JP6950340B2 - 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 VOC (volatile organic compound) reduction demands 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, it is possible to improve the reproducibility of the texture on the surface of the decorative molded product by imparting the texture to the surface of the decorative sheet. 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 forming 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 that 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 manufacturing 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. be. That is, it is important to apply the amount of heat required for softening or melting the surface of the molded body and the film, or to use a molded body 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 thermoforming 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 (7).
(1) A decorative film for being adhered onto a resin molded body by thermal molding, and the decorative film is formed on a layer (I) made of a resin composition (A) containing a polypropylene-based resin (A). A bonding layer (III) made of a polyolefin adhesive resin (C) is laminated, and the polyolefin adhesive resin (C) is a polyolefin resin having a polar functional group containing at least one hetero atom. its MFR (230 ° C., 2.16 kg load) of not more than 100 g / 10 min, the polar functional group, mosquitoes Rubokishi group or a metal salt thereof, selected from the group consisting of contact and acid anhydride groups, wherein the polypropylene-based A decorative film characterized in that the resin (A) satisfies the following requirements (Ai) and (Aii).
(Ai) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 minutes or less (Ai) Strain hardening degree λ is 1.1 or more (2) The resin composition The decorative film according to (1) above, wherein the object (A) satisfies the following requirements (A-i') and (A-ii').
(A-i') MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 minutes or less (A-ii') Strain hardening degree λ is 1.8 or more (3) The decorative film according to (1) above, wherein the resin composition (A) satisfies the following requirements (Ai ″) and (Aii ″).
(A-i ") MFR (A) (230 ° C., 2.16 kg load) is 12 g / 10 minutes or less (A-ii") Strain hardening degree λ is 2.3 or more (4) The decorative film according to any one of (1) to (3) above, wherein the polypropylene-based resin (A) is a polypropylene-based resin (A-1) having a long-chain branched structure.
(5) The decorative film according to (4) above, wherein the polypropylene-based resin (A-1) is a polypropylene-based resin having a small amount of gel produced by a method other than the cross-linking method.
(6) The decorative film is characterized by having a surface decorative layer (II) made of a surface decorative layer resin on the surface of the layer (I) opposite to the sticking layer (III). The decorative film according to any one of (1) to (5) above.
(7) The addition according to (6) above, wherein the surface decorative layer resin is made of a polypropylene-based resin (B), and the polypropylene-based resin (B) has a strain hardening degree of 1 or less. Decorative film.

Further, the method for producing a decorative molded product of the present invention comprises the following constitutions (8), (9) or (10).
(8) The step of preparing the decorative film according to any one of (1) to (7), 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 body, which is characterized by the above.
(9) 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 (8) above, wherein the decorative molded body is made of a polar resin material.
(10) The method for producing a decorative molded body according to (8) 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 contain a polypropylene-based resin (A) and include a layer (I) composed of a resin composition (A) having a specific MFR and a strain curing degree λ. Therefore, even if it does not contain a thermosetting resin layer, it has excellent thermoformability during three-dimensional decorative heat molding, and the heating time can be sufficiently lengthened. Since the attachment layer (III) made of MFR and the polyolefin adhesive resin (C) having a functional group 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 structure of the decorative film is different. 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. FIG. 5 is a schematic cross-sectional view illustrating a state in which a resin molded body and a 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 bonded to each other, and has a step of thermoforming the decorative film along the bonding surface of the molded body and simultaneously bonding 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 adhered onto a resin molded body by thermal molding, and is a layer (I) composed of a resin composition (A) containing a polypropylene-based resin (A) and a polyolefin. The resin composition (A) containing the seal layer (III) made of the adhesive resin (C) and the polypropylene-based resin (A) has a specific MFR and strain curability in elongation viscosity measurement, and has polyolefin adhesiveness. The resin (C) is characterized by having an MFR (230 ° C., 2.16 kg load) of 100 g / 10 minutes or less.

Resin composition (A) containing polypropylene-based resin (A)
By containing the layer (I) made of the resin composition (A) containing the polypropylene-based resin (A), the decorative film suppresses the occurrence of appearance defects due to the film breaking or violent during thermoforming. Can be done. 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. The resin composition (A) can be composed of only the polypropylene-based resin (A) or a blend of the polypropylene-based resin (A) and another polypropylene-based resin. When the resin composition (A) is composed only of the polypropylene-based resin (A), the polypropylene-based resin (A) satisfies the requirements (A-i) and (A-ii) described later. Further, when the resin composition (A) is composed of a blend of the polypropylene-based resin (A) and another polypropylene-based resin, at least the polypropylene-based resin (A) is required to be described later in addition to the resin composition (A). It is preferable to satisfy Ai) and (Aii). The blend of the polypropylene-based resin (A) and the other polypropylene-based resin is not particularly limited, and may be a mixture of pellets and / or powder, a melt blend, or a solution blend, and may be a combination thereof.

The strain hardening degree of the resin composition (A) containing the polypropylene-based resin (A) satisfies the following requirement (A-ii), preferably satisfies the requirement (A-iii'), and more preferably the requirement (A-ii'). By setting the strain hardening degree of the resin composition (A) to a value in the following range, a decorative molded product having a good appearance can be obtained.
(A-ii) Strain hardening degree λ is 1.1 or more (A-ii') Strain hardening degree λ is 1.8 or more (A-ii ″) Strain hardening degree λ is 2.3 or more To be

The upper limit of the strain curing degree of the resin composition (A) is not particularly limited, but is preferably 50 or less, more preferably 20 or less. By setting the degree of strain curing to a value in the above range, the appearance of the decorative film can be improved.

The degree of strain curability of the resin composition (A) is determined based on the measurement of strain curability in the extensional viscosity measurement. Regarding strain curability (non-linearity) of extensional viscosity, "Lecture / Rheology", edited by Society of Rheology, Japan, Polymer Publishing Association, 1992, pp. 221-222, in the present specification, the strain hardening degree λ shall be calculated by a method according to the method shown in FIG. 7-20 of the same document, and the strain hardening degree shall be calculated as the value of the shear viscosity. η ^* (0.01) is adopted as the value of extensional viscosity, and ηe (3.5) is adopted, and the strain hardening degree λ is defined by the following equation (1).
λ = ηe (3.5) / {3 × η ^* (0.01)} Equation (1)
In the above formula (1), η ^* (0.01) is a complex viscosity coefficient measured by a dynamic frequency sweep experiment at a measurement temperature of 180 ° C. and an angular frequency of ω = 0.01 rad / s [Unit: Pa · s. ], And the complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and the angular frequency ω by η ^* = G ^* / ω. Further, ηe (3.5) is the extensional viscosity measured by measuring the extensional viscosity at a measurement temperature of 180 ° C., a strain rate of 1.0 s- ¹ , and a strain amount of 3.5.

Usually, the data obtained by these viscoelasticity measurements is a collection of numerical values such as elastic modulus and viscosity at each discrete frequency or measurement time interval. Therefore, when the measurement is carried out under a device or condition different from that used in the present invention, the complex viscosity η ^* (0.01) at an angular frequency ω = 0.01 and the elongation at a strain of 3.5 are necessarily obtained. There may be cases where the data of viscosity ηe (3.5) does not exist, but in that case, it is possible to estimate the corresponding value by performing interpolation such as linear interpolation and spline interpolation using the data before and after that. forgiven. When performing interpolation, it is common practice to use a logarithmic scale for the stress and time scales.

At this time, if the sample does not have strain curability (non-linearity) in extensional viscosity, the strain curability λ shows a value of about 1 (for example, 0.9 or more and less than 1.1) or less than 1, and the strain curability (for example, is 0.9 or more and less than 1.1). The stronger the non-linearity), the larger the value of strain hardening degree λ.

On the other hand, even if it has strain curability, if the viscosity is too low, sufficient molding stability cannot be obtained. Therefore, the resin composition (A) containing the polypropylene-based resin (A) has a constant viscosity. It is necessary, and this specification defines MFR (230 ° C., 2.16 kg load) as an index of this viscosity.

In the present specification, the MFR (230 ° C., 2.16 kg load) of the resin composition (A) containing the polypropylene-based resin (A) is referred to as MFR (A). The MFR (A) satisfies the following requirement (Ai), preferably the requirement (Ai'), and more preferably the requirement (Ai ″). The MFR of the resin composition (A). By setting (A) to the following value or less, a decorative molded product having a good appearance can be obtained.
(Ai) MFR (A) is 40 g / 10 minutes or less (Ai') MFR (A) is 20 g / 10 minutes or less (Ai ″) MFR (A) is 12 g / Must be 10 minutes or less

The lower limit of the MFR (A) of the resin composition (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 (A) 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 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.

General crystalline polypropylene is a linear polymer and usually does not have strain curability. On the other hand, the polypropylene-based resin (A) used in the present invention is preferably a polypropylene-based resin (A-1) having a long-chain branched structure, and is a resin composition (A) containing the polypropylene-based resin (A). ) Can exhibit strain curability.

The long-chain branched structure in the present invention means that the carbon skeleton (main chain of the branch) constituting the branch has a number of carbon atoms of several tens or more and a molecular weight of several hundreds or more in order to exhibit strain curability. Say the structure. This long-chain branched structure is distinguished from the short-chain branched formed by copolymerizing with an α-olefin such as 1-butene.

As a method for introducing a long-chain branched structure into a polypropylene-based resin, a method using high-energy ionized radiation (Japanese Patent Laid-Open No. 62-121704) and a method using an organic peroxide (Japanese Patent Laid-Open No. 2001-524565). Alternatively, a method of producing a macromonomer having a terminal unsaturated bond using a metallocene catalyst having a specific structure and copolymerizing it with propylene to form a long-chain branched structure (Japanese Patent Laid-Open No. 2001-525460). However, regardless of which method is used, the strain hardening degree of the polypropylene-based resin can be greatly improved.

The polypropylene-based resin (A-1) having a long-chain branched structure is not particularly limited as long as it has a long-chain branched structure, but has a comb-shaped chain structure and has a long-chain branched structure during polymerization. Those obtained by a method using the formed macromer copolymerization method are preferable. Examples of such a method include, for example, Japanese Patent Application Laid-Open No. 2001-525460, Japanese Patent Application Laid-Open No. 10-338717, Japanese Patent Application Laid-Open No. 2002-523575, Japanese Patent Application Laid-Open No. 2009-57542, Japanese Patent Application Laid-Open No. 05027353, Japanese Patent Application Laid-Open No. Examples thereof include the methods disclosed in Kaihei 10-338717. In particular, the macromer copolymerization method of JP-A-2009-57542 is suitable for the present invention because it can obtain a long-chain branch-containing polypropylene resin without generating gel.

Having a long-chain branched structure in polypropylene is defined by a method based on the rheological properties of the resin, a method of calculating the branching index g'using the relationship between the molecular weight and the viscosity, a method ^{using 13} C-NMR, and the like. In the present invention, the long-chain branched structure is defined by the ^{branching index g'and / or 13 C-NMR as shown below.}

The branching index g'is known as a direct indicator of the long-chain branching structure. Although detailed explanation is given in "Developments in Polymer Charactization-4" (JV Dawkins ed. Applied Science Publics, 1983), the definition of the branching index g'is as follows.
Branch index g'= [η] br / [η] lin
[Η] br: Intrinsic viscosity of polymer (br) having a long-chain branched structure [η] lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br) As is clear from the above definition, the branching index g'is If a value smaller than 1 is taken, it is determined that a long-chain branched structure exists, and the value of the branching index g'becomes smaller as the number of long-chain branched structures increases.

The branching index g'can be obtained as a function of the absolute molecular weight Mabs by using a GPC equipped with a light scatterometer and a viscometer as a detector. Details of the method for measuring the branching index g'in the present invention are described in Japanese Patent Application Laid-Open No. 2015-40213, and are as follows.
[Measuring method]
GPC: Alliance GPCV2000 (manufactured by Waters)
Detector: Listed in connection order Multi-angle laser light scattering detector (MALLS): DAWN-E (manufactured by Waitt Technology)
Differential Refractometer (RI): Attached to GPC Viscometer: Attached to GPC Mobile phase solvent: 1,2,4-trichlorobenzene (Irganox 1076 added at a concentration of 0.5 mg / mL)
Mobile phase flow rate: 1 mL / min Column: Two GMHHR-H (S) HTs manufactured by Tosoh Co., Ltd. are connected. Sample injection part temperature: 140 ° C.
Column temperature: 140 ° C
Detector temperature: All 140 ° C
Sample concentration: 1 mg / mL
Injection volume (sample loop volume): 0.2175 mL

[analysis method]
Data processing attached to MALLS in determining the absolute molecular weight (Mabs) obtained from the multi-angle laser light scattering detector (MALLS), the squared average inertia radius (Rg), and the limit viscosity ([η]) obtained from the Viscometer. The calculation is performed using the software ASTRA (version 4.73.04) with reference to the following documents.
References:
1. 1. "Developments in Polymer Charactization-4" (JV Dawkins ed. Applied Science Publics, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004)
3. 3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

In the decorative film of the present invention, if the polypropylene-based resin contains a gel, the appearance of the film deteriorates. Therefore, it is preferable to use the resin composition (A) that does not contain the gel. That is, the polypropylene-based resin (A-1) having a long-chain branched structure is preferably a polypropylene-based resin produced by a method other than the cross-linking method and having a small amount of gel. In particular, as the polypropylene-based resin (A-1) having the above-mentioned long-chain branched structure, a macromonomer having a terminal unsaturated bond is produced using a metallocene catalyst having a specific structure, and the macromonomer is copolymerized with propylene. Those produced by using a method for forming a long-chain branched structure are preferable. In particular, it is preferable that the branching index g'at an absolute molecular weight Mabs of 1,000,000, which is described below, satisfies 0.3 or more and less than 1.0, more preferably 0.55 or more and 0.98 or less, and further preferably 0. It is 75 or more and 0.96 or less, most preferably 0.78 or more and 0.95 or less. When the branching index g'is in this range, highly crosslinked components are not formed, gel is not formed, or very little, so that the layer (I) containing the polypropylene resin (A-1) is particularly present. Does not deteriorate the appearance when forming the surface of the product.

[ ¹³ C-NMR]
¹³ C-NMR can distinguish between a short-chain branched structure and a long-chain branched structure as described above. Macromol. Chem. Phys. 2003, vol. Detailed explanations are given in 204 and 1738, and the outline is as follows.

The propylene-based polymer having a long-chain branched structure has a specific branched structure as shown in the following structural formula (1). In the structural formula (1), Ca, Cb, and Cc indicate methylene carbon adjacent to the branched carbon, Cbr indicates the methine carbon at the root of the branched chain, and P1, P2, and P3 are propylene-based polymer residues. Is shown.

The propylene-based polymer residues P1, P2, and P3 may contain a branched carbon (Cbr) different from the Cbr described in the structural formula (1) in itself.

Such a branched structure is ^{identified by 13} C-NMR analysis. The attribution of each peak is described in Macromolecules, Vol. 35, No. 10. The description on pages 3839-3842, 2002 can be referred to. That is, a total of three methylene carbons (Ca, Cb, Cc) were observed at 43.9 to 44.1 ppm, 44.5 to 44.7 ppm, and 44.7 to 44.9 ppm, respectively, 31.5. Methine carbon (Cbr) is observed at ~ 31.7 ppm. The methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as branched methine carbon (Cbr) below.

It is characterized in that three methylene carbons adjacent to the branched methine carbon Cbr are observed in three non-equivalent diastereotopics.

¹³ Such a branched chain assigned by C-NMR shows a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer, and the branch having 4 or less carbon atoms is branched. Since it can be distinguished by the difference in the peak position of carbon, in the present invention, the presence or absence of the long-chain branched structure can be determined by confirming the peak of this branched methine carbon.
^{The 13} C-NMR measurement method in the present invention is as follows.

[ ¹³ C-NMR measurement method]
An NMR sample having an inner diameter of 10 mmφ with 200 mg of a sample together with o-dichlorobenzene / benzene deuterated bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift. It was placed in a tube and dissolved, and ¹³ C-NMR measurement was performed.
¹³ C-NMR measurement was performed using an AV400M type NMR apparatus of Bruker Biospin Co., Ltd. equipped with a cryoprobe having a diameter of 10 mm.
The measurement was carried out at a sample temperature of 120 ° C. by the proton complete decoupling method. Other conditions are as follows.
Pulse angle: 90 °
Pulse interval: 4 seconds Accumulation number: 20000 times The chemical shift was set with the methyl carbon peak of hexamethyldisiloxane set to 1.98 ppm, and the chemical shift of peaks with other carbons was based on this.
The amount of long chain branching can be calculated using the peak around 44 ppm.

^{In the 13} C-NMR spectrum of the polypropylene-based resin (A-1) having a long-chain branched structure, the amount of long-chain branched quantified from the peak near 44 ppm is preferably 0.01 / 1000 total propylene or more. It is more preferably 0.03 pieces / 1000 total propylene or more, and further preferably 0.05 pieces / 1000 total propylene or more. If this value is too large, it may cause poor appearance of gels, fish eyes, etc., so it is preferably 1.00 pieces / 1000 total propylene or less, more preferably 0.50 pieces / 1000 total propylene or less, and further preferably 0. .30 pieces / 1000 total propylene or less.

The polypropylene-based resin (A-1) having such a long-chain branched structure is contained in the resin composition (A) containing the polypropylene-based resin (A) in an amount sufficient to impart strain curability. I just need to be there. The polypropylene-based resin (A-1) is preferably contained in an amount of 1 to 100% by weight, more preferably 5% by weight or more, based on 100% by weight of the resin composition (A).

The polypropylene-based resin (A-1) in the present invention is of various types such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), and a propylene block copolymer (block polypropylene). A propylene-based polymer or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of the propylene monomer.

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 140 ° C. or higher, more preferably 145 to 170 ° C., and even more preferably 150 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 resin composition (A) containing the polypropylene-based resin (A) includes a plurality of polypropylene-based resins other than the polypropylene-based resin (A-1) having a long-chain branched structure, additives, fillers, colorants, and others. It may contain a resin component or the like. At this time, the total amount of additives, fillers, colorants, other resin components and the like is preferably 50% by weight or less with respect to the polypropylene-based resin composition containing them.

When the decorative molded product of the present invention is molded as a colored molded product, a colorant needs to be used only on 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, aluminum P-t-butyl benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 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 Syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-benzylene sorbitol, p-ethyl-benzylene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples include (4-propylphenyl) methylene] -nonitol, a 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, 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 comprises a sticking layer (III) made of a polyolefin adhesive resin (C) on a sticking surface with a resin molded body (base) to form a base 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 polyolefin adhesive resin is formed on the layer (I) composed of the resin composition (A) containing the polypropylene resin composition (A) by an extrusion molding method. The adhesive layer (III) made of (C) 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 has a polarity having at least one hetero atom from the viewpoint of improving the adhesiveness with the layer (I) made of the resin composition (A) containing the polypropylene resin (A). A polyolefin resin having a functional group is preferable.

The polar functional group having a hetero atom, mosquito carbonyl group, an ester group, mosquitoes Rubokishi group or a metal salt thereof, A sill group, an acyloxy group, an acid anhydride group, and the like. Specific examples of polyolefins having such a polar functional group include maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, acid-modified polypropylene and acrylic acid-modified polypropylene; et styrene / acrylic acid copolymer, ethylene / methacrylic acid copolymer Polymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / acrylic Isobutyl acid acid copolymer, 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate copolymer Polymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethyl ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / metal acrylate Salt copolymer, ethylene / metal methacrylate copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic acid ethyl acrylate / glycidyl methacrylate copolymers, ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer. 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 (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpenephenol 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, Phenol resins (alkylphenols, phenolxylene formaldehydes, rosin-modified phenol resins, etc.), xylene resins and the like can be mentioned, 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 above-mentioned additives include antioxidants, metal deactivators, phosphorus-based processing stabilizers, ultraviolet absorbers, ultraviolet stabilizers, metal soaps, stabilizers such as antioxidant adsorbents, or cross-linking agents and chain transfer agents. Examples thereof include nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, fluorescent whitening agents, etc., 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 resin composition (A) containing 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, the decorative film is a double-layer film composed of the layer (I) and the adhesive layer (III), but is a multilayer film composed of the layer (I), the adhesive 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 resin composition (A) containing 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 resin composition (A) containing the polypropylene-based resin (A) constitutes a surface layer opposite to the surface to be attached to the resin molded product. , The sticking layer (III) made of the polyolefin adhesive resin (C) constitutes the sticking layer of the sticking surface to the resin molded body.

When the decorative film is a multilayer film having three or more layers, the layer (I) made of the resin composition (A) containing the polypropylene-based resin (A) is the decorative film in order to sufficiently exhibit solvent resistance. It is preferably the outermost layer, and between the layer (I) made of the resin composition (A) containing the polypropylene resin (A) and the adhesive layer (III) made of the polyolefin adhesive resin (C), etc. Layer structure (including a plurality of layers) is 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 body. show. 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 attached. ), The layer (I) made of the resin composition (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 side opposite to the surface side to be attached to the resin molded body. The surface decorative layer (II) is preferably provided on the outermost surface on the side opposite to the side on which the resin molded product is attached. 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, by further providing the surface decorative layer (II) made of polypropylene-based resin (B) on the surface layer of the decorative film, it is possible to improve the gloss and grain transferability without significantly reducing the thermoforming property. You can. 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 surface 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 a strain hardening degree of less than 1.1, more preferably 1 or less. By setting the strain curing degree of the polypropylene-based resin (B) to less than 1.1, the appearance of the decorative molded product can be improved. The degree of strain hardening of the polypropylene resin (B) shall be determined by the method described above.

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 with respect to the polypropylene-based resin composition.

As the additive, an additive or the like that may be contained in the resin composition (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 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, 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 extrusion-molding a layer made of a resin composition (A) containing a polypropylene-based resin (A), a method of co-extruding a layer (I) made of a resin composition (A) and another layer, in advance. A thermal lamination method in which the other layer is bonded by applying heat and pressure on one surface of one of the extruded layers, and a dry lamination method in which the layer (I) and the other layer are bonded via an adhesive. Examples thereof include a wet lamination method, an extrusion lamination method in which a polypropylene-based resin is melt-extruded onto one surface of one layer extruded in advance, and a sand lamination method. 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 the film is formed. 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. Alternatively, as the resin molded product to be decorated, various molded products made of polypropylene-based resin or polypropylene-based resin composition can be preferably 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 body of the present invention, the resin molded body and the decorative film are set in a step of preparing the above-mentioned decorative film, a step of preparing a resin molded body, and a chamber box capable of reducing pressure. 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. do.

In three-dimensional decorative thermoforming, a decorative object and a decorative film are set in a 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 decorative object to form a 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). NS. 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 where the decorative object 5 and the decorative film 1 are attached may be within this range, and the upper and lower chamber boxes may be up and down. 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. 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) Strain hardening degree λ
The strain hardening degree λ was obtained by the method described above. ^{At this time, η *} (0.01) used as the value of shear viscosity and ηe (3.5) used as the value of extensional viscosity were measured by the following methods. The sample used for the measurement at this time was formed into flat plates having a thickness of 0.7 mm and 2 mm by pressing for 1 hour under the conditions of a temperature of 180 ° C. and a pressure of 10 MPa, and was a sample having a thickness of 0.7 mm. Was used for the extensional viscosity measurement, and a 2 mm sample was used for the dynamic frequency sweep experiment.

(Ii-1) Shear viscosity η ^* (0.01)
A dynamic frequency sweep experiment was performed using ARES manufactured by Rheometric Scientific. A parallel disk having a diameter of 25 mm was used for the measurement geometry. The measurement was carried out in the measurement mode Dynamic Frequency Swep Test using the device control software TA Orchestrator. As the sample, a press-molded product having a thickness of 2 mm prepared by the above method was used. The measurement temperature was 180 ° C. The angular frequency ω was measured at 5 points per digit between 0.01 and 100 rad / s so as to be evenly spaced on a logarithmic scale.
As an index showing the viscosity of the sample at a low shear rate, the complex viscosity ratio η ^* (0.01) [unit: Pa · s] at ω = 0.01 rad / s is adopted. The complex viscosity η * is calculated from the complex elastic modulus G ^* [unit: Pa] and ω by η ^* = G ^* / ω.

(Ii-2) Extensional viscosity ηe (3.5)
Extensional viscosity measurement was performed using Extension Viscometer Fixture manufactured by TA Instruments Co., Ltd. as a measuring jig of ARES manufactured by Rheometric Scientific. The measurement was performed in the measurement mode Extension Viscosity Test using the device control software TA Orchestrator. As the sample, a test piece having a thickness of 0.7 mm formed by the above method was used. The width of the test piece was 10 mm and the length was 18 mm. The strain rate is 1.0 s ^-1 and the measurement temperature is 180 ° C. Other measurement parameters were set as follows.
Sampleing Mode: log
Points Per Zone: 200
Solid Density: 0.9
Melt Density: 0.8
Prestretch Rate: 0.05s ^-1
Relaxation after Press: 30sec
Under this condition, data is collected at least for a time of 3.7 seconds from the start of measurement. The software provides time-dependent data on extensional viscosities. The value of the extensional viscosity of the obtained extensional viscosity curve at a time of 3.5 sec (that is, the amount of strain 3.5) was defined as ηe (3.5) [unit: Pa · s].

(Iii) Melting point:
Using a differential scanning 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 then 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.

(Iv) Measurement of branching index g'at absolute molecular weight Mabs of 1,000,000:
According to the above-mentioned method, the measurement was performed using a GPC equipped with a light scatterometer and a viscometer as a detector, and the branching index g'was obtained based on the above-mentioned analysis method.

(V) ¹³ Detection of long-chain branched structure using C-NMR:
According to the method described above ^{, measurement was performed using 13} C-NMR, and the presence or absence of a long-chain branched structure was measured.

2. Materials used (1) Polypropylene resin (A)
The following polypropylene resins were used.
(A-1-1): A propylene homopolymer having a long chain branch produced by the macromer copolymerization method, manufactured by Japan Polypropylene Corporation, trade name "WAYMAX (registered trademark) MFX8", MFR = 1.0 g / 10 minutes, strain hardening degree λ = 9.7, Tm = 154 ° C., absolute molecular weight Mabs at 1 million branch index g'= 0.89, ¹³ C-NMR measurement confirmed that it had a long-chain branched structure.
(A-1-2): A propylene homopolymer having a long chain branch produced by the macromer copolymerization method, manufactured by Japan Polypropylene Corporation, trade name "WAYMAX (registered trademark) MFX3", MFR = 8.8 g / 10 minutes, strain hardening degree λ = 7.8, Tm = 154 ° C., absolute molecular weight Mabs at 1 million branch index g'= 0.85, ¹³ C-NMR measurement confirmed that it had a long-chain branched structure.
(A-1-3): A propylene homopolymer having a long chain branch produced by a cross-linking method, manufactured by Borealis, trade name "Daproy (registered trademark) WB140", MFR = 2.2 g / 10 minutes, strain curing. Degree λ = 10.6, Tm = 158 ° C., Absolute molecular weight Mabs was confirmed to have a long-chain branched structure by measurement ^{of branching index g'= 0.58 at 1 million, 13 C-NMR.}
(A-1-4): Polypropylene resin composition obtained by blending 96% by weight of polypropylene resin (A-1-1) with 4% by weight of black pigment MB (EPP-K-12601 manufactured by Polycol Kogyo Co., Ltd.). (MFR = 1.0 g / 10 minutes, strain hardening degree λ = 9.3)
(A-2-1): A propylene homopolymer having no long-chain branch (MFR = 10 g / 10 minutes, Tm = 161 ° C., strain hardening degree λ = 1.0), manufactured by Japan Polypropylene Corporation, trade name. "Novatec (registered trademark) FA3KM", absolute molecular weight Mabs confirmed to have no long-chain branched structure by measurement ^{of branch index g'= 1.0 at 1 million, 13 C-NMR.}
(A-2-2): A propylene homopolymer having no long-chain branch (MFR = 2.4 g / 10 minutes, Tm = 161 ° C., strain hardening degree λ = 0.9), manufactured by Japan Polypropylene Corporation, It was confirmed that the product name "Novatec (registered trademark) FY6", the absolute molecular weight Mabs had a branching index g'= 1.0 at 1 million, and ¹³ C-NMR did not have a long-chain branched structure.
(2) Polypropylene resin (B)
(B-1): Polypropylene in which 0.4 parts by weight of a nucleating agent (manufactured by Milliken Japan Co., Ltd., trade name "Milllad NX8000J") is blended with 100 parts by weight of polypropylene resin (A-2-1). Based resin composition (MFR = 10 g / 10 minutes, Tm = 164 ° C)
(B-2): Metallocene-catalyzed propylene-α-olefin copolymer (MFR = 7 g / 10 minutes, Tm = 125 ° C.), manufactured by Japan Polypropylene Corporation, trade name "Wintech (registered trademark) WFX4M"
(B-3): Polypropylene resin (B-2) 100 parts by weight blended with 0.4 parts by weight of a nucleating agent (trade name "Milllad NX8000J" manufactured by Milliken Japan Co., Ltd.) Composition (MFR = 7 g / 10 minutes, Tm = 127 ° C.)
(B-4): Polypropylene resin (A-2-1) 96% by weight, MFR = 11 g / 10 minutes white pigment MB (EPP-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80 weight) %) Blended in 4% by weight of a polypropylene resin composition (MFR = 10 g / 10 minutes, Tm = 161 ° C.)
(B-5): Polypropylene resin composition (MFR =) in which 96% by weight of polypropylene resin (A-2-1) is blended with 4% by weight of silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyo Color Co., Ltd.). 10 g / 10 minutes, Tm = 161 ° C)
(3) Polyolefin adhesive resin (C)
(C-1): Maleic anhydride-modified polyolefin (MFR = 7.0 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) Polar resin (X) used for the resin molded body (base)
The following polar resins (X-1) to (X-3) were used.
(X-1): PMMA resin, manufactured by Mitsubishi Rayon Co., Ltd., "Acrypet 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
-Manufacturing 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. A polypropylene resin (A-1-1) was charged into the extruder-1, and a polyolefin adhesive resin (C-1) was charged into the sticking layer extruder-2. The resin temperature was 240 ° C., and the extruder-1 was used. The melt extrusion was performed under the conditions that the discharge rate of the above was 12 kg / h and the discharge rate 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. The sticking layer was set on No. 13 so as to be downward. 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 a 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. 40 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 body ( 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 base material 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. The decorative molded body has a beautiful appearance.
Δ: Since the decorative film was slightly drawn down during the three-dimensional decorative thermoforming, the decorative film came into contact with the decorative film from the center of the substrate, and contact unevenness occurred at the upper end of the substrate, but the appearance of the decorative molded body was maintained. There is.
X: During the three-dimensional decorative thermoforming, the decorative film drew down significantly, so that contact unevenness occurred on the entire surface of the substrate, and the appearance of the decorative molded body was not suitable for practical use.

(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 of 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.

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

The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Examples 2-3, 7-8
In the production of the decorative film of Example 1, the polypropylene-based resin (A-1-1) was blended with the polypropylene-based resin (A-1-1) and (A-2-1) shown in Table 1 (resin). Molding and evaluation were carried out in the same manner as in Example 1 except that the composition (A) was changed. The evaluation results are shown in Table 1.
The MFR of the resin composition (A) is 40 g / 10 minutes or less, the strain curing degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less. Therefore, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Example 4
In the production of the decorative molded product of Example 3, molding and evaluation were carried out in the same manner as in Example 3 except that the base material was changed to a resin molded product made of polar resin (X-2). The evaluation results are shown in Table 1.
The MFR of the resin composition (A) is 40 g / 10 minutes or less, the strain curing degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less. Therefore, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Example 5
In the production of the decorative film of Example 3, molding and evaluation were carried out in the same manner as in Example 3 except that the base material was changed to a resin molded body made of polar resin (X-3). The evaluation results are shown in Table 1.
The MFR of the resin composition (A) is 40 g / 10 minutes or less, the strain curing degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / 10 minutes or less. Therefore, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Example 6
In the production of the decorative film of Example 3, the evaluation was carried out in the same manner as in Example 3 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.
The MFR of the resin composition (A) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-2) having a maleic anhydride group is 100 g / 10 minutes or less. Therefore, the obtained decorative molded product was excellent in appearance and adhesive strength.

Example 9
In the production of the decorative film of Example 1, molding and evaluation were carried out in the same manner as in Example 1 except that the polypropylene-based resin (A-1-1) was changed to the polypropylene-based resin (A-1-2). rice field. The evaluation results are shown in Table 2.
The MFR of the polypropylene resin (A-1-2) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Examples 10 to 13
In the production of the decorative film of Example 9, the polypropylene-based resin (A-1-2) was blended with the polypropylene-based resin (A-1-2) and (A-2-1) shown in Table 1 (resin). Molding and evaluation were carried out in the same manner as in Example 9 except that the composition (A) was changed. The evaluation results are shown in Table 2.
The MFR of the polypropylene resin (A-1-2) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance.

Example 14
In the production of the decorative film of Example 1, molding and evaluation were carried out in the same manner as in Example 1 except that the polypropylene-based resin (A-1-1) was changed to the polypropylene-based resin (A-1--3). rice field. The evaluation results are shown in Table 2.
The MFR of the polypropylene resin (A-1-3) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance. However, gel was observed in the obtained film.

Example 15
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. The extruder-1 is a polypropylene resin (A-1-1), the sticking layer extruder-2 is a polyolefin adhesive resin (C-1), and the surface layer extruder-3 is a polypropylene resin (A). -2-1) was charged, the resin temperature was 240 ° C., the discharge rate of the extruder-1 was 12 kg / h, the discharge rate of the sticking layer extruder-2 was 8 kg / h, and the discharge rate of the surface layer extruder-3. The melt extrusion was performed under the condition that the discharge amount of the above was 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. 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 2.
The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance. Further, since the polypropylene-based resin (A-2-1) is laminated on the outermost surface side as the surface decorative layer [layer (II)], the result is that the gloss is superior to that of the decorative molded product of Example 1. Met.

Example 16
In the production of the decorative film of Example 15, molding and evaluation were carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-1-1) was changed to the polypropylene-based resin (A-1-2). rice field. The evaluation results are shown in Table 2.
The MFR of the polypropylene resin (A-1-2) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance, adhesive strength, and chemical resistance. Further, since the polypropylene-based resin (A-2-1) is laminated on the outermost surface side as the surface decorative layer [layer (II)], the result is that the gloss is superior to that of the decorative molded product of Example 9. Met.

Comparative Example 1
In the production of the decorative film of Example 1, except that the polypropylene-based resin (A-1-1) constituting the layer (I) was changed to the polypropylene-based resin (A-2-2) having no long-chain branching. , Molding and evaluation were carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.
Since polypropylene resin (A-2-2) has a strain curing degree λ of less than 1.1, it is inferior in thermoforming stability, and the decorative film is greatly drawn down during three-dimensional decorative thermoforming, so that the entire surface of the substrate is covered. The result was that uneven contact occurred and the appearance of the decorative molded product was significantly inferior.

Comparative Example 2
In the production of the decorative film of Example 1, the polyolefin adhesive resin (C-1) constituting the adhesive layer (III) was changed to a polypropylene-based resin (A-2-1) having no functional group. Was evaluated in the same manner as in Example 1. The results are shown in Table 2.
Since the polypropylene resin composition (A-2-1) is not the polyolefin adhesive resin (C), it does not have polarity, does not adhere to the base material, and has poor chemical resistance.

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

Example 17
In the production of the decorative film of Example 15, the evaluation was carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-2-1) used for the surface layer was changed to the polypropylene-based resin (B-1). rice field. The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product 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 [layer (II)], resulting in excellent gloss.

Example 18
In the production of the decorative film of Example 15, the evaluation was carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-2-1) used for the surface layer was changed to the polypropylene-based resin (B-2). rice field. The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-2) was laminated on the outermost surface side as the surface decorative layer [layer (II)], resulting in excellent gloss.

Example 19
In the production of the decorative film of Example 15, the evaluation was carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-2-1) used for the surface layer was changed to the polypropylene-based resin (B-3). rice field. The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance and adhesive strength. Further, the polypropylene-based resin (B-3) to which the nucleating agent was added was laminated on the outermost surface side as the surface decorative layer [layer (II)], resulting in excellent gloss.

Example 20
In the production of the decorative film of Example 15, the evaluation was carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-2-1) used for the surface layer was changed to the polypropylene-based resin (B-4). rice field. The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-1) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance and adhesive strength. Further, since the surface layer [layer (II)] having excellent gloss was colored white, the appearance was excellent.

Example 21
In the production of the decorative film of Example 5, the evaluation was carried out in the same manner as in Example 15 except that the polypropylene-based resin (A-1-1) was changed to the polypropylene-based resin (A-1--4). The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-4) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance and adhesive strength. Further, since the layer (I) was colored black, the appearance was excellent. Further, the polypropylene-based resin (A-2-1) was laminated on the outermost surface side as the surface decorative layer [layer (II)], resulting in excellent gloss.

Example 22
In the production of the decorative film of Example 21, the evaluation was carried out in the same manner as in Example 21 except that the polypropylene-based resin (A-2-1) used for the surface layer was changed to the polypropylene-based resin (B-5). rice field. The results obtained are shown in Table 3.
The MFR of the polypropylene resin (A-1-4) is 40 g / 10 minutes or less, the strain hardening degree λ is 1.1 or more, and the MFR of the polyolefin adhesive resin (C-1) having a maleic anhydride group is 100 g / Since it took 10 minutes or less, the obtained decorative molded product was excellent in appearance and adhesive strength. Further, since the polypropylene-based resin (B-5) was laminated on the outermost surface side as the surface decorative layer [layer (II)], the result was excellent in gloss. Further, since the layer (I) is colored black and the layer (II) is colored silver, the film becomes a metallic film 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 (10)

A decorative film for being attached onto a resin molded body by thermoforming, and the decorative film has polyolefin adhesiveness to a layer (I) made of a resin composition (A) containing a polypropylene-based resin (A). The adhesive layer (III) made of the resin (C) is laminated,
The polyolefin adhesive resin (C) is a polyolefin resin having a polar functional group containing at least one heteroatom, and has an MFR (230 ° C., 2.16 kg load) of 100 g / 10 minutes or less. polar functional groups, mosquitoes Rubokishi group or a metal salt thereof, selected from the group consisting of contact and acid anhydride groups, wherein the resin composition (a) is the following requirements (a-i) and to satisfy the (a-ii) A decorative film featuring.
(A-i) MFR (A) (230 ° C, 2.16 kg load) is 40 g / 10 minutes or less (A-ii) Strain hardening degree λ is 1.1 or more. The decorative film according to claim 1, wherein the resin composition (A) satisfies the following requirements (Ai') and (Aii').
(A-i') MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 minutes or less (A-ii') Strain hardening degree λ is 1.8 or more. The decorative film according to claim 1, wherein the resin composition (A) satisfies the following requirements (Ai ″) and (Aii ″).
(A-i ") MFR (A) (230 ° C., 2.16 kg load) is 12 g / 10 minutes or less (A-ii") Strain hardening degree λ is 2.3 or more. The decorative film according to any one of claims 1 to 3, wherein the polypropylene-based resin (A) is a polypropylene-based resin (A-1) having a long-chain branched structure. The decorative film according to claim 4, wherein the polypropylene-based resin (A-1) is a polypropylene-based resin having a small amount of gel, which is produced by a method other than the cross-linking method. The decorative film is characterized by having a surface decorative layer (II) made of a surface decorative layer resin on the surface of the layer (I) opposite to the sticking layer (III). The decorative film according to any one of claims 1 to 5. The decorative film according to claim 6, wherein the surface decorative layer resin is made of a polypropylene-based resin (B), and the polypropylene-based resin (B) has a strain curing degree of 1 or less. The step of preparing the decorative film according to any one of claims 1 to 7, 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 8, wherein the decorative molded body is made of a resin material. The method for producing a decorative molded product according to claim 8, wherein the resin molded product is made of a propylene-based resin composition.

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