its low MFR, but is a decorative film. By further providing a surface decorative layer (II) made of a polypropylene resin (B) having an MFR of more than 2 g / 10 minutes on the surface layer, gloss and grain transferability are improved without significantly reducing thermoformability. Can be done. Further, by using the polypropylene-based resin (B), it is possible to suppress the complexity of the layer structure and the deterioration of recyclability. In addition, by using the polypropylene-based resin (B) as the surface decorative layer of the decorative film, it is possible to improve the solvent resistance and the like. Further, by using the polypropylene resin (B) for the surface decoration layer, the transferability of the surface during the production and thermoforming of the decoration film is improved, and if a mirror roll is used during the thermoforming, the decoration has high gloss. It can be a film.

The polypropylene-based resin (B) in the present invention is various types of propylene-based resins such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), and a propylene block copolymer (block polypropylene). Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of the propylene monomer. The propylene-based polymer preferably does not contain a polar group-containing monomer unit. The polypropylene-based resin (B) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance and the like. Further, from the viewpoint of gloss and transparency (color development), a propylene-α-olefin copolymer is preferable. In the present invention, the polypropylene-based resin (B) constituting the surface decorative layer (II) may be the same as or different from the polyolefin adhesive resin (C) constituting the adhesive layer (III).

The polypropylene-based resin (B) in the present invention preferably has an MFR (230 ° C., 2.16 kg load) of more than 2 g / 10 minutes, more preferably 5 g / 10 minutes or more, and further preferably 9 g / 10 minutes or more. .. By setting the MFR of the polypropylene resin (B) to the above value range, effects such as improvement of the gloss of the decorative film and improvement of the grain transferability can be obtained, and the required surface shape of the molded product ( It is possible to obtain a decorative molded product having a good appearance with respect to gloss, non-gloss, grain, etc.).

The upper limit of the MFR of the polypropylene resin (B) is not particularly limited, but is preferably 100 g / 10 minutes or less, and more preferably 50 g / 10 minutes or less. By setting the MFR in the above value range, good oil resistance, solvent resistance, scratch resistance and the like can be exhibited.

The polypropylene-based resin (B) may contain additives, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) of a propylene-based polymer and an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components and the like is preferably 50% by weight or less based on the polypropylene-based resin composition.

As the additive, an additive or the like that may be contained in the polypropylene-based resin (A) can be used.

The polypropylene-based resin composition is prepared by a method of melt-kneading a propylene-based polymer with additives, fillers, other resin components, etc., and a method of melt-kneading a propylene-based polymer with additives, fillers, etc., and drying the other resin components. It can be produced by a method of blending, a method of dry blending a masterbatch in which additives, fillers and the like are dispersed in a carrier resin in addition to a propylene polymer and other resin components at a high concentration.

The decorative film of the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, still more preferably about 80 μm or more. By increasing the thickness of the decorative film to such a value or more, the effect of imparting designability is improved, the stability during molding is also improved, and it is possible to obtain a better decorative molded product. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, still more preferably about 0.8 mm or less. By reducing the thickness of the decorative film to such a value or less, the time required for heating during thermoforming is shortened, the productivity is improved, and it becomes easy to trim unnecessary parts.

In the decorative film of the present invention, the ratio of the thickness of the layer (I) to the total thickness of the decorative film is preferably 30 to 99%, and the ratio of the sticking layer (III) is preferably 1 to 70. %. When the ratio of the thickness of the layer (I) to the entire decorative film is within the above value range, it is possible to avoid insufficient thermoformability of the decorative film. Further, if the ratio of the thickness of the adhesive layer (III) to the entire decorative film is within the above value range, sufficient adhesive strength can be obtained with the substrate made of the polar resin material.

Further, in the multilayer film provided with the surface decorative layer (II) made of polypropylene resin (B) on the outermost surface of the decorative film, the thickness of the entire decorative film having the thickness of the layer (II) in the decorative film. The ratio to the above is preferably 30% or less.

Production of Decorative Film The decorative film of the present invention can be produced by various known molding methods.
For example, a method of extruding a layer made of polypropylene resin (A), a method of coextruding a layer (I) made of polypropylene resin (A) and another layer, or one of the layers extruded in advance. Thermal lamination method in which another layer is bonded by applying heat and pressure on the surface of the surface, dry lamination method and wet lamination method in which the layer (I) and the other layer are bonded via an adhesive, extrusion molding in advance. Examples thereof include an extrusion lamination method and a sand lamination method in which a polypropylene-based resin is melt-extruded on one surface of one of the layers. As an apparatus for forming the decorative film, a known coextrusion T-die molding machine or a known laminating molding machine can be used. Among these, a coextrusion T-die molding machine is preferably used from the viewpoint of productivity.

As a method of cooling the molten decorative film extruded from the die, a method of bringing the molten decorative film into contact with one cooling roll through the air discharged from the air knife unit or the air chamber unit, or Examples thereof include a method of crimping with a plurality of cooling rolls to cool the film.

In order to impart gloss to the decorative film of the present invention, a method of surface-transferring a mirror-shaped cooling roll to the design surface of the product to perform mirror surface processing is used.

Further, the surface of the decorative film of the present invention may have a textured shape. Such a decorative film is a method in which a molten resin extruded from a die is directly pressure-bonded between a roll having an uneven shape and a smooth roll to transfer the uneven shape to a surface. It can be manufactured by a method of surface-transferring an uneven shape by pressure-welding a heat-applied roll and a smooth roll. Examples of the grain shape include satin finish, animal skin tone, hairline tone, carbon tone and the like.

The decorative film of the present invention may be heat-treated after film formation. Examples of the heat treatment method include a method of heating with a heat roll, a method of heating with a heating furnace or a far-infrared heater, a method of blowing hot air, and the like.

Decorative molded body As the molded body (decoration target) to be decorated in the present invention, preferably polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, etc. Various molded bodies (hereinafter, may be referred to as "base") made of a melamine resin, a polyphenylene ether resin, and a polar resin material selected from a composite material thereof can be used. Further, as the molded product (to be decorated), various molded products made of a propylene-based resin or a propylene-based resin composition may be used. Further, various molded products made of a propylene-based resin and a resin composition composed of the above-mentioned polar resin may be used. Further, additives such as reinforcing agents such as inorganic fillers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, and lubricants may be added to these resins, and these additives may be used alone or 2 More than one type may be used together. The molding method is not particularly limited, and examples thereof include injection molding, blow molding, press molding, extrusion molding and the like.

Since the non-polar polypropylene-based resin is a difficult-to-adhere resin in the polar resin material described above, it is not usually heat-bonded. On the other hand, since the decorative film in the present invention contains the adhesive layer (III) made of the polyolefin adhesive resin (C), the decorative object and the film can be thermally adhered to each other, and high adhesive strength is exhibited. Can be done. As the polyolefin adhesive resin (C), a modified polyolefin resin grafted with α, β-unsaturated carboxylic acids can be preferably exemplified.

In the decorative molded body in which the decorative film of the present invention is attached to various molded bodies formed of polypropylene-based resin in a three-dimensional shape, VOC contained in coating or adhesive is greatly reduced. It can be suitably used as home appliances, vehicles (railroads, etc.), building materials, daily necessities, etc.

In the method for producing a decorative molded article of the present invention, the resin molded article and the decorative film are set in a step of preparing the above-mentioned decorative film, a step of preparing a resin molded article, and a decompressable chamber box. It is characterized by including a step of depressurizing the inside of the chamber, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the inside of the chamber to atmospheric pressure. To do.

In the three-dimensional decorative heat molding, the decoration target and the decoration film are set in the chamber box that can be depressurized, the film is heated and softened while the inside of the chamber is depressurized, and the film is pressed against the decoration target to form the chamber. It has a basic process of attaching the decorative film to the surface of the object to be decorated by returning the inside to atmospheric pressure or pressurizing the inside, and the film is attached under reduced pressure. As a result, it is possible to obtain a clean decorative molded product that does not generate air pools. In the production method of the present invention, any known technique can be used as long as the apparatus and conditions are suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the decoration object, the decoration film, the mechanism for pressing the decoration film, the device for heating the decoration film, and the like, or depending on the decoration film. It may be a plurality of divided ones.

Further, the mechanism for pressing the decoration target and the decoration film may be any type of a mechanism for moving the decoration target, a mechanism for moving the decoration film, and a mechanism for moving both of them.
More specifically, a typical molding method is illustrated below.

Hereinafter, a method of attaching a decorative film to a decorative object by using a three-dimensional decorative thermoforming machine will be exemplified with reference to the drawings.

As shown in FIG. 2, the three-dimensional decorative thermoforming machine of this embodiment includes chamber boxes 11 and 12 at the top and bottom, and thermoforms the decorative film 1 in the two chamber boxes 11 and 12. I am trying to do it. A vacuum circuit (not shown) and an air circuit (not shown) are piped to the upper and lower chamber boxes 11 and 12, respectively.

Further, a jig 13 for fixing the decorative film 1 is provided between the upper and lower chamber boxes 11 and 12. Further, a table 14 capable of ascending / descending is installed in the lower chamber box 12, and the resin molded body (decoration target) 5 is set on the table 14 (via a jig or the like or directly). To. A heater 15 is incorporated in the upper chamber 11, and the decorative film 1 is heated by the heater 15.

As such a three-dimensional decorative thermoforming machine, a commercially available molding machine (for example, NGF series manufactured by Fuse Vacuum Co., Ltd.) can be used.

As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 open, the decoration target 5 is placed on the table 14 in the lower chamber box 12, and the table 14 is lowered. Subsequently, the decorative film 1 is set on the film fixing jig 13 between the upper and lower chamber boxes 11 and 12 so that the adhesive layer (III) faces the substrate.

As shown in FIG. 4, the upper chamber box 11 is lowered, the upper and lower chamber boxes 11 and 12 are joined to close the inside of the box, and then the insides of the respective chamber boxes 11 and 12 are put into a vacuum suction state, and the heater 15 is used. The decorative film 1 is heated by the above method.

After the decorative film 1 is heated and softened, as shown in FIG. 5, the table 14 in the lower chamber box 12 is raised while the upper and lower chamber boxes 11 and 12 are in a vacuum suction state. The decorative film 1 is pressed against the decorative object 5 to cover the decorative object 5. Further, as shown in FIG. 6, by opening the upper chamber box 11 under atmospheric pressure or supplying compressed air from the air pressure tank, the decorative film 1 is brought into close contact with the decorative object 5 with a larger force.

Subsequently, the insides of the upper and lower chamber boxes 11 and 12 are opened under atmospheric pressure, and the decorative molded body 6 is taken out from the lower chamber box 12. Finally, as illustrated in FIG. 7, the edges of the unnecessary decorative film 1 around the decorative molded body 6 are trimmed.

Molding conditions The depressurization in the chamber boxes 11 and 12 may be such that no air pool is generated, and the pressure in the chamber is 10 KPa or less, preferably 3 KPa, more preferably 1 KPa or less.

Further, in the two chamber boxes 11 and 12 divided into upper and lower parts by the decorative film 1, the pressure inside the chamber box on the side to which the decorative object 5 and the decorative film 1 are attached may be within this range, and the upper and lower parts may be used. The drawdown of the decorative film 1 can be suppressed by changing the pressures of the chamber boxes 11 and 12 of the above.

At this time, a film made of a general polypropylene resin may be significantly deformed and ruptured by a slight pressure fluctuation due to a decrease in viscosity during heating.

The decorative film 1 of the present invention is not only difficult to draw down, but also resistant to film deformation due to pressure fluctuations.

The heating of the decorative film 1 is controlled by the heater temperature (output) and the heating time. It is also possible to measure the surface temperature of the film with a thermometer such as a radiation thermometer and use it as a guideline for appropriate conditions.

In the present invention, in order to attach the polypropylene-based decorative film 1 to the decorative object 5 made of polypropylene-based resin, it is necessary that the surface of the resin molded body 5 and the decorative film 1 are sufficiently softened or melted.

Therefore, the heater temperature needs to be higher than the melting temperature of the polypropylene-based resin constituting the decoration target 5 and the polypropylene-based resin constituting the decoration film 1. The heater temperature is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher.

The higher the heater temperature, the shorter the time required for heating, but the heater side is sufficiently heated until the inside of the decorative film 1 (or the surface opposite to the heater when the heater is installed on only one side) is sufficiently heated. The heater temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, and most preferably 400 ° C., because not only the moldability is deteriorated but also the resin is thermally deteriorated when the temperature is too high. It is as follows.

The appropriate heating time varies depending on the heater temperature, but it is preferably 2 seconds or more after the polypropylene-based decorative film is heated and the tensioning back called springback is completed.

That is, the decorative film heated by the heater expands thermally when heated from the solid state and sags once as the crystal melts, and when the crystal melt progresses, the molecules relax and the springback temporarily rebounds. Is observed, and then it hangs down due to its own weight, but after springback, the crystals of the film are completely melted and the molecules are sufficiently relaxed, so that sufficient adhesive strength can be obtained.

On the other hand, if the heating time is too long, the film may hang down due to its own weight or may be deformed due to the pressure difference between the upper and lower chambers. Therefore, the heating time is preferably less than 120 seconds after the end of springback.

When decorating a molded product having an uneven shape or achieving higher adhesive strength, it is preferable to supply compressed air when the decorative film is brought into close contact with the substrate. The pressure in the upper chamber box when compressed air is introduced is 150 kPa or more, preferably 200 kPa or more, and more preferably 250 kPa or more. The upper limit is not particularly limited, but if the pressure is too high, the equipment may be damaged. Therefore, 450 kPa or less, preferably 400 kPa or less is preferable.

Hereinafter, the present invention will be described in more detail as examples, but the present invention is not limited to this example.

1. 1. Measurement method of various physical properties (i) MFR
Measured at 230 ° C. with a 2.16 kg load according to ISO 1133: 1997 Connections M. The unit is g / 10 minutes.

(Ii) Melting point:
Using a differential operating calorimeter (DSC), once raise the temperature to 200 ° C and hold for 10 minutes, then lower the temperature to 40 ° C at a temperature lowering rate of 10 ° C / min, and then raise the temperature again at a heating rate of 10 ° C / min. The temperature at the top of the endothermic peak at the time of measurement was taken as the melting point. The unit is ° C.

2. Materials used (1) Polypropylene resin (A)
The following polypropylene resins were used.
(A-1): Propylene homopolymer (MFR = 0.4 g / 10 minutes, Tm = 161 ° C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) EA9"
(A-2): Propylene homopolymer (MFR = 2.4 g / 10 minutes, Tm = 161 ° C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FY6"
(A-3): Polypropylene resin composition (MFR = 0.) In which 96% by weight of polypropylene resin (A-1) is blended with 4% by weight of black pigment MB (EPP-K-12601 manufactured by Polycol Kogyo Co., Ltd.). 4 g / 10 minutes, Tm = 161 ° C)
(2) Polyolefin adhesive resin (C)
(C-1): Maleic anhydride-modified polyolefin (MFR = 7 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F534A"
(C-2): Maleic anhydride-modified polyolefin (MFR = 1.6 g / 10 minutes), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F532"
(3) Polypropylene resin (B)
(B-1): Propylene homopolymer (MFR = 10 g / 10 minutes, Tm = 161 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FA3KM"
(B-2): Polypropylene resin composition blended with 100 parts by weight of polypropylene resin (B-1) by 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Milllad NX8000J"). (MFR = 10 g / 10 minutes, Tm = 164 ° C)
(B-3): Metallocene-catalyzed propylene-α-olefin copolymer (MFR = 7 g / 10 minutes, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Japan Polypropylene Corporation, trade name " Wintech (registered trademark) WFX4M "
(B-4): Polypropylene resin composition blended with 100 parts by weight of polypropylene resin (B-3) by 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Milllad NX8000J"). (MFR = 7 g / 10 minutes, Tm = 127 ° C)
(B-5): Polypropylene resin (B-1) 96% by weight with MFR = 11 g / 10 minutes white pigment MB (EPP-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80% by weight) Polypropylene resin composition blended by 4% by weight (MFR = 10 g / 10 minutes, Tm = 161 ° C.)
(B-6): Polypropylene resin composition (MFR = 10 g / 10) in which 96% by weight of polypropylene resin (B-1) is blended with 4% by weight of silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyo Color Co., Ltd.). Minutes, Tm = 161 ° C)
(4) Polar resin (X) used for the resin molded body (base)
The following polar resins were used.
(X-1): PMMA resin, manufactured by Mitsubishi Rayon Co., Ltd., "Acrylic MD"
(X-2): ABS resin, manufactured by Techno Polymer Co., Ltd., "ABS130"
(X-3): PC resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., "Novalex 7022A"

3. 3. Production of Resin Mold (Base) Polar resins (X-1) to (X-3) were dried at 80 ° C. for 2 hours using a box oven. The dried resin was injection-molded by the following method to obtain an injection-molded body.
3-1. PMMA resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 100 tons Cylinder temperature: 230 ° C
Mold temperature: 40 ° C
Injection mold: Width x Height x Thickness = 120 mm x 120 mm x 3 mm Flat plate Condition adjustment: Hold for 5 days in a constant temperature and humidity chamber with a temperature of 23 ° C and a humidity of 50% RH 3-2. ABS resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 100 tons Cylinder temperature: 210 ° C
Mold temperature: 40 ° C
Injection mold: Width x Height x Thickness = 120 mm x 120 mm x 3 mm Flat plate Condition adjustment: Hold for 5 days in a constant temperature and humidity chamber with a temperature of 23 ° C and a humidity of 50% RH 3-3. PC resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure 100 tons Cylinder temperature: 290 ° C
Mold temperature: 80 ° C
Injection mold: Width x Height x Thickness = 120 mm x 120 mm x 3 mm Flat plate Condition adjustment: Hold for 5 days in a constant temperature and humidity chamber with a temperature of 23 ° C and a humidity of 50% RH

Example 1
-Manufacture of decorative film Two types 2 with a lip opening of 0.8 mm and a die width of 400 mm, to which an extruder-1 with a diameter of 40 mm (diameter) and an extruder-2 for a sticking layer with a diameter of 30 mm (diameter) are connected. A layer T die was used. Polypropylene resin (A-1) is charged into the extruder-1, and polyolefin adhesive resin (C-1) is charged into the extruder-2 for the adhesive layer. The resin temperature is 240 ° C., and the extruder-1 is discharged. Melt extrusion was performed under the conditions that the amount was 12 kg / h and the discharge amount of the sticking layer extruder-2 was 8 kg / h. The melt-extruded film was cooled and solidified by a cooling roll rotating at 3 m / min at 80 ° C. so that the adhesive layers were in contact with each other, and the adhesive layer having a thickness of 100 μm and the layer having a thickness of 150 μm were laminated. An unstretched film of the layer was obtained.

-As the three-dimensional decorative thermoformed resin molded body (base) 5, an injection molded body made of the polar resin (X-1) obtained above was used. As a three-dimensional decorative thermoforming apparatus, "NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used. The decorative film 1 is cut out in a width of 250 mm × a length of 350 mm so that the adhesive layer faces the substrate and the longitudinal direction is the MD direction of the film, and a film fixing jig having an opening size of 210 mm × 300 mm. It was set to 13. The resin molded body (base) 5 is placed on a sample setting table having a height of 20 mm, which is installed on a table 14 located below the film fixing jig 13, and is manufactured by Nichiban Co., Ltd. “Nystack NW-K15”. I pasted it through. The film fixing jig 13 and the table 14 were installed in the chambers 11 and 12, and the chamber was closed to seal the chamber boxes 11 and 12. The chamber box is divided into upper and lower parts via the decorative film 1. With the upper and lower boxes vacuum sucked and the pressure reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80% to form the decorative film 1. It was heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. Twenty seconds after the decorative film 1 is heated and temporarily sags, and then the springback phenomenon of tensioning back is completed, the table 14 installed in the lower chamber box 12 is moved upward to form a resin molded product. The (base) 5 was pressed against the decorative film 1, and immediately after that, compressed air was sent so that the pressure in the upper chamber box 11 became 270 kPa to bring the resin molded body (base) 5 and the decorative film 1 into close contact with each other. In this way, the decorative molded body 6 to which the decorative film 1 was attached to the upper surface and the side surface of the resin molded body (base) 5 was obtained.

・ Evaluation of physical properties (1) Evaluation of the appearance of the decorative molded product The draw-down state of the decorative film during three-dimensional decorative thermoforming, and the application of the decorative film of the decorative molded product with the decorative film attached to the substrate. The state of wearing was visually observed and evaluated according to the criteria shown below.
◯: During three-dimensional decorative thermoforming, the decorative film did not draw down and the substrate and the decorative film were in contact with each other at the same time on the entire contact surface, so that contact unevenness did not occur and the film was evenly attached. ing.
Δ: Since the decorative film was slightly drawn down during the three-dimensional decorative thermoforming, it came into contact with the decorative film from the center of the substrate, and uneven contact occurred at the upper end of the substrate.
X: During three-dimensional decorative thermoforming, the decorative film drew down significantly, causing uneven contact on the entire surface of the substrate.

(2) Gloss The gloss near the center of the decorative molded product to which the decorative film was attached was measured at an incident angle of 60 ° using a GLOSS meter Gloss Meter VG2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. The measuring method was based on JIS K7105-1981. The measurement results are shown in Table 1.

(3) Adhesive strength between the resin molded body (base) and the decorative film "Craft Adhesive Tape No. 712N" manufactured by Nitoms Co., Ltd. was cut out to a width of 75 mm and a length of 120 mm, and from the end of the resin molded body (base). It was attached to a resin molded body (base) in a range of 75 mm × 120 mm and subjected to masking treatment (the exposed portion on the surface of the base has a width of 45 mm and a length of 120 mm). It was installed in the three-dimensional decorative thermoforming apparatus NGF-0406-SW so that the masking surface of the resin molded body (base) was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

The decorative film surface of the obtained decorative molded product was cut to the surface of the substrate with a width of 10 mm using a cutter in the direction perpendicular to the longitudinal direction of the adhesive tape to prepare a test piece. In the obtained test piece, the adhesive surface between the substrate and the decorative film has a width of 10 mm and a length of 45 mm. Attached to a tensile tester so that the base part of the test piece and the decorative film part are 180 °, 180 ° peel strength of the adhesive surface is measured at a tensile speed of 200 mm / min, and the maximum strength at the time of peeling or breaking is measured. (N / 10 mm) was measured 5 times, and the average strength was taken as the adhesive strength.

Table 1 shows the results of physical property evaluation of the obtained decorative molded product.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength.

(4) Chemical resistance A product name "DNails Nail Polish Remover EX" (nail polish remover) manufactured by D-Up Co., Ltd. was dropped on the surface of the decorative film of the decorative molded product, and left at 23 ° C. for 5 minutes. After that, the droplets were absorbed with a cloth and removed, and the appearance was visually observed and evaluated according to the criteria shown below.
◯: No change.
Δ: A slight mark remains.
X: Remarkably marks remain.

Example 2
In the production of the decorative molded product of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the base material was changed to the resin molded product made of polar resin (X-2). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength.

Example 3
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the base material was changed to a resin molded product made of polar resin (X-3). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength.

Example 4
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the polyolefin adhesive resin (C-1) used for the bonding layer was changed to the polyolefin adhesive resin (C-2). went. The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-2) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength.

Example 5
An extruder with a diameter of 40 mm (diameter), an extruder for a sticking layer with a diameter of 30 mm (diameter) -2, and an extruder for a surface layer with a diameter of 30 mm (diameter)-3 are connected to manufacture a decorative film. A three-kind three-layer T-die having a lip opening of 0.8 mm and a die width of 400 mm was used. Polypropylene resin (A-1) is used for the extruder-1, polyolefin adhesive resin (C-1) is used for the sticking layer extruder-2, and polypropylene resin (B-1) is used for the surface layer extruder-3. ), The resin temperature is 240 ° C., the discharge amount of the extruder-1 is 12 kg / h, the discharge amount of the sticking layer extruder-2 is 8 kg / h, and the discharge amount of the surface layer extruder-3. Melt extrusion was performed under the condition of 4 kg / h.

The melt-extruded film was cooled and solidified on a cooling roll rotating at 80 ° C. and 3 m / min so that the surface decorative layer was in contact with the film, and a sticking layer having a thickness of 100 μm, a layer having a thickness of 150 μm, and a thickness of 50 μm were obtained. A three-layer unstretched film in which the surface decoration layers of the above were laminated was obtained.

The evaluation was carried out in the same manner as in Example 1 except that the unstretched film obtained in the above-mentioned production of the decorative film was used. The evaluation results are shown in Table 1.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-1) was laminated on the outermost surface side as the surface decorative layer [layer (II)], resulting in excellent gloss.

Comparative Example 1
In the production of the decorative film of Example 1, the evaluation was carried out in the same manner as in Example 1 except that the polypropylene-based resin (A-1) constituting the layer (I) was changed to the polypropylene-based resin (A-2). It was. The evaluation results are shown in Table 1.
Since polypropylene resin (A-2) has a high MFR of 2.4 g / 10 minutes, it is inferior in thermoforming stability, and the decorative film is greatly drawn down during three-dimensional decorative thermoforming, resulting in uneven contact on the entire surface of the substrate. As a result, the appearance of the decorative molded product was significantly inferior.

Comparative Example 2
In the production of the decorative film of Example 1, the polypropylene-based resin (A-1) constituting the layer (I) is attached to the polypropylene-based resin (A-2), and the polyolefin adhesive resin constituting the bonding layer (III). Evaluation was carried out in the same manner as in Example 1 except that (C-1) was changed to polypropylene resin (A-2). The results are shown in Table 1.
Since the polypropylene resin composition (A-2) is not the polyolefin adhesive resin (C), it does not have polarity and does not adhere to the base material. Further, since the polypropylene resin composition (A-2) has a high MFR of 2.4 g / 10 minutes, it is inferior in thermoforming stability, and the decorative film is greatly drawn down during three-dimensional decorative thermoforming, so that the base material is used. Contact unevenness occurred on the entire surface, resulting in a significantly inferior appearance of the decorative molded product.

Comparative Example 3
The chemical resistance was evaluated using only the injection molded product made of the polar resin (X-1) obtained by producing the resin molded product according to Example 1. The results are shown in Table 1.
Since no solvent-resistant decorative film was attached, the surface was dissolved by the nail polish remover, resulting in strong droplet marks.

Comparative Example 4
The evaluation was carried out in the same manner as in Comparative Example 3 except that the polar resin (X-1) of Example 3 was changed to the polar resin (X-2). The results are shown in Table 1.
Since no solvent-resistant decorative film was attached, the surface was dissolved by the nail polish remover, resulting in strong droplet marks.

Comparative Example 5
The evaluation was carried out in the same manner as in Comparative Example 3 except that the polar resin (X-1) of Example 3 was changed to the polar resin (X-3). The results are shown in Table 1.
Since no solvent-resistant decorative film was attached, the surface was dissolved by the nail polish remover, resulting in strong droplet marks.

Example 6
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (B-1) used for the surface layer was changed to the polypropylene-based resin (B-2). The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-1) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorative layer (II), resulting in excellent gloss.

Example 7
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (B-1) used for the surface layer was changed to the polypropylene-based resin (B-3). The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-3) was laminated on the outermost surface side as the surface decorative layer (II), resulting in excellent gloss.

Example 8
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (B-1) used for the surface layer was changed to the polypropylene-based resin (B-4). The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-4) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorative layer (II), resulting in excellent gloss.

Example 9
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (B-1) used for the surface layer was changed to the polypropylene-based resin (B-5). The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-1) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, since the surface decorative layer (II) having excellent gloss was colored white, the appearance was excellent.

Example 10
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (A-1) was changed to the polypropylene-based resin (A-3). The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-3) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, since the layer (I) was colored black, the appearance was excellent. Further, the polypropylene-based resin (B-1) was laminated on the outermost surface side as the surface decorative layer (II), resulting in excellent gloss.

Example 11
In the production of the decorative film of Example 10, the evaluation was carried out in the same manner as in Example 5 except that the polypropylene-based resin (B-1) used for the surface decorative layer was changed to the polypropylene-based resin (B-6). It was. The results obtained are shown in Table 2.
Since the MFR of the polypropylene-based resin (A-3) is 2 g / 10 minutes or less and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less, the obtained decorative molding is performed. The body was excellent in appearance and adhesive strength. Further, since the polypropylene-based resin (B-6) was laminated on the outermost surface side as the surface decorative layer (II), the result was excellent in gloss. Further, since the layer (I) is colored black and the surface decorative layer (II) is colored silver, the film is metallic and has an excellent appearance.

1 Decorative film 2 layers (I)
3 Adhesive layer (III)
4 Surface decorative layer (II)
5 Resin molded body (decoration target, substrate)
6 Decorative molding 11 Upper chamber box 12 Lower chamber box 13 Jig 14 Table 15 Heater

Claims (6)

It is a decorative film for being attached to a resin molded body by thermoforming, and the decorative film is attached to a layer (I) made of polypropylene-based resin (A) and made of a polyolefin adhesive resin (C). Layer (III) is laminated and
The polypropylene-based resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 minutes or less, and the polyolefin adhesive resin (C) is a polyolefin having a polar functional group containing at least one hetero atom. A decorative film which is a resin and has an MFR (230 ° C., 2.16 kg load) of 100 g / 10 minutes or less. The decorative film is characterized by having a surface decorative layer (II) made of a surface decorative layer resin on the side of the layer (I) opposite to the surface side of the adhesive layer (III). The decorative film according to claim 1. 2. The surface decorative layer resin is made of a polypropylene-based resin (B), and the MFR (230 ° C., 2.16 kg load) of the polypropylene-based resin (B) exceeds 2 g / 10 minutes. The decorative film described in. The step of preparing the decorative film according to any one of claims 1 to 3, the step of preparing a resin molded body, the step of setting the resin molded body and the decorative film in a decompressable chamber box, and the chamber. The decoration includes a step of reducing the pressure inside, a step of heating and softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the inside of the chamber to atmospheric pressure. A method for manufacturing a molded product. The resin molded body has a polarity selected from polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, polyphenylene ether resin, and composite materials thereof. The method for producing a decorative molded body according to claim 4, wherein the decorative molded body is made of a resin material. The method for producing a decorative molded product according to claim 4, wherein the resin molded product is made of a propylene-based resin composition.

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