JP2018154110A - Decorative film and method for producing decorative molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve both sufficient adhesive strength and product appearance, to reduce grain return, to make scratches on a substrate inconspicuous, to reduce product defects, and to facilitate recycling. Provided is a decorative film used for molding and a method for manufacturing a decorative molded body using the decorative film. SOLUTION: The decorative film 1 is to be attached onto a resin molded body by thermal molding, and the decorative film 1 contains a polypropylene-based resin (A) and a thermoplastic elastomer (B) as main components. , The seal layer (I) 3 composed of a resin composition having a weight ratio of the polypropylene-based resin (A) and the thermoplastic elastomer (B) of 97: 3 to 5:95, and the polypropylene-based resin or the polypropylene-based resin composition. The decorative film 1 includes the layer (II) 2 composed of (C). [Selection diagram] Fig. 1

Description

  The present invention relates to a decorative film for sticking by thermoforming on a resin molded body and a method for producing a decorative molded body using the decorative film. Specifically, it can suppress wrinkling and film breakage of the film at the time of thermoforming, can exhibit sufficient adhesive strength to the resin molded body, and is included in the film at the time of wrinkle return after thermoforming and at the time of thermoforming. The present invention relates to a decorative film for sticking by thermoforming on a resin molded body with little damage to the film such that the additive moves out of the film, and a method for producing a decorative molded body using the decorative film.

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

  In particular, a technique has been proposed in which a decorative film that replaces a coating film is applied to a molded body by vacuum pressure forming or vacuum forming to form a decorative molded product in which the decorative film and the molded body are integrated (for example, Patent Document 1). In recent years, it has attracted particular attention.

  Decorative molding by vacuum pressure forming and vacuum forming has a greater degree of freedom than other decorative moldings typified by insert molding, and the end face of the decorative film is rolled up to the back side of the decorative object. Because it does not occur, it has excellent appearance, and can be thermoformed at a relatively low temperature and low pressure. By applying embossing on the surface of the decorative film, the reproducibility of embossing on the surface of the decorative molded body It has the advantage that it is excellent.

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

  For such problems, a decorative film including an adhesive layer containing a polypropylene resin is applied to a base body (molded body) made of a polypropylene resin, so that the decorative film and the molded body are heat-sealed. (For example, refer to Patent Documents 2 and 3). In the inventions disclosed in Patent Documents 2 and 3, a polypropylene resin is used as the adhesive layer of the decorative film. However, the surface layer on the adhesive layer, and the acrylic layer on the bonding layer and the bulk layer are substantially further provided. It is necessary to provide a layer of resin, polyurethane resin, polycarbonate or the like. In this way, by combining different raw materials, thermoformability such as draw-down property is expressed, and it is possible to ensure thermoformability in a decorative film made of a polypropylene resin that does not contain these different raw materials. However, it was not possible to obtain a decorative molded body having an excellent appearance because holes, wrinkles, and air were easily entrapped on the surface of the molded article on which this was adhered. In particular, when a polyurethane resin is included as a heterogeneous raw material, the polyurethane resin, which is a thermosetting resin, does not melt when heated, and thus easily maintains the form of the film and greatly improves thermoformability, but has a problem of extremely low recyclability. It was.

  In other words, the decorative films described in Patent Documents 2 and 3 include different raw materials to ensure thermoformability such as adhesion and appearance, the layer structure is complicated, and the manufacturing requires many steps. In addition, there is a problem that it is difficult to recycle the decorative film in which different raw materials are combined.

  Furthermore, there is a problem that a wrinkle return phenomenon occurs in which wrinkles and the like on the film surface disappear due to heating and melting of the film during thermoforming.

  In addition, decorative thermoforming by vacuum pressure forming and vacuum forming has the advantage that a molded product with a high degree of integrity between the base and the decorative film formed by a process such as injection molding can be obtained, while the decorative film is the base. The surface of the decorative molded body is picked up and scratches on the surface of the decorative molded body tend to cause poor appearance due to the effect of the scratch on the surface of the substrate.

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

  In the prior art, a decorative film made of a propylene-based resin that is easy to recycle and can achieve both excellent adhesiveness and appearance has not been achieved yet. In view of the above problems, the object of the present invention is to make it possible to achieve both sufficient adhesive strength and product appearance, less wrinkle return, and less product defects by making the substrate scratch inconspicuous. It is providing the manufacturing method of the decoration film used for the three-dimensional decoration thermoforming which makes it easy, and a decoration molded object using the same.

In three-dimensional decorative thermoforming, in order to stick a solid decorative film to a solid resin molded body, it is necessary that the surface of the molded body and the film are sufficiently softened or melted. Therefore, it is important to add a heat amount necessary for softening or melting the surface of the molded body and the film, or to use a molded body and a film that are easily softened or melted. On the other hand, if the film is heated too much, the viscosity of the film decreases, and the film breaks or rampages due to the pushing up of the molded body in the three-dimensional decorative thermoforming process or the inflow of air when the vacuum chamber is returned to atmospheric pressure. Doing so leads to poor appearance. Moreover, since the additive contained in a film will transfer out of a film if it heats too much, the problem that the provision function derived from additives, such as heat resistance, a weather resistance, and a nucleation performance will fall will arise. Furthermore, the problem that the wrinkle return is likely to occur occurs. Therefore, the present inventors have examined the configuration of a decorative film that not only solves these problems but also makes the scratches on the substrate surface inconspicuous. As a result, the sealing layer (I) made of a resin composition that has a polypropylene resin (A) and a thermoplastic elastomer (B) as a main component and can exhibit good adhesive strength, and suppresses a decrease in the viscosity of the entire film. The present inventors have found that the above problem can be solved by a combination of a layer (II) made of a polypropylene resin or a polypropylene resin composition (C) that maintains thermoformability and suppresses wrinkle return.
Furthermore, surprisingly, such a decorative film has a high effect of making the scratches inconspicuous, and the present invention has been completed.

That is, the present invention includes the following.
[1] A decorative film for attaching to a resin molded body by thermoforming,
The decorative film includes a polypropylene resin (A) and a thermoplastic elastomer (B) as main components,
Seal layer (I) made of a resin composition having a weight ratio of 97: 3 to 5:95, and a polypropylene resin or a polypropylene resin composition (C). A layer (II) consisting of
The polypropylene resin (A) satisfies the following requirement (a1),
The thermoplastic elastomer (B) satisfies the following requirements (b1) to (b3),
The polypropylene resin or the polypropylene resin composition (C) satisfies the following requirements (c1) to (c2).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) A thermoplastic elastomer mainly composed of propylene and / or butene.
(B2) The density is 0.850 to 0.950 g / cm ³ .
(B3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 min.
(C1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 40 g / 10 min or less.
(C2) The strain hardening degree λ is 1.1 or more.
[2] The thermoplastic elastomer (B) is a propylene-ethylene copolymer having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of 50% by weight. The decorative film according to [1], which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer.
[3] The decorative film according to [1] or [2], wherein the thermoplastic elastomer (B) satisfies the following requirement (b4).
(B4) Melting peak temperature (Tm (B)) is 30-170 degreeC.
[4] The polypropylene resin or polypropylene resin composition (C) satisfies the following requirements (c1 ′) to (c2 ′), according to any one of [1] to [3]. Decorative film.
(C1 ′) MFR (B) is 20 g / 10 min or less.
(C2 ′) The strain hardening degree λ is 1.8 or more.
[5] The polypropylene resin or polypropylene resin composition (C) satisfies the following requirements (c1 ″) to (c2 ″), according to any one of [1] to [4]: Decorative film.
(C1 ″) MFR (B) is 12 g / 10 min or less.
(C2 ″) The strain hardening degree λ is 2.3 or more.
[6] The polypropylene resin or the polypropylene resin composition (C) includes a polypropylene resin (C-1) having a long-chain branched structure, and any one of [1] to [5] The decorative film according to item.
[7] The decorative film according to [6], wherein the polypropylene-based resin (C-1) is a polypropylene-based resin with a low gel produced by a method other than the crosslinking method.
[8] In the step of preparing the decorative film according to any one of [1] to [7], the step of preparing a resin molded body, and the decompressed chamber box, the resin molded body and the decorative film A step of setting a film, a step of depressurizing the inside of the chamber box, a step of softening the decorative film by heating, a step of pressing the decorative film against the resin molded body, and returning the inside of the decompressed chamber box to atmospheric pressure Or the manufacturing method of the decorative molded object characterized by including the step to pressurize.
[9] The method for producing a decorative molded body according to [8], wherein the resin molded body is made of a propylene-based resin composition.

  According to the decorative film of the present invention, the three-dimensional decorative thermoformability is good, the adhesive strength with the molded body is high, and it can be attached to the molded body in a short heating time, so that the wrinkle return is suppressed, Since the scratches on the surface of the molded body can be made inconspicuous, it is possible to improve the appearance of the three-dimensional decorative molded body and to obtain a decorative film with good recyclability.

  According to the method for producing a decorative molded body of the present invention, there are no holes or wrinkles on the surface, there is no air entrainment between the decorative film and the resin molded body, and the reproducibility of texture such as wrinkles is good, A beautiful decorative molded body in which scratches are not noticeable can be obtained. In addition, a decorative film can be neatly adhered to a resin molded body that has been difficult to bond. Furthermore, the decorative molded body obtained in this way has an appearance even if it is recycled because the constituent material of the decorative film is a polypropylene resin and may or may not contain a thermosetting resin layer. The performance degradation is small and the recyclability is high.

It is a figure which shows the example of the laminated constitution of the decorating film 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. It is a figure which shows the example of a layer structure of the obtained decorative molded 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 film in the present invention is a decorative film for sticking on a resin molded body by thermoforming, and the decorative film is mainly composed of a polypropylene resin (A) and a thermoplastic elastomer (B). And a sealing layer (I) comprising a resin composition in which the weight ratio of the polypropylene resin (A) and the thermoplastic elastomer (B) is 97: 3 to 5:95, and the polypropylene resin or the polypropylene resin composition Including the layer (II) comprising the product (C), the polypropylene resin (A) satisfies the following requirement (a1),
The thermoplastic elastomer (B) satisfies the following requirements (b1) to (b3),
The polypropylene resin or the polypropylene resin composition (C) is a decorative film characterized by satisfying the following requirements (c1) to (c2).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) A thermoplastic elastomer mainly composed of propylene and / or butene.
(B2) The density is 0.850 to 0.950 g / cm ³ .
(B3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 min.
(C1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 40 g / 10 min or less.
(C2) The strain hardening degree λ is 1.1 or more.

[Sealing layer (I)]
The decorative film of the present invention includes a seal layer (I) made of a resin composition containing a polypropylene resin (A) and a thermoplastic elastomer (B) as main components. The seal layer (I) is a layer in contact with the resin molded body (base) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during the three-dimensional decorative thermoforming is short, and scratches on the substrate surface can be made inconspicuous.

[Polypropylene resin (A)]
The polypropylene resin (A) in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The propylene 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.

(A1) Melt flow rate (MFR (A))
The melt flow rate (230 ° C., 2.16 kg load) MFR (A) of the polypropylene resin (A) contained in the sealing layer (I) needs to exceed 0.5 g / 10 minutes, preferably 1 g. / 10 minutes or more, more preferably 2 g / 10 minutes or more. Within the above range, the relaxation during the three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited, and scratches on the substrate are less noticeable. Although there is no restriction | limiting in the upper limit of MFR (A), 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 and the polypropylene resin composition described later was measured in accordance with ISO 1133: 1997 Conditions M under the conditions of 230 ° C. and 2.16 kg load. The unit is g / 10 minutes.

(A2) Melting peak temperature (Tm (A))
The melting peak temperature of the polypropylene resin (A) (DSC melting peak temperature, sometimes referred to as “melting point” in this specification) (Tm (A)) is preferably 110 ° C. or higher, and 115 ° C. or higher. It is more preferable that it is 120 degreeC or more. Within the above range, the moldability during three-dimensional decorative thermoforming is good. Although there is no restriction | limiting in the upper limit of melting peak temperature, it is preferable that it is 170 degrees C or less, and sufficient adhesive strength can be exhibited as it is the said range.

  The polypropylene resin (A) in the present invention can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst propylene polymer or a metallocene catalyst propylene polymer.

[Thermoplastic elastomer (B)]
The thermoplastic elastomer (B) used as an essential component in the seal layer (I) of the present invention has the following characteristics (b1) to (b3), preferably (b4) and / or (b5). .

(B1) Composition The thermoplastic elastomer (B) of the present invention is a thermoplastic elastomer mainly composed of propylene and / or butene. Here, “a thermoplastic elastomer mainly composed of propylene and / or butene” means (i) a thermoplastic elastomer mainly composed of propylene, (ii) a thermoplastic elastomer mainly composed of butene, and (iii) propylene. And a thermoplastic elastomer containing as a main component a total of butene. In the present specification, the unit “wt%” means weight%.

The content of propylene or butene in the thermoplastic elastomer (B) is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. For example, the thermoplastic elastomer (B) can contain more than 35% by weight of propylene or butene.
Further, the thermoplastic elastomer (B) may contain both propylene and butene. In this case, the total component of propylene and butene becomes the main component of the thermoplastic elastomer (B), and the total content of propylene and butene is Preferably it is 30 weight% or more, More preferably, it is 40 weight% or more, More preferably, it is 50 weight% or more. When both propylene and butene are contained, for example, the thermoplastic elastomer (B) can contain more than 35% by weight of propylene and butene in total. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the effect of making scratches on the substrate less noticeable is high. In addition, it is thought that the thermoplastic elastomer which has propylene or a butene as a main component has the high uniform dispersibility to a polypropylene resin (A), and it has improved the effect which makes the damage | wound attached to a base | substrate less conspicuous. The thermoplastic elastomer (B) can also be a single component of propylene or butene.

(B2) the density of the density thermoplastic elastomer (B) is required to be 0.850~0.950g / cm ^3, preferably 0.855~0.940g / cm ^3, more preferably 0.86 ˜0.93 g / cm ³ . Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, and film formability is also improved.

(B3) Melt flow rate (MFR (B))
The melt flow rate (230 ° C., 2.16 kg load) MFR (B) of the thermoplastic elastomer (B) needs to be 0.1 to 100 g / 10 minutes, preferably 0.5 to 50 g / 10. Min, more preferably 1-30 g / 10 min. Within the above range, the effect of making the scratches on the substrate less noticeable is high.

(B4) Melting peak temperature (Tm (B))
The melting temperature peak (DSC melting peak temperature) Tm (B) of the thermoplastic elastomer (B) is preferably 30 to 170 ° C, more preferably 35 to 168 ° C, and further preferably 40 to 165 ° C or more. . When it is in the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

(B5) Ethylene content [E (B)]
The thermoplastic elastomer (B) of the present invention can be appropriately selected and used as long as the above properties (b1) to (b3) are satisfied, but the propylene-ethylene copolymer having an ethylene content of less than 50% by weight. A butene-ethylene copolymer having an ethylene content of less than 50% by weight, a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer having an ethylene content of less than 50% by weight. It is preferable.

  The ethylene content [E (B)] of the propylene-ethylene copolymer, butene-ethylene copolymer or propylene-ethylene-butene copolymer is more preferably 45% by weight or less, still more preferably 40% by weight or less. In the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

[Calculation method of ethylene content [E (B)]]
When the thermoplastic elastomer (B) is an elastomer containing ethylene, the ethylene content [E (B)] of the thermoplastic elastomer (B) can be determined from the integrated intensity obtained by ¹³ C-NMR measurement.

[Calculation method 1 (binary system)]
The ethylene content [E (B)] in a binary elastomer (such as propylene-ethylene copolymer or butene-ethylene copolymer) composed of two types of repeating units will be described. The ethylene content of the ethylene-α-olefin binary elastomer can be determined by (Formula-1-1) and (Formula 1-1-2).
Ethylene content (mol%) = IE × 100 / (IE + IX) (Formula-1-1)
Ethylene content (wt%) = [ethylene content (mol%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + α-olefin content (mol%) × α-olefin molecular weight] (Formula-1-2)

Here, IE and IX are integral intensities for ethylene and α-olefin, respectively, and can be obtained by the following (formula-2) and (formula-3).
_{IE = (I ββ + I γγ} + I βδ + I γδ + I δδ) / 2 + (I αγ + I αδ) / 4 ··· ( Formula -2)
_{IX = I αα + (I αγ} + I αδ) / 2 ··· ( wherein -3)
Here, the subscript symbol I on the right side represents carbon described in the following structural formulas (a) to (d). For example, αα represents a methylene carbon based on an α-olefin chain, and I _αα represents an integrated intensity of a signal of methylene carbon based on an _α -olefin chain.

In structural formula (d), n represents an odd number of 1 or more.
The integrated intensity used in (Formula-2) and (Formula-3) is described below.
If it is a propylene-ethylene copolymer, the following integrated intensity | strength is substituted into (Formula-2) and (Formula-3), and ethylene content is calculated | required.
I _ββ = I _25.0-24.2
I γγ = I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _48.0-43.9
I _αγ + I _αδ = I _39.0-36.2

Here, I indicates the integral intensity, and the numerical value of the subscript I on the right side indicates the range of chemical shift. For example, I _39.0-36.2 indicates the integrated intensity of the ¹³ C signal detected between 39.0 ppm and 36.2 ppm.
The chemical shift was set such that the ¹³ C signal of hexamethyldisiloxane was set to 1.98 ppm, and the other chemical shifts of signals due to ¹³ C were based on this.
If it is a butene-ethylene copolymer, the value of the following integrated intensity | strength is substituted into (Formula-2) and (Formula-3), and ethylene content [E (B)] is calculated | required.
_I ββ = I _24.6-24.4
I γγ = I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ = I _30.5-30.2
I _δδ = I _30.2-28.0
I αα = I _39.3-38.1
I _αγ + I _αδ = I _34.5-33.8

[Calculation method 2 (ternary system)]
Next, the ethylene content [E (B)] in the ternary elastomer composed of three types of repeating units will be described. The ethylene content of the propylene-ethylene-butene ternary elastomer can be determined by the following (formula-4-1) and (formula-4-2).
Ethylene content (mol%) = IE × 100 / (IE + IP + IB) (Formula-4-1)
Ethylene content [E (B)] (weight%) = [ethylene content (mol%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + propylene content (mol%) × propylene molecular weight + Butene content (mol%) × butene molecular weight] (Formula-4-2)
Here, IE, IP, and IB are integral intensities for ethylene, propylene, and butene, respectively, and can be obtained by (Equation-5), (Equation-6), and (Equation-7).
_{IE = (I ββ + I γγ} + I βδ + I γδ + I δδ) / 2 + (I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B)) / 4 ··· ( wherein -5)
IP = 1/3 × [I _{CH3 (P)} + I _{CH (P)} + I _{αα (PP)} + 1/2 × (I _{αα ( PB)} + I _{αγ (P)} + I _{αδ (P)} )] _(formula− 6)
IB = 1/4 × [(I _{CH3 (B)} + I _{CH (B)} + I _2B2 + I _{αα (BB)} ) + 1/2 × (I _{αα ( PB)} + I _{αγ (B)} + I _{αδ (B)} )] (Formula-7)
Here, the subscript (P) means a signal based on propylene-derived methyl group branching, and similarly, (B) means a signal based on butene-derived ethyl group branching.
Αα (PP) means a methylene carbon signal based on a propylene chain, similarly αα (BB) means a methylene carbon signal based on a butene chain, and αα (PB) means a methylene carbon based on a propylene-butene chain. Signal.

Here, since the γγ signal overlaps with the tail of the methine carbon CH (PPE) of central propylene aligned with propylene-propylene-ethylene, it is difficult to separate the γγ signal.
The γγ signal appears in the structural formula (c) with two ethylene chains, and (Formula-8) holds for the integrated intensity of γγ derived from ethylene and the integrated intensity of βδ in the structural formula (c).
I _βδ (Structural Formula (c)) = 2 × I _γγ (Formula-8)
Further, βδ appears in the structural formula (d) having three or more ethylene chains, and the integrated strength of βδ in the structural formula (d) is equal to the integrated strength of γδ (Formula-9).
I _βδ (Structural Formula (d)) = I _γδ (Formula-9)
Therefore, βδ based on the structural formula (c) and the structural formula (d) is obtained by (Formula-10).
I _βδ = I _βδ (Structural Formula (c)) + I _βδ (Structural Formula (d)) = 2 × I _γγ + I _γδ (Formula-10)
_{That, I γγ = (I βδ -I} γδ) / 2 ··· ( wherein -10 ')
Therefore, when (Expression-10 ′) is substituted into (Expression-5), IE can be replaced with (Expression-11).
_{IE = (I ββ + I δδ} ) / 2 + (I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B) + 3 × I βδ + I γδ) / 4 ··· ( wherein -11)
Here, the βδ signal corrects the overlap of ethyl branches based on 1-butene, and becomes (Equation-12).
_{I βδ = I αγ (P)} + I αδ (P) + I αγ (B) + I αδ (B) -2 × I ββ ··· ( wherein -12)
From (Formula-11) and (Formula-12), IE becomes (Formula-13).
IE = I _δδ / 2 + I _γδ / 4-I _ββ + I _{αγ (P)} + I _{αδ (P)} + I _{αγ (B)} + I _{αδ (B)} (Formula-13)
Substitute the following into (Formula-13), (Formula-6), and (Formula-7) to determine the ethylene content.
I _ββ = I _25.2-23.8
I _γδ = I _30.4-30.2
I _δδ = I _30.2-29.8
I _{αγ (P)} + I _{αδ (P)} = I _39.5-37.3
I _{αγ (B)} + I _{αδ (B)} = I _34.6-33.9
I _{CH3 (P)} = I _22.6-19.0
I _{CH (P)} = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I _{αα (PP)} = I _48.0-45.0
I _{CH3 (B)} = I _11.4-10.0
I _{CH (B)} = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
I _{αα (BB)} = I _40.3-40.0
I _{αα (PB)} = I _44.2-42.0
I _2B2 = I _26.7-26.4

The assignment of each signal referred to the following five documents;
Macromolecules, Vol. 10, no. 4, 1977,
Macromolecules, Vol. 36, no. 11, 2003,
Analytical Chemistry, Vol. 76, no. 19, 2004,
Macromolecules, 2001, 34, 4757-4767,
Macromolecules, Vol. 25, no. 1,1992

  The thermoplastic elastomer (B) may be a copolymer of propylene and an α-olefin other than butene as long as the effects of the present invention are not impaired. 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. Among these, 1-hexene and 1-octene are particularly preferably used.

  Such a thermoplastic elastomer is produced by copolymerizing each monomer in the presence of a catalyst. Specifically, thermoplastic elastomers use propylene propylene in a process such as a gas phase method, a solution method, a high pressure method, a slurry method, etc., using a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst as an olefin polymerization catalyst. , 1-butene, ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like can be produced by copolymerization.

Moreover, the thermoplastic elastomer (B) used for the seal layer (I) of the present invention can be used singly or in combination of two or more kinds as long as the effects of the present invention are not impaired.
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 VISAMAXXX series manufactured by ExxonMobil Chemical.

[Resin composition]
The resin composition constituting the seal layer (I) includes a polypropylene resin (A) and a thermoplastic elastomer (B). The resin composition may be a mixture or a melt-kneaded product of the polypropylene resin (A) and the thermoplastic elastomer (B), or the sequential polymerization of the polypropylene resin (A) and the thermoplastic elastomer (B). It may be a thing.

  In the resin composition constituting the sealing layer (I), the weight ratio ((A) :( B)) of the polypropylene resin (A) and the thermoplastic elastomer (B) is comprised between 97: 3 and 5:95. Preferably 95: 5 to 10:90, more preferably 93: 7 to 20:80. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the adhesiveness between the sealing layer (I) and the layer (II) is good. Become.

  The resin composition may contain additives, fillers, other resin components, and the like. The total amount of additives, fillers, and other resin components is preferably 50% by weight or less based on the 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. 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 modified polyolefin, petroleum resin, and other thermoplastic resins.

  The method for producing the resin composition includes a method of melt-kneading the polypropylene resin (A), the thermoplastic elastomer (B), an additive, a filler, and other resin components, and the polypropylene resin (A) and the additive. , A method in which a thermoplastic elastomer (B) is dry blended into a melt-kneaded filler or other resin component, and a polypropylene resin (A) added to the thermoplastic elastomer (B). It can be produced by a method of dry blending a master batch in which a product or the like is dispersed in a carrier resin at a high concentration.

[Layer (II)]
Layer (II) contained in the decorative film of the present invention contains a polypropylene resin or a polypropylene resin composition (C). By providing the decorative film with the layer (II), it is possible to suppress the occurrence of poor appearance due to the film breaking or rampage during the three-dimensional decorative thermoforming. Thereby, the decorative film does not need to contain the thermosetting resin layer which is excellent in the thermoformability for improving thermoformability.
The layer (II) can be composed of a polypropylene resin (C) or a polypropylene resin composition (C) containing a plurality of polypropylene resins, and other than the polypropylene resin (C) The polypropylene resin may be present. When the layer (II) is made of a polypropylene resin (C), the polypropylene resin (C) satisfies the requirements (c1) and (c2) described later. When the layer (II) is composed of the polypropylene resin composition (C), the polypropylene resin composition (C) satisfies the requirements (c1) and (c2) described later. In addition to the polypropylene resin (C), when other polypropylene resin is present, in addition to the polypropylene resin composition (C), at least the polypropylene resin (C) must satisfy the requirements (c1) and It is preferable to satisfy (c2). The blend of the polypropylene resin (C) 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.

[Polypropylene resin or polypropylene resin composition (C)]
Next, the polypropylene resin or polypropylene resin composition (C) constituting the layer (II) will be described.

(C1) Melt flow rate (MFR (C))
In the present invention, the polypropylene-based resin or the polypropylene-based resin composition (C) cannot obtain sufficient molding stability if the viscosity is too low, so the polypropylene-based resin or the polypropylene-based resin composition (C) is constant. It is necessary to have a viscosity of In the present invention, MFR (230 ° C., 2.16 kg load) is defined as an index of this viscosity.

In the present invention, the melt flow rate (230 ° C., 2.16 kg load) MFR (C) of the polypropylene resin or polypropylene resin composition (C) satisfies the following requirement (c1), preferably the requirement (c1 ′ ), And more preferably, the requirement (c1 ″) is satisfied. By making the MFR (C) of the polypropylene resin or the polypropylene resin composition (C) equal to or less than the following values, a decorative molded article having a good appearance Can be obtained.
(C1) MFR (C) is 40 g / 10 min or less.
(C1 ′) MFR (C) is 20 g / 10 min or less.
(C1 ″) MFR (C) is 12 g / 10 min or less.

  Although there is no restriction | limiting in particular about the minimum of MFR (C) of a polypropylene resin or a polypropylene resin composition (C), Preferably it is 0.1 g / 10min or more, More preferably, it is 0.3 g / 10min or more. By making MFR (C) 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.

(C2) Degree of strain hardening λ
The strain hardening degree λ of the polypropylene resin or the polypropylene resin composition (C) satisfies the following requirement (c2), preferably satisfies the requirement (c2 ′), and more preferably satisfies the requirement (c2 ″). By setting the strain hardening degree λ of the resin or the polypropylene resin composition (C) to a value within the following range, it is possible to obtain a decorative molded body with good moldability during decorative thermoforming and excellent appearance. it can.
(C2) The strain hardening degree λ is 1.1 or more.
(C2 ′) The strain hardening degree λ is 1.8 or more.
(C2 ″) The strain hardening degree λ is 2.3 or more.

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

The strain hardening degree λ of the polypropylene resin or the polypropylene resin composition (C) is obtained based on the measurement of the strain hardening property in the 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. In the present invention, the strain hardening degree λ is calculated by a method according to the method illustrated in FIG. 7-20 of the same book, and η ^* (0. 01) is adopted as the value of the extensional viscosity, and ηe (3.5) is adopted, and the strain hardening degree λ is defined by the following formula (b-2).
λ = ηe (3.5) / {3 × η ^* (0.01)} Formula (b-2)
In the above formula (b-2), 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], and the complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and the angular frequency ω at 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 rad / s and the strain amount 3.5 are not necessarily obtained. There is a possibility that the data of elongation viscosity ηe (3.5) does not exist at that time, but in that case, the corresponding value is estimated by performing interpolation such as linear interpolation and spline interpolation using the data before and after that. It is allowed to do. 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 (for example, 0.9 or more and less than 1.1) or smaller, and strain hardening is achieved. As the property (nonlinearity) increases, the value of the strain hardening degree λ increases.

  General crystalline polypropylene is a linear polymer and usually does not have strain hardening. On the other hand, the polypropylene resin (C) used in the present invention is preferably a polypropylene resin (C-1) having a long-chain branched structure, and the polypropylene resin or the polypropylene resin composition (C) is Strain hardenability can be expressed.

  The long-chain branched structure in the present invention refers to a branched structure composed of molecular chains in which the carbon skeleton (branched main chain) constituting the branches has several tens of carbon atoms and several hundred or more in molecular weight. 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-based resin, a method of irradiating polypropylene having no long-chain branched structure with high energy ionizing radiation (Japanese Patent Laid-Open No. Sho 62-121704), or a long-chain branched structure is used. A method of reacting an organic peroxide with a polypropylene which does not have (Special Table 2001-524565) or a method of producing a macromonomer having a terminal unsaturated bond and copolymerizing it with propylene (Special Table 2001-525460) In any case, the strain hardening degree λ of the polypropylene resin can be increased.

  The polypropylene resin (C-1) having a long chain branched structure is not particularly limited as long as it has a long chain branched structure, but may be a polypropylene resin produced by a method other than the crosslinking method. Preferably, those obtained by a method using a macromer copolymerization method having a comb chain structure and forming a long chain branched structure upon polymerization are preferred. Examples of such a method include, for example, JP-T-2001-525460, JP-A-10-338717, JP-A-2002-523575, JP-A-2009-57542, JP5027353, 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 can obtain a long-chain branched polypropylene resin (C-1) without generation of gel and is suitable for the present invention.

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.

[Branching index g ′]
The branching index g ′ is known as a direct index regarding the long chain branching structure. There is a detailed description in “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983). The definition of the branching index g ′ is as follows.
Branch index g ′ = [η] br / [η] lin
[Η] br: Intrinsic viscosity of polymer (br) having a long-chain branched structure [η] lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br) As is clear from the above definition, 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 software ASTRA (version 4.73.04) with reference to the following documents 1-4.
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 or the polypropylene resin composition (C) contains a gel, the appearance of the film deteriorates, so that the polypropylene resin or the polypropylene resin does not contain a gel. It is preferable to use the composition (C). In particular, by producing a macromonomer having a terminal unsaturated bond using a metallocene catalyst having a specific structure as a polypropylene resin (C-1) having the above-mentioned long-chain branched structure, and copolymerizing it with propylene What was manufactured using the method of forming a long chain branched structure is preferable. 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. In the present invention, “less gel” means that the branching index g ′ of a polypropylene resin having an absolute molecular weight Mabs of 1,000,000 is within the above range. 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 (C-1) in particular. Does not deteriorate the appearance when constituting the surface of the product.

[ ¹³ C-NMR]
¹³ C-NMR can distinguish between short-chain branched structures and long-chain branched structures. 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 branched methine carbon (C _br ).

The ¹³ C-NMR spectrum of the propylene-based polymer having a long-chain branched structure shows that three methylene carbons adjacent to the branched methine carbon C _br are divided into three non-equivalently diastereotopics. It is a feature.

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, and measured ¹³ C-NMR.
^{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 (C-1) having a long-chain branched structure preferably has a long-chain branch amount determined from a peak near 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, and still more preferably 0. 30 pieces / 1000 total propylene or less.

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

  The polypropylene resin (C-1) having a long-chain branched structure in the present invention is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), or a propylene block copolymer (block polypropylene). Various types of propylene-based polymers, or combinations thereof can be selected. The propylene polymer preferably contains 50 mol% or more of polymer units derived from a propylene monomer.

Melting peak temperature (Tm (C))
The melting peak temperature (Tm (C)) in the DSC measurement of the polypropylene resin or polypropylene resin composition (C) is not particularly limited, but is preferably 130 ° C or higher, more preferably 140 to 170 ° C, More preferably, it is 150-168 degreeC. The polypropylene resin (C) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point, and is scratch-resistant if it contains a low crystalline component even if the melting point is high. The polypropylene resin or the polypropylene resin composition (C) preferably does not contain an ethylene-α-olefin copolymer having an ethylene content of 50 to 70% by weight because the properties and solvent resistance are lowered.

  The polypropylene resin composition (C) includes a plurality of polypropylene resins other than the polypropylene resin (C-1) having a long-chain branched structure, additives, fillers, colorants, and other resin components. It may be. 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 (C) including them.

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

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

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

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

[Decorative film]
The decorative film in the present invention includes a seal layer (I) made of a polypropylene resin (A) and a thermoplastic elastomer (B), and a layer (II) made of a polypropylene resin or a polypropylene resin composition (C). . The decorative film can take various configurations in addition to the sealing layer (I) and the layer (II). That is, even if the decorative film is a two-layer film composed of the sealing layer (I) and the layer (II), it is a multilayer film of three or more layers composed of the sealing layer (I) and the layer (II) 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 the shape of the decoration object, and the end face of the decoration film is rolled up to the back side of the decoration object, so there is no seam, and the surface of the decoration film is wrinkled. Various textures can be expressed by adding. 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 (I) and the layer (II), 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 (II) made of the polypropylene resin or the polypropylene resin composition (C) 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 (I) and the layer (II) 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 sealing layer (I) and the layer (II) can be distinguished from the sealing layer (I) and the layer (II), the MFR (230 ° C., 2.16 kg) of the polypropylene resin constituting the layer is used. (Load) is not particularly limited. 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 seal layer (I) constitutes a seal layer on the surface to be bonded to the resin molded body, and the layer (II) is opposite to the surface to be bonded to the resin molded body. Configure the surface layer.

  When the decorative film is a multilayer film of three or more layers, and when other layers are interposed between the sealing layer (I) and the layer (II), the effect of suppressing the relief of scratches on the substrate surface is reduced. There is. For this reason, the multilayer film preferably has a configuration of sealing layer (I) / layer (II) / other layers (including a plurality of layers) from the sticking surface side of the resin molded body.

  8A to 8C are explanatory views schematically illustrating a cross section of an embodiment of a decorative film attached to a resin molded body. In FIGS. 8A to 8C, the arrangement of the sealing layer (I) and the layer (II) is specified and explained for easy understanding, but the layer structure of the decorative film is limited to these examples. Are not to be interpreted. In the present specification, reference numeral 1 in the drawing denotes a decorative film, reference numeral 2 denotes a layer (II), reference numeral 3 denotes a sealing layer (I), reference numeral 4 denotes a surface decoration layer (III), and reference numeral 5 denotes a resin molded body. . FIG. 8A is an example in which the decorative film is a two-layer film, and a seal layer (I) made of a polypropylene resin (A) and a thermoplastic elastomer (B) is attached to the resin molded body 5. A layer (II) made of a polypropylene resin or a polypropylene resin composition (C) is laminated on the seal layer (I). The decorative film in FIG. 8B is composed of a seal layer (I), a layer (II), and a surface layer. The seal layer (I) is adhered to the surface of the resin molded body 5, and the top of the seal layer (I). The layer (II) and the surface layer are laminated in this order. The decorative film in FIG. 8C is composed of a seal layer (I), a layer (II), and a surface decorative layer (III), and the seal layer (I) is adhered to the surface of the resin molded body 5, A layer (II) and a surface decoration layer (III) are laminated in this order on (I).

  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).

  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 (C). By setting the value within the above range, a more beautiful surface texture can be expressed.

  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 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 (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. 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 (A) constituting the seal layer (I).

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

  As an additive, the additive etc. which may be contained in the resin composition which comprises said sealing layer (I) can be used.

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

  When the polypropylene resin (D) constituting the surface decoration layer (III) is a polypropylene resin composition, this polypropylene resin composition is composed of the propylene resin (A) constituting the seal layer (I). The same or different polypropylene resin composition may be used.

  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 (I) to the total thickness of the decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. If the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above range, sufficient adhesive strength can be exhibited, and scratches on the resin molded body (substrate) can be raised on the surface. Can be suppressed. Moreover, if the ratio of the thickness of the layer (II) 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 whole surface decoration film of the thickness of layer (III) in a decoration film The proportion of the thickness is preferably 30% or less.

[Manufacture of decorative film]
The decorative film of the present invention can be produced by various known forming methods.
For example, a method of coextrusion molding a seal layer (I) made of a polypropylene resin (A) and a thermoplastic elastomer (B) and a layer (II) made of a polypropylene resin or a polypropylene resin composition (C), a seal Method of co-extrusion of layer (I) and layer (II) with another layer, heat to bond the other layer on one side of the previously extruded layer by applying heat and pressure Lamination method, dry lamination method and laminating method using adhesives, extrusion lamination method and sand lamination method that melt-extrusion polypropylene resin on one side of one layer that has been extruded in advance It is done. 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.

[Decorative molded body]
As the molded article (decoration target) to be decorated in the present invention, various molded articles (hereinafter sometimes referred to as “substrate”) preferably made of a polypropylene resin or a polypropylene resin composition can be used. . The molding method of the molded body is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

  Polypropylene resin is a non-polar polymer because it is nonpolar, but the decorative film in the present invention is a sealing layer (I) composed of a polypropylene resin (A) and a thermoplastic elastomer (B), And a layer (II) composed of a polypropylene resin or a polypropylene resin composition (C), exhibiting very high adhesive strength by adhering a decoration object and a decoration film made of a polypropylene resin. In addition, the scratches on the surface of the object to be decorated can be made inconspicuous.

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

  The decorative molded body obtained by sticking the decorative film in the present invention to various molded bodies formed in a three-dimensional shape made of a polypropylene resin greatly reduces the VOC contained in the paint and the adhesive. It can be suitably used as home appliances, vehicles (railways, etc.), building materials, daily necessities and the like.

[Manufacture of decorative molded bodies]
In the method for producing a decorative molded body of the present invention, the resin molded body and the decorative film are set in a step of preparing the above-described decorative film, a step of preparing the resin molded body, and a chamber box capable of decompression. A step of depressurizing the interior of the chamber box, a step of heat-softening the decorative film, a step of pressing the decorative film against the resin molding, and a step of returning or pressurizing the decompressed chamber box to atmospheric pressure. It is characterized by including.

  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 items 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 a propylene-type resin composition as a base | substrate.

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

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

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

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

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

[Molding condition]
The pressure in the chamber boxes 11 and 12 may be reduced so long as 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.

  However, since the decorative film 1 of the present invention includes the layer (II) made of a specific polypropylene resin or polypropylene resin composition (C), not only is it difficult to draw down, but also film deformation due to pressure fluctuations. Tolerant.

  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 the polypropylene-based decorative film is heated even if it is short, and the heating is performed for a period of time before or after the start of stretching called spring back.
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.
Furthermore, the decorative film of the present invention is surprisingly capable of strongly adhering to the substrate even if it is subjected to decorative thermoforming before the end of rebounding, so the additive contained in the film during thermoforming Can reduce the damage to the film that has been transferred to the outside of the film, and also has a great effect in suppressing the wrinkle return.

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

(Ii) Melting peak temperature (melting point)
For the melting peak temperature, 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 the temperature rising rate was 10 again. The temperature at the top of the endothermic peak when measured at ° C./min was taken as the melting peak temperature. The unit is ° C.

(Iii) Density The density of the thermoplastic elastomer (B) was measured according to the density gradient tube method of JIS K7112 (1999).

(Iv) Ethylene content [E (B)]
The ethylene content [E (B)] of the thermoplastic elastomer (B) was determined from the integrated intensity obtained by ¹³ C-NMR measurement based on the method as described above. Sample preparation and measurement conditions are as follows.
200 mg of the sample thermoplastic elastomer (B) was mixed with o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and hexamethyl which is a reference substance for chemical shift. It was dissolved together with disiloxane in an NMR sample tube having an inner diameter of 10 mmφ.
The NMR measurement was performed using an AV400 NMR apparatus manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
^{The 13} C-NMR measurement conditions were as follows: the sample temperature was 120 ° C., the pulse angle was 90 °, the pulse interval was 20 seconds, and the number of integrations was 512 times.

(V) 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.

(V-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 as η ^* = G ^* / ω from the complex modulus G ^* [unit: Pa] and ω.

(V-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: 0.05 s ⁻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].

(Vi) Measurement of the branching index g ′ when the absolute molecular weight Mabs is 1 million:
According to the method described above, measurement was performed using a GPC equipped with a light scatterometer and a viscometer in the detector, and the branching index g ′ was determined based on the analysis method described above.

(Vii) Detection of long-chain branched structure using ¹³ C-NMR:
According to the method mentioned above, the measurement using < ¹³ > C-NMR was performed and the presence or absence of the long chain branched structure was measured.

2. Materials used (1) Polypropylene resin The following polypropylene resins were used.
(A-1): Propylene-α-olefin copolymer (MFR (A) = 7 g / 10 min, Tm (A) = 146 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FW3GT "
(A-2): Propylene homopolymer (MFR (A) = 10 g / 10 min, Tm (A) = 161 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FA3KM”
(A-3): Propylene-α-olefin copolymer (MFR (A) = 5 g / 10 min, Tm (A) = 127 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) FX4G "
(C-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 (C) = 9 g / 10 minutes, strain hardening degree λ = 7.8, Tm (C) = 154 ° C., branching index g ′ = 0.85 when the absolute molecular weight Mabs is 1 million, and has a long chain branched structure as measured by ¹³ C-NMR Confirm that.
(C-1-2): Propylene homopolymer having a long-chain branch produced by a macromer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX (registered trademark) MFX8”, MFR (C) = 1 g / 10 minutes, strain hardening degree λ = 9.7, Tm (C) = 154 ° C., branching index g ′ = 0.89 when absolute molecular weight Mabs is 1 million, and has a long-chain branched structure as measured by ¹³ C-NMR Confirm that.
(C-1-3): Polypropylene resin composition obtained by blending 96% by weight of polypropylene resin (C-1-1) with 4% by weight of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.), MFR (C) = 9 g / 10 min, strain hardening degree λ = 7.3, Tm (C) = 154 ° C.
(D-1): Polypropylene resin composition obtained by blending 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.) with 100 parts by weight of a polypropylene resin (A-2). Product, MFR (D) = 10 g / 10 min, Tm (D) = 164 ° C.
(D-2): Propylene-α-olefin copolymer with metallocene catalyst (MFR (D) = 7 g / 10 min, Tm (D) = 125 ° C., Mw / Mn = 2.5), Nippon Polypro Co., Ltd. Product name "Wintech (registered trademark) WFX4M"
(D-3): Polypropylene resin composition obtained by blending 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.) with 100 parts by weight of a polypropylene resin (D-2). Product, MFR (D) = 7 g / 10 min, Tm (D) = 127 ° C.
(D-4): Polypropylene resin (A-2) 96% by weight of white pigment MB with MFR = 11 g / 10 min (EPP-W-59578 manufactured by Polycol Kogyo Co., Ltd., titanium oxide content 80% by weight) 4% by weight blended polypropylene resin composition, MFR (D) = 10 g / 10 min, Tm (D) = 161 ° C.
(D-5): Polypropylene resin composition in which 96% by weight of polypropylene resin (A-2) is blended with 4% by weight of silver pigment MB (PPCM913Y-42 SILVER21X manufactured by Toyocolor Co., Ltd.), MFR = 10 g / 10 Min, Tm = 161 ° C.

(2) Thermoplastic elastomer (B)
The following thermoplastic elastomers were used.
(B-1): Propylene-butene random copolymer mainly composed of propylene (MFR (B) = 7.0 g / 10 min, Tm (B) = 75 ° C., density = 0.85 g / cm ³ , propylene Content = 69 wt%, butene content = 31 wt%, ethylene content [E (B)] = 0 wt%): manufactured by Mitsui Chemicals, Inc., trade name “Tuffmer XM7070”
(B-2): Butene homopolymer (MFR (B) = 5.0 g / 10 min, Tm (B) = 125 ° C., density = 0.915 g / cm ³ , ethylene content [E (B)] = 0 (% By weight): Made by Mitsui Chemicals, trade name “Toughmer BL4000”
(B-3): Propylene-ethylene-butene random copolymer containing propylene as the main component (MFR (B) = 6.0 g / 10 min, Tm (B) = 160 ° C., density = 0.868 g / cm ³ Propylene content = 84 wt%, ethylene content [E (B)] = 9 wt%, butene content = 7 wt%): Mitsui Chemicals, trade name “Tuffmer PN2060”
(B-4): propylene-ethylene random copolymer containing propylene as a main component (MFR (B) = 8.0 g / 10 min, Tm (B) = 61 ° C., density = 0.87 1 g / cm ³ , propylene Content = 89 wt%, ethylene content [E (B)] = 11 wt%): ExxonMobil Chemical Co., Ltd., trade name “VISTAMAX3000”

3. Production of Resin Molded Body (Substrate) An injection molded body was obtained by the following method using the following polypropylene resins (X-1) to (X-3).
(X-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 165 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC (registered trademark) MA04H”
(X-2): Propylene ethylene block copolymer (MFR = 30 g / 10 min, Tm = 164 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “Novatech (registered trademark) NBC03HR”
(X-3): 60% by weight of polypropylene resin (X-2), 20% by weight of EBR (Tafmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Talc) Polypropylene resin composition injection molding machine blended with 20% by weight of talc P-6 (manufactured by Co., Ltd., average particle size 4.0 μm): Toshiba Machine Co., Ltd. “IS100GN”, mold clamping pressure 100 ton cylinder temperature: 200 ° C.
Mold temperature: 40 ℃
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate condition adjustment: hold for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 50% RH

Further, the obtained injection molded article was scratched by the following method to obtain a resin molded article (substrate).
Scratch evaluation processing: In a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% RH, using a scratch tester (“SCRATCH & MAR TESTER” manufactured by ROCKWOOD SYSTEMS AND EQUIPMENT) at a load of 25 N, the shape (curvature radius 0. The scratched tip was scratched at the scratching tip at a scratching speed of 100 mm / min.

  The scratch on the surface of the resin molded body (substrate) was measured with a shape measuring instrument laser microscope (“VX-X200” manufactured by KEYENCE), and the depth of the scratch was 16 μm. The scratches were whitening wounds.

Example 1
-Manufacture of a decorative film Lip opening degree 0.8mm to which the extruder 1 for sealing layers (I) with a diameter of 30 mm (diameter) and the extruder 2 for layers (II) with a diameter of 40 mm (diameter) were connected A two-type two-layer T die having a die width of 400 mm was used. For the layer (II), a polypropylene resin (A-1) and a thermoplastic elastomer (B-1) blended so as to have a weight ratio of 85:15 to the extruder 1 for the seal layer (I) Polypropylene resin (C-1-1) having a long-chain branched structure is charged into Extruder-2, the resin temperature is 240 ° C., the discharge rate of Extruder-1 for seal layer (I) is 4 kg / h, (II) Melt extrusion was carried out at a discharge rate of the extruder-2 of 12 kg / h. The melt-extruded film was cooled and solidified while being pressed with an air knife against a first roll rotating at 80 ° C. at 3 m / min so that the seal layer (I) was on the outside, and a seal layer (I) having a thickness of 50 μm, A two-layer unstretched film in which a layer (II) having a thickness of 150 μm was laminated was obtained.

-Three-dimensional decoration thermoforming As the resin molding (base | substrate) 5, the injection molding which consists of the polypropylene resin (X-1) obtained by the above was used.
As a three-dimensional decorative thermoforming apparatus, “NGF-0406-SW” manufactured by Fuse Vacuum Co., Ltd. was used. 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 seal layer (I) faces the base and the longitudinal direction is the MD direction of the film. It set to the jig 13 for film fixing whose size is 210 mm x 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 chamber boxes 11 and 12, the chamber box was 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 5 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 ( The substrate 5 was pressed against the decorative film 1, and immediately after that, compressed air was fed so that the pressure in the upper chamber box 11 was 270 kPa, thereby bringing the resin molded body (substrate) 5 and the decorative film 1 into close contact. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was adhered to the upper surface and the side surface of the resin molded body (substrate) 5 was obtained.

・ Evaluation of physical properties (1) Evaluation of formability (appearance of decorative molded body)
The drawdown 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 attached to the base are visually observed, and the criteria shown below It was evaluated with.
○: 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: Since the decorative film was drawn down during three-dimensional decorative thermoforming, 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) Evaluation of the effect of making scratches inconspicuous A shape measurement laser microscope is used to measure the depth of scratches in a part of a three-dimensional decorative thermoformed product of a molded body (substrate) scratched with a load of 25 N. ("VX-X200" manufactured by KEYENCE). The number of times of measurement was n = 5, and the average value was taken as the flaw depth (μm).
Further, as a whitening appearance, whether or not the whitening damage of the molded body (substrate) scratched with a load of 25 N was not noticeable by the decorative film was visually determined and evaluated according to the following criteria.
○: Traces of whitening scratches are not noticeable and the appearance is excellent.
X: Whitening scratches remain and the appearance is poor.

(4) Recyclability evaluation The obtained decorative molded body was pulverized, a recycled molded body was obtained by injection molding in the same manner as in the production of a resin molded body (substrate), and the appearance was visually evaluated.

(5) 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 1 shows the results of evaluating physical properties of the obtained decorative molded body and the like.
Since the polypropylene resin (A), the thermoplastic elastomer (B-1) and the polypropylene resin (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 2
In the production of the decorative film of Example 1, the polypropylene resin (C-1-1) having a long chain branching structure used for the layer (II) was replaced with the polypropylene resin (C-1-) having a long chain branching structure. Evaluation was performed in the same manner as in Example 1 except that 1) and the polypropylene resin (A-2) were changed to a blend having a weight ratio of 30:70. The evaluation results are shown in Table 1.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 3
In the production of the decorative film of Example 1, the polypropylene resin (C-1-1) having a long chain branching structure used for the layer (II) was replaced with the polypropylene resin (C-1-) having a long chain branching structure. Evaluation was performed in the same manner as in Example 1 except that the blend of 1) and the polypropylene resin (A-2) was changed so that the weight ratio was 5:95. The evaluation results are shown in Table 1.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 4
In the production of the decorative film of Example 1, the polypropylene resin (C-1-1) having a long chain branching structure used for the layer (II) was replaced with the polypropylene resin (C-1-) having a long chain branching structure. Evaluation was performed in the same manner as in Example 1 except that the procedure was changed to 2). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, and has scratches. It was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 5
In the production of the decorative film of Example 1, the polypropylene resin (C-1-1) having a long chain branching structure used for the layer (II) was replaced with the polypropylene resin (C-1-) having a long chain branching structure. Evaluation was performed in the same manner as in Example 1 except that 2) and the polypropylene resin (A-2) were changed to those blended so that the weight ratio was 30:70. The evaluation results are shown in Table 1.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 6
In the production of the decorative film of Example 1, the polypropylene resin (C-1-1) having a long chain branching structure used for the layer (II) was replaced with the polypropylene resin (C-1-) having a long chain branching structure. Evaluation was performed in the same manner as in Example 1 except that 2) and the polypropylene-based resin (A-2) were changed to those blended so that the weight ratio was 5:95. The evaluation results are shown in Table 1.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 7
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the blending ratio of the polypropylene resin (A-1) and the thermoplastic elastomer (B-1) was set to 70:30. went. The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 8
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the blending ratio of the polypropylene resin (A-1) and the thermoplastic elastomer (B-1) was 30:70. went. The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 9
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the thermoplastic elastomer used for the seal layer was changed to (B-2). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 10
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the thermoplastic elastomer used for the seal layer was changed to (B-3). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 11
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the thermoplastic elastomer used for the seal layer was changed to (B-4). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 12
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the polypropylene resin used for the seal layer was changed to (A-2). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 13
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that the polypropylene resin used for the seal layer was changed to (A-3). The evaluation results are shown in Table 1.
Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 14
In the production of a decorative film, an extruder 1 for a sealing layer (I) having a diameter of 30 mmφ, an extruder 2 for a layer (II) having a diameter of 40 mmφ, and an extruder 3 for a surface decorative layer (III) having a diameter of 30 mmφ 3 type 3 layer T die having a lip opening of 0.8 mm and a die width of 400 mm were used. For the layer (II), a polypropylene resin (A-1) and a thermoplastic elastomer (B-1) blended so as to have a weight ratio of 85:15 to the extruder 1 for the seal layer (I) A polypropylene resin (C-1-1) having a long-chain branched structure is introduced into Extruder-2, and a polypropylene resin (A-2) is introduced into Extruder-3 for the surface decoration layer (III). Temperature 240 ° C., discharge rate of extruder 1 for sealing layer (I) 4 kg / h, discharge rate of extruder 1 for layer (II) 8 kg / h, extruder for surface decorative layer (III) — Melt extrusion was carried out under the condition of 1 discharge rate of 4 kg / h.
The melt-extruded film was cooled and solidified while being pressed by an air knife against a first roll rotating at 3 m / min at 80 ° C. so that the surface decorative layer (III) was in contact with the sealing layer (I) having a thickness of 50 μm, A three-layer unstretched film in which a layer (II) having a thickness of 100 μm and a surface decoration layer (III) having a thickness of 50 μm were laminated was obtained.
Otherwise, the evaluation was performed in the same manner as in Example 1. The obtained results are shown in Table 1. Since the polypropylene-based resin (A), the thermoplastic elastomer (B), and the polypropylene-based resin (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, Was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯). Moreover, the decorative molded body which was more excellent in surface gloss was able to be obtained by providing surface decoration layer (III).

Comparative Example 1
In the production of the decorative film of Example 1, the thermoplastic elastomer (B) is not blended in the seal layer (I) and only the polypropylene resin (A-1) is used, and the layer (II) has a long chain branched structure. Evaluation was performed in the same manner as in Example 1 except that only a polypropylene resin (A-2) was used without blending a polypropylene resin. The evaluation results are shown in Table 1.
Since the sealing layer (I) does not contain the thermoplastic elastomer (B), the adhesive strength is small, and since the layer (II) does not contain a polypropylene resin having a long-chain branched structure, the drawdown of the film is severe. The appearance of the decorative molded body was inferior, and scratches and surface gloss were not evaluated.

Comparative Example 2
In the production of the decorative film of Example 1, the same as Example 1 except that only the polypropylene resin (A-2) was used without blending the polypropylene resin having a long chain branched structure in the layer (II). Was evaluated. The evaluation results are shown in Table 1.
Since layer (II) does not contain a polypropylene-based resin having a long-chain branched structure, the drawdown of the film is severe, the appearance of the decorative molded body is inferior, and scratches and surface gloss were not evaluated. .

Comparative Example 3
In the production of the decorative film of Example 1, evaluation was performed in the same manner as in Example 1 except that only the polypropylene resin (A-1) was used in the sealing layer (I) without blending the thermoplastic elastomer (B). Went. The evaluation results are shown in Table 1.
Since the sealing layer (I) does not contain the thermoplastic elastomer (B), the adhesive strength is small, and it is not possible to sufficiently suppress the scratches, resulting in poor whitening appearance.

Example 15
In the three-dimensional decorative thermoforming of Example 1, evaluation was performed in the same manner as in Example 1 except that the base was changed to an injection-molded body using resin (X-2). The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 16
In the three-dimensional decorative thermoforming of Example 1, evaluation was performed in the same manner as in Example 1 except that the base was changed to an injection-molded body using resin (X-3). The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯).

Example 17
In manufacture of the decorative film of Example 14, it implemented except having changed the polypropylene resin (A-2) thrown into the extruder 3 for surface decoration layers (III) into the polypropylene resin (D-1). Evaluation was performed in the same manner as in Example 14. The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯). 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 the surface decorating layer (III).

Example 18
In manufacture of the decorative film of Example 14, it implemented except having changed the polypropylene resin (A-2) thrown into the extruder 3 for surface decoration layers (III) into the polypropylene resin (D-2). Evaluation was performed in the same manner as in Example 14. The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯). Moreover, it was a result which was excellent in glossiness by having laminated | stacked polypropylene resin (D-2) on the outermost surface side as surface decoration layer (III).

Example 19
In manufacture of the decorative film of Example 14, it implemented except having changed the polypropylene resin (A-2) thrown into the extruder 3 for surface decoration layers (III) into the polypropylene resin (D-3). Evaluation was performed in the same manner as in Example 14. The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) satisfy all the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength, The wound was inconspicuous. The recycled molded body was excellent in appearance (evaluation: ◯). Moreover, it was a result which was excellent in glossiness because the polypropylene resin (D-3) to which the nucleating agent was added was laminated on the outermost surface side as the surface decoration layer (III).

Example 20
In manufacture of the decorative film of Example 14, it implemented except having changed the polypropylene resin (A-2) thrown into the extruder 3 for surface decoration layers (III) into the polypropylene resin (D-4). Evaluation was performed in the same manner as in Example 14. The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the decorative film colored in white was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since the surface decoration layer (III) excellent in gloss was colored in white, it was excellent in the external appearance.

Example 21
In the production of the decorative film of Example 14, evaluation was performed in the same manner as in Example 14 except that the polypropylene resin (C-1-1) was changed to the polypropylene resin (C-1-3). The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the decorative film colored in black was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since layer (II) was colored black, it was excellent in appearance. Furthermore, since the polypropylene resin (A-2) was laminated on the outermost surface side as the surface decoration layer (III), the result was excellent in gloss.

Example 22
In manufacture of the decorative film of Example 21, it implemented except having changed the polypropylene resin (A-2) thrown into the extruder 3 for surface decoration layers (III) into the polypropylene resin (D-5). Evaluation was carried out in the same manner as in Example 21. The obtained results are shown in Table 2.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) all satisfy the requirements of the present invention, the obtained decorative molded body is excellent in appearance and adhesive strength. It was. Moreover, combined with the fact that the colored decorative film was stuck, the wound was sufficiently concealed so that the damaged part could not be specified. Therefore, the wound depth was not measured. Moreover, since the polypropylene resin (D-5) was laminated on the outermost surface side as the surface decoration layer (III), the result was excellent in gloss. Furthermore, since the layer (II) was colored black and the surface decoration layer (III) was colored silver, it became a metallic film and was excellent in appearance.

Example 23
-Manufacture of a decoration film In manufacture of the decoration film of Example 22, the discharge amount of the extruder-1 for sealing layer (I) is 4 kg / h, and the discharge amount of the extruder-2 for layer (II) is 12 kg / h. h, the extrusion amount of the surface decoration layer (III) extruder-3 is melt-extruded under the condition of 4 kg / h, and the obtained three-layer unstretched film is slit into a width of 200 mm, thereby obtaining a thickness of 50 μm. A three-layer unstretched film in which a surface decoration layer, a layer having a thickness of 150 μm, and a seal layer having a thickness of 50 μm were laminated was obtained.

-Manufacture of embossed film Yuri Roll Co., Ltd. electric heating type test embossing machine was used as an embossing molding apparatus. The electric heating type test embossing machine has an upper concavo-convex shape by heating and pressing the film with a roll (embossing roll) with a heatable concavo-convex shape installed in the upper stage and a smooth roll installed in the lower stage. Has a mechanism for transferring the film to the film surface. The embossing roll used a hairline pattern with a depth of 30 μm.
The three-layer unstretched film obtained by the production of the decorative film was fed out to two rolls of an embossing machine so that the surface decorative layer (III) was in contact with the embossing roll. By performing emboss transfer under the conditions of an embossing roll temperature of 145 ° C., a contact pressure of 3 MPa, and a roll speed of 3 m / min, a decorative film having a hairline pattern transferred to the surface of the surface decorative layer (III) was obtained.

-Three-dimensional decorative thermoforming A three-dimensional decorative thermoformed product was obtained in the same manner as in Example 1.

-Physical property evaluation (1) Evaluation of emboss transfer The depth of the hairline pattern site | part given to the surface decoration layer of the obtained decorating film was measured with the shape measurement laser microscope ("VX-X200" by KEYENCE company). . The number of measurements was n = 5, and the average value was the emboss depth (μm).

(2) Evaluation of embossed pattern after thermoforming The remaining embossed pattern after three-dimensional decorative thermoforming was visually observed and evaluated according to the following criteria.
○: An embossed pattern remains on the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design is excellent.
X: The embossed pattern has disappeared on most of the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design is poor.

Table 3 shows the physical property evaluation results of the obtained decorative molded body and the like.
Since the polypropylene resin (A), the thermoplastic elastomer (B) and the polypropylene resin composition (C) all satisfy the requirements of the present invention, the emboss depth of the film obtained by the production of the embossed film is 25 μm. And was excellent. In addition, the hair alignment pattern remained strongly on the surface of the three-dimensional decorative thermoformed product after the three-dimensional decorative thermoforming, and the design was excellent.

  According to the present invention, it is possible to achieve both sufficient adhesive strength and excellent product appearance, less wrinkle return, and less product defects by making the substrate inconspicuous, making recycling easier. There are provided a decorative film used for three-dimensional decorative thermoforming and a method for producing a decorative molded body using the decorative film.

1 decorative film 2 layers (II)
3 Sealing layer (I)
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 (9)

A decorative film for sticking by thermoforming on a resin molded body,
The decorative film includes a polypropylene resin (A) and a thermoplastic elastomer (B) as main components,
Seal layer (I) made of a resin composition having a weight ratio of 97: 3 to 5:95, and a polypropylene resin or a polypropylene resin composition (C). A layer (II) consisting of
The polypropylene resin (A) satisfies the following requirement (a1),
The thermoplastic elastomer (B) satisfies the following requirements (b1) to (b3),
The polypropylene resin or the polypropylene resin composition (C) satisfies the following requirements (c1) to (c2).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) A thermoplastic elastomer mainly composed of propylene and / or butene.
(B2) The density is 0.850 to 0.950 g / cm ³ .
(B3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) is 0.1 to 100 g / 10 min.
(C1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 40 g / 10 min or less.
(C2) The strain hardening degree λ is 1.1 or more.   The thermoplastic elastomer (B) is a propylene-ethylene copolymer having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of less than 50% by weight. The decorative film according to claim 1, which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer. The decorative film according to claim 1 or 2, wherein the thermoplastic elastomer (B) satisfies the following requirement (b4).
(B4) Melting peak temperature (Tm (B)) is 30-170 degreeC. The decorative film according to any one of claims 1 to 3, wherein the polypropylene-based resin or the polypropylene-based resin composition (C) satisfies the following requirements (c1 ') to (c2').
(C1 ′) MFR (B) is 20 g / 10 min or less.
(C2 ′) The strain hardening degree λ is 1.8 or more. The decorative film according to any one of claims 1 to 4, wherein the polypropylene resin or the polypropylene resin composition (C) satisfies the following requirements (c1 ") to (c2").
(C1 ″) MFR (B) is 12 g / 10 min or less.
(C2 ″) The strain hardening degree λ is 2.3 or more.   The said polypropylene resin or polypropylene resin composition (C) contains the polypropylene resin (C-1) which has a long chain branched structure, The addition as described in any one of Claims 1-5 characterized by the above-mentioned. Decorative film.   The said polypropylene resin (C-1) is a polypropylene resin with few gels manufactured by methods other than the crosslinking method, The decorating film of Claim 6 characterized by the above-mentioned.   The step of preparing the decorative film according to any one of claims 1 to 7, the step of preparing a resin molded body, and the step of setting the resin molded body and the decorative film in a chamber box capable of decompression. A step of reducing the pressure inside the chamber box, a step of softening the decorative film, a step of pressing the decorative film against the resin molded body, and a step of returning or pressurizing the reduced pressure inside the chamber box. The manufacturing method of the decorative molded object characterized by including.   The method for producing a decorative molded body according to claim 8, wherein the resin molded body is made of a propylene-based resin composition.