JP2019136912A - Decorative molded body and method for producing same - Google Patents

Abstract

To provide a decorative molded body that is light weight, is excellent in heat insulation or acoustic insulation, cushioning, energy absorption, etc., and is excellent in molded body surface appearance such as surface gloss, and in hand touch-texture.SOLUTION: Provided is a decorative molded body 6 having a polypropylene-based decorative film 1 adhered on an injection foamed resin molded body 5 by thermoforming, and in which the injection foamed resin molded body 5 is a resin molded body comprising a polypropylene-based resin (a) satisfying the following requirements (i) to (ii) and having an expansion ratio of 1.1 times or more and 10 times or less. (i): the melting peak temperature Tm is 110°C or higher. (ii): MFR (230°C, 2.16 kg load) is 0.01 g/10 min or more and 300 g/10 min or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative molded body and a method for producing the same. Specifically, a decorative molded body excellent in surface shape obtained by sticking a polypropylene decorative film to the surface of an injection foamed resin molded body made of polypropylene resin by thermoforming, and a method for producing the decorative molded body About.

Polypropylene resin injection-foamed molded articles have excellent properties such as heat insulation, sound insulation, cushioning and energy absorption, and are therefore used in a wide range of applications such as automotive parts. In recent years, in particular, from the viewpoint of environmental measures such as low emissions and improved fuel consumption, weight reduction of materials and reduction of environmental burden have become important technological development issues, so the technical area where foamed molded products are used tends to expand. There is a growing demand for resins with high foaming performance.

  Until now, various attempts have been made to mold injection-molded foams made of polypropylene resin. As an attempt to improve the polypropylene resin, a method of increasing the melt tension of the polypropylene resin composition by adding a crosslinking agent or a silane graft thermoplastic resin to the linear polypropylene resin (Patent Documents 1 and 2), strain hardening To obtain a foamed molded product using HMS-PP (High Melt Strength-Polypropylene) with high properties (Patent Document 3). Addition of polypropylene resin with high melt tension to linear polypropylene improves foaming performance A method (Patent Document 4) is proposed.

  As an approach from the molding method, for example, a method in which the inside of the mold cavity is previously pressurized at a pressure equal to or higher than the foaming pressure (Patent Document 5), and a non-foamable resin and a foamable resin are sequentially injected and filled into the mold cavity. A method (Patent Document 6), a method of heating a mold in advance to a high temperature (Patent Document 7), and the like are known. Further, in recent years, molding methods such as a counter pressure method and a heat and cool method have been proposed.

JP 61-152754 A Japanese Patent Laid-Open No. 7-109372 JP 2001-26032 A JP 2011-068819 A JP 59-227425 A JP 58-197029 A JP 2002-307473 A

The methods of Patent Documents 1 to 4 have not yet improved the appearance defects called silver streak (or swirl mark) or flow mark on the surface of the molded body. The methods disclosed in Patent Documents 5 to 7 have problems in economic efficiency such as the complexity and enlargement of molds and molding apparatuses. In the molding methods such as the counter pressure method and the heat and cool method, there are problems that appearance defects called avatars occur and the expansion ratio can only be increased to 2 times or less.
The object of the present invention is to provide a decorative molded body that is light in weight, excellent in heat insulation, sound insulation, cushioning, energy absorption, etc., and has a molded article surface appearance such as surface gloss and excellent touch. It is to provide.

  As a result of diligent research, the present inventors have made it possible to bond a polypropylene decorative film composed of a specific layer made of a polypropylene resin satisfying specific requirements to a foamed resin molded body made of a polypropylene resin. Therefore, it is possible to provide a decorative molded body that is lightweight, excellent in heat insulation, sound insulation, cushioning, energy absorption, etc., and has a molded product surface appearance such as surface gloss and excellent touch.

The present invention has the following configuration. That is, the present invention is a decorative molded body in which a polypropylene decorative film is attached by thermoforming on an injection foamed resin molded body, and the injection foamed resin molded body has the following requirements (i) to (ii): A decorative molded body characterized in that it is a decorative molded body characterized by being a resin molded body having a foaming ratio of 1.1 times or more and 10 times or less. is there.
Polypropylene resin (A)
(I): Melting peak temperature Tm is 110 ° C. or higher.
(Ii): MFR (230 ° C., 2.16 kg load) is 0.01 g / 10 min or more and 300 g / 10 min or less.

Moreover, this invention contains the layer (I) which the said polypropylene decorative film consists of the resin composition (A) containing a polypropylene resin (A), and the said resin composition (A) is the following requirements (A- It is the said decorative molded body characterized by satisfying i) and (A-ii).
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more

In the present invention, the polypropylene decorative film includes a layer (I) made of the resin composition (A) containing the polypropylene resin (A) and a seal layer (II) made of the polypropylene resin (B), The resin composition (A) satisfies the following requirements (A-i) and (A-ii), and the polypropylene resin (B) has an MFR (230 ° C., 2.16 kg load) of 2 g / 10 min. It is a multilayer decorative film exceeding the above-mentioned decorative molded body, wherein the multilayer decorative film and the injection-foamed resin molded body are bonded via a seal layer (II).
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more

In addition, the present invention is the decorative molded body, wherein the resin composition (A) satisfies the following requirements (Ai ′) and (A-ii ′).
(Ai ′) MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 min or less (Aii ′) Strain hardening degree λ is 1.8 or more. The decorative molded body is characterized in that the resin composition (A) satisfies the following requirements (Ai ″) and (A-ii ″).
(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.

In addition, the present invention provides the decorative molded body, wherein the polypropylene resin (A) is a polypropylene resin (A-1) having a long chain branched structure.
In addition, the present invention is the decorative molded body, characterized in that the polypropylene resin (A-1) is a polypropylene resin with less gel produced by a method other than the crosslinking method.

In the present invention, the polypropylene decorative film includes a layer (I) composed of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) composed of a polypropylene resin (C), The resin composition (A) satisfies the following requirements (Ai) to (A-ii), and the polypropylene resin (C) is a multilayer decorative film that satisfies the following requirements (c1) to (c5). Yes, the decorative molded body is characterized in that the multilayer decorative film and the resin molded body are bonded via a seal layer (II).
(Ai) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more (c1) Metallocene catalyst system Propylene polymer.
(C2) MFR (C) (230 ° C., 2.16 kg load) exceeds 0.5 g / 10 min.
(C3) Melting peak temperature Tm (C) is less than 150 ° C.
(C4) The molecular weight distribution (Mw / Mn (C)) obtained by GPC measurement is 1.5 to 3.5.
(C5) When the melting peak temperature of the polypropylene resin (A) is Tm (A) and the melting peak temperature of the polypropylene resin (C) is Tm (C), Tm (A) and Tm (C) are The following relational expression (5) is satisfied.
Tm (A)> Tm (C) (5)

In addition, the present invention is the decorative molded body, wherein the polypropylene resin (C) is a propylene / α-olefin copolymer.
Moreover, this invention is said decoration molded object characterized by the melting peak temperature Tm (C) of the said polypropylene resin (C) being 140 degrees C or less.

In addition, the present invention is the decorative molded body, wherein the resin composition (A) satisfies the following requirements (Ai ′) and (A-ii ′).
(Ai ′) MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 min or less (Aii ′) Strain hardening degree λ is 1.8 or more. The decorative molded body is characterized in that the resin composition (A) satisfies the following requirements (Ai ″) and (A-ii ″).
(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.

In addition, the present invention provides the decorative molded body, wherein the polypropylene resin (A) is a polypropylene resin (A-1) having a long chain branched structure.
In addition, the present invention is the decorative molded body, characterized in that the polypropylene resin (A-1) is a polypropylene resin with less gel produced by a method other than the crosslinking method.

In the present invention, the polypropylene decorative film has a surface decorative layer (III) made of a surface decorative layer resin on a surface opposite to a surface to be bonded to the injection foamed resin molded body. It is the said decorative molded object characterized by the above-mentioned.
In the present invention, the surface decoration layer resin is made of a polypropylene resin (D), and the MFR (230 ° C., 2.16 kg load) of the polypropylene resin (D) exceeds 2 g / 10 minutes. It is the said decorative molded object characterized by the above-mentioned.

  Moreover, this invention is a method of manufacturing the said decorative molded object, Comprising: The step which prepares a polypropylene-type decorative film, The step which prepares the injection foaming resin molding whose expansion ratio is 1.1 times or more and 10 times or less , A step of setting the injection-foamed resin molded body and the decorative film in a depressurizable chamber box, a step of depressurizing the interior of the chamber, a step of heat-softening the decorative film, It is the manufacturing method of the decoration molded object characterized by including the step which presses a decoration film, and the step which returns or pressurizes the inside of a chamber.

According to the decorative molded body of the present invention, a polypropylene decorative film composed of a specific layer made of a polypropylene resin satisfying specific requirements is bonded to an injection foamed resin molded body made of a specific polypropylene resin. Because it is lightweight, it is possible to provide a decorative molded body that is lightweight, has excellent heat insulation, sound insulation, cushioning, energy absorption, etc., and has a molded product surface appearance such as surface gloss and excellent touch. did.
Furthermore, according to the method for producing a decorative molded body of the present invention, there is no hole or wrinkle on the surface, there is no air entrainment between the decorative film and the resin molded body, and a beautiful decorative molding in which scratches are not noticeable. You can get a body. In addition, a decorative film can be neatly adhered to a resin molded body having a complicated shape that has been difficult to bond. Furthermore, since the decorative molded body thus obtained does not include a thermosetting resin layer, the appearance and performance are not significantly reduced during recycling, and the suitability for recycling is high.

It is a figure which shows the example of the layer structure of the decorative molded body of this invention. It is typical sectional drawing explaining the outline | summary of the apparatus used for the manufacturing method of the decorative molded body of this invention. It is typical sectional drawing explaining a mode that the resin molding and the decorating film were set in the apparatus of FIG. It is typical sectional drawing explaining a mode that the inside of the apparatus of FIG. 2 is heated and pressure-reduced. It is typical sectional drawing explaining a mode that a decorating film is pressed on the resin molding in the apparatus of FIG. It is typical sectional drawing explaining a mode that it returns to atmospheric pressure or pressurizes the inside of the apparatus of FIG. It is a typical sectional view explaining signs that the edge of an unnecessary decoration film was trimmed in the obtained decoration fabrication object.

  In this specification, the decorative film refers to a film for decorating a molded body. Decorative molding refers to molding in which a decorative film and a molded body are attached. Three-dimensional decorative thermoforming is a process of adhering a decorative film and a molded body, and has a step of applying a decorative film at the same time as thermoforming along the adhesive surface of the molded body, In order for this process to suppress air from being caught between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is adhered to the molded body, and pressure is applied. It refers to molding, which is a step of bringing in close contact by release (pressurization). Hereinafter, embodiments for carrying out the present invention will be described in detail.

The decorative molded body of the present invention is a decorative molded body in which a polypropylene decorative film is bonded to an injection foamed resin molded body by thermoforming, and the injection foamed resin molded body has the following requirements (i): A decorative molded body comprising a polypropylene-based resin (a) satisfying (ii) and having a foaming ratio of 1.1 to 10 times.
Polypropylene resin (A)
(I): Melting peak temperature Tm is 110 ° C. or higher.
(Ii): MFR (230 ° C., 2.16 kg load) is 0.01 g / 10 min or more and 300 g / 10 min or less.

The polypropylene decorative film of the present invention is not particularly limited as long as it is a film or a multilayer film including a layer containing a polypropylene resin, but as a first aspect, a resin composition (A) containing a polypropylene resin (A) A film comprising a layer (I) consisting of
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more As a second aspect, The resin composition (A) includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (B). The resin composition (A) has the following requirements (A -I) and (A-ii), the polypropylene resin (B) is a multilayer film having an MFR (230 ° C., 2.16 kg load) of more than 2 g / 10 minutes,
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) strain hardening degree λ is 1.1 or more As a third aspect, The resin composition (A) includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (C). The resin composition (A) has the following requirements (A Examples of the polypropylene resin (C) that satisfy -i) to (A-ii) include multilayer films that satisfy the following requirements (c1) to (c5).
(Ai) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more (c1) Metallocene catalyst system Propylene polymer.
(C2) MFR (C) (230 ° C., 2.16 kg load) exceeds 0.5 g / 10 min.
(C3) Melting peak temperature Tm (C) is less than 150 ° C.
(C4) The molecular weight distribution (Mw / Mn (C)) obtained by GPC measurement is 1.5 to 3.5.
(C5) When the melting peak temperature of the polypropylene resin (A) is Tm (A) and the melting peak temperature of the polypropylene resin (C) is Tm (C), Tm (A) and Tm (C) are The following relational expression (5) is satisfied.
Tm (A)> Tm (C) (5)

Resin composition (A) containing polypropylene resin (A)
In one embodiment of the present invention, the decorative film includes the layer (I) made of the resin composition (A) including the polypropylene resin (A), so that the film is broken or rampaged during thermoforming. It is possible to suppress the appearance failure due to. Thereby, since a decorative film improves thermoformability, it does not need to contain the thermosetting resin layer which is excellent in thermoformability. The resin composition (A) can be composed of only the polypropylene resin (A) or a blend of the polypropylene resin (A) and another polypropylene resin. When the resin composition (A) is composed of only the polypropylene resin (A), the polypropylene resin (A) satisfies the requirements (Ai) and (A-ii) described later. When the resin composition (A) is composed of a blend of the polypropylene resin (A) and another polypropylene resin, in addition to the resin composition (A), at least the polypropylene resin (A) is a requirement described later ( It is preferable to satisfy A-i) and (A-ii). The blend of the polypropylene resin (A) and other polypropylene resins is not particularly limited, and may be any of pellet and / or powder mixing, melt blending, solution blending, or a combination thereof.

The strain hardening degree of the resin composition (A) containing the polypropylene resin (A) satisfies the following requirement (A-ii), preferably satisfies the requirement (A-ii ′), more preferably the requirement (A- ii ″) is satisfied. By setting the strain hardening degree of the resin composition (A) to a value within the following range, a decorative molded body 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. Be

  Although there is no restriction | limiting in particular about the upper limit of the strain hardening degree of a resin composition (A), Preferably it is 50 or less, More preferably, it is 20 or less. By setting the strain hardening degree to a value within the above range, the appearance of the decorative film can be improved.

The strain hardening degree of a resin composition (A) is calculated | required based on the measurement of the strain hardening property in an extensional viscosity measurement. Regarding the strain hardening property (non-linearity) of elongational viscosity, “Lecture / Rheology” edited by Japanese Society of Rheology, Kobunshi Shuppankai, 1992, pp. 221-222, and in this specification, the strain hardening degree λ is calculated by the method according to the method shown in FIG. η ^* (0.01) is used as the value of elongational viscosity, ηe (3.5) is adopted, and the strain hardening degree λ is defined by the following formula (1).
λ = ηe (3.5) / {3 × η ^* (0.01)} Formula (1)
In the above formula (1), η ^* (0.01) is measured by a dynamic frequency sweep experiment, and is a complex viscosity at a measurement temperature of 180 ° C. and an angular frequency ω = 0.01 rad / s [unit: Pa · s. 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 an extensional viscosity at a measurement temperature of 180 ° C., a strain rate of 1.0 s ⁻¹ , and a strain amount of 3.5, as measured by extensional viscosity measurement.

Normally, data obtained by these viscoelasticity measurements is a collection of numerical values such as elastic modulus and viscosity at discrete frequencies or measurement time intervals. Therefore, when the measurement is carried out with an apparatus and conditions different from those used in the present invention, the complex viscosity η ^* (0.01) at the angular frequency ω = 0.01 and the elongation at the strain 3.5 are not necessarily obtained. There may be cases where the data of viscosity ηe (3.5) does not exist. 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 usual to use a logarithmic scale for stress and time.

  At this time, if the sample has no strain hardening property (non-linearity) in the extensional viscosity, the strain hardening degree λ is about 1 (eg, 0.9 or more and less than 1.1) or less than 1, and the strain hardening property ( As the non-linearity increases, the value of strain hardening λ increases.

  On the other hand, even if it has strain hardening property, if the viscosity is too low, sufficient molding stability cannot be obtained. Therefore, the resin composition (A) containing the polypropylene resin (A) has a certain viscosity. In this specification, MFR (230 ° C., 2.16 kg load) is defined as an index of the viscosity.

In this specification, MFR (230 degreeC, 2.16kg load) of the resin composition (A) containing a polypropylene resin (A) is set to MFR (A). MFR (A) satisfies the following requirement (Ai), preferably satisfies the requirement (Ai ′), more preferably satisfies the requirement (Ai ″). MFR of the resin composition (A) By setting (A) to the following value or less, a decorative molded body having a good appearance can be obtained.
(Ai) MFR (A) is 40 g / 10 min or less (Ai ′) MFR (A) is 20 g / 10 min or less (Ai ″) MFR (A) is 12 g / Less than 10 minutes

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

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

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

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

  As a method for introducing a long chain branched structure into a polypropylene resin, a method using high energy ionizing radiation (Japanese Patent Laid-Open No. 62-121704) or a method using an organic peroxide (Japanese Patent Publication 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 Publication No. 2001-525460) However, even when it is manufactured using any method, the strain hardening degree of the polypropylene resin can be greatly improved.

  The polypropylene resin (A-1) having a long-chain branch structure is not particularly limited as long as it has a long-chain branch structure, but has a comb-type chain structure and has a long-chain branch structure during polymerization. What was obtained by the method of using the formed macromer copolymerization method is preferable. Examples of such a method include, for example, JP-T-2001-525460, JP-A-10-338717, JP-A-2002-523575, JP-A-2009-57542, JP-A-05027353, Examples include the method disclosed in Kaihei 10-338717. In particular, the macromer copolymerization method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 is suitable for the present invention because it does not generate gel and can obtain a long-chain branched polypropylene resin.

Having a long-chain branched structure in polypropylene is defined by a method based on the rheological properties of the resin, a method for calculating a branching index g ′ using the relationship between molecular weight and viscosity, a method using ¹³ C-NMR, and the like. In the present invention, a 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 index regarding the long chain branching structure. “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publics)
hers, 1983), the branching index g ′ is defined 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, branching index g ′ is When a value smaller than 1 is taken, it is determined that a long chain branching structure exists, and the value of the branching index g ′ decreases as the long chain branching structure increases.

The branching index g ′ can be obtained as a function of the absolute molecular weight Mabs by using GPC with a light scatterometer and viscometer in the detector. The method for measuring the branching index g ′ in the present invention is described in detail in JP-A-2015-40213, but is as follows.
[Measuring method]
GPC: Alliance GPCV2000 (Waters)
Detector: Described in the order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (manufactured by Wyatt Technology)
Differential refractometer (RI): attached to GPC Viscometer (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: manufactured by Tosoh Corporation Two GMHHR-H (S) HTs Sample injection part temperature: 140 ° C.
Column temperature: 140 ° C
Detector temperature: 140 ° C for all
Sample concentration: 1 mg / mL
Injection volume (sample loop volume): 0.2175 mL

[analysis method]
When calculating the absolute molecular weight (Mabs) obtained from the multi-angle laser light scattering detector (MALLS), the root mean square radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from the Viscometer, data processing attached to MALLS Calculation is performed using the software ASTRA (version 4.73.04) with reference to the following document.
References:
1. “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000)
4). Macromolecules, 33, 6945-6952 (2000)

  In the decorative film of the present invention, when the polypropylene resin contains a gel, the appearance of the film is deteriorated. Therefore, it is preferable to use a resin composition (A) containing no gel. In particular, as the above-mentioned polypropylene resin (A-1) having a long-chain branched structure, a polypropylene resin having a low gel produced by a method other than the crosslinking method, and a terminal unsaturated bond using a metallocene catalyst having a specific structure Those produced using a method of producing a long-chain branched structure by producing a macromonomer having the following formula and copolymerizing it with propylene are preferred. In particular, those having a branching index g ′ satisfying 0.3 or more and less than 1.0 when the absolute molecular weight Mabs is 1 million described below are preferable, more preferably 0.55 or more and 0.98 or less, and still more preferably 0.8. It is 75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less. When the branching index g ′ is within this range, a highly crosslinked component is not formed, and no gel is formed or very little. Therefore, the layer (I) containing the polypropylene resin (A-1) in particular. Does not deteriorate the appearance when constituting the surface of the product.

[ ¹³ C-NMR]
As described above, ¹³ C-NMR can distinguish between a short-chain branched structure and a long-chain branched structure. Macromol. Chem. Phys. 2003, vol. 204 and 1738 have detailed explanations, the outline of which 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 Structural Formula (1), C _a , C _b , and C _c represent methylene carbon adjacent to the branched carbon, C _br represents the methine carbon at the root of the branched chain, and P ¹ , P ² , and P ³ represent Represents a propylene-based polymer residue.

The propylene polymer residues P ¹ , P ² and P ³ may contain a branched carbon (C _br ) different from C _br described in the structural formula (1) in itself. obtain.

Such a branched structure is identified by ¹³ C-NMR analysis. The assignment of each peak is described in Macromolecules, Vol. 35, no. 10. The description of 2002, pages 3839-3842 can be referred to. That is, a total of three methylene carbons (C _a , C _b , C _c ) are observed, each at 43.9-44.1 ppm, 44.5-44.7 ppm, and 44.7-44.9 ppm, Methine carbon (C _br ) is observed at 31.5-31.7 ppm. Hereinafter, the methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as a branched methine carbon (C _br ).

The three methylene carbons adjacent to the branched methine carbon C _br are characterized by being observed in three non-equivalent diastereotopics.

Such a branched chain assigned by ¹³ C-NMR indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer, and this and a branch having 4 or less carbon atoms are branched. Since the carbon peak positions can be distinguished from each other, in the present invention, the presence or absence of a long-chain branched structure can be determined by confirming the peak of the branched methine carbon.
In addition, about the measuring method of ¹³ C-NMR in this invention, it is as follows.

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

The ¹³ C-NMR spectrum of the polypropylene-based resin (A-1) having a long-chain branched structure preferably has a long-chain branch amount determined from a peak around 44 ppm of 0.01 / 1000 total propylene or more. More preferably 0.03 / 1000 total propylene or more, and still more preferably 0.05 / 1000 total propylene or more. If this value is too large, it may cause appearance defects such as gel and fish eyes. Therefore, it is preferably 1.00 / 1000 total propylene or less, more preferably 0.50 / 1000 total propylene or less, more preferably 0. 30 pieces / 1000 total propylene or less.

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

  The polypropylene 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 propylene monomer.

  The polypropylene resin (A) in the present invention preferably has higher crystallinity from the viewpoints of heat resistance, scratch resistance and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene resin (A) is preferably 140 ° C. or higher, more preferably 145 to 170 ° C., and further preferably 150 to 168 ° C. The polypropylene resin (A) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point.

  The resin composition (A) containing the polypropylene resin (A) includes a plurality of polypropylene resins other than the polypropylene resin (A-1) having a long chain branched structure, additives, fillers, colorants, and the like. A resin component or the like may be included. At this time, the total amount of additives, fillers, colorants, and other resin components is preferably 50% by weight or less with respect to the polypropylene resin composition including them.

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

  Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants. Examples of the neutralizing agent include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, benzotriazoles, and benzophenones.

  Examples of the crystal nucleating agent include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (4 , 6-Di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) aluminum hydroxide salt and organic compound complex, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ (4-Propylphenyl) methylene] -nonitol, sodium salt of rosin and the like.

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

  As a filler, various well-known fillers which can be used for polypropylene resin, such as an inorganic filler and an organic filler, can be mix | blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber. Examples of the organic filler include crosslinked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles.

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

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

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

Decorating film The decorating film of the 1st aspect in this invention contains the layer (I) which consists of a resin composition (A) containing a polypropylene resin (A). That is, the decorative film may be a single layer film composed of the layer (I) or a multilayer film composed of the layer (I) and another layer. The decorative film of the present invention can take various configurations in addition to the layer (I). In addition, the decorative film of the present invention may have a surface with embossing, embossing, printing, sand plasting, scratching, or the like.

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

  The multilayer film can include a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a colored layer, a base material layer, a seal 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) may be any layer constituting the multilayer film.

  As a preferable aspect of the decorative film, when it is a single layer film, it is a film made of the resin composition (A) having an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more.

  As another preferable aspect of the decorative film, in the case of a multilayer film having a two-layer structure, the surface layer that is the surface of the decorative molded body and / or the inner layer to be attached to the molded body is MFR 40 g / 10 min or less, This is a layer made of the resin composition (A) having a strain hardening degree λ of 1.1 or more. More preferably, the inner layer adhered to the molded body is a layer made of the resin composition (A).

  As another preferred embodiment of the decorative film, in the case of a multilayer film having a three-layer structure, the surface layer that is the surface of the decorated molded body, the inner layer to be adhered to the molded body and / or the intermediate between the surface layer and the inner layer The intermediate layer interposed in the layer is a layer made of the resin composition (A) having an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more. More preferably, the inner layer adhered to the molded body is a layer made of the resin composition (A).

  Further, even in the case of a multilayer film having a more complicated layer structure, similarly, from the resin composition (A) in which at least one layer constituting the multilayer film is MFR 40 g / 10 min or less and the strain hardening degree λ is 1.1 or more. Become.

  In the multilayer film, the layer other than the layer (I) made of the resin composition (A) is preferably a layer made of a thermoplastic resin, more preferably a layer made of a polypropylene resin other than the polypropylene resin (A). is there. Each layer is preferably a layer that does not contain a thermosetting resin. Recyclability is improved by using a thermoplastic resin. Furthermore, by using a polypropylene resin other than the polypropylene resin (A), the complication of the layer structure can be suppressed, and the recyclability is further improved.

  As still another preferred embodiment of the decorative film, a surface decorative layer resin provided on the surface opposite to the bonding surface of the layer (I) comprising the resin composition (A) and the resin molded body of the layer. The multilayer film containing surface decoration layer (III) which consists of is mentioned.

  The surface decorating layer resin is preferably made of a thermoplastic resin, more preferably a polypropylene resin (D). By using the polypropylene resin (D), it is possible to suppress complication of the layer structure and a decrease in recyclability. In addition, solvent resistance etc. can be made excellent by using a polypropylene resin (D) for the surface decorating layer of a decorating film. Moreover, by using a polypropylene resin (D) for the surface decoration layer, the surface transferability at the time of production of the decorative film and at the time of thermoforming is improved, and if a mirror roll is used at the time of thermoforming, it has a higher gloss. It can be set as a decorative film.

  In the present invention, the polypropylene resin (D) is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of propylene monomer. The propylene polymer preferably does not contain a polar group-containing monomer unit. The polypropylene resin (D) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance, and the like. Further, from the viewpoint of gloss and transparency (coloring property), a propylene-α-olefin copolymer is preferable.

  The polypropylene resin (D) in the present invention preferably has a strain hardening degree of less than 1.1, more preferably 1.0 or less. By making the strain hardening degree of the polypropylene resin (D) less than 1.1, the appearance of the decorative molded body can be improved. The strain hardening degree of polypropylene resin (D) shall be calculated | required by the method mentioned above.

  The polypropylene resin (D) 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 (D) within the above range, effects such as improvement of the gloss of the decorative film and improvement of the texture transfer property can be obtained, and the required surface shape of the molded product ( A decorative molded body having a good appearance can be obtained with respect to gloss, non-gloss, grain and the like.

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

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

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

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

  The decorative film of the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, and further preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting design properties is improved, the stability at the time of molding is improved, and a better decorative molded body can be obtained. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film below such a value, the time required for heating at the time of thermoforming is shortened so that productivity is improved and it becomes easy to trim unnecessary portions.

  When the decorative film is a single layer film, the ratio of the thickness of the layer (I) to the entire decorative film thickness is 100%. When the decorative film is a multilayer film, the ratio of the thickness of the layer (I) to the entire decorative film thickness is preferably 30% or more, more preferably 50% or more. Although there is no restriction | limiting in particular about an upper limit, Preferably it is less than 100%. If the ratio of the thickness of the layer (I) to the whole decorative film is in the range of the above value, it is possible to avoid the thermoformability of the decorative film becoming insufficient.

In one embodiment of the present invention (second embodiment), as a decorative film, a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer made of a polypropylene resin (B) ( II), the resin composition (A) satisfies the following requirements (Ai) and (A-ii), and the polypropylene resin (B) has MFR (230 ° C., 2.16 kg load). Examples include multilayer films exceeding 2 g / 10 min.
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more

Polypropylene resin (A)
As the polypropylene resin (A), the descriptions of the polypropylene resin (A), the resin composition (A), and the layer (I) can be applied as they are or as appropriate.

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

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

  In order for the decorative film to exhibit such effects, the degree of strain hardening λ of the polypropylene resin (B) is preferably less than 1.1.

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

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

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

  The polypropylene resin (B) may contain additives, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) comprising a propylene polymer and additives, fillers, and other resin components. The total amount of additives, fillers, and other resin components is preferably 95% by weight or less based on the polypropylene resin composition.

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

  Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants. Examples of the neutralizing agent include higher fatty acid salts such as calcium stearate and zinc stearate. Examples of the light stabilizer and the ultraviolet absorber include hindered amines, benzotriazoles, and benzophenones.

  Examples of the crystal nucleating agent include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (4 , 6-Di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) aluminum hydroxide salt and organic compound complex, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ (4-Propylphenyl) methylene] -nonitol, sodium salt of rosin and the like.

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

  As a filler, various well-known fillers which can be used for polypropylene resin, such as an inorganic filler and an organic filler, can be mix | blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber. Examples of the organic filler include crosslinked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles.

  Other resin components include ethylene-α-olefin random copolymers, thermoplastic elastomers based on propylene and / or butene, styrene elastomers, aromatic hydrocarbon resins, and polar functional groups having heteroatoms. The polyolefin resin etc. which have can be illustrated.

The ethylene-α-olefin random copolymer is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene. Of these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferably used.
Commercially available products of such ethylene-α-olefin random copolymers include Kernel Series manufactured by Nippon Polyethylene Co., Ltd., Tuffmer P Series, Tuffmer A Series manufactured by Mitsui Chemicals, Inc., Engage EG Series manufactured by DuPont Dow. Etc.

The thermoplastic elastomer mainly composed of propylene and / or butene includes a thermoplastic elastomer mainly composed of propylene, a thermoplastic elastomer mainly composed of butene, and a thermoplastic composed mainly of components composed of propylene and butene. Elastomers are included. Such a thermoplastic elastomer is preferably a copolymer of propylene and / or butene and α-olefin other than propylene and butene. Specific examples of the α-olefin include ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Examples include hexadecene and 1-eicosene. These α-olefins can be used alone or in combination.
Examples of such thermoplastic elastomers include commercially available products such as Tuffmer XM series, Tuffmer BL series, and Tuffmer PN series manufactured by Mitsui Chemicals, Inc., and VISTAMAXX series manufactured by ExxonMobil Chemical.

Styrene elastomers include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), styrene-ethylene / butylene copolymer elastomer (SEB), and styrene. -Ethylene / propylene copolymer elastomer (SEP), Styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), Styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), Hydrogenated styrene / butadiene elastomer (HSBR) ), Styrene-ethylene / propylene-styrene copolymer elastomer (SEPS), styrene-ethylene / ethylene / propylene-styrene copolymer elastomer (SEEPS), styrene- Tajien butylene - styrene copolymer elastomer (SBBS) or the like can be exemplified, those hydrogenated can be particularly preferably used.
Examples of commercially available products include the Dynalon series manufactured by JSR Corporation, the Clayton G series manufactured by Kraton Polymer Japan Corporation, and the Tuftec series manufactured by Asahi Kasei Corporation.

  As an aromatic hydrocarbon resin, a hydrocarbon resin obtained by polymerizing one or a mixture of two or more dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc. as a main raw material, Examples include hydrogenated coumarone / indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, etc. Specifically, the Arukawa series manufactured by Arakawa Chemical Co., Ltd., the T-REZ series manufactured by Tonen Chemical Co., Ltd., the Quantone series manufactured by Nippon Zeon Co., Ltd., and manufactured by Idemitsu Kosan Co., Ltd. The Imabe series can be mentioned.

Examples of the polar functional group having a hetero atom include an epoxy group, a carbonyl group, an ester group, an ether group, a hydroxy group, a carboxy group or a metal salt thereof, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an acid anhydride group, Examples thereof include an amino group, an imide group, an amide group, a nitrile group, a thiol group, a sulfo group, an isocyanate group, and a halogen group. Specific examples of the polyolefin having such a polar functional group include: acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer Polymer, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer , Ethile / Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / methacrylic acid Butyl copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic Acid metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / Ethyl acrylate / glycidyl methacrylate Copolymers, ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer; and chlorinated polyolefins such as chlorinated polypropylene chlorinated polyethylene. Examples of commercially available products include “Admer” manufactured by Mitsui Chemicals, “Modic” manufactured by Mitsubishi Chemical, and “Umex” manufactured by Sanyo Kasei.

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

Decorative film The decorative film of the second aspect includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (B). The decorative film can take various configurations in addition to the layer (I) and the seal layer (II).
That is, the decorative film may be a two-layer film composed of the layer (I) and the seal layer (II), or a multilayer film composed of the layer (I) and the seal layer (II) and other layers. . The seal layer (II) is stuck along the resin molded body (base). In addition, the decorative film may have a surface with embossing, embossing, printing, sand plasting, scratching, or the like.

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

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

  In the multilayer film, the layer other than the layer (I) and the seal layer (II) is preferably a layer made of a thermoplastic resin, more preferably a layer made of a polypropylene resin. As long as the layers other than the layer (I) and the sealing layer (II) can be distinguished from the layer (I) and the sealing layer (II), the MFR (230 ° C., 2.16 kg load) of the polypropylene resin to be formed is There is no particular limitation. Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication of the layer structure can be suppressed, and the recyclability is further improved.

  When the decorative film is a two-layer film, the layer (I) made of the resin composition (A) containing the polypropylene resin (A) constitutes a surface layer opposite to the surface to be adhered to the resin molded body. The sealing layer (II) made of polypropylene resin (B) constitutes the sealing layer on the surface to be adhered to the resin molded body.

  When the decorative film is a multilayer film of three or more layers, the layer (I) made of the resin composition (A) containing the polypropylene resin (A) and the seal layer (II) made of the polypropylene resin (B) When other layers are interposed between them, the effect of suppressing the surface of the substrate surface from being scratched may be reduced. For this reason, the multilayer film is a layer (I) made of a resin composition (A) containing a sealing layer (II) made of a polypropylene resin (B) / a polypropylene resin (A) from the sticking surface side of the resin molded body. A configuration of other layers (including a plurality of layers) is preferable.

  Another preferred embodiment of the decorative film is a multilayer film including a surface decorative layer (III) made of a surface decorative layer resin on the outermost surface opposite to the surface to be adhered to the resin molded body. The surface decorating layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (D) having an MFR (230 ° C., 2.16 kg load) exceeding 2 g / 10 min. That is, by providing the surface layer of the decorative film with a layer (III) made of a polypropylene resin (D), gloss and texture transfer can be improved without greatly degrading thermoformability. Further, by using the polypropylene resin (D), it is possible to suppress complication of the layer structure and a decrease in recyclability. In addition, solvent resistance etc. can be made excellent by using a polypropylene resin (D) for the surface decorating layer of a decorating film. In addition, the use of polypropylene resin (D) for the surface decoration layer improves the transferability of the surface during the production of the decorative film and during thermoforming. It can be a decorative film.

Polypropylene resin (D)
As the polypropylene resin (D), the description of the polypropylene resin (D) and the surface decorating layer (III) can be applied as it is or appropriately.

  In the second aspect, the polypropylene resin (D) constituting the surface decoration layer (III) may be the same as or different from the polypropylene resin (B) constituting the seal layer (II).

  In the second embodiment, when the polypropylene resin (D) constituting the surface decoration layer (III) is a polypropylene resin composition, the polypropylene resin composition is a propylene resin constituting the seal layer (II). It may be the same as or different from the polypropylene resin composition constituting the resin (B). When both polypropylene resin compositions are the same, the seal layer (II) and the surface decoration layer (III) can be formed by using a feed block or the like with one extruder. Have advantages.

  The decorative film of the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, and further preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting design properties is improved, the stability at the time of molding is improved, and a better decorative molded body can be obtained. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film below such a value, the time required for heating at the time of thermoforming is shortened so that productivity is improved and it becomes easy to trim unnecessary portions.

  In the decorative film of the second aspect, the ratio of the thickness of the layer (I) in the total thickness of the decorative film is preferably 30 to 99%, and the ratio of the seal layer (II) is preferably 1 to 1. 70%. If the ratio of the thickness of the layer (I) to the whole decorative film is in the range of the above value, it is possible to avoid the thermoformability of the decorative film becoming insufficient. Moreover, if the ratio of the thickness of the sealing layer (II) to the whole decorative film is in the range of the above value, it is possible to prevent the scratches on the resin molded body (substrate) from being raised on the surface.

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

In one embodiment (third embodiment) of the present invention, as a decorative film, a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer made of a polypropylene resin (C) ( II), the resin composition (A) satisfies the following requirements (Ai) to (A-ii), and the polypropylene resin (C) satisfies the following requirements (c1) to (c5). A multilayer film is mentioned.
(Ai) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more (c1) Metallocene catalyst system Propylene polymer.
(C2) MFR (C) (230 ° C., 2.16 kg load) exceeds 0.5 g / 10 min.
(C3) Melting peak temperature Tm (C) is less than 150 ° C.
(C4) The molecular weight distribution (Mw / Mn (C)) obtained by GPC measurement is 1.5 to 3.5.
(C5) When the melting peak temperature of the polypropylene resin (A) is Tm (A) and the melting peak temperature of the polypropylene resin (C) is Tm (C), Tm (A) and Tm (C) are The following relational expression (5) is satisfied.
Tm (A)> Tm (C) (5)

Polypropylene resin (A)
As the polypropylene resin (A), the descriptions of the polypropylene resin (A), the resin composition (A), and the layer (I) can be applied as they are or as appropriate.

Polypropylene resin (C)
The decorative film of the third aspect includes a seal layer (II) made of a polypropylene resin (C). The seal layer (II) is a layer in contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. The polypropylene resin (C) is preferably a resin that is easily melted and relaxed. By providing the sealing layer (II), generation of holes, wrinkles, air entrainment, etc. on the surface of the decorative molded body can be suppressed, and scratches on the substrate surface can be made inconspicuous.

  The melt flow rate (230 ° C., 2.16 kg load) MFR (C) of the polypropylene resin (C) needs to exceed 0.5 g / 10 minutes, preferably 1 g / 10 minutes or more, more preferably It is 2 g / 10 minutes or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (C), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

Mw / Mn of the polypropylene resin (C) is 1.5 to 3.5, preferably 2 to 3. The above range is preferable because there are few components having a relatively long relaxation time, and it is easy to relax sufficiently.
Mn and Mw are described in “Basics of Polymer Chemistry” (edited by the Society of Polymer Science, Tokyo Kagaku Dojin, 1978), etc., and are values calculated from molecular weight distribution curves by GPC.

  The melting point (DSC melting peak temperature) of the polypropylene resin (C) is less than 150 ° C, preferably 145 ° C or less, more preferably 140 ° C or less, and further preferably 130 ° C or less. When it is in the above range, sufficient adhesive strength can be exhibited. If Tm (C) is too low, the heat resistance may be reduced and problems may occur in the use of the molded product. Therefore, the temperature is preferably 100 ° C or higher, more preferably 110 ° C or higher.

  The melting peak temperature (Tm (C)) in the DSC measurement of the polypropylene resin (C) needs to be lower than Tm (A), and Tm (A)> Tm (C). Within the above range, the thermoformability is good.

  The polypropylene resin (C) of the present invention is a so-called metallocene catalyst-based propylene polymer polymerized by a metallocene catalyst. Since the metallocene catalyst has a single active site, the propylene-based polymer polymerized by the metallocene catalyst has a narrow molecular weight distribution and crystallinity distribution, and is easy to melt and relax. Can be fused.

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

The polypropylene resin (C) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties, and the propylene-α-olefin copolymer usually has a lower melting point than the propylene homopolymer. Since the crystallization temperature is also lowered, the effect of making the scratches inconspicuous is easier to deform during thermoforming.
As the α-olefin, one or a combination of two or more selected from ethylene and an α-olefin having 3 to 8 carbon atoms can be used.

  The polypropylene resin (C) may contain additives, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) comprising a propylene polymer and additives, fillers, and other resin components. The total amount of additives, fillers, and other resin components is preferably 95% by weight or less based on the polypropylene resin composition.

  When the polypropylene resin (C) is a polypropylene resin composition, the polypropylene resin composition preferably has the characteristics of the polypropylene resin (C).

  As the additive, filler, and other resin components, the additive, filler, and other resin components that may be contained in the polypropylene resin (B) can be used.

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

Decorative film The decorative film of the third aspect includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (C). The decorative film can take various configurations in addition to the sealing layer (II) and the layer (I). That is, even if the decorative film is a two-layer film composed of the sealing layer (II) and the layer (I), it is a multilayer film of three or more layers composed of the sealing layer (II) and the layer (I) and other layers. There may be. The seal layer (I) is adhered along the resin molded body (base). In addition, the decorative film may have a surface with embossing, embossing, printing, sand plasting, scratching, or the like.

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

  In addition to the sealing layer (II) and the layer (I), the multilayer film can be provided between the surface layer, the surface decoration layer, the printing layer, the light shielding layer, the colored layer, the base material layer, the barrier layer, and these layers. Tie layer layer etc. can be included. The layer (I) made of the polypropylene resin (A) may be any layer other than the seal layer among the layers constituting the multilayer film.

  In the multilayer film, the layers other than the seal layer (II) and the layer (I) are preferably layers made of a thermoplastic resin, more preferably a layer made of a polypropylene resin. As long as the layers other than the seal layer (II) and the layer (I) can be distinguished from the seal layer (II) and the layer (I), the MFR (230 ° C., 2.16 kg load) of the polypropylene-based resin to be configured is There is no particular limitation. Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication of the layer structure can be suppressed, and the recyclability is further improved.

  When the decorative film is a two-layer film, the sealing layer (II) made of the polypropylene resin (C) constitutes the sealing layer on the surface to be adhered to the resin molded body, and the polypropylene resin or the polypropylene resin composition The layer (I) comprising (A) constitutes a surface layer opposite to the sticking surface to the resin molded body.

  When the decorative film is a multilayer film of three or more layers, between the sealing layer (II) made of polypropylene resin (C) and the layer (I) made of polypropylene resin or polypropylene resin composition (A) If other layers are present, the effect of suppressing the surface of the substrate surface from being raised may be reduced. For this reason, the multilayer film comprises a sealing layer (II) made of a polypropylene resin (C) / a layer (I) made of a polypropylene resin composition or a polypropylene resin composition (A) from the sticking surface side of the resin molded body / others. The structure of the layer (including a plurality of layers) is preferable.

  Another preferred embodiment of the decorative film is a multilayer film including a surface decorative layer (III) made of a surface decorative layer resin on the outermost surface opposite to the surface to be adhered to the resin molded body. The surface decoration layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (D).

Polypropylene resin (D)
As the polypropylene resin (D), the description of the polypropylene resin (D) and the surface decorating layer (III) can be applied as it is or appropriately.

  The melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) of the polypropylene resin (D) in the present invention preferably satisfies MFR (D)> MFR (A). By setting the value within the above range, a more beautiful surface texture can be expressed.

  In the present invention, the polypropylene resin (D) constituting the surface decoration layer (III) may be the same as or different from the polypropylene resin (C) constituting the seal layer (II).

  At this time, when the polypropylene resin (D) constituting the surface decorating layer (III) is a polypropylene resin composition, the polypropylene resin composition comprises a polypropylene resin (C) constituting the seal layer (II). ) May be the same as or different from the polypropylene-based resin composition.

  The decorative film of the present invention has a thickness of preferably about 20 μm or more, more preferably about 50 μm or more, and further preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting design properties is improved, the stability at the time of molding is improved, and a better decorative molded body can be obtained. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film below such a value, the time required for heating at the time of thermoforming is shortened so that productivity is improved and it becomes easy to trim unnecessary portions.

  In the decorative film of the present invention, the ratio of the thickness of the sealing layer (II) in the total thickness of the decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (I) is preferably 30 to 99%. If the ratio of the thickness of the sealing layer (II) to the entire decorative film is within the above range, sufficient adhesive strength can be exhibited, and scratches on the resin molded body (substrate) are raised on the surface. Can be suppressed. Moreover, if the ratio of the thickness of the layer (I) which occupies for the whole decoration film is the said value range, it can avoid that the thermoformability of a decoration film becomes inadequate.

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

Production of decorative film The decorative film of the present invention can be produced by various known forming methods.
For example, a method of extruding layer (I), a method of coextruding layer (I) and layer (II), a method of coextruding layer (I) and layer (II) and still another layer, On one side of one layer that has been extruded in advance, a heat lamination method in which the other layer is bonded by applying heat and pressure, a dry lamination method in which bonding is performed using an adhesive, and a wet lamination method. An extrusion lamination method or a sand lamination method in which a polypropylene resin is melt-extruded on one surface of one layer may be used. As a device for forming the decorative film, a known coextrusion T-die molding machine or a known laminate molding machine can be used. Among these, from the viewpoint of productivity, a coextrusion T-die molding machine is preferably used.

  As a method of cooling the molten decorative film extruded from the die, a method of bringing the molten decorative film into contact with one cooling roll through the air discharged from the air knife unit or the air chamber unit, There is a method of cooling by pressure bonding with a plurality of cooling rolls.

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

  Furthermore, the surface of the decorative film of the present invention may have a textured shape. Such a decorative film is a method in which a resin in a molten state extruded from a die is directly pressure-bonded with a roll having a concavo-convex shape and a smooth roll to transfer the concavo-convex shape to a surface, Can be manufactured by a method such as surface transfer by pressing with a heated roll and a smooth cooling roll. Examples of the wrinkle shape include satin finish, animal skin tone, hairline tone, and carbon tone.

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

Injection Foamed Resin Molded Body The injection foamed resin molded body (decoration target) decorated in the present invention is a resin molded body that includes a polypropylene resin (A) and has an expansion ratio of 1.1 to 10 times. This is a decorative molded body characterized by that.

Polypropylene resin (A)
The polypropylene resin composition (a) used in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, a propylene block copolymer, a polypropylene resin having a branched structure, or the like. A polypropylene resin selected from various known types is included as a main component, and the following requirements (i) to (ii) are satisfied.
(I): Melting peak temperature Tm is 110 ° C. or higher.
(Ii): MFR (230 ° C., 2.16 kg load) is 0.01 g / 10 min or more and 300 g / 10 min or less.

  The melting peak temperature Tm of the polypropylene resin (A) is 110 ° C. or higher, preferably 125 ° C. or higher, more preferably 130 ° C. or higher, because problems arise in practical use due to a decrease in heat resistance and a decrease in rigidity. It is. The melting peak temperature Tm can be controlled by adjusting the catalyst used and the content of ethylene copolymerized with propylene.

  The MFR (230 ° C., 2.16 kg load) of the polypropylene resin (a) is 0.01 g / 10 min or more and 300 g / 10 min or less, preferably 0.5 to 200 g / 10 min, more preferably 1 to 1 g. 150 g / 10 min, more preferably 5 to 100 g / 10 min. Within the above range, it is possible to suppress the deterioration of the molded appearance that occurs during the production of the molded article, such as a decrease in weld appearance.

  Polypropylene resins are mainly composed of various known propylene monomers such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymers, propylene block copolymers, and polypropylene resins having a branched structure. You can choose the right type.

Polypropylene resin (A)
The polypropylene tree (a) of the present invention is a thermoplastic elastomer, a modified polyolefin, a molecular weight depressant, a lubricant, an antioxidant, a neutralizing agent, light as long as it does not significantly impair the effects of the present invention as an optional additive component. Various optional additives such as a stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antistatic agent, a metal deactivator, and a filler can be contained.
Two or more optional additives may be used in combination. In the present invention, the total amount of optional added components is preferably 50% by weight or less based on the polypropylene resin composition, and is appropriately selected according to the purpose.

  When the polypropylene resin (a) is a polypropylene resin composition, the polypropylene resin composition preferably has the characteristics of the polypropylene resin (a). That is, the melting peak temperature Tm of the polypropylene resin composition is 110 ° C. or more, and the MFR (230 ° C., 2.16 kg load) of the polypropylene resin composition is 0.01 g / 10 min or more and 300 g / 10 min or less. .

The thermoplastic elastomer represents a thermoplastic elastomer selected from olefin-based elastomers and styrene-based elastomers.
Examples of the olefin elastomer include ethylene / propylene copolymer elastomer (EPR), ethylene / butene copolymer elastomer (EBR), ethylene / hexene copolymer elastomer (EHR), and ethylene / octene copolymer elastomer (EOR). ) And other ethylene / α-olefin copolymer elastomers; ethylene / propylene / ethylidene norbornene copolymers, ethylene / propylene / butadiene copolymers, ethylene / propylene / isoprene copolymers, etc. Examples thereof include an original copolymer elastomer.
Examples of the styrene elastomer include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), styrene-ethylene / butylene copolymer elastomer ( SEB), styrene-ethylene / propylene copolymer elastomer (SEP), styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene / Butadiene elastomer (HSBR), Styrene-ethylene / propylene-styrene copolymer elastomer (SEPS), Styrene-ethylene / ethylene / propylene-styrene copolymer elastomer (SEEPS) , Styrene - butadiene butylene - styrene copolymer elastomer (SBBS) can be exemplified.
Furthermore, hydrogenated polymer-based elastomers such as ethylene-ethylene / butylene-ethylene copolymer elastomer (CEBC) can also be mentioned.
In particular, when at least one selected from the group consisting of an ethylene / octene copolymer elastomer (EOR), an ethylene / butene copolymer elastomer (EBR) and an ethylene / propylene copolymer elastomer is used, a resin composition and a molded article thereof Are preferable from the viewpoints of excellent performance such as low shrinkage, tactile sensation and impact strength, and excellent economic efficiency.
In addition, 2 or more types of thermoplastic elastomers can also be used together.

The modified polyolefin is an acid-modified polyolefin and / or a hydroxy-modified polyolefin. By improving the interfacial strength between the polypropylene resin and the filler, the physical properties such as rigidity and impact strength are improved in the resin composition and the molded product thereof. This is effective.
There is no restriction | limiting in particular as acid-modified polyolefin, A conventionally well-known thing can be used. Examples of the acid-modified polyolefin include polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene compound copolymer (EPDM, etc.), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber. For example, a polyolefin obtained by graft copolymerization with an unsaturated carboxylic acid such as maleic acid or maleic anhydride is modified. This graft copolymerization is performed, for example, by reacting the polyolefin with an unsaturated carboxylic acid in a suitable solvent using a radical generator such as benzoyl peroxide. Moreover, the component of unsaturated carboxylic acid or its derivative can also be introduce | transduced in a polymer chain by random or block copolymerization with the monomer for polyolefin.
Further, the hydroxy-modified polyolefin is a modified polyolefin containing a hydroxyl group. The modified polyolefin may have a hydroxyl group at an appropriate site, for example, at the end of the main chain or at the side chain. Examples of the olefin resin constituting the hydroxy-modified polyolefin include, for example, homo- or copolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene, α -A copolymer of an olefin and a copolymerizable monomer can be exemplified. As hydroxy-modified polyolefin, hydroxy-modified polyethylene (for example, low density, medium density or high density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, ethylene- (meth) acrylate copolymer, ethylene-vinyl acetate copolymer). Polymers), hydroxy-modified polypropylene (for example, polypropylene homopolymers such as isotactic polypropylene, random copolymers of propylene and α-olefins (for example, ethylene, butene, hexane, etc.), propylene-α-olefin block copolymers Polymer), hydroxy-modified poly (4-methylpentene-1), and the like.

The molecular weight depressant is effective for imparting and improving moldability (fluidity) and the like.
As the molecular weight depressant, for example, various organic peroxides and so-called decomposition (oxidation) accelerators can be used, and organic peroxides are preferable.
Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di- (benzoylperoxide). Oxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexa Noate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butyl Luperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) Cyclohexane, 2,2-bis-t-butylperoxybutane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1 , 1,3,3-tetra-methylbutyl hydroperoxide and 2,5-di-methyl-2,5-di- (hydroperoxy) hexane selected from the group consisting of one or more Can be mentioned.

The lubricant is effective for imparting and improving the releasability during molding of the resin composition and its molded body.
Examples of the lubricant include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide, butyl stearate, and silicone oil.

Antioxidants are effective in preventing quality deterioration of the resin composition and its molded product.
Examples of the antioxidant include a phenol-based, phosphorus-based and sulfur-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, and benzophenones.

  Examples of the crystal nucleating agent include amide nucleating agents such as aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, and metal salts of rosin. Among these crystal nucleating agents, pt-butyl aluminum benzoate, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, 2,2′-methylenebisphosphate (4 , 6-Di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho Syn-6-oxide) aluminum hydroxide salt and organic compound complex, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ (4-Propylphenyl) methylene] -nonitol, sodium salt of rosin and the like.

  Examples of the antistatic agent include fatty acid partial esters such as glycerin fatty acid monoester. Examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

  As a filler, various well-known fillers which can be used for polypropylene resin, such as an inorganic filler and an organic filler, can be mix | blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber. Examples of the organic filler include crosslinked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles.

Further, the polypropylene resin composition of the present invention contains a polyolefin resin other than the polypropylene resin (a), a thermoplastic resin such as a polyamide resin and a polyester resin, etc. within a range that does not significantly impair the effects of the present invention. Can do.
As these optional components, various products are commercially available from many companies, and desired products can be obtained and used according to the purpose.

Production of Polypropylene Resin (A) The polypropylene resin (a) of the present invention can be produced through a kneading step in which optional components are added as necessary, blended by a conventionally known method, and melt kneaded. it can.

  Mixing is usually performed using a mixing device such as a tumbler, V blender, or ribbon blender, and melt kneading is usually performed by a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, stirring. Using a kneading machine such as a granulator (semi) melt kneading and granulating. When manufacturing by (semi) melt-kneading and granulating, the compound of the above components may be kneaded at the same time, and each component may be divided and kneaded to improve performance. You can also.

Manufacture of a molded object The injection-foamed resin-molded article of the present invention can be obtained by subjecting a polypropylene resin (A) to injection foam molding. Known injection molding conditions and known injection molding apparatuses can be applied to the injection foam molding. For example, the step of injecting the melt of the resin composition into the cavity of the mold in a closed state so that the volume of the cavity is smaller than the total volume of the melt of the resin composition, In the middle and / or after the process, the mold is opened to the volume of the final molded body, and a mold opening injection foaming process including foaming with a gas generated by thermal decomposition of a chemical foaming agent or a gas such as nitrogen or carbon dioxide It is possible to use a method (so-called core back method) or a short shot injection foaming method (short shot method) in which foaming is performed by injecting a reduced amount of resin into the mold with respect to the mold volume into which the resin is injected. . Among these, in the physical foaming in which the appearance of silver streak is remarkably deteriorated, it is preferably molded by a short shot method.

Foaming agent In the production of the foamed molded article in the present invention, it is preferable to blend a foaming agent.
As the foaming agent, a known foaming agent used for plastics, rubber, and the like can be used without any problem. Conventional foaming agents such as physical foaming agents, chemical foaming agents (degradable foaming agents), and microcapsules containing a thermal expansion agent can be used.

Examples of physical foaming agents include aliphatic hydrocarbons such as propane, butane, pentane, and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, chlorodifluoromethane, difluoromethane, trifluoromethane, trichlorofluoromethane, and dichlorodifluoromethane. , Chloromethane, dichloromethane, chloroethane, dichlorotrifluoroethane, dichlorofluoroethane, chlorodifluoroethane, dichloropentafluoroethane, tetrafluoroethane, difluoroethane, pentafluoroethane, trifluoroethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloro One kind of halogenated hydrocarbons such as pentafluoroethane and perfluorocyclobutane, and inorganic gases such as water, carbon dioxide and nitrogen A combination of two or more thereof.
Of these, aliphatic hydrocarbons such as propane, butane, and pentane and carbon dioxide are preferable because they are inexpensive and have high solubility in the polypropylene resin (a). Carbon dioxide gas is in a supercritical state at 7.4 MPa or higher and 31 ° C. or higher in relative pressure to atmospheric pressure, and is in a state excellent in diffusion and solubility in polypropylene resin.

  In obtaining a polypropylene-based foam using a physical foaming agent, an air-conditioning agent can be used as necessary. Examples of the air conditioner include inorganic decomposable foaming agents such as ammonium carbonate, sodium bicarbonate, ammonium bicarbonate and ammonium nitrite, azo compounds such as azodicarbonamide, azobisisobutyronitrile and diazoaminobenzene, N, N′- Nitroso compounds such as dinitrosopentanemethylenetetramine and N, N'-dimethyl-N, N'-dinitrosotephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p, p'-oxybisbenzenesulfonyl semicarbazide, p- Degradable foaming agents such as toluenesulfonyl semicarbazide, trihydrazinotriazine, barium azodicarboxylate, inorganic powders such as talc and silica, acid salts such as polyvalent carboxylic acids, reaction of polyvalent carboxylic acids with sodium carbonate or sodium bicarbonate Such as mixtures , It can also be used singly or in combination.

  When a polypropylene foam is obtained with a chemical foaming agent (decomposable foaming agent), for example, a mixture of organic acid such as sodium bicarbonate and citric acid, azodicarbonamide, Azo foaming agents such as barium azodicarboxylate, nitroso foaming agents such as N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide, p, p′- Examples thereof include sulfohydrazide-based blowing agents such as oxybisbenzenesulfonyl hydrazide and p-toluenesulfonyl semicarbazide, and trihydrazinotriazine.

  The blending amount of the foaming agent varies depending on the foaming ratio of the final product, the type of foaming agent and the molding temperature at the time of molding, but is 0.01 to 20 parts by weight, preferably 0 with respect to 100 parts by weight of the polypropylene resin (a). 0.05 to 15 parts by weight, which can be appropriately selected depending on the intended expansion ratio.

Mixing of foaming agent Mixing of the polypropylene resin (A) and the foaming agent is performed using a general mixing device such as a tumbler, V blender, ribbon blender, etc., and is put into a hopper of an injection molding machine. However, when a physical foaming agent is used, it is necessary to use a system that press-fits directly into the cylinder of the injection molding machine.

Decorative molded body The molded body (decoration target) decorated in the present invention is an injection foam molded body made of a polypropylene resin composition, and is a nonpolar resin, which is hardly adhesive, but in the present invention. The decorative film is made of a layer (I) made of a resin composition (A) containing a polypropylene resin (A), a seal layer (II) made of a polypropylene resin (B), or a polypropylene resin (C). By including the sealing layer (II), the decorative object made of polypropylene resin and the decorative film are adhered to each other, thereby exhibiting very high adhesive strength, and silver streaks generated on the surface of the decorative object Since the decorative film covers appearance defects such as flow marks and avatars, the surface of the decorative molded body becomes smooth, so the appearance of the decorative molded body is improved.

  The decorative molded body in which the decorative film of the present invention is bonded to various injection foam molded bodies formed in a three-dimensional shape made of polypropylene resin is lightweight, heat insulating, sound insulating, cushioning, energy absorbing, etc. Excellent in surface appearance such as surface gloss such as surface gloss and touch, and VOC contained in paint and adhesive is greatly reduced, so it is suitable for automobile parts, home appliances, vehicles (railways, etc.), building materials, daily necessities, etc. Can be used for

  Drawing 1 (a)-(c) is an explanatory view which illustrates typically a section of an embodiment of a decoration fabrication object by which a decoration film was stuck on a resin fabrication object. 1 (a) to 1 (c), the arrangement of the layer (I) is specified and described for easy understanding, but the layer structure of the decorative molded body is interpreted as being limited to these examples. is not. In the present specification, reference numeral 1 in the drawings denotes a decorative film, reference numeral 2 denotes a layer (I), reference numeral 3 denotes a sealing layer (II), reference numeral 4 denotes a surface decoration layer (III), and reference numeral 5 denotes a resin molded body. . FIG. 1A is an example in which the decorative film is made of a single layer film, and the layer (I) made of the resin composition (A) is adhered to the resin molded body 5. FIGS. 1B and 1C are examples in which the decorative film is a multilayer film. The decorative film in FIG. 1 (b) is composed of a layer (I) and a seal layer (II). The seal layer (II) is adhered to the surface of the resin molded body 5, and the surface decoration is applied on the layer (I). Layer (III) is laminated. The decorative film in FIG. 1C is composed of a layer (I), a seal layer (II), and a surface decorative layer (III), and the seal layer (II) is adhered to the surface of the resin molded body 5, and the seal layer The layer (I) and the surface decoration layer (III) are laminated in this order on (II).

Manufacturing method of decorative molded body The manufacturing method of the decorative molded body of the present invention includes the step of preparing the above-described decorative film, the step of preparing an injection foamed resin molded body, and the injection foaming in a chamber box capable of decompression. A step of setting the resin molded body and the decorative film (when there is a seal layer, a step of setting the injection foamed resin molded body and the seal layer of the decorative film to face each other), in the chamber box A step of heating and softening the decorative film, a step of pressing the decorative film against the injection-foamed resin molded article, and a step of returning or pressurizing the reduced-pressure chamber box to atmospheric pressure. It is characterized by.

  Three-dimensional decorative thermoforming sets the object to be decorated and a decorative film in a chamber box that can be decompressed, heat-softens the film in a state where the inside of the chamber box is decompressed, and presses the film against the object to be decorated, The chamber box has a basic process of returning the atmospheric pressure to atmospheric pressure or applying pressure to the surface of the object to be decorated, and applying the film under reduced pressure. As a result, it is possible to obtain a beautiful decorative molded body free from air accumulation. In the production method of the present invention, any known technique can be used as long as the apparatus and conditions are suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the object to be decorated, the decorative film, the mechanism for pressing it, the device for heating the decorative film, etc. A plurality of divided parts may be used.
Moreover, the mechanism for pressing a decorating object and a decorating film may be any type that moves the decorating object, moves the decorating film, or moves both.

More specifically, typical molding methods are exemplified below.
Hereinafter, a method for sticking a decorative film to a decoration object using a three-dimensional decorative thermoforming machine will be exemplarily described with reference to the drawings.

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

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

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

  As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 opened, the decoration object 5 is placed on the table 14 in the lower chamber box 12, and the table 14 is lowered. Subsequently, when the decorative film 1 has the sealing layer (II) on the jig 13 for fixing the film between the upper and lower chamber boxes 11, 12, the sealing layer (II) is set so as to face the substrate.

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

After the decoration film 1 is heated and softened, as shown in FIG. 5, the table 14 in the lower chamber box 12 is raised while the inside of the upper and lower chamber boxes 11 and 12 is kept in a vacuum suction state. The decorative film 1 is pressed against the decoration target 5 to cover the decoration target 5. Further, as shown in FIG. 6, the decorative film 1 is brought into close contact with the decoration object 5 with a larger force by opening the upper chamber box 11 under atmospheric pressure or supplying compressed air from a pressurized air tank.
Subsequently, the interiors of the upper and lower chamber boxes 11 and 12 are opened to atmospheric pressure, and the decorative molded body 6 is taken out from the lower chamber box 12. Finally, as illustrated in FIG. 7, an unnecessary edge of the decorative film 1 around the decorative molded body 6 is trimmed.

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

Moreover, in the two chamber boxes 11 and 12 divided | segmented up and down by the decorating film 1, the chamber box pressure in the side by which the decorating object 5 and the decorating film 1 are affixed should just be this range, and up and down The draw-down of the decorative film 1 can also be suppressed by changing the pressure of the chamber boxes 11 and 12.
At this time, a film made of a general polypropylene resin may be greatly deformed or broken by a slight pressure fluctuation due to a decrease in viscosity during heating.
The decorative film 1 of the present invention is not only difficult to draw down, but also has resistance to film deformation due to pressure fluctuations.

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

In the present invention, in order to attach the polypropylene decorative film 1 to the decorative object 5 made of polypropylene resin, it is necessary that the surface of the resin molded body 5 and the decorative film 1 are sufficiently softened or melted.
Therefore, the heater temperature needs to be higher than the melting temperature of the polypropylene resin constituting the decorating object 5 and the polypropylene resin constituting the decorating film 1. The heater temperature is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher.

  The higher the heater temperature, the shorter the time required for heating. However, until the interior of the decorative film 1 (or the surface opposite to the heater when the heater is installed only on one side) is sufficiently heated, If the temperature of the resin is too high, the moldability is deteriorated and the resin is thermally deteriorated. Therefore, the heater temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, most preferably 400 ° C. It is as follows.

Although an appropriate heating time varies depending on the heater temperature, it is preferable that at least the polypropylene decorative film is heated and heated until the rebound called spring back starts.
In other words, the decorative film heated by the heater expands by heating from the solid state and sags once with the melting of the crystal. However, after the spring back, the film is completely melted and the molecules are sufficiently relaxed, so that sufficient adhesion strength can be obtained.
On the other hand, if the heating time is too long, the film hangs down due to its own weight or deforms due to the pressure difference between the upper and lower chamber boxes. Therefore, it is preferable that the heating time is less than 120 seconds after the end of the springback.

  In the case of decorating a complex shaped article having irregularities or achieving higher adhesion, it is preferable to supply compressed air when the decorative film is brought into close contact with the substrate. The pressure in the upper chamber box when compressed air is introduced is 150 kPa or more, preferably 200 kPa or more, more preferably 250 kPa or more. Although there is no particular limitation on the upper limit, 450 kPa or less, preferably 400 kPa or less is preferable because the device may be damaged if the pressure is too high.

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

1. Measurement method of various physical properties (i) MFR
In accordance with ISO 1133: 1997 Conditions M, measurement was performed at 230 ° C. and a load of 2.16 kg. The unit is g / 10 minutes.
(Ii) Degree of strain hardening λ
The method of obtaining the strain hardening degree λ was performed by the method described above. At this time, η ^* (0.01) used as the shear viscosity value and ηe (3.5) used as the extension viscosity value were measured by the following methods. In addition, the sample used for the measurement at this time was formed into a flat plate 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. 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 conducted using ARES manufactured by Rheometric Scientific. A parallel disk having a diameter of 25 mm was used for the measurement geometry. Using the apparatus control software TA Orchestrator, the measurement was performed in the measurement mode Dynamic Frequency Sweep Test. As a sample, a press-molded body 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 so as to be equally spaced on a logarithmic scale between 0.01 and 100 rad / s.
The complex viscosity η ^* (0.01) [unit: Pa · s] at ω = 0.01 rad / s is adopted as an index indicating the viscosity of the sample at a low shear rate. The complex viscosity η ^* is calculated from η * = G ^* / ω from the complex elastic modulus G ^* [unit: Pa] and ω.
(Ii-2) Elongation viscosity ηe (3.5)
The extensional viscosity measurement was performed using an Extended Viscosity Fixture manufactured by TA Instruments Co., Ltd. on an ARES measuring jig manufactured by Rheometric Scientific. Measurement was carried out in the measurement mode “Extensional Visibility Test” using the apparatus control software TA Orchestrator. As a 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.
Sampling Mode: log
Points Per Zone: 200
Solid Density: 0.9
Melt Density: 0.8
Prestrate Rate: 0.05s-1
Relaxation after Prestitch: 30 sec
Under these conditions, data is collected for at least 3.7 seconds from the start of measurement. The software provides time dependent data for elongational viscosity. The value of the extensional viscosity at the time of 3.5 sec (that is, the amount of strain of 3.5) of the obtained extensional viscosity curve was ηe (3.5) [unit: Pa · s].

(Iii) Melting peak temperature Tm:
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 again at a temperature rising rate of 10 ° C./min. The temperature at the top of the endothermic peak at the time of measurement was defined as the melting peak temperature Tm. The unit is ° C.

(Iv) GPC measurement GPC measurement was performed under the following apparatus and conditions, and Mw / Mn was calculated.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
-Mobile phase solvent: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL, and create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

2. Materials used (1) Polypropylene resin The following polypropylene resin was used.
(A-1-1): Propylene homopolymer having a long chain branch produced by a macromer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX (registered trademark) MFX3”, MFR = 9 g / 10 min Strain hardening degree λ = 7.8, Tm = 154 ° C., branching index g ′ = 0.85 when absolute molecular weight Mabs is 1 million, confirmed to have long chain branched structure by ¹³ C-NMR measurement.
(A-1-2): Propylene homopolymer having a long chain branch produced by the macromer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX (registered trademark) MFX8”, MFR = 1 g / 10 min Strain hardening degree λ = 9.7, Tm = 154 ° C., branching index g ′ = 0.89 when absolute molecular weight Mabs is 1 million, confirmed to have long chain branched structure by ¹³ C-NMR measurement.
(A-2-1): normal propylene homopolymer (without long chain branching) (MFR = 10 g / 10 min, Tm = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered) Trademark) FA3KM "

(B-1): Propylene-α-olefin copolymer (MFR = 5 g / 10 min, Tm = 127 ° C., Mw / Mn = 4.0) by Ziegler-Natta catalyst, manufactured by Nippon Polypro Co., Ltd. Name “NOVATEC (registered trademark) FX4G”
(B-2): Propylene-α-olefin copolymer (MFR = 7 g / 10 min, Tm = 146 ° C., Mw / Mn = 4.3) by Ziegler-Natta catalyst, manufactured by Nippon Polypro Co., Ltd. Name "NOVATEC (registered trademark) FW3GT"
(C-1): Propylene-α-olefin copolymer (MFR = 7 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.5) by metallocene catalyst, product name “Nippon Polypro Co., Ltd.” Wintech (registered trademark) WFX4M "
(C-2): Propylene-α-olefin copolymer by metallocene catalyst (MFR = 25 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.4), manufactured by Nippon Polypro Co., Ltd., trade name “ Wintech (registered trademark) WSX03 "
(C-3): Propylene-α-olefin copolymer by metallocene catalyst (MFR = 7 g / 10 min, Tm = 135 ° C., Mw / Mn = 2.3), manufactured by Nippon Polypro Co., Ltd., trade name “ Wintech (registered trademark) WFW4M "
(C-4): Propylene-α-olefin copolymer with metallocene catalyst (MFR = 3.5 g / 10 min, Tm = 143 ° C., Mw / Mn = 2.8), manufactured by Nippon Polypro Co., Ltd. Name "Wintech (registered trademark) WFW5T"

(D-1): Polypropylene resin (A-2-1) 100 parts by weight of polypropylene blended with 0.4 part by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Ltd.) Resin composition (MFR = 10 g / 10 min, Tm = 164 ° C.)
(D-2): A polypropylene resin composition obtained by blending 100 parts by weight of a polypropylene resin (C-1) with 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.). (MFR = 7 g / 10 min, Tm = 127 ° C.)
(D-3): A polypropylene resin composition (MFR = 10 g) obtained by blending 100 parts by weight of a polypropylene resin (A-2-1) with 4 parts by weight of a silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyocolor Co., Ltd.). / 10 minutes, Tm = 161 ° C.)

(A-1): Propylene homopolymer (MFR = 40 g / 10 minutes, Tm = 158 ° C.) by Ziegler-Natta catalyst, manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) MA04A”
(A-2): The grade of the following composition of the brand name "Novatec (trademark)" by Nippon Polypro Co., Ltd. was used.
This is a propylene / ethylene block copolymer polymerized using a Ziegler-Natta catalyst. The propylene / ethylene block copolymer as a whole has a melting peak temperature Tm of 161 ° C. and an MFR (230 ° C., 2.16 kg load) of 28 g / 10 minutes, content of propylene homopolymer portion with respect to the entire propylene / ethylene copolymer is 73% by weight, content of propylene / ethylene copolymer portion is 27% by weight, ethylene content of propylene / ethylene copolymer portion 37% by weight.
(A-3) Polypropylene resin (A-2) 60% by weight, 20% by weight of EBR (Tafmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Talc) Polypropylene resin composition (A-4) blended with 20% by weight of talc P-6 (average particle size 4.0 μm) manufactured by Co., Ltd .: Polypropylene resin (A-1) 80% by mass with glass fiber ( A polypropylene resin composition blended by 20% by mass of Nippon Electric Glass Co., Ltd. glass fiber, “T480H”, chopped strand, fiber diameter 7 μm, fiber length 6 mm)

(2) Foaming agent Chemical foaming agent master batch (manufactured by Eiwa Kasei Co., Ltd., Polyslen EE25C, foaming agent concentration 20%, amount of generated gas 75-90 ml / 2.5 g (220 ° C constant temperature, 20 minutes)), sodium bicarbonate Citric acid based, low density polyethylene base

(4) Other resins The following resins were used.
(E-1): Ethylene-butene random copolymer (MFR = 6.8 g / 10 min, Tm = 66 ° C., density = 0.85 g / cm ³ , ethylene content = 84 wt%): Mitsui Chemicals, Inc. Product name "Toughmer A4085S"
(E-2): ethylene-octene random copolymer (MFR = 2.0 g / 10 min, Tm = 77 ° C., density = 0.85 g / cm ³ , ethylene content = 85 wt%): manufactured by DuPont Dow Product name “Engage EG8003”
(E-3): ethylene-hexene random copolymer (MFR = 3.5 g / 10 min, Tm = 60 ° C., density = 0.880 g / cm ³ , ethylene content = 76 wt%): Nippon Polyethylene Co., Ltd. Product name "Kernel KS340T"
(E-4): Propylene-butene random copolymer (MFR = 7.0 g / 10 min, Tm = 75 ° C., density = 0.85 g / cm ³ , propylene content = 69 wt%, butene content = 31 wt% ): Made by Mitsui Chemicals, Inc., trade name “Toughmer XM7070”
(E-5): Butene homopolymer (MFR = 5.0 g / 10 min, Tm = 125 ° C., density = 0.915 g / cm ³ ): manufactured by Mitsui Chemicals, Inc., trade name “Toughmer BL4000”
(E-6): Propylene-ethylene-butene random copolymer (MFR = 6.0 g / 10 min, Tm = 160 ° C., density = 0.868 g / cm ³ , propylene content = 84 wt%, ethylene content = 9 % By weight, butene content = 7% by weight): manufactured by Mitsui Chemicals, Inc., trade name “Toughmer PN2060”
(E-7): Propylene-ethylene random copolymer (MFR = 8.0 g / 10 min, Tm = 61 ° C., density = 0.871 g / cm ³ , propylene content = 89 wt%, ethylene content = 11 wt% ): Product name “VISTAMAX3000” manufactured by ExxonMobil Chemical Co., Ltd.
(E-8): Styrenic elastomer (SEBS): manufactured by Kraton Polymer Japan, trade name “Clayton G1645”
(E-9): Hydrogenated styrene elastomer (HSBR): manufactured by JSR Corporation, trade name “Dynalon 1320P”
(E-10): Alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name “Arcon-P125”
(E-11): Maleic anhydride-modified polyolefin (MFR = 7.0 g / 10 min): manufactured by Mitsubishi Chemical Corporation, trade name “Modic AP (registered trademark) F534A”

3. Production of resin molded body (substrate) (Production of resin molded body (substrate) (A-1))
(1) Production of injection-foamed molded article Using the polypropylene resin (A-1), mold-opening injection-foam molding was performed by the following method to obtain an injection-foamed resin molded body (substrate) (A-1).
FANUC "α-300" as an injection molding machine, and as a mold for injection molding, the dimensions of a molded product part for molding a foam molded body are width x height = 400 mm x 200 mm, variable thickness flat plate shape Using a material having a mold cavity clearance (T0) of 2.0 mm this time, foam molding was performed by the method described below.
In the melting step (A), 3 parts by weight of the chemical foaming agent masterbatch and black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.) are added to 100 parts by weight of the polypropylene resin (A-1). 4 parts by weight was added and the cylinder temperature was set to 200 ° C. and melted.
The mold used in the injection process (B) is composed of a fixed mold and a movable mold capable of moving forward and backward, and an initial mold cavity clearance (T0) is set to 2 mm, and obtained from the melting process (A). The molten or semi-molten polypropylene resin composition (temperature is 200 ° C. of the cylinder temperature of the melting step (A)) was injected and filled into the mold cavity. The filling time was 1.0 to 1.5 seconds.
After 1 ± 0.5 seconds have elapsed after filling in the injection process (B), the mold cavity clearance (T1) corresponding to the shape position of the foam molded body that can obtain the movable mold in the foaming process (C) is up to 4 mm. Retreated. Thereafter, the product filled in the cavity of the mold cavity was cooled and solidified (expansion temperature of mold cavity 40 ° C., cooling time 20 seconds) by the expansion pressure of the foaming agent.
The obtained foamed molded article was held for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH.

(2) Manufacture of unfoamed molded body In the production of the injection foam molded body of (1), the foaming step (C) is not performed, and the product is cooled and solidified at a mold cavity set temperature of 40 ° C. and a cooling set time of 20 seconds. I let you.
The obtained unfoamed molded article was maintained for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH.

(3) Manufacture of resin molded body (base body) The injection foam molded body obtained in the manufacture of the injection foam molded body of (1) is cut into a width x height = 120 mm x 120 mm using a diamond saw, and the resin A molded body (substrate) was obtained.

-Physical property evaluation (1) Density measurement The center part of an injection-foamed molded product and an unfoamed molded product is cut into a width x height = 5 cm x 2 cm, and an alpha mirage hydrometer MD-300S (a hydrometer based on Archimedes' principle) The medium was water), the weights in air and water were measured, and the volume of both molded bodies was obtained from both to calculate the density (automatic calculation).
(2) Thickness measurement The center part of the injection-foamed molded article and the unfoamed molded article was cut into a width × height = 2 cm × 2 cm, and the thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(3) Measurement of expansion ratio (3-1) Evaluation of expansion ratio using thickness The expansion ratio (thickness) was defined by the formula (1).
Foaming ratio (thickness) = thickness of injection-foamed molded article / thickness of unfoamed molded article (Formula 1)
(3-2) Evaluation of foaming ratio using density The foaming ratio (density) was defined by the formula (2).
Foaming ratio (density) = density of unfoamed molded article / density of injection foam molded article (Formula 2)
In the injection foam molding, even if the foaming magnification (thickness) by the evaluation method of (3-1) is a molded body having the same value, it depends on the resin temperature, mold temperature, injection speed, etc. at the time of injection foam molding. Since the thickness of the non-foamed layer (skin layer) formed on both surface sides of the molded body may vary, the value may differ from the foaming ratio (density). In the present invention, the expansion ratio (thickness) is used as the expansion ratio.
Table 1 shows the evaluation results of physical properties of the obtained resin molded body and the like. The thickness of the injection-foamed molded product matches the cavity clearance (T1) in the foaming step (C), and the thickness of the unfoamed molded product matches the cavity clearance (T0) in the injection step (B). It was.

(Production of resin molded body (substrate) (A-2) to (A-4))
An injection foamed molded article, an unfoamed molded article, and a resin molded article (substrate) using the polypropylene resins (A-2) to (A-4) in the same manner as in the production of the resin molded product (substrate) (A-1). )
Table 1 shows the evaluation results of physical properties of the obtained resin molded body and the like.

Example 1
-Production of decorative film A T-die having a lip opening of 0.8 mm and a die width of 400 mm, to which an extruder 1 having a diameter of 40 mm (diameter) was connected, was used. 4 parts by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.) is blended with 100 parts by weight of the polypropylene resin (A-1-1), and the mixture is charged into the extruder-1 to obtain a resin temperature. Melt extrusion was carried out at 240 ° C. and a discharge rate of 12 kg / h. The melt-extruded film was cooled and solidified while being pressed by an air knife against a first roll rotating at 80 ° C. at 3 m / min to obtain a single-layer unstretched film having a thickness of 150 μm.

-Three-dimensional decoration thermoforming As the resin molding (base | substrate) 5, the injection foaming molding which consists of the polypropylene resin composition (a-1) obtained by the above was used. As a three-dimensional decorative thermoforming apparatus, “NGF-0406-SW” manufactured by Fuse Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 is cut out with a width of 250 mm × a length of 350 mm so that the cooling roll contact surface faces the substrate and the longitudinal direction is the MD direction of the film, and the size of the opening Was set on a film fixing jig 13 of 210 mm × 300 mm. The resin molded body (base body) 5 is placed on a table 14 positioned below the film fixing jig 13 and placed on a sample mounting table having a height of 20 mm, “Nystack NW-K15” manufactured by Nichiban Co., Ltd. ”Pasted through. The film fixing jig 13 and the table 14 were installed in the chambers 11 and 12, the chambers were closed, and the chamber boxes 11 and 12 were sealed. The chamber box is divided up and down via the decorative film 1. In the state which vacuum-sucked the upper and lower boxes and reduced pressure from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80%, and the decorative film 1 is Heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated to sag temporarily, and then 20 seconds after the end of the springback phenomenon, the table 14 installed in the lower chamber box 12 is moved upward to form a resin molded body. (Substrate) 5 was pressed against the decorative film 1, and immediately after that, compressed air was fed so that the pressure in the upper chamber box 11 was 270 kPa, thereby bringing the resin molded body (substrate) 5 and the decorative film 1 into close contact. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was adhered to the upper surface and the side surface of the resin molded body (substrate) 5 was obtained.

-Physical property evaluation (1) Evaluation of thermoformability The draw-down state of the decorative film at the time of three-dimensional decorative thermoforming, and the sticking state of the decorative film of the decorative molded body in which the decorative film is stuck to the substrate It observed visually and evaluated by the reference | standard shown below.
○: At the time of three-dimensional decorative thermoforming, the decorative film did not draw down, and the contact between the substrate and the decorative film was made simultaneously on the entire contact surface, so contact unevenness did not occur and it was evenly attached ing.
X: During the three-dimensional decorative thermoforming, the decorative film was greatly drawn down, so contact unevenness occurred on the entire surface of the substrate.

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

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

(3) Appearance of the decorative molded body The external appearance of the decorative film of the decorative molded body in which the decorative film was bonded to the base was visually observed and evaluated according to the following criteria.
◯: No appearance defects due to silver streaks, surface roughness, and fiber-shaped irregularities are observed, and the appearance is smooth.
X: Appearance defects due to silver streaks, surface roughness, and fiber-shaped irregularities are observed, and the appearance is not suitable for practical use.

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

Table 2 shows the physical property evaluation results of the obtained decorative molded body and the like.
Since all the requirements of the present invention are satisfied, the obtained decorative molded body is excellent in thermoformability and adhesive force, and the surface of the molded body is covered with a decorative film, so that the appearance due to silver streak or surface roughness No defects were observed and the appearance was excellent.

(Examples 2 to 4)
In the three-dimensional decorative thermoforming described in Example 1, the resin molded body (substrate) 5 was changed to the resin molded body (substrate) (A-2) to (A-4) in the same manner as in Example 1. Evaluation was performed. The evaluation results are shown in Table 2, respectively.
Since all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in thermoformability and adhesive force, and the surface of the molded body is covered with a decorative film, so that silver streaks and rough surfaces are obtained. The appearance defect due to the fiber-shaped unevenness was not observed, and the appearance was excellent.

(Examples 5 to 8)
In the production of the decorative film of Example 1, the polypropylene resin (A-1-1) was blended with the polypropylene resins (A-1-1) and (A-2-1) listed in Table 3 (resin A single-layer unstretched film was obtained in the same manner as in Example 1 except that the composition (A) was changed.
Using the unstretched film obtained by the above-mentioned decorative film production, in the three-dimensional decorative thermoforming, except that the resin molded body (base body) 5 was changed to the resin molded body (base body) (A-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

Example 9
In the production of the decorative film described in Example 1, a single layer unstretched as in Example 1 except that the polypropylene resin (A-1-1) is changed to a polypropylene resin (A-1-2). A film was obtained.
Using the unstretched film obtained by the above-mentioned decorative film production, in the three-dimensional decorative thermoforming, except that the resin molded body (base body) 5 was changed to the resin molded body (base body) (A-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Examples 10 to 13)
In the production of the decorative film of Example 9, the polypropylene resin (A-1-2) was blended with the polypropylene resins (A-1-2) and (A-2-1) listed in Table 3 (resin Except having changed into the composition (A)), it shape | molded and evaluated similarly to Example 9. FIG. The evaluation results are shown in Table 3.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Example 14)
In the production of the decorative film of Example 1, a lip opening of 0.8 mm and a die width connected to an extruder 1 having a diameter of 40 mm (diameter) and an extruder 3 for a seal layer having a diameter of 30 mm (diameter) were connected. A 400 mm two-type two-layer T-die was used. 4 parts by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.) is blended with 100 parts by weight of the polypropylene resin (A-1-1), and the polypropylene resin ( B-1) is respectively charged into the seal layer extruder-3, the resin temperature is 240 ° C., the discharge amount of the extruder-1 is 12 kg / h, and the discharge amount of the seal layer extruder-3 is 4 kg / h. And melt extrusion was performed.
The melt-extruded film was cooled and solidified so that the sealing layer was in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a 150 μm thick layer and a 50 μm thick surface decoration layer were laminated. A two-layer unstretched film was obtained.
Using the unstretched film obtained by the above-mentioned decorative film production, in the three-dimensional decorative thermoforming, except that the resin molded body (base body) 5 was changed to the resin molded body (base body) (A-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 4.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Example 15)
In the production of the decorative film described in Example 14, molding and evaluation were performed in the same manner as in Example 14 except that the polypropylene resin (B-1) was changed to the polypropylene resin (B-2). The evaluation results are shown in Table 4.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Examples 16 to 19)
In the production of the decorative film of Example 14, molding was performed in the same manner as in Example 14 except that the polypropylene resin (B-1) was changed to polypropylene resins (C-1) to (C-4), respectively. Evaluation was performed. The evaluation results are shown in Table 4.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Example 20)
In the production of the decorative film of Example 1, a lip opening of 0.8 mm and a die width connected to an extruder 1 having a diameter of 40 mm (diameter) and an extruder 2 for a surface layer having a diameter of 30 mm (diameter) were connected. A 400 mm two-type two-layer T-die was used. 4 parts by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.) is blended with 100 parts by weight of the polypropylene resin (A-1-1), and the polypropylene resin ( A-2-1) was introduced into the surface layer extruder-2, the resin temperature was 240 ° C., the discharge amount of the extruder-1 was 12 kg / h, and the discharge amount of the surface layer extruder-2 was 4 kg / h. The melt extrusion was carried out under the following conditions.
The melt-extruded film is cooled and solidified so that the layer made of the polypropylene resin (A-1-1) is in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a layer having a thickness of 150 μm is obtained. A two-layer unstretched film in which a surface decoration layer of 50 μm was laminated was obtained.
Using the unstretched film obtained by the above-mentioned decorative film production, in the three-dimensional decorative thermoforming, except that the resin molded body (base body) 5 was changed to the resin molded body (base body) (A-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (A-2-1) on the outermost surface side as a surface decoration layer [layer (III)].

(Example 21)
In the production of the decorative film of Example 1, an extruder 1 having a diameter of 40 mm (diameter), an extruder 2 for a surface layer having a diameter of 30 mm (diameter), and an extruder 3 for a seal layer having a diameter of 30 mm (diameter). 3 type 3 layer T die having a lip opening of 0.8 mm and a die width of 400 mm were used. 4 parts by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.) is blended with 100 parts by weight of the polypropylene resin (A-1-1), and the polypropylene resin ( A-2-1) is introduced into the surface layer extruder-2, and the polypropylene resin (C-1) is introduced into the seal layer extruder-3. The resin temperature is 240 ° C., and the discharge amount of the extruder-1 is changed. Melt extrusion was performed under the conditions of 12 kg / h, the discharge amount of the surface layer extruder-2 of 4 kg / h, and the discharge amount of the seal layer extruder-3 of 4 kg / h.
The melt-extruded film is cooled and solidified so that the sealing layer is in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a layer having a thickness of 150 μm, a surface decoration layer having a thickness of 50 μm, and a thickness of 50 μm. A three-layer unstretched film on which the sealing layer was laminated was obtained.
Using the unstretched film obtained by the above-mentioned decorative film production, in the three-dimensional decorative thermoforming, except that the resin molded body (base body) 5 was changed to the resin molded body (base body) (A-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (A-2-1) on the outermost surface side as a surface decoration layer [layer (III)].

(Example 22)
In the production of the decorative film of Example 21, molding and evaluation were performed in the same manner as in Example 21 except that the polypropylene resin (C-1) was changed to the polypropylene resin (B-1). The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (A-2-1) on the outermost surface side as a surface decoration layer [layer (III)].

(Example 23)
In the production of the decorative film of Example 22, molding and evaluation were performed in the same manner as in Example 22 except that the polypropylene resin (A-2-1) was changed to the polypropylene resin (D-1). The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was a result which was excellent in glossiness because the polypropylene resin (D-1) to which the nucleating agent was added was laminated on the outermost surface side as a surface decorating layer [layer (III)].

(Example 24)
In the production of the decorative film of Example 22, molding and evaluation were performed in the same manner as in Example 22 except that the polypropylene resin (A-2-1) was changed to the polypropylene resin (C-1). The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was the result which was excellent in glossiness by having laminated | stacked polypropylene resin (C-1) on the outermost surface side as a surface decoration layer [layer (III)].

(Example 25)
In the production of the decorative film of Example 22, molding and evaluation were performed in the same manner as in Example 22 except that the polypropylene resin (A-2-1) was changed to the polypropylene resin (D-2). The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, it was a result which was excellent in glossiness because the polypropylene resin (D-2) to which the nucleating agent was added was laminated on the outermost surface side as a surface decorating layer [layer (III)].

(Example 26)
In the production of the decorative film of Example 22, molding and evaluation were performed in the same manner as in Example 22 except that the polypropylene resin (A-2-1) was changed to the polypropylene resin (D-3). The evaluation results are shown in Table 5.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent. Moreover, since the layer (I) was black and the surface decoration layer (III) was colored silver, it became a metallic film and was excellent in appearance.

(Example 27)
In the production of the decorative film of Example 21, the polypropylene resin (C-1) charged into the seal layer extruder-3 was replaced with the polypropylene resin (B-1) and the other resin (E-1). Molding and evaluation were carried out in the same manner as in Example 21 except that the weight ratio was changed to 70:30. The evaluation results are shown in Table 6.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Examples 28 to 35)
In the production of the decorative film of Example 27, molding and evaluation were performed in the same manner as in Example 27 except that the other resin (E-1) was changed to other resins (E-2) to (E-9). went. The evaluation results are shown in Table 6.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Example 36)
In the production of the decorative film of Example 27, the other resin (E-1) was changed to the other resin (E-10), and the polypropylene resin (B-1) and the other resin (E-10) Except that the weight ratio was changed to 85:15, molding and evaluation were performed in the same manner as in Example 27. The evaluation results are shown in Table 6.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Example 37)
In the production of the decorative film of Example 27, molding and evaluation were performed in the same manner as in Example 27 except that the other resin (E-1) was changed to the other resin (E-11). The evaluation results are shown in Table 6.
Since all satisfy the requirements of the present invention, the resulting decorative molded body is excellent in thermoformability and adhesive strength, and the surface of the molded body is covered with a decorative film, resulting in silver streaks and surface roughness No appearance defect was observed, and the appearance was excellent.

(Comparative Example 1)
Evaluation was performed using only the resin molded body (substrate) (A-1). The results are shown in Table 7.
Since no decorative film was attached, silver streaks and surface roughness were conspicuous, and the surface shape was not practical.

(Comparative Examples 2 to 4)
Evaluation was performed in the same manner as in Comparative Example 1 except that the injection molded body was changed from the resin molded body (substrate) (A-1) to (A-2) to (A-4). The results are shown in Table 7.
Since none of the injection-foamed molded articles had a decorative film attached thereto, appearance defects due to silver streaks, surface roughness, and fiber shape irregularities were observed, and the surface shape was not practical.

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

Claims (17)

A decorative molded body in which a polypropylene decorative film is bonded to an injection foamed resin molded body by thermoforming, and the injection foamed resin molded body satisfies the following requirements (i) to (ii): A decorative molded body comprising (a) and having a foaming ratio of 1.1 to 10 times.
Polypropylene resin (A)
(I): Melting peak temperature Tm is 110 ° C. or higher.
(Ii): MFR (230 ° C., 2.16 kg load) is 0.01 g / 10 min or more and 300 g / 10 min or less. The polypropylene decorative film includes a layer (I) composed of a resin composition (A) including a polypropylene resin (A), and the resin composition (A) has the following requirements (A-i) and (A The decorative molded body according to claim 1, wherein -ii) is satisfied.
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more The polypropylene decorative film includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (B), and the resin composition ( A) satisfies the following requirements (A-i) and (A-ii), and the polypropylene resin (B) is a multilayer decorative film having an MFR (230 ° C., 2.16 kg load) exceeding 2 g / 10 min. The decorative molded body according to claim 1, wherein the multilayer decorative film and the injection-foamed resin molded body are bonded via a seal layer (II).
(A-i) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more The decorative molded body according to claim 2 or 3, wherein the resin composition (A) satisfies the following requirements (Ai ') and (A-ii').
(Ai ′) MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 min or less (Aii ′) Strain hardening degree λ is 1.8 or more. The decorative molded body according to claim 2 or 3, wherein the resin composition (A) satisfies the following requirements (A-i ") and (A-ii").
(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 molded body according to claim 2 or 3, wherein the polypropylene resin (A) is a polypropylene resin (A-1) having a long-chain branched structure. The decorative molded body according to claim 6, wherein the polypropylene-based resin (A-1) is a polypropylene-based resin with a low gel produced by a method other than the crosslinking method. The polypropylene decorative film includes a layer (I) made of a resin composition (A) containing a polypropylene resin (A) and a seal layer (II) made of a polypropylene resin (C), and the resin composition ( A) satisfies the following requirements (Ai) to (A-ii), and the polypropylene resin (C) is a multilayer decorative film that satisfies the following requirements (c1) to (c5). The decorative molded body according to claim 1, wherein the decorative film and the resin molded body are attached via a seal layer (II).
(Ai) MFR (A) (230 ° C., 2.16 kg load) is 40 g / 10 min or less (A-ii) Strain hardening degree λ is 1.1 or more (c1) Metallocene catalyst system Propylene polymer.
(C2) MFR (C) (230 ° C., 2.16 kg load) exceeds 0.5 g / 10 min.
(C3) Melting peak temperature Tm (C) is less than 150 ° C.
(C4) The molecular weight distribution (Mw / Mn (C)) obtained by GPC measurement is 1.5 to 3.5.
(C5) When the melting peak temperature of the polypropylene resin (A) is Tm (A) and the melting peak temperature of the polypropylene resin (C) is Tm (C), Tm (A) and Tm (C) are The following relational expression (5) is satisfied.
Tm (A)> Tm (C) (5)   The decorative molded body according to claim 8, wherein the polypropylene resin (C) is a propylene / α-olefin copolymer.   The decorative molded body according to claim 8 or 9, wherein a melting peak temperature Tm (C) of the polypropylene resin (C) is 140 ° C or lower. The said resin composition (A) satisfy | fills the following requirements (Ai ') and (A-ii'), The decorative molded object in any one of Claims 8-10 characterized by the above-mentioned.
(Ai ′) MFR (A) (230 ° C., 2.16 kg load) is 20 g / 10 min or less (Aii ′) Strain hardening degree λ is 1.8 or more. The decorative molded body according to any one of claims 8 to 10, wherein the resin composition (A) satisfies the following requirements (A-i ") and (A-ii").
(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 molded body according to any one of claims 8 to 12, wherein the polypropylene resin (A) is a polypropylene resin (A-1) having a long-chain branched structure.   The decorative molded body according to claim 13, wherein the polypropylene-based resin (A-1) is a polypropylene-based resin with less gel manufactured by a method other than the crosslinking method.   The polypropylene-based decorative film has a surface decorative layer (III) made of a surface decorative layer resin on a surface opposite to a surface to be bonded to the injection-foamed resin molded body. The decorative molded body according to any one of 2 to 14. The said surface decoration layer resin consists of polypropylene resin (D), MFR (230 degreeC, 2.16kg load) of this polypropylene resin (D) exceeds 2 g / 10min, It is characterized by the above-mentioned. 15. The decorative molded body according to 15.   A method for producing a decorative molded body according to any one of claims 1 to 16, wherein a step of preparing a polypropylene decorative film, an injection foamed resin molded body having an expansion ratio of 1.1 to 10 times A step of setting the resin molded body and the decorative film in a depressurizable chamber box, a step of depressurizing the interior of the chamber, a step of heat-softening the decorative film, and the resin molded body A method for producing a decorative molded body, comprising a step of pressing a decorative film and a step of returning or pressurizing the inside of the chamber to atmospheric pressure.

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