JP2018008514A - Decorative film and method for producing decorative molded body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene-based decorative film which can achieve both sufficient adhesive strength and product appearance and is used in three-dimensional decorative thermoforming that facilitates recycling, and to provide a method for producing a decorative molded body using the same.SOLUTION: In a decorative film to be stuck onto a resin molded body by thermoforming, the decorative film contains a layer (I) formed of a polypropylene-based resin (A) and a seal layer (III) formed of a polypropylene-based resin (C), and the polypropylene-based resin (A) has an MFR (230°C and load of 2.16 kg) of 2 g/10 min or less and the polypropylene-based resin (C) has an MFR (230°C and load of 2.16 kg) of more than 2 g/10 min.SELECTED DRAWING: Figure 5

Description

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

  In recent years, there has been an increasing demand for decoration techniques that can replace painting due to VOC (volatile organic compound) reduction requirements, and various proposals for decoration techniques have been made.

  In particular, there is proposed a technique for forming a decorative molded product in which a decorative sheet and a molded body are integrated by applying a decorative sheet instead of a coating film to the molded body by vacuum pressure forming or vacuum forming (see, for example, Patent Document 1). In recent years, it has become particularly noticeable.

  Decorative molding by vacuum pressure forming and vacuum forming has a greater degree of freedom of shape than other decorative moldings typified by insert molding, and the end face of the decorative sheet is rolled up to the back side of the decoration target, so that the seam is formed. Since it does not occur, it has excellent appearance, and since it can be thermoformed at a relatively low temperature and low pressure, it is excellent in the reproducibility of wrinkles and the like on the surface of the decorative molded body by imparting wrinkles etc. It has the following advantages.

  In such vacuum pressure forming and decorative forming by vacuum forming, when the decorative sheet and the molded body are stuck, the decorative sheet may be broken or wrinkled, or the bonding strength between the decorative sheet and the molded body is sufficient. There was a problem that could not be obtained. In addition, the use of adhesives, tackifiers, etc. has been proposed as a layer for improving the adhesive strength, but it is expensive, the layer structure becomes extremely complicated, and the solvent resistance and heat resistance are insufficient. , Etc. have problems.

  For such a problem, by applying a decorative sheet including an adhesive layer containing a polypropylene resin to a base body (molded body) made of a polypropylene resin, the decorative sheet and the molded body can be heat-sealed. It has been proposed (see, for example, Patent Documents 2 and 3). The inventions disclosed in Patent Documents 2 and 3 use a polypropylene-based resin as the adhesive layer of the decorative sheet, but substantially further, a surface layer on the adhesive layer, an acrylic resin on the bonding layer and the bulk layer. It is necessary to provide a layer of polyurethane resin, polycarbonate or the like. In this way, by combining different raw materials, thermoformability such as draw-down property is expressed, and a decorative sheet made of polypropylene resin that does not contain these different raw materials can ensure thermoformability. Furthermore, holes, wrinkles, and air were easily generated on the surface of the molded product on which this was adhered, and furthermore, a decorative molded body having an excellent appearance could not be obtained due to film breakage. In particular, when a polyurethane resin is included as a heterogeneous raw material, the polyurethane resin, which is a thermosetting resin, does not melt when heated, and thus easily maintains the form of the film and greatly improves thermoformability, but has a problem of extremely low recyclability. It was.

  That is, the decorative sheets described in Patent Documents 2 and 3 contain different raw materials to ensure thermoformability such as adhesiveness and appearance, have a complicated layer structure, and require many steps for manufacturing. There is a problem that it is difficult to recycle a decorative sheet in which different raw materials are combined.

  In addition, vacuum thermoforming and decorative thermoforming by vacuum forming have the advantage that a molded product with a high degree of integrity between the substrate molded in the process such as injection molding and the decorative sheet can be obtained, while the decorative sheet is on the surface of the substrate. Since the appearance of the surface of the molded product is easily deteriorated due to the influence of the scratch on the surface of the substrate, the management of the scratch on the surface of the substrate must be strictly controlled.

JP 2002-67137 A JP 2013-14027 A JP 2014-124940 A

  In the prior art, a decorative film made of a propylene-based resin that is easy to recycle and can achieve both adhesiveness and appearance has not been achieved yet. In view of the above-mentioned problems, the object of the present invention is a three-dimensional structure that can achieve both sufficient adhesive strength and product appearance, can reduce product defects by making scratches on the substrate inconspicuous, and can be easily recycled. The object is to provide a decorative film used for decorative thermoforming and a method for producing a decorative molded body using the same.

  In three-dimensional decorative thermoforming, in order to stick a solid decorative film to a solid resin molded body, it is necessary that the surface of the molded body and the film are sufficiently softened or melted. It is important to add the amount of heat necessary to soften or melt the surface of the molded body and the film, or to use a molded body and film that are easily softened or melted. However, if the film is heated sufficiently, the viscosity of the film decreases. In the three-dimensional decorative thermoforming process, the molded body is pushed up and the flow of air when the vacuum chamber is returned to atmospheric pressure causes the film to break or run out, leading to poor appearance, and also attached to the substrate surface In order to make the scratches inconspicuous, we examined the composition of the decorative film. As a result, the decorative film includes a layer made of a specific polypropylene resin that improves thermoformability, and further includes a seal layer. The fluidity of this seal layer is compared to the fluidity of the layer that improves thermoformability. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the decorative film of the present invention has any one of the following configurations (i) to (iv).
(I) A decorative film for attaching to a resin molded body by thermoforming, the decorative film comprising a layer (I) made of a polypropylene resin (A) and a polypropylene resin (C). Including the sealing layer (III), the polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene resin (C) has an MFR (230 ° C., 2. A decorative film characterized in that (16 kg load) exceeds 2 g / 10 min.
(Ii) When the MFR of the polypropylene resin (A) is MFR (A) and the MFR of the polypropylene resin (C) is MFR (C), the following general formula (1) is satisfied. The decorative film as described in said (i).
MFR (C) / MFR (A)> 1.5 (1)
(Iii) The decorating film has a surface decorating layer (II) made of a surface decorating layer resin on the side opposite to the sticking side with the resin molded body, The decorative film as described in i) or (ii).
(Iv) The surface decorative layer resin is made of a polypropylene resin (B), and the MFR (230 ° C., 2.16 kg load) of the polypropylene resin (B) exceeds 2 g / 10 minutes. The decorative film according to (iii).

Moreover, the manufacturing method of the decorative molded body of this invention consists of the following structures (v) or (vi).
(V) The step of preparing the decorative film according to any one of (i) to (iv), the step of preparing a resin molded body, the pressure-reducible chamber box, the resin molded body and the decorative film A step of reducing the pressure inside 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. A method for producing a decorative molded body characterized by the above.
(Vi) The method for producing a decorative molded body according to (v), wherein the resin molded body is made of a propylene-based resin composition.

  As a result of diligent research, the present inventors have determined that the decorative film includes a layer (I) made of a polypropylene resin (A) having a specific MFR, and a polypropylene resin (B) having a specific MFR on the bonding surface of the substrate. Since the sealing layer (III) is included, the thermoforming property at the time of three-dimensional decorative thermoforming is excellent and the heating time can be sufficiently extended without including the thermosetting resin layer. It is possible to achieve both high adhesion strength to the polypropylene resin molded body, which has been difficult to bond, and the appearance of the product, and to make the scratches on the substrate surface less noticeable and to reduce product defects.

  According to the method for producing a decorative molded body of the present invention, a beautiful decorative molded body having no holes or wrinkles on its surface, no air entrainment between the decorative film and the resin molded body, and no noticeable scratches. Can be obtained. In addition, a decorative film can be neatly adhered to a resin molded body that has been difficult to bond. Furthermore, in the decorative molded body obtained in this way, since the constituent material of the decorative film is a polypropylene resin (A) and does not need to contain the thermosetting resin layer, it does not need to be contained. Small deterioration in appearance and performance, high recyclability.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which illustrates embodiment of the decorative molded object which stuck the decorative film of this invention to the molded object, (a)-(c) is the example which varied the layer structure of the decorative film, respectively. It is. It is typical sectional drawing explaining the outline | summary of the apparatus used for the manufacturing method of the decorative molded body of this invention. It is typical sectional drawing explaining a mode that the resin molding and the decorating film were set in the apparatus of FIG. It is typical sectional drawing explaining a mode that the inside of the apparatus of FIG. 2 is heated and pressure-reduced. It is typical sectional drawing explaining a mode that a decorating film is pressed on the resin molding in the apparatus of FIG. It is typical sectional drawing explaining a mode that it returns to atmospheric pressure or pressurizes the inside of the apparatus of FIG. It is a typical sectional view explaining signs that the edge of an unnecessary decoration film was trimmed in the obtained decoration fabrication object.

  In this specification, the decorative film refers to a film for decorating a molded body. Decorative molding refers to molding in which a decorative film and a molded body are attached. Three-dimensional decorative thermoforming is a process of adhering a decorative film and a molded body, and has a step of applying a decorative film at the same time as thermoforming along the adhesive surface of the molded body, In order for this process to suppress air from being caught in the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is adhered to the molded body, and the pressure is released (pressed). Pressure)), which is the process of making it adhere. 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 sticking on a resin molded body by thermoforming, and includes a layer (I) made of a polypropylene resin (A) and a seal made of a polypropylene resin (C). Including the layer (III), the polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene resin (C) has an MFR (230 ° C., 2.16 kg load). Is more than 2 g / 10 minutes.

Polypropylene resin (A)
By including the layer (I) made of the polypropylene resin (A), the decorative film can suppress the appearance failure due to the film breaking or rampage during thermoforming. Thereby, since a decorative film improves thermoformability, it does not need to contain the thermosetting resin layer which is excellent in thermoformability.

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

  The polypropylene resin (A) in the present invention has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, preferably 1.5 g / 10 min or less, more preferably 1 g / 10 min or less. By setting the MFR of the polypropylene resin (A) to be equal to or less than the above value, a decorative molded body having a good appearance can be obtained.

  Although there is no restriction | limiting in particular about the minimum of MFR of a polypropylene resin (A), Preferably it is 0.1 g / 10min or more, More preferably, it is 0.3 g / 10min or more. By making MFR more than said value, the moldability at the time of manufacture of a decoration film improves, and it can suppress that the appearance defect called a shark skin and interface roughness generate | occur | produces on the film surface.

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

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

  The polypropylene 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 polymer and additives, fillers, colorants, other resin components, and the like. The total amount of additives, fillers, colorants, and other resin components is preferably 50% by weight or less based on the polypropylene resin composition.

  When the polypropylene resin (A) is a polypropylene resin composition, the polypropylene resin composition preferably has the characteristics of the polypropylene resin (A). That is, the MFR (230 ° C., 2.16 kg load) of the polypropylene resin composition is 2 g / 10 min or less.

  When the decorative molded body of the present invention is molded as a colored molded body, it is only necessary to use a colorant only for the decorative film, and therefore, the use of an expensive colorant is used compared to the case where the entire resin molded body is colored. Can be suppressed. Moreover, the physical property change accompanying mixing | blending a coloring agent can be suppressed.

  Additives can be used for polypropylene resins such as antioxidants, neutralizers, light stabilizers, UV absorbers, crystal nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc. Various known additives can be blended.

  Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants. 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, and benzophenones.

  Examples of the crystal nucleating agent include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (4 , 6-Di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) aluminum hydroxide salt and organic compound complex, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, sodium salt of rosin, and the like.

  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, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

  As a filler, various well-known fillers which can be used for polypropylene resin, such as an inorganic filler and an organic filler, can be mix | blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber and carbon fiber. 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 resins, polyolefins such as ethylene elastomers, modified polyolefins, and other thermoplastic resins.

  Moreover, it is also possible to color in order to provide designability, and various colorants, such as an inorganic pigment, an organic pigment, and dye, can be used for coloring. Further, bright materials such as aluminum flakes, titanium oxide flakes, and (synthetic) mica can also be used.

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

Polypropylene resin (C)
The decorative film of the present invention includes a sealing layer (III) made of a polypropylene resin (C) on the surface to be adhered to the resin molded body (base), thereby making the scratches on the substrate surface less noticeable. This makes it possible to reduce product defects.

  This is because the flowability of the polypropylene resin (C) constituting the sealing layer (III) is higher than that of the polypropylene resin composition (A) constituting the layer (I) imparting thermoformability. It is easier for the layer (III) to be deformed than when (I) is deformed, and the seal layer (III) is deformed in accordance with the shape of the wound to the surface of the decorative molded body. Suppresses scratches.

In order for the decorative film to exhibit such an effect, the MFR (230 ° C., 2.16 kg load) of the polypropylene resin (C) needs to exceed 2 g / 10 minutes, preferably 4 g / 10 minutes or more. Further, when the MFR of the polypropylene resin (A) is MFR (A) and the MFR of the polypropylene resin (C) is MFR (C), the following general formula (1) is preferably satisfied.
MFR (C) / MFR (A)> 1.5 (1)

  The MFR ratio MFR (C) / MFR (A) of the polypropylene resin (C) and the polypropylene resin (A) is more preferably 2 or more, and even more preferably 10 or more. The higher the MFR (C) and the larger MFR (C) / MFR (A), the greater the effect of suppressing the relief of scratches. However, if MFR (C) / MFR (A) is too large, the film will be laminated during film formation. Therefore, MFR (C) / MFR (A) is preferably 1000 or less, and more preferably 100 or less.

  The polypropylene resin (C) in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of propylene monomer. The propylene polymer preferably does not contain a polar group-containing monomer unit.

  The melting point (DSC melting peak temperature) of the polypropylene resin (C) is preferably 100 to 170 ° C, more preferably 115 to 165 ° C.

  The polypropylene resin (C) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties, and the propylene-α-olefin copolymer usually has a lower melting point than the propylene homopolymer. Since the crystallization temperature is also lowered, the effect of making the scratches inconspicuous is easier to deform during thermoforming.

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

  As an additive, the additive etc. which may be contained in the said polypropylene resin (A) can be used.

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

Decorative film The decorative film in this invention contains the layer (I) which consists of polypropylene resin (A), and the sealing layer (III) which consists of polypropylene resin (C). The decorative film can take various configurations in addition to the layer (I) and the seal layer (III). That is, the decorative film may be a two-layer film composed of the layer (I) and the seal layer (III), or a multilayer film composed of the layer (I) and the seal layer (III) and other layers. . The seal layer (III) is stuck along the resin molded body (base). In addition, the decorative film may have a surface with embossing, embossing, printing, sand plasting, scratching, or the like.

  The decorative film has a large degree of freedom in shape, and since the seam does not occur because the end surface of the decorative film is rolled up to the back side of the object to be decorated, it is excellent in appearance, and furthermore, the surface of the decorative film is given wrinkles or the like Can express various textures. For example, when a texture such as embossing is applied to the resin molded body, three-dimensional decorative thermoforming may be performed using a decorative film provided with embossing. For this reason, it is very difficult and expensive to perform molding with a molded body mold that gives embossing, that is, a molded body mold is required for each embossing pattern, and that complicated embossing is applied to a curved mold. Thus, it is possible to obtain a decorative molded body to which various patterns of embossing can be easily applied.

  The multilayer film can include a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a colored layer, a base material 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 resin (A) may be any layer other than the seal layer among the layers constituting the multilayer film.

  In the multilayer film, the layer other than the layer (I) and the seal layer (III) is preferably a layer made of a thermoplastic resin, and more preferably a layer made of a polypropylene resin. As long as the layers other than the layer (I) and the sealing layer (III) can be distinguished from the layer (I) and the sealing layer (III), the MFR (230 ° C., 2.16 kg load) of the polypropylene resin to be formed is There is no particular limitation. Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication 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 resin (A) constitutes a surface layer opposite to the sticking surface to the resin molded body, and the polypropylene resin (C) The resulting seal layer (III) constitutes the seal layer on the surface to be adhered to the resin molded body.

  When the decorative film is a multilayer film of three or more layers, other layers are interposed between the layer (I) made of the polypropylene resin (A) and the seal layer (III) made of the polypropylene resin (C). Then, the effect which suppresses the raising of the damage | wound of a base surface may fall. For this reason, the multilayer film has a sealing layer (III) made of polypropylene resin (C) / a layer (I) made of polypropylene resin (A) / other layers (multiple layers) from the sticking surface side of the resin molded body. Is preferably included).

  Drawing 1 (a)-(c) is an explanatory view which illustrates typically the section of the embodiment of the decoration film stuck on the resin fabrication object. 1A to 1C, for easy understanding, the arrangement of the layer (I) and the sealing layer (III) will be specifically described. However, the layer structure of the decorative film is limited to these examples. Are not to be interpreted. In the present specification, reference numeral 1 in the drawing denotes a decorative film, reference numeral 2 denotes a layer (I), reference numeral 3 denotes a sealing layer (III), reference numeral 4 denotes a surface decoration layer (II), and reference numeral 5 denotes a resin molded body. . FIG. 1 (a) is an example in which the decorative film is a two-layer film, and a seal layer (III) made of a polypropylene resin (C) is adhered to the resin molded body 5, and the top of the seal layer (III). A layer (I) made of polypropylene resin (A) is laminated on the substrate. The decorative film in FIG. 1 (b) is composed of a seal layer (III), a layer (I) and a surface layer. The seal layer (III) is adhered to the surface of the resin molded body 5, and the top of the seal layer (III). The layer (I) and the surface layer are laminated in this order. The decorative film in FIG. 1C is composed of a sealing layer (III), a surface decorative layer (II) composed of a layer (I) and a polypropylene resin (B), and the sealing layer (III) is formed on the surface of the resin molded body 5. ) Are stuck, and the layer (I) and the surface decoration layer (II) are laminated in this order on the seal layer (III).

  As another preferred embodiment of the decorative film, a multilayer film including a surface decorative layer (II) made of a surface decorative layer resin on the outermost surface on the side opposite to the surface to be adhered to the resin molded body is given. It is done. The surface decorating layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (B) having an MFR (230 ° C., 2.16 kg load) exceeding 2 g / 10 min. That is, the layer (I) composed of a polypropylene resin (A) having an MFR of 2 g / 10 min or less that improves thermoformability may generally be inferior in gloss and grain transferability due to its low MFR. By providing the surface layer with a layer (II) made of a polypropylene resin (B) having an MFR of more than 2 g / 10 min, gloss and texture transfer can be improved without greatly degrading thermoformability. . Further, by using the polypropylene resin (B), it is possible to suppress complication of the layer structure and a decrease in recyclability. In addition, solvent resistance etc. can be made excellent by using a polypropylene resin (B) for the surface decoration layer of a decoration film. In addition, the use of polypropylene resin (B) for the surface decoration layer improves the transferability of the surface during the production of the decorative film and during thermoforming. If a mirror roll is used during thermoforming, a high gloss can be applied. It can be a decorative film.

  In the present invention, the polypropylene resin (B) is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of propylene monomer. The propylene polymer preferably does not contain a polar group-containing monomer unit. The polypropylene 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 (coloring property), a propylene-α-olefin copolymer is preferable. In the present invention, the polypropylene resin (B) constituting the surface decoration layer (II) may be the same as or different from the polypropylene resin (C) constituting the seal layer (III).

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

  Although there is no restriction | limiting in particular about the upper limit of MFR of polypropylene resin (B), Preferably it is 100 g / 10min or less, More preferably, it is 50 g / 10min or less. By setting the MFR within the above range, good oil resistance, solvent resistance, scratch resistance and the like can be exhibited.

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

  As an additive, the additive etc. which may be contained in the said polypropylene resin (A) can be used.

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

  When the propylene resin (B) constituting the surface decoration layer (II) is a polypropylene resin composition, this polypropylene resin composition is composed of the propylene resin (C) constituting the seal layer (III). The same or different polypropylene resin composition may be used. When both polypropylene resin compositions are the same, the seal layer (III) and the surface decoration layer (II) can be formed using a feed block or the like with one extruder. Have advantages.

  The decorative film of the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, and further preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting design properties is improved, the stability at the time of molding is improved, and a better decorative molded body can be obtained. 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, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film below such a value, the time required for heating at the time of thermoforming is shortened so that productivity is improved and it becomes easy to trim unnecessary portions.

  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 seal layer (III) is preferably 1 to 70%. It is. If the ratio of the thickness of the layer (I) to the whole decorative film is in the range of the above value, it is possible to avoid the thermoformability of the decorative film becoming insufficient. Moreover, if the ratio of the thickness of the sealing layer (III) to the whole decorative film is within the above value range, it is possible to suppress the scratches on the resin molded body (substrate) from appearing on the surface.

  Moreover, in the multilayer film which provided the surface decoration layer (II) which consists of polypropylene resin (B) in the outermost surface of a decoration film, the thickness of the whole decoration film of the thickness of a layer (II) in a decoration film The ratio occupied in is preferably 30% or less.

Production of decorative film The decorative film of the present invention can be produced by various known forming methods.
For example, a method of co-extrusion molding of a layer (I) made of polypropylene resin (A) and a seal layer (III) made of polypropylene resin (C), layer (I), seal layer (III) and still other layers Co-extrusion method, thermal lamination method in which the other layer is bonded to one surface of one layer that has been previously extruded by applying heat and pressure, dry lamination method in which bonding is performed using an adhesive, and Examples include a wet lamination method, an extrusion lamination method in which a polypropylene resin is melt-extruded on one surface of one layer that has been previously extruded, and a sand lamination method. As a device for forming the decorative film, a known coextrusion T-die molding machine or a known laminate molding machine can be used. Among these, from the viewpoint of productivity, a coextrusion T-die molding machine is preferably used.

  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, There is a method of cooling by pressure bonding with a plurality of cooling rolls.

  In the case of imparting gloss to the decorative film of the present invention, a method is used in which a mirror-like cooling roll is surface-transferred to the design surface of the decorative film and mirror-finished.

  Furthermore, 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 resin in a molten state extruded from a die is directly pressed between a concavo-convex roll and a smooth roll to transfer the concavo-convex shape to a surface, and a smooth film having a concavo-convex shape. It can manufacture by the method etc. which press-contact with the applied heating roll and a smooth roll, and surface-transfer the uneven | corrugated shape. Examples of the wrinkle shape include satin finish, animal skin tone, hairline tone, and carbon tone.

  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 hot roll, a method of heating with a heating furnace or a far infrared heater, a method of blowing hot air, and the like.

Decorated molded body As the molded body (decoration object) to be decorated in the present invention, various molded bodies (hereinafter sometimes referred to as "substrate") preferably made of a polypropylene resin or a polypropylene resin composition. Can be used. The molding method of the molded body is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

  The polypropylene resin is a non-adhesive polymer because it is nonpolar, but the decorative film in the present invention consists of the layer (I) made of the polypropylene resin (A) and the polypropylene resin (C). By including the sealing layer (III), the decorative object made of polypropylene resin and the decorative film are adhered to each other, thereby exhibiting very high adhesive strength, and scratches on the surface of the decorative object are hardly noticeable. I can do it.

  As the base resin of the polypropylene resin and the polypropylene resin composition, various known propylene monomers such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, or a propylene block copolymer are mainly used. Various types of raw materials can be selected. Moreover, unless the effects of the present invention are impaired, a filler such as talc may be included for imparting rigidity, or an elastomer may be included for imparting impact resistance. Moreover, you may contain an additive component and another resin component similarly to the polypropylene resin composition which can comprise the decorating film mentioned above.

  Since the decorative molded body in which the decorative film in the present invention is attached to various molded bodies formed in a three-dimensional shape made of a polypropylene resin, VOCs contained in the coating and the adhesive are greatly reduced. It can be suitably used as a home appliance, vehicle (railway, etc.), building material, daily necessities and the like.

  In the method for producing a decorative molded body of the present invention, the resin molded body and the decorative film are set in a step of preparing the above-described decorative film, a step of preparing the resin molded body, and a chamber box capable of decompression. A step, a step of reducing the pressure in the chamber, a step of heat-softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the chamber to atmospheric pressure. To do.

  Three-dimensional decorative thermoforming sets the object to be decorated and a decorative film in a chamber box that can be depressurized, heat-softens the film in a state where the pressure in the chamber is reduced, and presses the film against the object to be decorated. It has the basic process of attaching the decorative film to the surface of the object to be decorated by returning the interior to atmospheric pressure or pressurizing the film, and the film is attached under reduced pressure. As a result, it is possible to obtain a beautiful decorative molded body free from air accumulation. 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 object to be decorated, the decorative film, the mechanism for pressing it, the device for heating the decorative film, etc. A plurality of divided parts may be used.

Moreover, the mechanism for pressing a decorating object and a decorating film may be any type that moves the decorating object, moves the decorating film, or moves both.
More specifically, typical molding methods are exemplified below.

  Hereinafter, a method for sticking a decorative film to a decoration object using a three-dimensional decorative thermoforming machine will be exemplarily described with reference to the drawings.

  As shown in FIG. 2, the three-dimensional decorative thermoforming machine of this embodiment includes upper and lower chamber boxes 11 and 12 and thermoforming the decorative film 1 in the two chamber boxes 11 and 12. I am doing so. A vacuum circuit (not shown) and an air circuit (not shown) are respectively connected to the upper and lower chamber boxes 11 and 12.

  Further, a jig 13 for fixing the decorative film 1 is provided between the upper and lower chamber boxes 11 and 12. The lower chamber box 12 is provided with a table 14 that can be raised and lowered, and the resin molded body (decoration target) 5 is set on the table 14 (via a jig or directly). The A heater 15 is incorporated in the upper chamber 11, and the decorative film 1 is heated by the heater 15. The decoration object 5 can use a propylene-type resin composition as a base | substrate.

  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 opened, the decoration object 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 jig 13 for fixing the film between the upper and lower chamber boxes 11 and 12 so that the seal layer (III) faces the substrate.

  As shown in FIG. 4, after the upper chamber box 11 is lowered and the upper and lower chamber boxes 11 and 12 are joined to close the inside of the boxes, the chamber boxes 11 and 12 are brought into a vacuum suction state, and the heater 15 To heat the decorative film 1.

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

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

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

  Moreover, in the two chamber boxes 11 and 12 divided | segmented up and down by the decorating film 1, the chamber box pressure in the side by which the decorating object 5 and the decorating film 1 are affixed should just be this range, and up and down The draw-down of the decorative film 1 can also be suppressed by changing the pressure of the chamber boxes 11 and 12.

  At this time, a film made of a general polypropylene resin may be greatly deformed or broken 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 has resistance 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 decorative film 1 to the decorative object 5 made of polypropylene 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 resin constituting the decorating object 5 and the polypropylene resin constituting the decorating 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. However, until the interior of the decorative film 1 (or the surface opposite to the heater when the heater is installed only on one side) is sufficiently heated, If the temperature of the resin is too high, the moldability is deteriorated and the resin is thermally deteriorated. Therefore, the heater temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, most preferably 400 ° C. It is as follows.

  Although an appropriate heating time varies depending on the heater temperature, it is preferably a heating time of 2 seconds or more after the polypropylene decorative film is heated and the rebound called spring back is completed.

  In other words, the decorative film heated by the heater expands by heating from the solid state and sags once with the melting of the crystal. After that, the film is completely melted in crystal after spring back, and the molecular relaxation is enough, so that sufficient adhesive strength can be obtained.

  On the other hand, if the heating time is too long, the film hangs down due to its own weight or deforms 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 the springback.

  In the case of decorating a complex shaped article having irregularities or achieving higher adhesion, 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, more preferably 250 kPa or more. Although there is no particular limitation on the upper limit, 450 kPa or less, preferably 400 kPa or less is preferable because the device may be damaged if the pressure is too high.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

1. Measurement method of various physical properties (i) MFR
In accordance with ISO 1133: 1997 Conditions M, measurement was performed at 230 ° C. and a load of 2.16 kg. The unit is g / 10 minutes.

(Ii) Melting point:
Using a differential operation calorimeter (DSC), once the temperature was raised to 200 ° C. and held for 10 minutes, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and again at a temperature rising rate of 10 ° C./min. The temperature at the top of the endothermic peak when measured was taken as the melting point. The unit is ° C.

2. Materials used (1) Polypropylene resin The following polypropylene resin was used.
(A-1): Propylene homopolymer (MFR = 0.4 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) EA9”
(A-2): Propylene homopolymer (MFR = 1.9 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) EA6A”
(A-3): Propylene homopolymer (MFR = 2.4 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FY6”
(A-4): Polypropylene resin composition (MFR = 0.0.00) obtained by blending 96% by weight of polypropylene resin (A-1) with 4% by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.). 4g / 10min, Tm = 161 ° C)
(B-1): Polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (C-1) with 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.). (MFR = 10 g / 10 min, Tm = 164 ° C.)
(B-2): Propylene-α-olefin copolymer by metallocene catalyst (MFR = 7 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Nippon Polypro Co., Ltd., trade name “ Wintech (registered trademark) WFX4M "
(B-3): Polypropylene resin composition obtained by blending 100 parts by weight of a polypropylene resin (B-2) with 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.). (MFR = 7 g / 10 min, Tm = 127 ° C.)
(B-4): Polypropylene resin (C-1) 96% by weight of white pigment MB with MFR = 11 g / 10 min (Epp-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80% by weight) 4% by weight blended polypropylene resin composition (MFR = 10 g / 10 min, Tm = 161 ° C.)
(B-5): Polypropylene resin composition (MFR = 10 g / 10) obtained by blending 96% by weight of polypropylene resin (C-1) with 4% by weight of silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyocolor Co., Ltd.) Min, Tm = 161 ° C.)
(C-1): Propylene homopolymer (MFR = 10 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FA3KM”
(C-2): Propylene homopolymer (MFR = 25 g / 10 min, Tm = 159 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) SA16”
(C-3): Propylene homopolymer (MFR = 5 g / 10 min, Tm = 160 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FY4Y9”
(C-4): Propylene-α-olefin copolymer (MFR = 7 g / 10 min, Tm = 146 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FW3GT”
(C-5): Propylene-α-olefin copolymer (MFR = 7 g / 10 min, Tm = 138 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FW4B”
(C-6): Propylene-α-olefin copolymer (MFR = 6 g / 10 min, Tm = 131 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FX4E”
(C-7): Propylene-α-olefin copolymer (MFR = 5 g / 10 min, Tm = 127 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FX4G”

(2) Polypropylene resin (X) used for resin molding
The following polypropylene resins were used.
(X-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 165 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) MA04H”
(X-2): Propylene ethylene block copolymer (MFR = 30 g / 10 min, Tm = 164 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “Novatech (registered trademark) NBC03HR”
(X-3): 60% by weight of polypropylene resin (X-2), 20% by weight of EBR (Tafmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Talc) Polypropylene resin composition blended with 20% by weight of Talc P-6, average particle size 4.0 μm, manufactured by

3. Production of Resin Molded Body (Substrate) Using polypropylene resins (X-1) to (X-3), an injection molded body was obtained by the following method. Further, the obtained injection molded article was scratched by the following method to obtain a resin molded article (substrate).
Injection molding machine: “IS100GN” manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 200 ° C.
Mold temperature: 40 ℃
Injection mold: width × height × thickness = 120 mm × 120 mm × 3 mm flat plate state adjustment: 5 days holding in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH Processing for scratch evaluation: a temperature of 23 ° C. and a humidity Using a scratch tester (“SCRATCH & MAR TESTER” manufactured by ROCKWOOD SYSTEMS AND EQUIMENT) in a constant temperature and humidity chamber of 50% RH, the shape (curvature radius 0.5 mm, ball shape) was applied with a load of 15 N Scratching was performed at the scratching tip at a scratching speed = 100 mm / min, and the above-mentioned injection-molded product was scratched.

  The scratch on the surface of the resin molded body (substrate) was measured with a shape measuring instrument laser microscope (“VX-X200” manufactured by KEYENCE), and the depth of the scratch was 13 μm. The scratches were whitening wounds.

Example 1
-Manufacture of a decorative film Two types and two layers with a lip opening of 0.8 mm and a die width of 400 mm, connected to a seal layer extruder 1 with a diameter of 30 mm (diameter) and an extruder 2 with a diameter of 40 mm (diameter) A T-die was used. The polypropylene resin (C-1) and the polypropylene resin (A-1) are fed into the seal layer extruder-1 and the extruder-2, respectively, and discharged at a resin temperature of 240 ° C. and the seal layer extruder-1. Melt extrusion was performed under the conditions of 4 kg / h for the amount and 12 kg / h for the discharge amount of the extruder-2. The melt-extruded film was cooled and solidified while being pressed with an air knife against a first roll rotating at 80 ° C. at 3 m / min so that the seal layer was on the outside, and a 50 μm thick seal layer and a 150 μm thick layer were formed. A two-layer unstretched film was obtained.

-Three-dimensional decorative thermoforming As the resin molding (base | substrate) 5, the injection molding which consists of the polypropylene resin resin (X-1) obtained by the 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 with a width of 250 mm × a length of 350 mm so that the seal layer faces the substrate and the longitudinal direction is the MD direction of the film, and the opening fixing size is 210 mm × 300 mm. Set. The resin molded body (base body) 5 is placed on a table 14 positioned below the film fixing jig 13 and placed on a sample mounting table having a height of 20 mm, “Nystack NW-K15” manufactured by Nichiban Co., Ltd. ”Pasted through. The film fixing jig 13 and the table 14 were installed in the chambers 11 and 12, the chambers were closed, and the chamber boxes 11 and 12 were sealed. The chamber box is divided up and down via the decorative film 1. In the state which vacuum-sucked the upper and lower boxes and reduced pressure 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%, and the decorative film 1 is Heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated to sag temporarily, and then 20 seconds after the end of the springback phenomenon, the table 14 installed in the lower chamber box 12 is moved upward to form a resin molded body. (Substrate) 5 was pressed against the decorative film 1, and immediately after that, compressed air was fed so that the pressure in the upper chamber box 11 was 270 kPa, thereby bringing the resin molded body (substrate) 5 and the decorative film 1 into close contact. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was adhered to the upper surface and the side surface of the resin molded body (substrate) 5 was obtained.

・ Evaluation of physical properties (1) Evaluation of the appearance of the decorative molded body (effect of making scratches less noticeable) Part of the molded body (substrate) scratched with a load of 15 N that had scratches on the three-dimensional decorative thermoformed product The depth of the wound was measured with a shape measurement laser microscope (“VX-X200” manufactured by KEYENCE). The number of times of measurement was n = 5, and the average value was taken as the flaw depth (μm).
Further, whether or not the whitening damage of the molded body (substrate) damaged by a load of 15 N was not noticeable by the decorative film was visually determined and evaluated according to the following criteria.
○: Traces of whitening scratches are not noticeable and the appearance is excellent.
(Triangle | delta): A whitening crack remains partially and an external appearance is bad.
X: Whitening scratches remain and the appearance is poor.

(2) Evaluation of thermoformability The draw-down state of the decorative film at the time of three-dimensional decorative thermoforming, and the sticking state of the decorative film of the decorative molded body in which the decorative film is stuck to the substrate are visually observed. Observed and evaluated according to the criteria shown below.
○: At the time of three-dimensional decorative thermoforming, the decorative film did not draw down, and the contact between the substrate and the decorative film was made simultaneously on the entire contact surface, so contact unevenness did not occur and it was evenly attached ing.
Δ: Since the decorative film was slightly drawn down during the three-dimensional decorative thermoforming, the decorative film contacted from the center of the base, and contact unevenness occurred at the upper end of the base.
X: During the three-dimensional decorative thermoforming, the decorative film was greatly drawn down, so contact unevenness occurred on the entire surface of the substrate.

(3) Adhesive strength between resin molded body (base) and decorative film “Craft adhesive tape No. 712N” manufactured by Nitoms Co., Ltd. was cut into a width of 75 mm and a length of 120 mm, from the end of the resin molded body (base). A masking process was applied to a resin molded body (substrate) in a range of 75 mm × 120 mm (substrate surface exposed portion was 45 mm wide and 120 mm long). It installed in the three-dimensional decorative thermoforming apparatus NGF-0406-SW so that the masking surface of the resin molded body (substrate) was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

The decorative film surface of the obtained decorative molded body was cut to the substrate surface with a width of 10 mm using a cutter in a direction perpendicular to the longitudinal direction of the adhesive tape to prepare a test piece. In the obtained test piece, the bonding surface between the base and the decorative film is 10 mm wide × 45 mm long. Attach to the tensile tester so that the base part of the test piece and the decorative film part are 180 °, measure the 180 ° peel strength of the adhesive surface at a tensile speed of 200 mm / min, and take the maximum strength at the time of peeling or breaking (N / 10 mm) was measured 5 times, and the average strength was defined as the adhesive strength.
Table 1 shows the physical property evaluation results of the obtained decorative molded body.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous.

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

(5) Recyclability evaluation The obtained decorative molded body was pulverized, and a recycled molded body was produced by injection molding in the same manner as in the production of a resin molded body (substrate). The obtained recycled molded article was excellent in appearance (evaluation “◯” in the table).

Example 2
In the production of the decorative film of Example 1, the evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-2). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-2) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 3
In the production of the decorative film of Example 1, the evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-3). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-3) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 4
In the production of the decorative film of Example 1, the evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-4). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-4) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 5
In the production of the decorative film of Example 1, the evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-5). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-5) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 6
In the production of the decorative film of Example 1, the evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-6). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-6) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 7
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (C-1) used for the seal layer was changed to (C-7). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-7) exceeds 2 g / 10 min, the decorative molded body obtained has excellent appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 8
In the production of the decorative film of Example 1, (A-2) is the polypropylene resin (A-1) used for the layer (I), and (C-1) is the polypropylene resin (C-1) used for the seal layer. Evaluation was performed in the same manner as in Example 1 except that the method was changed to -7). The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-2) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-7) exceeds 2 g / 10 min, the obtained decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 9
In the production of the decorative film of Example 1, 30 mm (diameter) diameter seal layer extruder-1, 40 mm diameter diameter extruder-2, and 30 mm diameter diameter surface layer extruder- Three types of three-layer T-dies having a lip opening of 0.8 mm and a die width of 400 mm connected to each other were used. Polypropylene resin (C-1) for Extruder-1 for sealing layer, Polypropylene resin (A-1) for Extruder-2, Polypropylene resin (C-1) for Extruder-3 for surface layer The resin temperature is 240 ° C., the discharge amount of the seal layer extruder-1 is 4 kg / h, the discharge amount of the extruder-2 is 8 kg / h, and the discharge amount of the surface layer extruder-3 is 4 kg / h. Melt extrusion was performed under the conditions of h.

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

Evaluation was performed in the same manner as in Example 1 except that the unstretched film obtained by the above-described decorative film production was used. The evaluation results are shown in Table 1.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (C-1) on the outermost surface side as surface decoration layer (II) [surface layer (II)]. The recycled molded body was excellent in appearance.

Comparative Example 1
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the polypropylene resin (A-1) used for the base material layer was changed to (A-3). The evaluation results are shown in Table 1.
Polypropylene resin (A-3) has a high MFR of 2.4 g / 10 min, so it is inferior in thermoforming stability, and the decorative film is greatly drawn down during three-dimensional decorative thermoforming. It was a result which generate | occur | produced and the appearance of a decorative molded object is remarkably inferior.

Example 10
In the three-dimensional decorative thermoforming of Example 1, evaluation was performed in the same manner as in Example 1 except that the base was changed to an injection-molded body using resin (X-2). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 11
In the three-dimensional decorative thermoforming of Example 1, evaluation was performed in the same manner as in Example 1 except that the base was changed to an injection-molded body using resin (X-3). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. The recycled molded body was excellent in appearance.

Example 12
In the production of the decorative film of Example 9, the evaluation was performed in the same manner as in Example 9 except that the polypropylene resin (C-1) used for the surface layer was changed to the polypropylene resin (B-1). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. In addition, the polypropylene resin (B-1) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorating layer (II) [surface layer (II)], resulting in excellent gloss. . The recycled molded body was excellent in appearance.

Example 13
In the production of the decorative film of Example 9, the evaluation was performed in the same manner as in Example 9 except that the polypropylene resin (C-1) used for the surface layer was changed to the polypropylene resin (B-2). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (B-2) on the outermost surface side as surface decoration layer (II) [surface layer (II)]. The recycled molded body was excellent in appearance.

Example 14
In the production of the decorative film of Example 9, the evaluation was performed in the same manner as in Example 9 except that the polypropylene resin (C-1) used for the surface layer was changed to the polypropylene resin (B-3). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. The traces of scratches were inconspicuous. In addition, the polypropylene resin (B-3) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorating layer (II) [surface layer (II)], resulting in excellent gloss. . The recycled molded body was excellent in appearance.

Example 15
In the production of the decorative film of Example 9, the evaluation was performed in the same manner as in Example 9 except that the polypropylene resin (C-1) used for the surface layer was changed to the polypropylene resin (B-4). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-1) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the decorative film colored in white was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since surface decoration layer (II) [surface layer (II)] which is excellent in glossiness is colored in white, it was excellent in appearance. The recycled molded body was excellent in appearance. The recycled molded body was excellent in appearance.

Example 16
In the production of the decorative film of Example 9, the evaluation was performed in the same manner as in Example 9 except that the polypropylene resin (A-1) was changed to the polypropylene resin (A-4). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-4) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the decorative film colored in black was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since layer (I) was colored black, it was excellent in appearance. Furthermore, since the polypropylene resin (C-1) was laminated on the outermost surface side as the surface decoration layer (II) [surface layer (II)], the result was excellent in gloss. The recycled molded body was excellent in appearance.

Example 17
In the production of the decorative film of Example 16, evaluation was performed in the same manner as in Example 16 except that the polypropylene resin (C-1) used for the surface layer was changed to the polypropylene resin (B-5). The obtained results are shown in Table 2.
Since the MFR of the polypropylene resin (A-4) is 2 g / 10 min or less and the MFR of the polypropylene resin (C-1) exceeds 2 g / 10 min, the resulting decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the colored decorative film was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since the polypropylene resin (C-1) was laminated on the outermost surface side as a surface decoration layer [layer (II)], the result was excellent in gloss. Further, since the layer (I) was colored black and the surface layer (II) was colored silver, it became a metal-like film and was excellent in appearance. The recycled molded body was excellent in appearance.

1 decorative film 2 layers (I)
3 Seal layer (III)
4 Surface decoration layer (II)
5 Resin molded body (decoration object, substrate)
6 Decorative Molded Body 11 Upper Chamber Box 12 Lower Chamber Box 13 Jig 14 Table 15 Heater

Claims (6)

A decorative film for sticking on a resin molded body by thermoforming, the decorative film comprising a layer (I) made of a polypropylene resin (A) and a seal layer made of a polypropylene resin (C) ( III),
The polypropylene resin (A) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min or less, and the polypropylene resin (C) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min. A decorative film characterized by exceeding. The following general formula (1) is satisfied, where MFR of the polypropylene resin (A) is MFR (A) and MFR of the polypropylene resin (C) is MFR (C). The decorative film described in 1.
MFR (C) / MFR (A)> 1.5 (1)   The said decorating film has the surface decorating layer (II) which consists of surface decorating layer resin in the surface opposite to the sticking surface side with the said resin molding, The Claim 1 or 2 characterized by the above-mentioned. The decorative film described.   The said surface decoration layer resin consists of a polypropylene resin (B), MFR (230 degreeC, 2.16kg load) of this polypropylene resin (B) exceeds 2 g / 10min, It is characterized by the above-mentioned. The decorative film described in 1.   A step of preparing the decorative film according to any one of claims 1 to 4, a step of preparing a resin molded body, a step of setting the resin molded body and the decorative film in a depressurizable chamber box, and a chamber A step of depressurizing the interior, 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 interior of the chamber to atmospheric pressure. Manufacturing method of a molded object.   The method for producing a decorative molded body according to claim 5, wherein the resin molded body is made of a propylene-based resin composition.

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