Decorative film and method for producing decorative shaped body using the same

Abstract

The present invention aims to provide a polypropylene-based decorative film that is easily recyclable, can simultaneously produce sufficient bonding strength and product appearance, and is used for three-dimensional decorative thermoforming; and to provide a method for producing a decorative molded body using the same decorative film. The present invention relates to a decorative film that is attached to a resin molded body using thermoforming, wherein the decorative film comprises a layer (II) comprising a resin composition (B) containing a polypropylene-based resin (B), and the resin composition (B) has (b1) an MFR (B) of less than 40 g / 10 min (230° C., load of 2.16 kg) and (b2) a strain hardening degree λ of more than 1.1.

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of August 9, 2017, application number 201780058496.X, and invention name "Decorative film and method for producing decorative molded body using the same". Technical Field

[0002] The present invention relates to a decorative film pasted on a resin molded body by thermoforming and a method for producing a decorative molded body using the decorative film. More specifically, the present invention relates to a decorative film pasted on a resin molded body by thermoforming, which can suppress shrinkage and cracking of the film during thermoforming and can exhibit sufficient bonding strength to the resin molded body, and a method for producing a decorative molded body using the decorative film. In addition, the present invention relates to a decorative film pasted on a resin molded body by thermoforming, which exhibits less fading of crimps after thermoforming and less damage to the film such as migration of additives contained in the film to the outside of the film during thermoforming, and a method for producing a decorative molded body using the decorative film. Background Art

[0003] In recent years, due to the requirement for reduction of VOC (volatile organic compounds) and the like, the demand for decoration techniques instead of coating has increased, and thus various decoration techniques have been proposed.

[0004] In particular, a technology for forming a decorative molded product has been proposed, in which a decorative sheet and a molded body are integrated by applying a decorative film (decorative sheet) instead of a coating film to the molded body by vacuum pressure forming or vacuum forming (for example, see Patent Document 1), and recently, this technology has particularly attracted attention.

[0005] Compared with other decorative forming represented by insert forming, decorative forming by vacuum pressure forming and vacuum forming has the following advantages: the degree of freedom of shape is large, the appearance is excellent because no seam is produced because the edge of the decorative film is wrapped to the back of the decorated object, and since thermoforming can be performed at relatively low temperature and low pressure, the reproducibility of embossing, etc. on the surface of the decorative formed body by embossing, etc. on the surface of the decorative film is excellent.

[0006] In such decorative forming by vacuum pressure forming and vacuum forming, there are problems that film cracks and / or wrinkles occur on the decorative film when the decorative film and the formed body are attached, and the bonding strength between the decorative film and the formed body cannot be sufficiently obtained. In addition, as a layer for improving the bonding strength, the use of adhesives, tackifiers, etc. has been proposed, but the problems of using them are that they are expensive, the layer structure becomes extremely complicated, and the solvent resistance and heat resistance are insufficient.

[0007] In order to solve these problems, it has been proposed to apply a decorative film having an adhesive layer containing a polypropylene resin to a substrate (molded body) composed of a polypropylene resin and thermally fuse the decorative film and the molded body (for example, see Patent Documents 2 and 3).

[0008] In addition, in automobile parts, electrical parts and building material parts, resin molded bodies composed of polar resin materials such as polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, polyurethane resin, melamine resin and polyphenylene ether resin are often used. Since these polar resin materials have poor water resistance and chemical resistance, it is expected to improve water resistance and chemical resistance by attaching a decorative film.

[0009] On the other hand, polyolefin-based resins have low polarity and excellent water resistance and chemical resistance, and therefore various decorative films composed of polyolefin-based resins have been proposed.

[0010] Citation List

[0011] Patent Literature

[0012] Patent Document 1: JP-A-2002-67137

[0013] Patent Document 2: JP-A-2013-14027

[0014] Patent Document 3: JP-A-2014-124940 Summary of the invention

[0015] Problem that the invention aims to solve

[0016] The inventions disclosed in Patent Documents 2 and 3 use polypropylene resin as the adhesive layer of the decorative film, but in reality, it is necessary to further provide a layer of acrylic resin, polyurethane resin, polycarbonate, etc. as a surface layer, a bonding layer, and / or a bulk layer on the adhesive layer. Thermoformability such as draw-down property is expressed by combining heterogeneous raw materials as they are, but thermoformability cannot be ensured in a decorative film composed of polypropylene resin that does not contain heterogeneous raw materials. Therefore, holes, wrinkles, and air entrapment are easily generated on the surface of the molded product to which the decorative film is attached, and further the film is broken, so that a decorative molded body with excellent appearance cannot be obtained. In particular, in the case of containing polyurethane resin as a heterogeneous raw material, the polyurethane resin as a thermosetting resin does not melt when heated, so it is easy to maintain the shape of the film and significantly improve the thermoformability, but there is a problem of extremely low recyclability.

[0017] That is, in the decorative films described in Patent Documents 2 and 3, there are problems that they contain heterogeneous raw materials for ensuring thermoformability such as adhesiveness and appearance, the layer structure is complicated and its production requires many steps, and it is difficult to recycle the decorative films combining heterogeneous raw materials.

[0018] In addition, there is a problem that an embossing disappearance phenomenon, that is, disappearance of embossing and the like, occurs on the film surface due to heating and melting of the film during thermoforming.

[0019] In addition, decorative thermoforming by vacuum pressure forming and vacuum forming has the following advantages: the molded product has high integrity between the substrate and the decorative film formed by steps such as injection molding, but on the other hand, the decorative film picks up scratches formed on the surface of the substrate, and appearance defects caused by the influence of scratches formed on the surface of the decorative molded body (substrate) are prone to occur on the surface of the decorative molded product, so the scratches on the surface of the substrate should be strictly controlled.

[0020] Furthermore, in automobile parts, electrical parts, and building material parts, since conventional decorative films composed of polyolefin resin materials have poor thermoformability and poor adhesion to resin materials having polarity, the films are not sufficiently adaptable to decorative forming by vacuum pressure forming and vacuum forming.

[0021] That is, in the conventional technology, a decorative film composed of an propylene resin that is easy to recycle and can achieve both excellent adhesiveness and appearance has not yet been obtained. In view of the above problems, an object of the present invention is to provide a decorative film for three-dimensional decorative thermoforming that can achieve both sufficient adhesive strength and product appearance and is easy to recycle, and a method for producing a decorative formed body using the decorative film.

[0022] In addition, an object of the present invention is to provide a decorative film capable of reducing product defects by making scratches on a substrate less noticeable and further showing less embossing disappearance, and a method for producing a decorative formed body using the decorative film.

[0023] Furthermore, in automobile parts, electric appliance parts, and building material parts, a decorative film composed of a polypropylene-based resin, which is suitable for decorative forming by vacuum pressure forming and vacuum forming and has satisfactory adhesion to a substrate having polarity, has not been developed in the conventional art. Therefore, an object of the present invention is also to provide a decorative film for three-dimensional decorative thermoforming, which can be adhered to a substrate having polarity and has excellent product appearance, and a method for producing a decorative formed body excellent in water resistance and chemical resistance using the decorative film.

[0024] Solutions for solving problems

[0025] In three-dimensional decorative thermoforming, in order to stick a solid decorative film to a solid resin molded body, the molded body surface and the film need to be fully softened or melted. In addition, also in the case where the resin molded body has polarity, the adhesive layer of the film needs to have polarity, and the molded body surface and the film are also fully softened or melted. Therefore, it becomes important to increase the heat required for softening or melting the molded body surface and the film, or to use molded bodies and films that are easy to soften or melt. On the other hand, when the film is overheated, the viscosity of the film decreases, and the film breaks or moves violently during the three-dimensional decorative thermoforming step due to the protrusion of the molded body and the inflow of air when the vacuum chamber returns to atmospheric pressure, resulting in appearance defects. Therefore, research was conducted while paying attention to this fact. It was found that a decorative film including a layer composed of a specific polypropylene resin can solve the above problems, thereby completing the present invention.

[0026] In addition, when the decorative film also has a specific sealing layer, it was found that the effect of making scratches formed on the surface less noticeable, and the effects of suppressing the reduction of functions derived from additives such as heat resistance, weather resistance and nucleation performance, maintaining thermoformability and suppressing the disappearance of embossing were obtained, thereby completing the present invention.

[0027] That is, the decorative film of the present invention includes any of the following structures (1) to (25).

[0028] (1) A decorative film to be attached to a resin molded body by thermoforming,

[0029] The decorative film comprises a layer (II) comprising a resin composition (B) containing a polypropylene resin (B), and the resin composition (B) meets the following requirements (b1) and (b2):

[0030] (b1) a melt flow rate (MFR) (B) (230°C, 2.16 kg load) of 40 g / 10 min or less, and

[0031] (b2) The strain hardening degree λ is 1.1 or more.

[0032] (2) The decorative film according to (1) above,

[0033] The decorative film further comprises a sealing layer (I) comprising a polypropylene-based resin (A), and the MFR (A) (230° C., load of 2.16 kg) of the polypropylene-based resin (A) is greater than 2 g / 10 min.

[0034] (3) The decorative film according to (1) above,

[0035] The decorative film further comprises a sealing layer (I) composed of a polypropylene resin (A), and the polypropylene resin (A) satisfies the following requirements (a1) to (a4), and the polypropylene resin (B) further satisfies the following requirement (b3):

[0036] (a1) The polypropylene resin (A) is a metallocene catalyst-based propylene polymer,

[0037] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0038] (a3) the melting peak temperature (Tm) (A) is lower than 150°C,

[0039] (a4) a molecular weight distribution (Mw / Mn) (A) measured by GPC is 1.5 to 3.5, and

[0040] (b3) Tm(B) satisfies the following relation (b-3) with respect to the above Tm(A):

[0041] Tm(B)>Tm(A)...Formula (b-3).

[0042] (4) The decorative film according to (1) above,

[0043] wherein the decorative film further comprises a sealing layer (I) comprising a resin composition (X), the resin composition (X) comprising a polypropylene-based resin (A) and an ethylene-α-olefin random copolymer (C) as main components, the weight ratio of the polypropylene-based resin (A) to the ethylene-α-olefin random copolymer (C) being 97:3 to 5:95, and

[0044] The polypropylene-based resin (A) satisfies the following requirement (a2) and the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3):

[0045] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0046] (c1) an ethylene content [E(C)] of 65% by weight or more,

[0047] (c2) Density 0.850 to 0.950 g / cm 3 ,and

[0048] (c3) MFR(C) (230°C, load of 2.16 kg) is 0.1 to 100 g / 10 min.

[0049] (5) The decorative film according to (1) above,

[0050] wherein the decorative film further comprises a sealing layer (I) comprising a resin composition (X), the resin composition (X) comprising a polypropylene-based resin (A) and a thermoplastic elastomer (D) as main components, the weight ratio of the polypropylene-based resin (A) to the thermoplastic elastomer (D) being 97:3 to 5:95, and

[0051] The polypropylene-based resin (A) satisfies the following requirement (a2) and the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d3):

[0052] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0053] (d1) the thermoplastic elastomer is a thermoplastic elastomer in which at least one of propylene and butene is a main component,

[0054] (d2) Density 0.850 to 0.950 g / cm 3 ,and

[0055] (d3) MFR(D) (230°C, load of 2.16 kg) is 0.1 to 100 g / 10 min.

[0056] (6) The decorative film according to (1) above,

[0057] wherein the decorative film further comprises a sealing layer (I) comprising a resin composition (X), the resin composition (X) comprising a polypropylene-based resin (A) and a thermoplastic resin (E) as main components, the weight ratio of the polypropylene-based resin (A) to the thermoplastic resin (E) being 97:3 to 5:95, and

[0058] The polypropylene-based resin (A) satisfies the following requirement (a2), the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X) satisfies the following requirement (x1):

[0059] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0060] (e1) the thermoplastic resin (E) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and

[0061] (x1) The isothermal crystallization time (t) (seconds) measured by differential scanning calorimetry (DSC) satisfies the following formula (x-1):

[0062] t(X)≥1.5×t(A)...Formula (x-1)

[0063] wherein t(A) represents the isothermal crystallization time (seconds) of the polypropylene based resin (A) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A), and t(X) represents the isothermal crystallization time (seconds) of the resin composition (X) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A).

[0064] (7) The decorative film according to (1) above,

[0065] The decorative film further comprises a sealing layer (I) comprising a propylene-ethylene block copolymer (F), and the propylene-ethylene block copolymer (F) satisfies the following requirements (f1) to (f3):

[0066] (f1) the propylene-ethylene block copolymer (F) contains 5 to 97% by weight of a component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and 3 to 95% by weight of a component (F2) consisting of a propylene-ethylene random copolymer having an ethylene content greater than that of the component (F1),

[0067] (f2) MFR (F) (230°C, 2.16 kg load) greater than 0.5 g / 10 min, and

[0068] (f3) The melting peak temperature (Tm) (F) is 110 to 170°C.

[0069] (8) The decorative film according to (1) above,

[0070] The decorative film further includes a sealing layer (I) containing a polyolefin adhesive resin (G), the polyolefin adhesive resin (G) is a polyolefin resin having a polar functional group containing at least one heteroatom, and its MFR (G) (230°C, load of 2.16 kg) is less than 100 g / 10 minutes.

[0071] (9) The decorative film according to any one of (1) to (8) above,

[0072] The resin composition (B) satisfies the following requirements (b1') and (b2'):

[0073] (b1')(MFR)(B) (230°C, 2.16 kg load) is 20 g / 10 min or less, and

[0074] (b2′) The strain hardening degree λ is 1.8 or more.

[0075] (10) The decorative film according to any one of (1) to (8) above,

[0076] The resin composition (B) satisfies the following requirements (b1") and (b2"):

[0077] (b1") (MFR) (B) (230°C, load of 2.16 kg) is 12 g / 10 min or less, and

[0078] (b2”) The strain hardening degree λ is greater than 2.3.

[0079] (11) The decorative film according to any one of (1) to (10) above,

[0080] The polypropylene resin (B) is a polypropylene resin (B-1) having a long-chain branched structure.

[0081] (12) The decorative film according to (11) above,

[0082] Among them, the polypropylene resin (B-1) is a polypropylene resin with less gel, which is prepared by a method other than a crosslinking method.

[0083] (13) A decorative film according to any one of (1) to (12) above, comprising a surface decorative layer (III) composed of a surface decorative layer resin, wherein the surface decorative layer (III) is located on the side of the layer (II) opposite to the bonding side having the resin molded body.

[0084] (14) The decorative film according to (13) above,

[0085] The surface decoration layer resin contains a polypropylene resin (H), and the polypropylene resin (H) has a strain hardening degree λ of 1 or less.

[0086] (15) The decorative film according to (3) above,

[0087] The polypropylene resin (A) is a propylene-α-olefin copolymer.

[0088] (16) The decorative film according to (3) or (15) above,

[0089] The above-mentioned Tm(A) is 140°C or lower.

[0090] (17) The decorative film according to (4) above,

[0091] The ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4):

[0092] (c4) The melting peak temperature (Tm) (C) is 30 to 130°C.

[0093] (18) The decorative film according to (4) or (17) above,

[0094] The ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c5):

[0095] (c5) The ethylene-α-olefin random copolymer (C) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

[0096] (19) The decorative film according to (5) above,

[0097] The thermoplastic elastomer (D) is a propylene-ethylene copolymer with an ethylene content of less than 50 wt%, a butene-ethylene copolymer with an ethylene content of less than 50 wt%, a propylene-ethylene-butene copolymer with an ethylene content of less than 50 wt%, a propylene-butene copolymer or a butene homopolymer.

[0098] (20) The decorative film according to (5) or (19) above,

[0099] The thermoplastic elastomer (D) further meets the following requirement (d4):

[0100] (d4) The melting peak temperature (Tm) (D) is 30 to 170°C.

[0101] (21) The decorative film according to (6) above,

[0102] The thermoplastic resin (E) is a styrene elastomer.

[0103] (22) The decorative film according to (6) above,

[0104] The thermoplastic resin (E) is an alicyclic hydrocarbon resin.

[0105] (23) The decorative film according to (7) above,

[0106] The propylene-ethylene block copolymer (F) further satisfies the following requirement (f4):

[0107] (f4) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.

[0108] (24) The decorative film according to (7) or (23) above,

[0109] The propylene-ethylene block copolymer (F) further satisfies the following requirement (f5):

[0110] (f5) The ethylene content of component (F1) is in the range of 0 to 6% by weight.

[0111] (25) The decorative film according to (7), (23) or (24) above,

[0112] The propylene-ethylene block copolymer (F) further satisfies the following requirement (f6):

[0113] (f6) The ethylene content of component (F2) is in the range of 5 to 90% by weight.

[0114] Furthermore, the method for producing a decorative molded body of the present invention includes any of the following configurations (26) to (28).

[0115] (26) A method for producing a decorative molded body, comprising:

[0116] preparing a decorative film according to any one of (1) to (25) above,

[0117] preparing a resin molded body,

[0118] Place the resin molded body and the decorative film in a decompressible cavity box.

[0119] Reduce the pressure in the chamber box,

[0120] Heat the decorative film to soften it.

[0121] The heated and softened decorative film is pressed against the resin molded body, and the interior of the decompression chamber box is returned to atmospheric pressure or pressurized.

[0122] (27) The method for producing a decorative molded body according to (26) above, wherein the resin molded body comprises a propylene-based resin composition.

[0123] (28) The method for producing a decorative molded body according to (26) above,

[0124] wherein the decorative film is a decorative film according to any one of (8) to (14) above, and

[0125] The resin molded body includes a polar resin material containing at least one selected from the following: polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, polyurethane resin, melamine resin, polyphenylene ether resin and their composite materials.

[0126] Effects of the Invention

[0127] Since the decorative film of the present invention includes a layer (II) composed of a resin composition (B) containing a polypropylene-based resin (B) having a specific melt flow rate (MFR), even when it does not include a thermosetting resin, the film is excellent in thermoformability during three-dimensional decorative thermoforming, the heating time can be sufficiently extended, and both high bonding strength to polypropylene-based molded bodies that have been difficult to bond heretofore and a satisfactory product appearance can be achieved.

[0128] In addition, since the decorative film further includes a specific sealing layer (adhesive layer) (I), scratches formed on the surface of the substrate can be made less noticeable, thereby reducing product defects. In addition, since the decorative film can be attached to the molded body in a short heating time, it is also possible to obtain a decorative film that suppresses the disappearance of embossing, is less likely to pick up scratches on the surface of the molded body, and has good recyclability.

[0129] According to the composition of the sealing layer (I), the decorative film can be attached to a substrate having polarity, and the decorative molded body including the decorative film and the substrate composed of a polar resin material has particularly excellent water resistance and chemical resistance.

[0130] According to the method for producing a decorative film of the present invention, a beautiful decorative molded body can be obtained, on the surface of which there are no holes or wrinkles, no air is trapped between the decorative film and the resin molded body, the reproducibility of textures such as embossing is satisfactory, and scratches are not noticeable. Moreover, the decorative film can be beautifully attached to a resin molded body that has been difficult to adhere to so far. In addition, since the constituent material of the decorative film is a resin composition (B) containing a polypropylene-based resin (B) and does not contain or may not contain a thermosetting resin layer, when the decorative molded body thus obtained is recycled, the reduction in appearance and performance is small, and therefore the recycling applicability is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0131] [ Figure 1A ] Figure 1A (a) to Figure 1A (c) is a schematic cross-sectional view illustrating an embodiment of a decorative formed body in which the decorative film of the present invention is adhered to a formed body, and is an example in which the layer configurations of the decorative films are each different.

[0132] [ Figure 1B ] Figure 1B (a) to Figure 1B (c) is a schematic cross-sectional view illustrating an embodiment of a decorative molded body in which the decorative film of the present invention is attached to a molded body, and is an example in which the layer configurations of the decorative films are respectively different.

[0133] [ Figure 1C ] Figure 1C (a) to Figure 1C (c) is a diagram showing an example of the layer structure of the decorative film of the present invention.

[0134] [ Figure 2 ] Figure 2 is a schematic cross-sectional view illustrating the outline of an apparatus used in the method for producing a decorative film of the present invention.

[0135] [ Figure 3 ] Figure 3 It is explained in Figure 2 Schematic cross-sectional view of a state in which a resin molded body and a decorative film have been placed in an apparatus.

[0136] [ Figure 4 ] Figure 4 It is explained in Figure 2 Schematic cross-sectional view of a state in which heating and decompression are performed in an apparatus.

[0137] [ Figure 5 ] Figure 5It is explained in Figure 2 Schematic cross-sectional view of a state in which a decorative film is pressed against a resin molded body in an apparatus.

[0138] [ Figure 6 ] Figure 6 It is explained in Figure 2 A schematic cross-sectional view showing a state in which the pressure in the device is returned to atmospheric pressure or pressurized.

[0139] [ Figure 7 ] Figure 7 This is a schematic cross-sectional view illustrating a state in which unnecessary edges of a decorative film are trimmed when a decorative molded body is obtained. DETAILED DESCRIPTION

[0140] In this specification, a decorative film refers to a film used to decorate a formed body. Decorative forming refers to forming in which a decorative film is pasted to a formed body. Three-dimensional decorative thermoforming refers to forming in which a decorative film is pasted to a formed body, which has the steps of thermoforming the decorative film along the pasting surface of the formed body and pasting the film thereto at the same time, the step of performing thermoforming under reduced pressure (vacuum) to suppress air from being drawn between the decorative film and the formed body, pasting the heated decorative film to the formed body and tightly bonding them by pressure release (pressurization). In addition, "to" showing a numerical range is used as a meaning including the numerical values ​​described before and after "to" as lower and upper limits.

[0141] The following will describe in detail the mode for carrying out the present invention.

[0142] <Layer (II)>

[0143] The decorative film in the present invention is a decorative film pasted on a resin molded body by thermoforming, wherein the decorative film includes a layer (II) composed of a resin composition (B) containing a polypropylene-based resin (B) (hereinafter sometimes simply referred to as "resin composition (B)" or "polypropylene-based resin composition (B)"), and the resin composition (B) has a specific melt flow rate (MFR) that satisfies the requirement (b1) mentioned below and a strain hardening property that satisfies the requirement (b1) mentioned below in the measurement of elongational viscosity.

[0144] By providing layer (II), the appearance defects caused by film breakage or violent movement during three-dimensional decoration thermoforming can be suppressed. Thus, the thermoformability of the decorative film is improved, so the decorative film can appropriately not contain a thermosetting resin layer with excellent thermoformability.

[0145] Furthermore, by improving the moldability of the resin composition (B) containing the polypropylene resin (B), a film having an extremely simple structure of a single layer (II) of the resin composition (B) or a laminated layer of a layer (II) composed of the resin composition (B) and a sealant layer can be used as a decorative film. When the film has such a structure, a decorative film can be formed by (co)extrusion.

[0146] [Resin composition (B) containing polypropylene resin (B)]

[0147] The decorative film comprises a layer (II) composed of a resin composition (B) comprising a polypropylene resin (B). The resin composition (B) may consist of only the polypropylene resin (B), may consist of a polypropylene resin composition (B) comprising a plurality of polypropylene resins, or may consist of a blend of the polypropylene resin (B) and another polypropylene resin.

[0148] The resin composition (B) satisfies both the requirements (b1) and (b2) mentioned below, but when the resin composition (B) is composed of only the polypropylene resin (B), the polypropylene resin (B) satisfies the requirements (b1) and (b2). In addition, when the resin composition (B) is composed of the polypropylene resin (B) and another polypropylene resin, it is preferred that at least the polypropylene resin (B) satisfies the requirements (b1) and (b2) except the resin composition (B). The blend of the polypropylene resin (B) and another polypropylene resin is not particularly limited and may be a mixture of pellets and / or powders, a melt blend or a solution blend, or a combination thereof.

[0149] In the present invention, since sufficient molding stability of the resin composition (B) cannot be obtained when the viscosity is too low, the resin composition (B) containing the polypropylene resin (B) should have a certain viscosity. In the present invention, as an index of viscosity, the melt flow rate (MFR) (230° C., 2.16 kg load) is defined.

[0150] Here, the MFR (230° C., load of 2.16 kg) of the resin composition (B) containing the polypropylene resin (B) is referred to as MFR (B). MFR (B) satisfies the following requirement (b1), preferably satisfies the requirement (b1′), and more preferably satisfies the requirement (b1″). By controlling the MFR (B) of the resin composition (B) to be below the following value, a decorative molded body having a satisfactory appearance can be obtained.

[0151] (b1) MFR (B) is 40 g / 10 min or less

[0152] (b1') MFR (B) is 20 g / 10 min or less

[0153] (b1") MFR (B) is less than 12g / 10min

[0154] The lower limit of the MFR (B) of the resin composition (B) is not particularly limited, but is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. By controlling the MFR (B) to a value above, the formability when producing a decorative film is improved, and the appearance defect called shark skin and a rough interface on the film surface can be suppressed.

[0155] Here, the MFR of the polypropylene-based resin or the resin composition is measured under the conditions of 230° C. and a load of 2.16 kg according to ISO 1133:1977 Condition M. The unit is g / 10 minutes.

[0156] The strain hardening degree λ of the resin composition (B) containing the polypropylene resin (B) satisfies the following requirement (b2), preferably satisfies the following requirement (b2'), and more preferably satisfies the following requirement (b2") . By controlling the strain hardening degree λ of the resin composition (B) to a value within the following range, a decorative molded product having satisfactory moldability during thermoforming and satisfactory appearance can be obtained.

[0157] (b2) The strain hardening degree λ is 1.1 or more.

[0158] (b2′) The strain hardening degree λ is 1.8 or more.

[0159] (b2”) The strain hardening degree λ is greater than 2.3.

[0160] The upper limit of the strain hardening degree of the resin composition (B) is not particularly limited, but is preferably 50 or less, more preferably 20 or less. By controlling the strain hardening degree to a value within the above range, the appearance of the decorative film can be made satisfactory.

[0161] The strain hardening degree of the resin composition (B) is determined based on the measurement of the strain hardening property in the extension viscosity measurement. The strain hardening property (non-linear) of the extension viscosity is described in "Koza Rheology" compiled by The Society of Rheology, Japan, Kobunshi Kankoukai, 1992, pp. 221-222. Herein, the strain hardening degree λ is determined by the method according to the book. Figure 7-2 0, and η*(0.01) is used as the value of shear viscosity, ηe(3.5) is used as the value of extension viscosity, and the strain hardening degree λ is defined by the following formula (b-1).

[0162] λ=ηe(3.5) / {3×η*(0.01)}...Formula (b-1)

[0163] In formula (b-1), η*(0.01) is the complex viscosity coefficient [unit: Pa.s] at a measurement temperature of 180°C and an angular frequency ω=0.01 rad / s, which is measured by a dynamic frequency sweep experiment, and the complex viscosity coefficient η* is calculated from the complex modulus G* [unit: Pa] and the angular frequency ω according to η*=G* / ω. In addition, ηe(3.5) is the complex viscosity coefficient [unit: Pa.s] at a measurement temperature of 180°C and an angular frequency ω=0.01 rad / s, which is measured by a dynamic frequency sweep experiment, and the complex viscosity coefficient η* is calculated from the complex modulus G* [unit: Pa] and the angular frequency ω according to η*=G* / ω. -1 The strain rate and extensional viscosity at a strain of 3.5.

[0164] In general, the data obtained by viscoelasticity measurement becomes a set of numerical values ​​of modulus, viscosity, etc. at discrete frequencies or measurement time intervals. Therefore, in the case of measurements performed on an apparatus different from that used in the present invention or under conditions different from those used in the present invention, there may be a case where data of the complex viscosity coefficient η*(0.01) at an angular frequency ω=0.01 and / or the elongational viscosity ηe(3.5) at a strain of 3.5 do not always exist, but in that case, it is allowed to estimate the relevant values ​​using data before and after the point by interpolation such as linear interpolation, spline interpolation, etc. When performing interpolation, it is a common method to use a logarithmic scale as a scale for stress and time.

[0165] At this time, when the sample has no strain hardening property (nonlinearity) to the extensional viscosity, the strain hardening degree λ shows a value of about 1 (e.g., 0.9 or more and less than 1.1) or less, and as the strain hardening property (nonlinearity) increases, the value of the strain hardening degree λ increases.

[0166] Ordinary crystalline polypropylene is a linear polymer and generally does not have strain hardening properties. On the other hand, the polypropylene resin (B) used in the present invention is preferably a polypropylene resin (B-1) having a long-chain branched structure, and therefore, the resin composition (B) containing the polypropylene resin (B) can exhibit more satisfactory strain hardening properties.

[0167] The long-chain branched structure in the present invention refers to a branched structure of a molecular chain for exhibiting strain hardening properties, wherein the carbon number of the carbon skeleton constituting the branched chain (the main chain of the branched chain) is more than several tens and its molecular weight is more than several hundred. The long-chain branched structure is different from the short-chain branched chain formed by copolymerization with an α-olefin such as 1-butene.

[0168] As a method for introducing a long-chain branched structure into a polypropylene-based resin, there can be mentioned a method of irradiating a polypropylene having no long-chain branched structure with high-energy ionizing radiation (JP-A-62-121704), a method of reacting a polypropylene having no long-chain branched structure with an organic peroxide (JP-T-2001-524565), or a method of producing a macromonomer having a terminal unsaturated bond using a metallocene catalyst having a specific structure and copolymerizing the macromonomer with propylene to form a long-chain branched structure (JP-T-2001-525460). In any case of production using any of these methods, the strain hardening degree of the polypropylene-based resin can be significantly improved.

[0169] The polypropylene resin (B-1) having a long-chain branched structure is not particularly limited as long as it has a long-chain branched structure, but is preferably a polypropylene resin produced by a method other than a crosslinking method, and more preferably a polypropylene resin having a comb-shaped chain structure obtained by a method using a macromolecular copolymerization method that forms a long-chain branched structure during polymerization. Examples of such methods include methods disclosed in JP-T-2001-525460, JP-T-10-338717, JP-T-2002-523575, JP-A-2009-57542, Japanese Patent No. 05027353, and JP-A-10-338717. In particular, the macromonomer copolymerization method of JP-A-2009-57542 can provide a polypropylene resin containing long-chain branches without generating a gel, and is therefore suitable for use in the present invention.

[0170] The presence of long-chain branching in polypropylene is determined by a method based on the rheological properties of the resin, a method for calculating the branching index g' using the relationship between molecular weight and viscosity, and a method for calculating the branching index g' using the relationship between molecular weight and viscosity. 13 In the present invention, the long chain branched structure is defined by the branching index g' and / or 13 C-NMR.

[0171] The branching index g' is known as a direct indicator of the long chain branching structure. It is described in detail in "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983), and the definition of the branching index g' is as follows.

[0172] Branching index g' = [η]br / [η]lin

[0173] [η]br: Intrinsic viscosity of a polymer with a long-chain branched structure (br)

[0174] [η]lin: intrinsic viscosity of a linear polymer having the same molecular weight as that of the polymer (br)

[0175] It is obvious from the above definition that when the branching index g' takes a value less than 1, it is judged that a long-chain branching structure exists, and the value of the branching index g' decreases as the long-chain branching structure increases.

[0176] By using GPC with a light scattering meter and a viscometer as detectors, the branching index g' can be obtained as a function of the absolute molecular weight Mabs. The measurement method of the branching index g' in the present invention is described in detail in JP-A-2015-40213 and is as follows.

[0177] {Measurement method}

[0178] GPC: Alliance GPCV2000 (manufactured by Waters)

[0179] Detectors: Described in order of connection

[0180] Multi-angle laser light scattering detector (MALLS): DAWN-E (manufactured by Wyatt Technology)

[0181] Differential Refractometer (RI): Connected to GPC

[0182] Viscosity detector (viscometer): connected to GPC

[0183] Mobile phase solvent: 1,2,4-trichlorobenzene (Irganox 1076 added at a concentration of 0.5 mg / mL)

[0184] Mobile phase flow rate: 1 mL / min

[0185] Column: Connect two GMHHR-H(S)HT columns manufactured by Tosoh Corporation

[0186] Sample injection port temperature: 140°C

[0187] Column temperature: 140°C

[0188] Detector temperature: all 140°C

[0189] Sample concentration: 1mg / mL

[0190] Injection volume: (sample loop volume): 0.2175mL

[0191] {Analysis Methods}

[0192] When determining the absolute molecular weight (Mabs), mean square radius of gyration (Rg) obtained from a multi-angle laser light scattering detector (MALLS), and the intrinsic viscosity ([η]) obtained from a viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS was used to calculate with reference to the following literature.

[0193] References:

[0194] 1."Developments in Polymer Characterization-4"(JVDawkins ed.AppliedScience Publishers,1983,Chapter 1.)

[0195] 2.Polymer,45,6495-6505(2004)

[0196] 3.Macromolecules,33,2424-2436(2000)

[0197] 4.Macromolecules,33,6945-6952(2000)

[0198] In the decorative film of the present invention, when the polypropylene resin (B) contains gel, the film appearance deteriorates, so it is preferred to use a resin composition (B) that does not contain gel. The above-mentioned polypropylene resin (B-1) having a long-chain branched structure is particularly preferred, which is a polypropylene resin with less gel produced by a method other than a crosslinking method, and more preferred is a polypropylene resin produced by a method of producing a macromonomer having a terminal unsaturated bond using a metallocene catalyst having a specific structure and copolymerizing the macromonomer with propylene to form a long-chain branched structure.

[0199] In particular, a polypropylene resin having a branching index g' of 0.3 or more and less than 1.0 at an absolute molecular weight Mabs of 1,000,000 is preferred, and the index is more preferably 0.55 or more and 0.98 or less, further preferably 0.75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less.

[0200] In the present invention, "less gel" means that the branching index g' of the 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, highly crosslinked components are not formed and gel is not formed or very little gel is formed, so in the case where the layer (II) containing the polypropylene resin (B-1) having a long-chain branched structure constitutes the surface of the product, the appearance is not deteriorated.

[0201] {13 C-NMR}

[0202] As mentioned above, 13 C-NMR can distinguish short-chain branched structures from long-chain branched structures. A detailed explanation is given in Macromol. Chem. Phys. 2003, vol. 204, 1738, the summary of which is as follows.

[0203] The propylene polymer having a long-chain branched structure has a specific branched structure as shown in the following structural formula (1). In the structural formula (1), C a , C b and C c represents the methylene carbon adjacent to the branch carbon, C br represents the methane carbon at the base of the branch chain, P 1 , P 2 and P 3 represents a propylene-based polymer residue.

[0204] Propylene polymer residue P 1 , P 2 and P 3 The residue itself may contain C different from that described in formula (1). br Branched carbon (C br ).

[0205] [Chemical formula 1]

[0206]

[0207] Structural formula (1)

[0208] This branched structure is 13 C-NMR analysis was used for identification. Each peak can be assigned with reference to the description on pages 3839 to 3842 in Macromolecules, Vol. 35, No. 10, 2002. That is, a total of three methylene carbons (C a , C b and C c ), and methine carbon (C br The methine carbon observed at 31.5 to 31.7 ppm is sometimes abbreviated as branched methine carbon (C br ).

[0209] Propylene polymer with long chain branching structure 13 The C-NMR spectrum is characterized by the branched methine carbon C brThe three adjacent methylene carbons are observed as three diastereoisomeric, nonequivalent peaks.

[0210] Depend on 13 Such a branch chain assigned by C-NMR indicates a propylene polymer residue having 5 or more carbon atoms branched from the main chain of the propylene polymer. Since the residue can be distinguished from a branch chain having 4 or less carbon atoms by the fact that the peak position of the branched carbon is different, in the present invention, the presence of a long-chain branched structure can be determined by confirming the peak of the branched methine carbon.

[0211] In addition, the present invention 13 The measurement method of C-NMR is as follows.

[0212] { 13 C-NMR measurement method}

[0213] 200 mg of sample was mixed with 2.4 ml of o-dichlorobenzene / deuterated bromobenzene (C 6 D 5 Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane as a reference substance for chemical shift were added to an NMR sample tube with an inner diameter of 10 mmφ, followed by dissolution and then 13 C-NMR measurement.

[0214] The NMR was carried out using a Burker-Biospin KK AV400 NMR instrument. 13 For C-NMR measurement, the apparatus was equipped with a 10 mmφ cryoprobe.

[0215] The measurement was performed by a complete proton decoupling method at a sample temperature of 120° C. Other conditions were as follows.

[0216] Pulse angle: 90°

[0217] Pulse interval: 4 seconds

[0218] Cumulative times: 20,000

[0219] Regarding the chemical shift, the peak of the methyl carbon of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shift of the peak derived from other carbons was used as a reference.

[0220] The peak around 44 ppm can be used to calculate the amount of long chain branches.

[0221] In the polypropylene resin (B-1) having a long-chain branched structure 13In the C-NMR spectrum, the amount of long chain branches quantitatively determined from the peak near 44 ppm is preferably 0.01 / 1000 total propylene or more, more preferably 0.03 / 1000 total propylene or more, and further preferably 0.05 / 1000 total propylene or more. Since a too large value may cause appearance defects such as gels and fish eyes, the amount is preferably 1.00 / 1000 total propylene or less, more preferably 0.50 / 1000 total propylene or less, and further preferably 0.30 / 1000 total propylene or less.

[0222] It is sufficient that such a polypropylene resin (B-1) having a long-chain branched structure is contained in the resin composition (B) containing the polypropylene resin (B) in an amount sufficient to impart strain hardening properties. The polypropylene resin (B-1) having a long-chain branched structure is contained in a ratio of preferably 1 to 100% by weight, more preferably 5% by weight or more, in 100% by weight of the resin composition (B).

[0223] As the polypropylene resin (B-1) having a long-chain branched structure in the present invention, one of various types of propylene polymers can be selected, such as a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene) and a propylene block copolymer (block polypropylene), or a combination thereof. The polypropylene polymer preferably contains 50 mol% or more of a propylene monomer.

[0224] From the viewpoint of heat resistance, scratch resistance and solvent resistance, the polypropylene resin (B) in the present invention preferably has high crystallinity. The melting point (DSC melting peak point) of the polypropylene resin (B) is preferably 130°C or higher, more preferably 140°C or higher, further preferably 140 to 170°C, further preferably 145 to 170°C, and particularly preferably 150 to 168°C. The polypropylene resin (B) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, since scratch resistance and solvent resistance are still reduced when a component with low crystallinity is contained even if the melting point is high, it is preferred that the polypropylene resin (B) does not contain an ethylene-α-olefin copolymer having an ethylene content of 50 to 70% by weight.

[0225] In addition, when the decorative film further includes a sealing layer (I) composed of the polypropylene resin (A) mentioned below and the polypropylene resin (A) satisfies the requirements (a1) to (a4) mentioned below, the melting peak temperature (Tm) (B) of the polypropylene resin (B) when measured by DSC is preferably higher than the melting peak temperature (Tm) (A) of the polypropylene resin (A) when measured by DSC. That is, relative to Tm (A), it is preferred to satisfy the following requirement (b3).

[0226] (b3)(Tm)(B) satisfies the following relational expression (b-3).

[0227] Tm(B)>Tm(A)...Formula (b-3)

[0228] In the above range, the hot formability becomes satisfactory.

[0229] The resin composition (B) containing the polypropylene resin (B) may contain a plurality of polypropylene resins other than the polypropylene resin (B-1) having a long-chain branched structure, additives, fillers, colorants, other resin components, etc. In this case, the total amount of the additives, fillers, colorants, other resin components, etc. is preferably 50% by weight or less relative to the resin composition (B) containing the polypropylene resin including them.

[0230] In the case where the decorative molded body of the present invention is formed into a colored molded body, the colorant can be used only in the decorative film, so the use of expensive colorants can be suppressed compared to the case where the entire resin molded body is colored. In addition, changes in physical properties that may be associated with the blending of the colorant can be suppressed.

[0231] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0232] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0233] Examples of the crystal nucleating agent include aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0234] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0235] As fillers, various known fillers that can be used in polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, etc. can be exemplified.

[0236] As other resin components, polyethylene-based resins, polyolefins such as ethylene-based elastomers, modified polyolefins, and other thermoplastic resins and the like can be exemplified.

[0237] In addition, in order to give a design, it can also be colored. For coloring, various colorants such as inorganic pigments, organic pigments and dyes can be used. In addition, bright materials such as aluminum flakes, titanium oxide flakes and (synthetic) mica can also be used.

[0238] The polypropylene resin composition can be prepared by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0239] <Sealing Layer (I)>

[0240] [1. Sealing layer (I) composed of polypropylene resin (A)]

[0241] As one embodiment of the decorative film of the present invention, in addition to the above-mentioned layer (II), it can also include a sealing layer (I) composed of a polypropylene resin (A) having an MFR (A) (230°C, load of 2.16 kg) greater than 2 g / 10 min.

[0242] By including a sealant layer (I) composed of a polypropylene resin (A) on the bonding surface with a resin molded body (substrate), scratches formed on the surface of the substrate can be made less noticeable, thereby reducing product defects.

[0243] This is because the fluidity of the polypropylene resin (A) constituting the sealant layer (I) is higher than the fluidity of the polypropylene resin composition (B) constituting the thermoformability-imparting layer (II), and therefore the sealant layer (I) is more easily deformed than the layer (II). Therefore, by deforming the sealant layer (I) according to the shape of the scratch relative to the scratch on the substrate, the appearance of scratches on the surface of the decorative molded body can be suppressed.

[0244] In order for the decorative film to exhibit such an effect, the strain hardening degree λ of the polypropylene-based resin (A) is preferably less than 1.1.

[0245] As the polypropylene resin (A) in this embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of propylene monomer. The propylene polymer preferably does not contain a monomer unit containing a polar group.

[0246] The melting point (DSC melting peak temperature) of the polypropylene-based resin (A) is preferably from 100 to 170°C, more preferably from 115 to 165°C.

[0247] From the viewpoint of sealing performance, the polypropylene resin (A) is preferably a propylene-α-olefin copolymer. Since the propylene-α-olefin copolymer generally has a lower crystallization temperature as the melting point decreases compared to the propylene homopolymer, the copolymer is more easily deformed during thermoforming, thereby having a high effect of making scratches less noticeable.

[0248] In addition, the polypropylene resin (A) may contain additives, fillers, and other resin components, etc. That is, the resin may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0249] As the additive, the additives that can be contained in the above-mentioned polypropylene-based resin (B) and the like can be used.

[0250] The above-mentioned resin composition (polypropylene-based resin composition) can be produced by a method of melt-kneading a propylene-based polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene-based polymer, additives, and fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-based polymer and other resin components.

[0251] [2. Sealing layer (I) composed of polypropylene resin (A)]

[0252] As one embodiment of the decorative film of the present invention, the decorative film further includes a sealing layer (I) composed of a polypropylene-based resin (A) in addition to the layer (II), and the polypropylene-based resin (A) satisfies the following requirements (a1) to (a4), and the polypropylene-based resin (B) may further satisfy the following requirement (b3):

[0253] (a1) it is a metallocene catalyst-based propylene polymer,

[0254] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0255] (a3) the melting peak temperature (Tm) (A) is lower than 150°C,

[0256] (a4) a molecular weight distribution (Mw / Mn) (A) measured by GPC is 1.5 to 3.5, and

[0257] (b3) Tm(B) satisfies the following relation (b-3) with respect to the above Tm(A):

[0258] Tm(B)>Tm(A)...Formula (b-3).

[0259] The sealing layer (I) composed of the polypropylene resin (A) in this embodiment is a layer that contacts the resin molded body (substrate) during the three-dimensional decorative thermoforming. The polypropylene resin (A) is preferably a resin that is easy to melt and relax. By providing the sealing layer (I), the generation of holes, wrinkles, and air entrapment on the surface of the decorative molded body can be suppressed, and the scratches formed on the surface of the substrate can be made less obvious.

[0260] The melt flow rate (230°C, load of 2.16 kg) MFR(A) of the polypropylene resin (A) needs to be greater than 0.5 g / 10 min (requirement (a2)), preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more. Within the above range, relaxation during thermoforming of three-dimensional decoration is sufficiently performed, and sufficient bonding strength can be exhibited. The upper limit of MFR(A) is not limited, but is preferably 100 g / 10 min or less. Within the above range, deterioration of bonding strength due to reduction in physical properties does not occur.

[0261] In the present embodiment, MFR of the polypropylene-based resin (A) and the polypropylene-based resin composition (A) mentioned later is measured under a load of 2.16 kg at 230° C. according to Condition M of ISO 1133:1997. The unit is g / 10 minutes.

[0262] The Mw / Mn(A) of the polypropylene-based resin (A) is 1.5 to 3.5 (requirement (a4)), preferably 2 to 3. Within the above range, the amount of the component having a relatively long relaxation time is small, and sufficient relaxation is easy to occur, so this range is preferred.

[0263] In addition, Mn and Mw are described in "Kobunshi no Kiso" (edited by The Society of Polymer Science, Japan, Tokyo Kagaku Dojin, 1978) and the like, and are values ​​calculated from a molecular weight distribution curve measured on GPC.

[0264] The melting point Tm(A) (DSC melting peak temperature) of the polypropylene resin (A) is lower than 150°C (requirement (a3)), preferably 145°C or lower, more preferably 140°C or lower, and further preferably 130°C or lower. Within the above range, sufficient adhesive strength can be exhibited. When Tm(A) is too low, heat resistance is reduced, and there is a possibility that problems may occur when using the molded article, so Tm(A) is preferably 100°C or higher, more preferably 110°C or higher.

[0265] Furthermore, the melting peak temperature (Tm(B)) of the polypropylene resin (B) measured by DSC needs to be higher than Tm(A), and Tm(B)>Tm(A) (requirement (b3)). Within the above range, thermoformability becomes satisfactory.

[0266] The melting point (Tm(B)) of the polypropylene resin (B) (melting peak temperature based on DSC measurement) is preferably 140° C. or higher, more preferably 145 to 170° C., further preferably 150 to 168° C. The polypropylene resin (B) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, since scratch resistance and solvent resistance are reduced when a low-crystalline component is contained even if the melting point is high, the polypropylene resin or the polypropylene resin composition (B) preferably does not contain an ethylene-α-olefin copolymer having an ethylene content of 50 to 70% by weight.

[0267] The polypropylene resin (A) of the present embodiment is a so-called metallocene catalyst-based propylene polymer polymerized by a metallocene catalyst (requirement (a1)). Since the metallocene catalyst has a single active site, the propylene polymer polymerized by the metallocene catalyst has a narrow molecular weight distribution and crystallinity distribution, and is easy to melt and relax, so it can be fused to the substrate without applying a large amount of heat.

[0268] As the polypropylene resin (A) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The polypropylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0269] From the viewpoint of sealing performance, the polypropylene resin (A) is preferably a propylene-α-olefin copolymer. Since the propylene-α-olefin copolymer generally has a lower crystallization temperature as the melting point decreases compared to the propylene homopolymer, the copolymer is more easily deformed during thermoforming, thereby having a high effect of making scratches less noticeable.

[0270] As the α-olefin, one selected from ethylene and α-olefins having 3 to 8 carbon atoms, or a combination of two or more thereof can be used.

[0271] In addition, the polypropylene resin (A) may contain additives, fillers, and other resin components, etc. That is, the resin may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0272] When the polypropylene-based resin (A) is a polypropylene-based resin composition (A), the polypropylene-based resin composition (A) preferably has the above-mentioned properties of the polypropylene-based resin (A).

[0273] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0274] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0275] Examples of the crystal nucleating agent include aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0276] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0277] As fillers, various known fillers that can be used for polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, and thermosetting resin hollow fine particles can be exemplified.

[0278] As other resin components, polyethylene-based resins, polyolefins such as ethylene-based elastomers, modified polyolefins, and other thermoplastic resins and the like can be exemplified.

[0279] The polypropylene resin composition (A) can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0280] [3. Sealing layer (I) composed of a resin composition (X) comprising a polypropylene-based resin (A) and an ethylene-α-olefin random copolymer (C) as main components]

[0281] As one embodiment of the decorative film of the present invention, in addition to layer (II), the decorative film preferably further comprises a sealing layer (I) composed of a resin composition (X) comprising a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) as main components, and the weight ratio of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95. The polypropylene resin (A) satisfies the following requirement (a2) and the ethylene-α-olefin random copolymer (C) may satisfy the following requirements (c1) to (c3):

[0282] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0283] (c1) an ethylene content [E(C)] of 65% by weight or more,

[0284] (c2) Density 0.850 to 0.950 g / cm 3 ,and

[0285] (c3) MFR(C) (230°C, load of 2.16 kg) is 0.1 to 100 g / 10 min.

[0286] The sealing layer (I) in this embodiment is a layer that contacts the resin molded body (substrate) during the three-dimensional decorative thermoforming. By providing the sealing layer (I), even if the film heating time is short during the three-dimensional decorative thermoforming, sufficient bonding strength can be exhibited, and scratches formed on the substrate surface can be made less noticeable.

[0287] {Polypropylene resin (A)}

[0288] As the polypropylene resin (A) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0289] (a2) Melt flow rate (MFR(A))

[0290] The melt flow rate MFR(A) (230°C, 2.16 kg load) of the polypropylene resin (A) contained in the sealing layer (I) needs to be greater than 0.5 g / 10 min (requirement (a2)), preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming is fully carried out, sufficient bonding strength can be exhibited, and scratches formed on the substrate also become less noticeable. There is no upper limit for MFR(A), but it is preferably 100 g / 10 min or less. Within the above range, deterioration of bonding strength due to reduced physical properties does not occur.

[0291] In the present embodiment, MFR of the polypropylene-based resin and the polypropylene-based resin composition mentioned below is measured under a load of 2.16 kg at 230° C. according to Condition M of ISO 1133:1997. The unit is g / 10 minutes.

[0292] (a3) Melting peak temperature (Tm(A))

[0293] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point") (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and further preferably 120°C or higher. Within the above range, the formability during thermoforming of the three-dimensional decoration is satisfactory. The upper limit of the melting peak temperature is not limited, but is preferably 170°C or lower. Within the above range, sufficient bonding strength can be exhibited.

[0294] The polypropylene resin (A) of the present embodiment is preferably a resin polymerized by a Ziegler catalyst, a metallocene catalyst, etc. That is, the polypropylene resin (A) may be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0295] {Ethylene-α-olefin random copolymer (C)}

[0296] The ethylene-α-olefin random copolymer (C) used as an essential component in the sealant layer (I) of the present embodiment has the following requirements (c1) to (c3), preferably further requirements (c4) and / or (c5).

[0297] (c1) an ethylene content [E(C)] of 65% by weight or more,

[0298] (c2) Density 0.850 to 0.950 g / cm 3 ,

[0299] (c3) MFR(C) (230°C, 2.16 kg load) of 0.1 to 100 g / 10 min,

[0300] (c4) a melting peak temperature (Tm) (C) of 30 to 130°C, and

[0301] (c5) The ethylene-α-olefin random copolymer (C) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

[0302] (c1) Ethylene content [E(C)]

[0303] The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) of the present embodiment is preferably 65% ​​by weight or more, more preferably 68% by weight or more, and further preferably 70% by weight or more relative to the total amount of the ethylene-α-olefin random copolymer (C). Within the above range, sufficient bonding strength can be exhibited during three-dimensional decoration thermoforming, and the heating time of the film can be shortened. The upper limit of the ethylene content [E(C)] is not particularly limited, but is preferably 95% by weight or less.

[0304] (Calculation method of ethylene content [E(C)])

[0305] The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) can be determined by 13 It was determined by the integrated intensity obtained by C-NMR measurement.

[0306] (Calculation method 1 (binary system))

[0307] First, the calculation method of the ethylene content [E(C)] in the binary copolymer composed of two repeating units is described. In this case, the ethylene content of the ethylene-α-olefin binary copolymer can be calculated based on (Formula c1-1) and (Formula c1-2).

[0308] Ethylene content (mol%) = IE × 100 / (IE + IX) ... (Formula c1-1)

[0309] Ethylene content [E(C)] (weight %) = [ethylene content (mol%) × molecular weight of ethylene] / [ethylene content (mol%) × molecular weight of ethylene + α-olefin content (mol%) × molecular weight of α-olefin] ... (Formula c1-2)

[0310] Here, IE and IX are the integrated intensity of ethylene and the integrated intensity of α-olefin, respectively, and can be obtained according to the following (Formula c-2) and (Formula c-3), respectively.

[0311] IE=(I ββ +I γγ +I βδ +I γδ +I δδ ) / 2+(I αγ +I αδ ) / 4...(Formula c-2)

[0312] IX=I αα +(I αγ +I αδ ) / 2...(Formula c-3)

[0313] Here, the subscript of I on the right side represents the 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 the integrated intensity of the signal based on the methylene carbon of the α-olefin chain.

[0314] [Chemical formula 2]

[0315]

[0316] In the structural formula (d), n represents an odd number of 1 or more.

[0317] The integrated intensity for (Formula c-2) and (Formula c-3) for each α-olefin of the ethylene-α-olefin binary copolymer will be described below.

[0318] (In the case of ethylene-propylene copolymer)

[0319] In the case where the α-olefin is propylene, the following integrated intensity values ​​are substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E(C)].

[0320] I ββ =I 25.0-24.2

[0321] I γγ =I 30.8-30.6

[0322] I βδ =I 27.8-26.8

[0323] I γδ =I 30.6-30.2

[0324] I δδ =I 30.2-28.0

[0325] I αα =I 48.0-43.9

[0326] I αγ +I αδ =I 39.0-36.2

[0327] Here, the subscript value of I on the right side indicates the range of chemical shift. For example, I 39.0-36.2 Indicates that the detected amount is between 39.0ppm and 36.2ppm 13 The integrated intensity of the C signal.

[0328] Regarding chemical shift, hexamethyldisiloxane 13 The C signal was set at 1.98 ppm, derived from other 13 The chemical shift of the signal of C uses it as a reference. Similar to the case of the ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer and an ethylene-1-octene copolymer will also be described below.

[0329] (In the case of ethylene-1-butene copolymer)

[0330] In the case where the α-olefin is 1-butene, the following integrated intensity value is substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E(C)].

[0331] I ββ =I 24.6-24.4

[0332] I γγ =I 30.9-30.7

[0333] I βδ =I 27.8-26.8

[0334] I γδ =I30.5-30.2

[0335] I δδ =I 30.2-28.0

[0336] I αα =I 39.3-38.1

[0337] I αγ +I αδ =I 34.5-33.8

[0338] (In the case of ethylene-1-hexene copolymer)

[0339] In the case where the α-olefin is 1-hexene, the following integrated intensity value is substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E(C)].

[0340] I ββ =I 24.5-24.4

[0341] I γγ =I 31.0-30.8

[0342] I βδ =I 27.5-27.0

[0343] I γδ =I 30.6-30.2

[0344] I δδ =I 30.2-28.0

[0345] I αα =I 40.0-39.0

[0346] I αγ +I αδ =I 35.0-34.0

[0347] (In the case of ethylene-1-octene copolymer)

[0348] In the case where the α-olefin is 1-octene, the methylene carbon based on the hexyl branch of 1-octene overlaps with the βδ signal and the αγ+αδ signal (5B6 and 6B6 in the following structural formula).

[0349] I βδ +I 5B6 =I 27.6-26.7

[0350] I αγ +I αδ +I 6B6 =I 35.0-34.0

[0351] [Chemical formula 3]

[0352]

[0353] Therefore, I in which the overlap of 5B6 and 6B6 has been corrected is used. βδ and I αγ +I αδ Alternatively, the following integrated intensity values ​​are substituted into (Formula-2) and (Formula-3) to determine the ethylene content [E(C)].

[0354] I ββ =I 24.7-24.2

[0355] I γγ +I γδ +I δδ =I 32.0-28.0

[0356] I βδ =2 / 3×I 27.6-26.7

[0357] I αα =I 40.8-39.6

[0358] I αγ +I αδ =I βδ +2×I ββ

[0359] (Calculation method 2 (ternary system))

[0360] Next, the method for calculating the ethylene content [E(C)] in the terpolymer composed of three types of repeating units is described.

[0361] For example, the ethylene content of the ethylene-propylene-butene terpolymer can be determined from the following (Formula c4-1) and (Formula c4-2).

[0362] Ethylene content (mol%) = IE × 100 / (IE + IP + IB) ... (Formula c4-1)

[0363] Ethylene content [E(C)] (weight %) = [ethylene content (mol%) × molecular weight of ethylene] / [ethylene content (mol%) × molecular weight of ethylene + propylene content (mol%) × molecular weight of propylene + butene content (mol%) × molecular weight of butene] ... (Formula C4-2)

[0364] Here, IE, IP and IB are integrated intensity values ​​of ethylene, propylene and butene, respectively, and can be obtained according to (Formula c-5), (Formula c-6) and (Formula c-7).

[0365] 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...(Formula c-5)

[0366] IP = 1 / 3 × [I CH3(P) +I CH(P) +I αα(PP) +1 / 2×(I αα(PB) +I αγ(P) +I αδ(P) )]...(Formula c-6)

[0367] 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 c-7)

[0368] Here, the subscript (P) indicates that the signal is based on the methyl branch derived from propylene, and similarly, the subscript (B) indicates that the signal is based on the ethyl branch derived from butene.

[0369] Furthermore, αα(PP) represents a signal based on methylene carbon of a propylene chain, similarly, αα(BB) represents a signal based on methylene carbon of a butene chain, and αα(PB) represents a signal based on methylene carbon of a propylene-butene chain.

[0370] Here, since the γγ signal overlaps with the skirt portion of the signal of the methine carbon CH (PPE) of the central propylene in the propylene-propylene-ethylene arrangement, it is difficult to separate the γγ signal.

[0371] The γγ signal appears in the structural formula (c) containing two ethylene chains, and (Formula c-8) is established between the integrated intensity of γγ derived from ethylene and the integrated intensity of βδ of the structural formula (c).

[0372] I βδ (Structural formula (c)) = 2 × I γγ ...(Formula c-8)

[0373] Furthermore, βδ appears in the structural formula (d) in which three or more ethylene chains exist, and the integrated intensity of βδ in the structural formula (d) is equal to the integrated intensity of γδ, and (Formula c-9) holds.

[0374] I βδ (Structural formula (d)) = I γδ ...(Formula c-9)

[0375] Therefore, βδ based on the structural formula (c) and the structural formula (d) is calculated by (Formula c-10).

[0376] I βδ =I βδ (Structural formula (c))+I βδ (Structural formula (d)) = 2 × I γγ +I γδ ...(Formula c-10)

[0377] Right now,

[0378] I γγ =(I βδ -I γδ ) / 2...(Formula c-10')

[0379] Therefore, when (Formula c-10') is substituted into (Formula c-5), IE can be replaced by (Formula c-11).

[0380] IE=(I ββ +I δδ ) / 2+(I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) +3×I βδ +I γδ ) / 4...(Formula c-11)

[0381] Here, when the overlap based on the ethyl branch of 1-butene is corrected, the βδ signal becomes (Formula c-12).

[0382] I βδ =I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) -2×I ββ ...(Formula c-12)

[0383] From (Formula c-11) and (Formula c-12), IE becomes (Formula c-13).

[0384] IE=I δδ / 2+I γδ / 4-I ββ +I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) ...(Formula c-13)

[0385] The ethylene content is determined by substituting the following into (Equation c-13), (Equation c-6), and (Equation c-7).

[0386] I ββ = I 25.2-23.8

[0387] I γδ = I 30.4-30.2

[0388] I δδ = I 30.2-29.8

[0389] I αγ(P) + I αδ(P) = I 39.5-37.3

[0390] I αγ(B) + I αδ(B) = I 34.6-33.9

[0391] I CH3(P) = I 22.6-19.0

[0392] I CH(P) = I 29.5-27.6 + I 31.2-30.4 + I 33.4-32.8

[0393] I αα(PP) = I 48.0-45.0

[0394] I CH3(B) = I 11.4-10.0

[0395] I CH(B) = I 35.5-34.7 + I 37.4-36.8 + I 39.7-39.6

[0396] I αα(BB) = I 40.3-40.0

[0397] I αα(PB) = I 44.2-42.0

[0398] I 2B2 = I 26.7-26.4

[0399] In addition, to assign each signal, refer to the following five references.

[0400] Macromolecules, Vol. 10, No. 4, 1977,

[0401] Macromolecules,Vol.36,No.11,2003,

[0402] Analytical Chemistry,Vol.76,No.19,2004,

[0403] Macromolecules,2001,34,4757-4767,

[0404] Macromolecules, Vol. 25, No. 1, 1992.

[0405] Likewise, when the α-olefin of the ethylene-α-olefin random copolymer is not the above, the ethylene content [E(C)] can be determined in the same manner as in the above case while attributing each signal.

[0406] (c2) Density

[0407] The density of the ethylene-α-olefin random copolymer (C) needs to be 0.850 to 0.950 g / cm 3 , more preferably 0.855 to 0.900 g / cm 3 , further preferably 0.860 to 0.890 g / cm 3 Within the above range, sufficient bonding strength can be exhibited during the three-dimensional decoration thermoforming, and further, film formability is also satisfactory.

[0408] (c3) Melt flow rate (MFR(C))

[0409] The melt flow rate (230°C, load of 2.16 kg) MFR (C) of the ethylene-α-olefin random copolymer (C) needs to be 0.1 to 100 g / 10 min, preferably 0.5 to 50 g / 10 min, and more preferably 1 to 30 g / 10 min. Within the above range, the effect of making the scratches formed on the substrate less noticeable is high.

[0410] (c4) Melting peak temperature (Tm(C))

[0411] The melting peak temperature (DSC melting peak temperature) Tm(C) of the ethylene-α-olefin random copolymer (C) is preferably 30 to 130° C., more preferably 35 to 120° C., further preferably 40 to 110° C. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decoration thermoforming.

[0412] (c5) α-olefin (C) of ethylene-α-olefin random copolymer

[0413] The ethylene-α-olefin random copolymer (C) is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin having 3 to 20 carbon atoms, there can be specifically mentioned propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, etc. Among these, in particular, propylene, 1-butene, 1-hexene, and 1-octene are preferably used.

[0414] This ethylene-α-olefin random copolymer (C) is produced by copolymerizing each monomer in the presence of a catalyst. Specifically, the ethylene-α-olefin random copolymer (C) can be produced by copolymerizing ethylene with an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene by a method such as a gas phase method, a solution method, a high pressure method or a slurry method using a catalyst such as a Ziegler catalyst, a Philips catalyst or a metallocene catalyst as an olefin polymerization catalyst.

[0415] Furthermore, the ethylene-α-olefin random copolymer (C) used for the sealant layer (I) of the present embodiment may be used alone or in combination of two or more thereof within the range not impairing the advantages of the present invention.

[0416] As commercially available products of such ethylene-α-olefin random copolymer (C), Kernel series manufactured by Japan Polyethylene Corporation, TAFMER P series and TAFMER A series manufactured by Mitsui Chemicals, Inc., Engage EG series manufactured by DowDuPont Inc., and the like can be mentioned.

[0417] {Resin composition (X)}

[0418] The resin composition (X) constituting the sealant layer (I) contains a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) as main components, and may be a mixture of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) or a melt-kneaded product thereof, or a product of sequential polymerization of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C).

[0419] In the resin composition (X) of the sealant layer (I), the weight ratio ((A):(C)) of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) needs to be selected in the range of 97:3 to 5:95, preferably 95:5 to 10:90, and more preferably 93:7 to 20:80. Within the above range, sufficient bonding strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the bonding between the sealant layer (I) and the layer (II) is also satisfactory.

[0420] The resin composition (X) constituting the sealant layer (I) may contain additives, fillers, other resin components, etc. However, the total amount of the additives, fillers, other resin components, etc. is preferably 50% by weight or less relative to the resin composition (X).

[0421] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0422] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0423] Examples of the crystal nucleating agent include aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0424] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0425] As fillers, various known fillers that can be used in polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, etc. can be exemplified.

[0426] As other resin components, modified polyolefins, petroleum resins, and other thermoplastic resins and the like can be exemplified.

[0427] The resin composition (X) can be produced by a method of melt-kneading the polypropylene based resin (A), the ethylene-α-olefin random copolymer (C), additives, fillers, and other resin components, etc., a method of melt-kneading the polypropylene based resin (A), additives, fillers, etc. and dry-blending the ethylene-α-olefin random copolymer (C) into the melt blend, or a method of adding the polypropylene based resin (A) to the ethylene-α-olefin random copolymer (C) and dry-blending a masterbatch in which the additives, fillers, and other resin components, etc. are dispersed in a carrier resin at a high concentration.

[0428] [4. Sealing layer (I) composed of a resin composition (X) comprising a polypropylene-based resin (A) and a thermoplastic elastomer (D) as main components]

[0429] As one embodiment of the decorative film of the present invention, in addition to layer (II), the decorative film may further include a sealing layer (I) composed of a resin composition (X) comprising a polypropylene resin (A) and a thermoplastic elastomer (D) as main components, and the weight ratio of the polypropylene resin (A) to the thermoplastic elastomer (D) is 97:3 to 5:95. It is preferred that the polypropylene resin (A) satisfies the following requirement (a2) and the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d3):

[0430] (a2) melt flow rate (MFR(A)) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0431] (d1) the thermoplastic elastomer (D) is a thermoplastic elastomer in which at least one of propylene and butene is a main component,

[0432] (d2) Density 0.850 to 0.950 g / cm 3 ,and

[0433] (d3) MFR(D) (230°C, load of 2.16 kg) is 0.1 to 100 g / 10 min.

[0434] The sealing layer (I) in this embodiment is a layer that contacts the resin molded body (substrate) during the three-dimensional decoration thermoforming. By providing the sealing layer (I), even when the heating time of the film is shortened, sufficient bonding strength can be exhibited during the three-dimensional decoration thermoforming, and scratches formed on the substrate surface can also be made less noticeable.

[0435] {Polypropylene resin (A)}

[0436] As the polypropylene resin (A) of the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0437] (a2) Melt flow rate (MFR(A))

[0438] The melt flow rate (MFR(A)) of the polypropylene resin (A) contained in the sealing layer (I) needs to be greater than 0.5 g / 10 min (requirement (a2)), preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more. Within the above range, relaxation during thermoforming of three-dimensional decoration is fully carried out, sufficient bonding strength can be exhibited, and scratches formed on the substrate also become less noticeable. There is no upper limit for MFR(A), but it is preferably 100 g / 10 min or less. Within the above range, deterioration of bonding strength due to reduction in physical properties does not occur.

[0439] In the present embodiment, MFR of the polypropylene-based resin and the polypropylene-based resin composition mentioned later is measured under a load of 2.16 kg at 230° C. according to Condition M of ISO 1133:1997. The unit is g / 10 minutes.

[0440] (a3) Melting peak temperature (Tm(A))

[0441] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point") (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and further preferably 120°C or higher. Within the above range, the formability during thermoforming of the three-dimensional decoration is satisfactory. The upper limit of the melting peak temperature is not limited, but is preferably 170°C or lower. Within the above range, sufficient bonding strength can be exhibited.

[0442] The polypropylene resin (A) of the present embodiment is preferably a resin polymerized by a Ziegler catalyst, a metallocene catalyst, etc. That is, the polypropylene resin (A) may be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0443] {Thermoplastic elastomer (D)}

[0444] The thermoplastic elastomer (D) used as an essential component in the sealing layer of the present embodiment has the following requirements (d1) to (d3), and preferably further has requirements (d4) and / or (d5):

[0445] (d1) which is a thermoplastic elastomer in which at least one of propylene and butene is a main component,

[0446] (d2) Density 0.850 to 0.950 g / cm 3 ,

[0447] (d3) MFR (D) (230°C, 2.16 kg load) is 0.1 to 100 g / 10 min,

[0448] (d4) a melting peak temperature (Tm) (D) of 30 to 170°C, and

[0449] (d5) The ethylene content [E(D)] is less than 50% by weight.

[0450] (d1) Composition

[0451] The thermoplastic elastomer (D) of the present embodiment is a thermoplastic elastomer in which at least one of propylene and butene is a main component. Here, the term "a thermoplastic elastomer in which at least one of propylene and butene is a main component" includes (i) a thermoplastic elastomer in which butene is a main component, (ii) a thermoplastic elastomer in which propylene is a main component, and (iii) a thermoplastic elastomer in which the components of propylene and butene are together a main component. The unit "wt%" means weight%.

[0452] The content of propylene or butene in the thermoplastic elastomer (D) 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 (D) may contain more than 35% by weight of propylene or butene.

[0453] Furthermore, the thermoplastic elastomer (D) may contain both propylene and butene, in which case the components of propylene and butene together are the main components of the thermoplastic elastomer (D). The total amount of the content of propylene and butene is preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 50% by weight or more. In the case of containing both propylene and butene, for example, the thermoplastic elastomer (D) may contain propylene and butene in an amount of more than 35% by weight in total.

[0454] Within the above range, sufficient bonding strength can be exhibited at the time of three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the effect of making scratches formed on the substrate less noticeable is high. In addition, the thermoplastic elastomer in which propylene or butene is a main component has high uniform dispersibility in the polypropylene-based resin (C), and it is considered that this fact further enhances the effect of making scratches formed on the substrate less noticeable. In addition, the thermoplastic elastomer (D) may be composed of propylene or butene as a single component.

[0455] (d2) Density

[0456] The density of the thermoplastic elastomer (D) needs to be 0.850 to 0.950 g / cm 3 , preferably 0.855 to 0.940 g / cm 3 , further preferably 0.860 to 0.93 g / cm 3 Within the above range, sufficient adhesive strength can be exhibited during the three-dimensional decoration thermoforming, and further, film formability also becomes satisfactory.

[0457] (d3) Melt flow rate (MFR(D))

[0458] The melt flow rate (MFR (D)) of the thermoplastic elastomer (D) (230°C, 2.16 kg load) needs to be 0.1 to 100 g / 10 min, preferably 0.5 to 50 g / 10 min, and more preferably 1 to 30 g / 10 min. Within the above range, the effect of making the scratches formed on the substrate less noticeable is high.

[0459] (d4) Melting peak temperature (Tm(D))

[0460] The melting peak temperature (DSC melting peak temperature) Tm(D) of the thermoplastic elastomer (D) is preferably 30 to 170° C., more preferably 35 to 168° C., further preferably 40 to 165° C. or higher. Within the above range, sufficient adhesive strength can be exhibited during thermoforming of the three-dimensional decoration.

[0461] (d5) Ethylene content [E(D)]

[0462] The thermoplastic elastomer (D) of the present embodiment can be appropriately selected and used as long as it satisfies the above-mentioned requirements (d1) to (d3), but it is preferably a propylene-ethylene copolymer having an ethylene content of less than 50 wt%, a butene-ethylene copolymer having an ethylene content of less than 50 wt%, a propylene-ethylene-butene copolymer having an ethylene content of less than 50 wt%, a propylene-butene copolymer or a butene homopolymer.

[0463] The ethylene content [E(D)] of the propylene-ethylene copolymer, butene-ethylene copolymer or propylene-ethylene-butene copolymer is more preferably 45 wt% or less, and further preferably 40 wt% or less. Within the above range, sufficient bonding strength can be exhibited during thermoforming of the three-dimensional decoration.

[0464] (Calculation method of ethylene content [E(D)])

[0465] In the case where the thermoplastic elastomer (D) is an elastomer containing ethylene, the ethylene content [E(D)] of the thermoplastic elastomer (D) can be determined by 13 It was determined by the integrated intensity obtained by C-NMR measurement.

[0466] (Calculation method 1 (binary system))

[0467] First, the calculation method of the ethylene content [E(D)] in a binary elastomer composed of two repeating units (propylene-ethylene copolymer or butene-ethylene copolymer, etc.) is described. The ethylene content of the ethylene-α-olefin binary copolymer can be calculated according to (Formula d1-1) and (Formula d1-2).

[0468] Ethylene content (mol%) = IE × 100 / (IE + IX) ... (Formula d1-1)

[0469] Ethylene content (weight %) = [ethylene content (mol %) × molecular weight of ethylene × 100] / [ethylene content (mol %) × molecular weight of ethylene + α-olefin content (mol %) × molecular weight of α-olefin] ... (Formula d1-2)

[0470] Here, IE and IX are the integrated intensity of ethylene and the integrated intensity of α-olefin, respectively, and can be obtained according to the following (Formula d-2) and (Formula d-3), respectively.

[0471] IE=(I ββ +I γγ +I βδ +I γδ +I δδ ) / 2+(I αγ +I αδ ) / 4...(Formula d-2)

[0472] IX=Iαα +(I αγ +I αδ ) / 2...(Formula d-3)

[0473] Here, the subscript of I on the right side represents the 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 the integrated intensity of the signal based on the methylene carbon of the α-olefin chain.

[0474] [Chemical formula 4]

[0475]

[0476]

[0477] In the structural formula (d), n represents an odd number of 1 or more.

[0478] The integrated intensity used in (Formula d-2) and (Formula d-3) will be described below.

[0479] In the case of a propylene-ethylene copolymer, the value of the following integrated intensity is substituted into (Formula d-2) and (Formula d-3) to determine the ethylene content [E(D)].

[0480] I ββ =I 25.0-24.2

[0481] I γγ =I 30.8-30.6

[0482] I βδ =I 27.8-26.8

[0483] I γδ =I 30.6-30.2

[0484] I δδ =I 30.2-28.0

[0485] I αα =I 48.0-43.9

[0486] I αγ +I αδ =I 39.0-36.2

[0487] Here, I represents the integrated intensity, and the subscript number on the right side of I represents the range of chemical shift. For example, I 39.0-36.2 Indicates that the detected amount is between 39.0ppm and 36.2ppm 13 The integrated intensity of the C signal.

[0488] Regarding chemical shift, hexamethyldisiloxane 13 The C signal was set at 1.98 ppm, derived from other 13 The chemical shift of the C signal was determined using it as a reference.

[0489] In the case of a butene-ethylene copolymer, the value of the following integrated intensity is substituted into (Formula d-2) and (Formula d-3) to determine the ethylene content [E(D)].

[0490] I ββ =I 24.6-24.4

[0491] I γγ =I 30.9-30.7

[0492] I βδ =I 27.8-26.8

[0493] I γδ =I 30.5-30.2

[0494] I δδ =I 30.2-28.0

[0495] I αα =I 39.3-38.1

[0496] I αγ +I αδ =I 34.5-33.8

[0497] (Calculation method 2 (ternary system))

[0498] Next, the calculation method of the ethylene content [E(D)] in the terpolymer composed of three repeating units is described. For example, the ethylene content of the ethylene-propylene-butene terpolymer can be calculated according to the following (Formula d4-1) and (Formula d4-2).

[0499] Ethylene content (mol%) = IE × 100 / (IE + IP + IB) ... (Formula d4-1)

[0500] Ethylene content [E(D)] (weight %) = [ethylene content (mol%) × molecular weight of ethylene × 100] / [ethylene content (mol%) × molecular weight of ethylene + propylene content (mol%) × molecular weight of propylene + butene content (mol%) × molecular weight of butene] ... (Formula d4-2)

[0501] Here, IE, IP, and IB are integrated intensity values ​​of ethylene, propylene, and butene, respectively, and can be obtained according to (Formula d-5), (Formula d-6), and (Formula d-7).

[0502] 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...(Formula d-5)

[0503] IP = 1 / 3 × [I CH3(P) +I CH(P) +I αα(PP) +1 / 2×(I αα(PB) +I αγ(P) +I αδ(P) )]...(Formula d-6)

[0504] 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 d-7)

[0505] Here, the subscript (P) indicates that the signal is based on the methyl branch derived from propylene, and similarly, the subscript (B) indicates that the signal is based on the ethyl branch derived from butene.

[0506] Furthermore, αα(PP) represents a signal based on methylene carbon of a propylene chain, similarly, αα(BB) represents a signal based on methylene carbon of a butene chain, and αα(PB) represents a signal based on methylene carbon of a propylene-butene chain.

[0507] Here, since the γγ signal overlaps with the skirt portion of the signal of the methine carbon CH of the central propylene in the propylene-propylene-ethylene (PPE) arrangement, it is difficult to separate the γγ signal.

[0508] The γγ signal appears in the structural formula (c) containing two ethylene chains, and (Formula d-8) is established between the integrated intensity of γγ derived from ethylene and the integrated intensity of βδ of the structural formula (c).

[0509] I βδ (Structural formula (c)) = 2 × I γγ ...(Formula d-8)

[0510] Furthermore, βδ appears in the structural formula (d) in which three or more ethylene chains exist, and the integrated intensity of βδ of the structural formula (d) is equal to the integrated intensity of γδ, and (Formula d-9) holds.

[0511] I βδ (Structural formula (d)) = I γδ ...(Formula d-9)

[0512] Therefore, βδ based on the structural formula (c) and the structural formula (d) is calculated by (Formula d-10).

[0513] I βδ =I βδ (Structural formula (c))+I βδ (Structural formula (d)) = 2 × I γγ +I γδ ...(Formula d-10)

[0514] Right now,

[0515] I γγ =(I βδ -I γδ ) / 2...(Formula d-10')

[0516] Therefore, when (Formula d-10') is substituted into (Formula d-5), IE can be replaced by (Formula d-11).

[0517] IE=(I ββ +I δδ ) / 2+(I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) +3×I βδ +I γδ ) / 4...(Formula d-11)

[0518] Here, when the overlap based on the ethyl branch of 1-butene is corrected, the βδ signal becomes (Formula d-12).

[0519] I βδ =I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) -2×I ββ ...(Formula d-12)

[0520] From (Formula d-11) and (Formula d-12), IE becomes (Formula d-13).

[0521] IE=I δδ / 2+I γδ / 4-I ββ +I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) ...(Formula d-13)

[0522] The ethylene content is determined by substituting the following into (Equation d-13), (Equation d-6), and (Equation d-7).

[0523] I ββ = I 25.2-23.8

[0524] I γδ = I 30.4-30.2

[0525] I δδ = I 30.2-29.8

[0526] I αγ(P) + I αδ(P) = I 39.5-37.3

[0527] I αγ(B) + I αδ(B) = I 34.6-33.9

[0528] I CH3(P) = I 22.6-19.0

[0529] I CH(P) = I 29.5-27.6 + I 31.2-30.4 + I 33.4-32.8

[0530] I αα(PP) = I 48.0-45.0

[0531] I CH3(B) = I 11.4-10.0

[0532] I CH(B) = I 35.5-34.7 + I 37.4-36.8 + I 39.7-39.6

[0533] I αα(BB) = I 40.3-40.0

[0534] I αα(PB) = I 44.2-42.0

[0535] I 2B2 = I 26.7-26.4

[0536] In addition, to assign each signal, refer to the following five references.

[0537] Macromolecules, Vol.10, No.4, 1977,

[0538] Macromolecules,Vol.36,No.11,2003,

[0539] Analytical Chemistry,Vol.76,No.19,2004,

[0540] Macromolecules,2001,34,4757-4767,

[0541] Macromolecules,Vol.25,No.1,1992.

[0542] In addition, the thermoplastic elastomer (D) may be a copolymer with an α-olefin other than propylene and butene, as long as the copolymer does not impair the advantages of the present invention. As the α-olefin, ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, etc. may be specifically mentioned. These α-olefins may be used alone or in combination. Among these, in particular, 1-hexene and 1-octene are preferably used.

[0543] This thermoplastic elastomer is produced by copolymerizing each monomer in the presence of a catalyst. Specifically, this thermoplastic elastomer can be produced by copolymerizing α-olefins such as propylene, 1-butene, ethylene, 1-hexene, 4-methyl-1-pentene and / or 1-octene by a method such as a gas phase method, a solution method, a high pressure method or a slurry method using a catalyst such as a Ziegler catalyst, a Philips catalyst or a metallocene catalyst as an olefin polymerization catalyst.

[0544] Furthermore, the thermoplastic elastomer (D) selectively used for the sealant layer (I) of the present embodiment may be used alone or in combination of two or more thereof within the range not impairing the advantages of the present invention.

[0545] As commercially available products of such thermoplastic elastomer (D), TAFMER XM series, TAFMER BL series and TAFMER PN series manufactured by Mitsui Chemicals, Inc., VISTAMAXX series manufactured by Exxon Mobile Chemical, Corporation, and the like can be mentioned.

[0546] {Resin composition (X)}

[0547] The resin composition (X) constituting the sealant layer (I) contains a polypropylene resin (A) and a thermoplastic elastomer (D) as main components. The resin composition (X) may be a mixture of the polypropylene resin (A) and the thermoplastic elastomer (D), or a melt-kneaded product thereof, or a sequential polymerization product of the polypropylene resin (A) and the thermoplastic elastomer (D).

[0548] In the resin composition (X) constituting the sealant layer (I), the weight ratio ((A):(D)) of the polypropylene resin (A) to the thermoplastic elastomer (D) needs to be 97:3 to 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 sealant layer (I) and the layer (II) also becomes satisfactory.

[0549] The resin composition (X) may contain additives, fillers, other resin components, etc. However, the total amount of the additives, fillers, other resin components, etc. is preferably 50% by weight or less relative to the resin composition (X).

[0550] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0551] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0552] Examples of the crystal nucleating agent include aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0553] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0554] As fillers, various known fillers that can be used in polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, etc. can be exemplified.

[0555] As other resin components, modified polyolefins, petroleum resins, and other thermoplastic resins and the like can be exemplified.

[0556] The resin composition (X) can be produced by a method of melt-kneading the polypropylene-based resin (A), the thermoplastic elastomer (D), additives, fillers, other resin components, etc., a method of melt-kneading the polypropylene-based resin (A), additives, fillers, other resin components, etc. and dry-blending the thermoplastic elastomer (D) into the molten blend, or a method of adding the polypropylene-based resin (A) to the thermoplastic elastomer (D) and dry-blending a masterbatch in which the additives, fillers, other resin components, etc. are dispersed in a carrier resin at a high concentration.

[0557] [5. Sealing layer (I) composed of a resin composition (X) comprising a polypropylene-based resin (A) and a thermoplastic resin (E) as main components]

[0558] As one embodiment of the decorative film of the present invention, in addition to layer (II), the decorative film may further include a sealing layer (I) composed of a resin composition (X) comprising a polypropylene resin (A) and a thermoplastic resin (E) as main components, and the weight ratio of the polypropylene resin (A) to the thermoplastic resin (E) is 97:3 and 5:95. Preferably, the polypropylene resin (A) satisfies the following requirement (c2), the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X) satisfies the following requirement (x1):

[0559] (a2) MFR (A) (230°C, 2.16 kg load) greater than 0.5 g / 10 min,

[0560] (e1) it contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and

[0561] (x1) The isothermal crystallization time (t) (seconds) measured by differential scanning calorimetry (DSC) satisfies the following relationship (x-1):

[0562] t(X)≥1.5×t(A)...Formula (x-1)

[0563] wherein t(A) represents the isothermal crystallization time (seconds) of the polypropylene based resin (A) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A), and t(X) represents the isothermal crystallization time (seconds) of the resin composition (X) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A).

[0564] The sealing layer (I) in this embodiment is a layer that contacts the resin molded body (substrate) during the three-dimensional decoration thermoforming. By providing the sealing layer (I), even when the heating time of the film is shortened, sufficient bonding strength can be exhibited during the three-dimensional decoration thermoforming, and scratches formed on the substrate surface can also be made less noticeable.

[0565] {Polypropylene resin (A)}

[0566] As the polypropylene resin (A) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The polypropylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0567] (a2) Melt flow rate (MFR(A))

[0568] The melt flow rate (MFR(A)) of the polypropylene resin (A) contained in the sealing layer (I) needs to be greater than 0.5 g / 10 min (requirement (a2)), preferably 1 g / 10 min or more, more preferably 2 g / 10 min or more. Within the above range, relaxation during thermoforming of three-dimensional decoration is fully carried out, sufficient bonding strength can be exhibited, and scratches formed on the substrate also become less noticeable. There is no upper limit for MFR(A), but it is preferably 100 g / 10 min or less. Within the above range, deterioration of bonding strength due to reduction in physical properties does not occur.

[0569] In the present embodiment, MFR of the polypropylene-based resin and the polypropylene-based resin composition mentioned below is measured under a load of 2.16 kg at 230° C. according to Condition M of ISO 1133:1997. The unit is g / 10 minutes.

[0570] (a3) Melting peak temperature (Tm(A))

[0571] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point") (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and further preferably 120°C or higher. Within the above range, the formability during thermoforming of the three-dimensional decoration is satisfactory. The upper limit of the melting peak temperature is not limited, but is preferably 170°C or lower. Within the above range, sufficient bonding strength can be exhibited.

[0572] The polypropylene resin (A) of the present embodiment is preferably a resin polymerized by a Ziegler catalyst, a metallocene catalyst, etc. That is, the polypropylene resin (A) may be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0573] {Thermoplastic resin (E)}

[0574] The thermoplastic resin (E) used as an essential component in the sealing layer (1) of the present embodiment is a component having the function of delaying the crystallization of the polypropylene resin (A) by introducing the resin (E) into the polypropylene resin (A). By delaying the crystallization of the polypropylene resin (A), it is possible to prevent the crystallization (curing) of the resin of the sealing layer (I) from reducing the adhesive force before the sealing layer (I) is thermally fused to the substrate surface during decorative molding. As a result, even when the heating time of the decorative film is short, a strong adhesive force can be exhibited, and the effect of making the scratches formed on the substrate surface less noticeable is also high. The effect of delaying the crystallization of the polypropylene resin (A) is evaluated using the isothermal crystallization temperature of the resin composition (X) mentioned later.

[0575] (e1) Resin composition

[0576] The thermoplastic resin (E) in this embodiment needs to contain at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group. When the thermoplastic resin (E) has the above-mentioned properties, when it is mixed with the polypropylene resin (A), it exhibits an effect of delaying the crystallization of the polypropylene resin (A) and has a high effect of making the scratches formed on the substrate surface less noticeable.

[0577] Specifically, as the alicyclic hydrocarbon group, there can be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and substituted derivatives, condensed ring derivatives, and crosslinked derivatives thereof, etc. In particular, it is preferred to contain a cyclopentyl group or a cyclohexyl group.

[0578] As the aromatic hydrocarbon group, phenyl, methylphenyl, biphenyl, indenyl, fluorenyl, and their substituted derivatives, condensed ring derivatives, and crosslinked derivatives, etc. can be mentioned. In particular, it is preferred to contain phenyl, biphenyl or indenyl. In addition, the alicyclic hydrocarbon group can be obtained by hydrogenating the aryl group contained in the resin.

[0579] Furthermore, as the thermoplastic resin (E), any one may be appropriately selected and used as long as the above-mentioned requirement (e1) is satisfied, but a styrene-based elastomer or an alicyclic hydrocarbon resin may be particularly preferably used, and both of them may be contained.

[0580] As styrene-based elastomers, there can be mentioned styrene-butadiene-styrene triblock copolymer elastomer (SBS), styrene-isoprene-styrene triblock copolymer elastomer (SIS), styrene-ethylene-butylene copolymer elastomer (SEB), styrene-ethylene-propylene copolymer elastomer (SEP), styrene-ethylene-butylene-styrene copolymer elastomer (SEBS), styrene-ethylene-butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene-butadiene elastomer (HSBR), styrene-ethylene-propylene-styrene copolymer elastomer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer elastomer (SEEPS), styrene-butadiene-butylene-styrene copolymer elastomer (SBBS), etc., and hydrogenated styrene-based elastomers can be particularly preferably used.

[0581] As commercially available products, DYNARON series manufactured by JSR Corporation, Kraton G series manufactured by Kraton Polymer Japan Corporation, Tuftec series manufactured by Asahi Kasei Corporation, and the like can be mentioned.

[0582] As the alicyclic hydrocarbon resin, for example, there can be mentioned hydrocarbon resins obtained by polymerizing dicyclopentadiene derivatives such as one of dicyclopentadiene, methyldicyclopentadiene and dimethyldicyclopentadiene or a mixture of two or more thereof as a main raw material, hydrogenated coumarone indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer-based petroleum resin, hydrogenated terpene resin, and hydrogenated rosin resin, etc. Commercially available products can be used, and specifically, Arkon series manufactured by Arakawa Chemical Industries, Ltd., etc. can be mentioned.

[0583] {Resin composition (X)}

[0584] The resin composition (X) constituting the sealant layer (I) contains a polypropylene resin (A) and a thermoplastic resin (E) as main components and may be a mixture of the polypropylene resin (A) and the thermoplastic resin (E) or a melt-kneaded product thereof.

[0585] In the resin composition (X) constituting the sealing layer (I), the weight ratio ((A):(E)) of the polypropylene resin (A) to the thermoplastic resin (E) needs to be selected from the range of 97:3 to 5:95, preferably 95:5 to 10:90, and more preferably 93:7 to 20:80. Here, a plurality of polypropylene resins (A) or thermoplastic resins (E) may be contained. For example, in the case of containing a thermoplastic resin (E1) and a thermoplastic resin (E2), the total amount of the thermoplastic resin (E1) and the thermoplastic resin (E2) is taken as the weight of the thermoplastic resin (E). Within the above range, sufficient bonding strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and scratches formed on the surface of the substrate can also be made less obvious. In addition, the bonding between the sealing layer (I) and the layer (II) is satisfactory.

[0586] (x1)Isothermal crystallization time (t(X))

[0587] For the resin composition (X), the isothermal crystallization time (t) (seconds) measured by a differential scanning calorimeter (DSC) needs to satisfy the following relationship (x-1), and preferably satisfies the relationship (x-2), and more preferably the relationship (x-3):

[0588] t(X)≥1.5×t(A)...Formula (x-1)

[0589] t(X)≥2.0×t(A)...Formula (x-2)

[0590] t(X)≥2.5×t(A)...Formula (x-3)

[0591] wherein t(A) represents the isothermal crystallization time (seconds) of the polypropylene based resin (A) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A), and t(X) represents the isothermal crystallization time (seconds) of the resin composition (X) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A).

[0592] When the isothermal crystallization time (t(X)) of the thermoplastic resin (X) is within the above range, the time for the sealing layer (I) of the decorative film to be thermally fused to the substrate surface can be gained during decorative molding, and the effect of achieving high adhesion and making scratches formed on the substrate surface less noticeable is high.

[0593] The upper limit of the isothermal crystallization time (t(X)) is not particularly limited, but when the relationship 30×t(A)≥t(X) is satisfied, the film formability is satisfactory, so this case is more preferred.

[0594] (Measurement of isothermal crystallization time by differential scanning calorimetry (DSC))

[0595] The isothermal crystallization time in the present embodiment is a value measured using a differential scanning calorimeter (DSC), and is measured in accordance with JIS-K7121:2012 “Method for measuring transition temperature of plastics”.

[0596] Specifically, 5 mg of a polypropylene-based resin (A) sample was placed in an aluminum holder and heated from 40° C. to 200° C. at a rate of 10° C. / min under a nitrogen atmosphere. After the temperature was maintained at 200° C. for 10 minutes, the resin crystallized to 40° C. at a cooling rate of 10° C. / min, at which time the crystallization start temperature was measured / calculated from the DSC curve.

[0597] Next, a 5 mg sample of the polypropylene resin (A) or the resin composition (X) is placed in an aluminum holder and heated from 40°C to 200°C at a rate of 10°C / min under a nitrogen atmosphere and maintained for 10 minutes to melt the sample. Subsequently, the sample is cooled at a rate of 40°C / min to a temperature 10°C higher than the crystallization start temperature of the polypropylene resin (A) determined by the above method (hereinafter sometimes referred to as the "measurement temperature"), and then maintained at the measurement temperature to measure the crystallization and heat generation behavior of the sample. The time period from the time when the sample temperature reaches the measurement temperature to the time when the heat generation peak is taken as the isothermal crystallization time. Here, since it is believed that the adhesive force is significantly reduced only by the slight crystallization of the sealing layer (I) of the decorative film during decorative molding, in the case where there are two or more heat generation peaks in the isothermal crystallization measurement, the time period to the first heat generation peak is taken as the isothermal crystallization time.

[0598] Furthermore, depending on the type of the polypropylene-based resin (A), there is a possibility that the isothermal crystallization time of the polypropylene-based resin (A) is extremely short (e.g., 120 seconds or less) or extremely long (e.g., 3,000 seconds or more) even in the measurement at a temperature 10°C higher than the crystallization start temperature. In that case, the isothermal crystallization time may be measured at a temperature 10±2°C higher than the crystallization start temperature. However, in the case of performing such measurement, the isothermal crystallization time of the resin composition (X) should be measured according to the measurement temperature of the polypropylene-based resin (A).

[0599] The resin composition (X) constituting the sealant layer (I) may contain additives, fillers, other resin components, etc. However, the total amount of the additives, fillers, other resin components, etc. is preferably 50% by weight or less relative to the resin composition (X).

[0600] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0601] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0602] Examples of the crystal nucleating agent include aromatic carboxylic acid metal salts, aromatic phosphoric acid metal salts, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0603] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0604] As fillers, various known fillers that can be used in polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, etc. can be exemplified.

[0605] As other resin components, elastomers such as modified polyolefins and ethylene-α-olefin copolymers, low-density polyethylene, high-density polyethylene, petroleum resins, and other thermoplastic resins and the like can be exemplified.

[0606] The resin composition (X) can be produced by a method of melt-kneading the polypropylene-based resin (A), the thermoplastic resin (E), additives, fillers, other resin components, etc., a method of melt-kneading the polypropylene-based resin (A), additives, fillers, other resin components, etc. and dry-blending the thermoplastic resin (E) into the molten blend, or a method of adding the polypropylene-based resin (A) to the thermoplastic resin (E) and dry-blending a masterbatch in which the additives, fillers, other resin components, etc. are dispersed in a carrier resin at a high concentration.

[0607] [6. Sealing layer (I) composed of propylene-ethylene block copolymer (F)]

[0608] As one embodiment of the decorative film of the present invention, in addition to layer (II), the decorative film may further include a sealing layer (I) composed of a propylene-ethylene block copolymer (F). The propylene-ethylene block copolymer (F) preferably meets the following requirements (f1) to (f3):

[0609] (f1) It contains 5 to 97% by weight of a component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and 3 to 95% by weight of a component (F2) consisting of a propylene-ethylene random copolymer having an ethylene content greater than that of the component (F1).

[0610] (f2) MFR (F) (230°C, 2.16 kg load) greater than 0.5 g / 10 min, and

[0611] (f3) The melting peak temperature (Tm) (F) is 110 to 170°C.

[0612] The sealing layer (I) in this embodiment is a layer that contacts the resin molded body (substrate) during the three-dimensional decoration thermoforming. By providing the sealing layer (I), even when the heating time of the film is short during the three-dimensional decoration thermoforming, sufficient bonding strength can be exhibited, and scratches formed on the substrate surface can also be made less noticeable.

[0613] {Propylene-ethylene block copolymer (F)}

[0614] The propylene-ethylene block copolymer (F) of the present embodiment comprises a component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and a component (F2) composed of a propylene-ethylene random copolymer having an ethylene content greater than that of the component (F1). Since the component (F2) is a rubber component in the propylene-ethylene block copolymer (F), the adhesion to the resin molded body (substrate) is improved. In addition, the component (F2) has a high uniformity in the form of propylene dispersion, and thus exhibits a high effect of making scratches less noticeable.

[0615] The propylene-ethylene block copolymer (F) is obtained by (co)polymerizing in a first polymerization step a component (F1) consisting of propylene alone or a propylene-ethylene random copolymer and in a second polymerization step a component (F2) consisting of a propylene-ethylene random copolymer having an ethylene content greater than that of the component (F1) in sequence.

[0616] (f1) Ratio of component (F1) to component (F2)

[0617] Regarding the content ratio of the proportion of the component (F1) and the proportion of the component (F2) constituting the propylene-ethylene block copolymer (F) in the present embodiment, it is necessary that the proportion of the component (F1) is 5 to 97% by weight and the proportion of the component (F2) is required to be 3 to 95% by weight (requirement (f1)). It is preferred that the proportion of the component (F1) is 30 to 95% by weight and the proportion of the component (F2) is 5 to 70% by weight, and it is further preferred that the proportion of the component (F1) is 52 to 92% by weight and the proportion of the component (F2) is 8 to 48% by weight.

[0618] When the ratio of component (F1) and the ratio of component (F2) are within the above ranges, sufficient adhesive strength can be exhibited, and the effect of making scratches less noticeable is high. In addition, within the above ranges, the film is not sticky, and film formability is satisfactory.

[0619] (f2) Melt flow rate (MFR(F))

[0620] The melt flow rate (MFR(F)) of the propylene-ethylene block copolymer (F) (230°C, load of 2.16 kg) needs to be greater than 0.5 g / 10 min (condition (f2)), preferably greater than 1 g / 10 min, more preferably greater than 2 g / 10 min. When the MFR(F) is within the above range, the relaxation of the propylene-ethylene block copolymer (F) is fully performed during the three-dimensional decorative thermoforming, sufficient bonding strength can be exhibited, and scratches formed on the substrate also become less noticeable. There is no upper limit to the MFR(F), but it is preferably less than 100 g / 10 min. Within the above range, deterioration of bonding strength due to reduction in physical properties does not occur.

[0621] In the present embodiment, MFR of the propylene-ethylene block copolymer (F), the polypropylene resin composition (B) and the polypropylene resin composition mentioned below is measured under a load of 2.16 kg at 230° C. according to Condition M of ISO 1133:1997. The unit is g / 10 min.

[0622] (f3) Melting peak temperature (Tm(F))

[0623] The melting point (melting peak temperature) (hereinafter referred to as "Tm(F)") of the propylene-ethylene block copolymer (F) needs to be 110 to 170°C (requirement (f3)). It is preferably 113 to 169°C, more preferably 115 to 168°C. When Tm(F) is within the above range, the formability during three-dimensional decorative thermoforming is satisfactory. The melting peak temperature mainly comes from the component (F1) with a small ethylene content, that is, the component (F1) with high crystallinity, and the melting peak temperature can be changed by the content of ethylene to be copolymerized.

[0624] (f4) Ethylene content in propylene-ethylene block copolymer (F) (E(F))

[0625] The ethylene content (hereinafter referred to as "E(F)") in the propylene-ethylene block copolymer (F) of the present embodiment is preferably 0.15 to 85 wt%. More preferably, it is 0.5 to 75 wt%, and further preferably, it is 2 to 50 wt%. When E(F) is within the above range, sufficient adhesive strength can be exhibited, the adhesiveness with the layer (II) of the decorative film is satisfactory, and the film formability is also excellent.

[0626] (f5) Ethylene content of component (F1) [E(F1)]

[0627] Component (F1) is preferably a propylene homopolymer or a propylene-ethylene random copolymer having a relatively high melting point and an ethylene content in the range of 0 to 6 wt % (hereinafter referred to as "E(F1)"). More preferably, it is 0 to 5 wt %. When E(F1) is within the above range, the formability during thermoforming of the three-dimensional decoration is satisfactory, the stickiness of the film is small, and the film formability is also excellent.

[0628] (f6) Ethylene content of component (F2) [E(F2)]

[0629] In component (F2), the ethylene content (hereinafter referred to as "E(F2)") is greater than the ethylene content E(F1) of component (F1). In addition, component (F2) is preferably a propylene-ethylene random copolymer having E(F2) in the range of 5 to 90 wt%. E(F2) is more preferably 7 to 80 wt%, further preferably 9 to 50 wt%. When E(F2) is within the above range, sufficient adhesive strength can be exhibited, and the effect of making scratches less noticeable is high.

[0630] {Production method of propylene-ethylene block copolymer (F)}

[0631] The propylene-ethylene block copolymer (F) used in the present embodiment and the component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and the component (F2) composed of a propylene-ethylene random copolymer constituting the copolymer (F) can preferably be produced by the following raw materials and polymerization methods. The production method of the propylene-ethylene block copolymer (F) used in the present invention will be explained below.

[0632] (Raw materials used)

[0633] As the catalyst used when producing the propylene-ethylene block copolymer (F) used in the present embodiment, a magnesium-supported catalyst having magnesium, halogen, titanium and an electron donor as catalyst components, a catalyst composed of a solid catalyst component having titanium trichloride as a catalyst and an organic aluminum composition, or a metallocene catalyst can be used. The specific method for producing the catalyst is not particularly limited, but for example, the Ziegler catalyst disclosed in JP-A-2007-254671 and the metallocene catalyst disclosed in JP-A-2010-105197 can be exemplified.

[0634] Furthermore, the raw material olefins to be polymerized are propylene and ethylene, and if necessary, other olefins such as 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene may be used in an amount not impairing the purpose of the present invention.

[0635] (Polymerization Step)

[0636] The polymerization step carried out in the presence of the above-mentioned catalyst includes a plurality of stages of a first polymerization step for producing component (F1) and a second polymerization step for producing component (F2).

[0637] -First polymerization step

[0638] The first polymerization step is a step of feeding propylene alone or a mixture of propylene / ethylene into a polymerization system to which a catalyst is added and producing a propylene homopolymer or a propylene-ethylene random copolymer to form component (F1) in an amount equivalent to 5 to 97 wt% of the total polymer amount.

[0639] The MFR of component (F1) (hereinafter referred to as "MFR (F1)") can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR (F1) of component (F1) becomes higher, and vice versa. In order to increase the hydrogen concentration in the polymerization tank, the feed amount of hydrogen to the polymerization tank is sufficiently increased, and the adjustment is very easy for those skilled in the art. In addition, in the case where component (F1) is a propylene-ethylene random copolymer, as a method for controlling the ethylene content, it is convenient to use a method for controlling the amount of ethylene fed to the polymerization tank. Specifically, when the amount ratio of ethylene to propylene fed to the polymerization tank (ethylene feed amount / propylene feed amount) increases, the ethylene content of component (F1) becomes higher, and vice versa. Although the relationship between the amount ratio of propylene to ethylene to be fed to the polymerization tank and the ethylene content of component (F1) varies depending on the type of catalyst used, it is very easy for those skilled in the art to obtain a component (F1) with a target ethylene content by appropriately adjusting the feed amount ratio.

[0640] - Second polymerization step

[0641] The second polymerization step is a step of subsequently further introducing the propylene / ethylene mixture into the first polymerization step and producing a propylene-ethylene random copolymer to form a component (F2) in an amount equivalent to 3 to 95 wt% of the total polymer amount.

[0642] The MFR of component (F2) (hereinafter referred to as "MFR (F2)") can be adjusted by using hydrogen as a chain transfer agent. The specific control method is the same as the control method of the MFR of component (F1). As a method for controlling the ethylene content of component (F2), it is convenient to use a method of controlling the amount of ethylene fed to the polymerization tank. The specific control method is the same as the case where component (F1) is a propylene-ethylene random copolymer.

[0643] Next, a method for controlling the index of the propylene-ethylene block copolymer (F) will be described.

[0644] First, a method for controlling the weight ratio of component (F1) to component (F2) is described. The weight ratio of component (F1) to component (F2) is controlled by the production amount in the first polymerization step for producing component (F1) and the production amount in the second polymerization step for producing component (F2). For example, in order to increase the amount of component (F1) and reduce the amount of component (F2), the production amount in the second polymerization step is sufficiently reduced while maintaining the production amount in the first polymerization step. For this purpose, the residence time in the second polymerization step is sufficiently shortened or the polymerization temperature is lowered. In addition, the weight ratio can also be controlled by adding a polymerization inhibitor such as ethanol or oxygen, or increasing its addition amount in the case of its initial addition, and vice versa.

[0645] In general, the weight ratio of component (F1) to component (F2) is defined by the production amount in the first polymerization step for producing component (F1) and the production amount in the second polymerization step for producing component (F2). The formula is shown below. Weight of component (F1): weight of component (F2) = W (F1): W (F2)

[0646] W(F1) = production amount in the first polymerization step / (production amount in the first polymerization + production amount in the second polymerization)

[0647] W(F2) = production amount in the second polymerization step / (production amount in the first polymerization + production amount in the second polymerization)

[0648] W(F1)+W(F2)=1

[0649] wherein W(F1) and W(F2) are the weight ratios of the component (F1) and the component (F2) in the propylene-ethylene block copolymer (F), respectively.

[0650] In industrial production equipment, the production volume is usually determined from the heat balance and material balance of each polymerization tank. In addition, when the crystallinity of component (F1) and component (F2) is sufficiently different from each other, the two can be separated and identified by analytical methods such as TREF (temperature rising elution fractionation method), and the amount ratio can be determined. The method of evaluating the crystallinity distribution of polypropylene by TREF measurement is well known to those skilled in the art, and the detailed measurement method is shown in the following documents: G. Glokner, J. Appl. Polym. Sci: Appl. Poly. Symp.; 45, 1-24 (1990), L. Wild, Adv. Polym. Sci.; 98, 1-47 (1990), JBP Soares, AE Hamielec, Polymer; 36, 8, 1639-1654 (1995), etc.

[0651] Next, the method for controlling the ethylene content will be described. Since the propylene-ethylene block copolymer (F) is a mixture of a component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and a component (F2) composed of a propylene-ethylene random copolymer, the following relationship holds true between the respective ethylene contents.

[0652] E(F)=E(F1)×W(F1)+E(F2)×W(F2)

[0653] wherein E(F), E(F1) and E(F2) are respectively the ethylene contents of the propylene-ethylene block copolymer (F), the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and the component (F2) consisting of a propylene-ethylene random copolymer.

[0654] This formula represents the material balance with respect to the ethylene content.

[0655] Therefore, when the weight ratio of component (F1) to component (F2) is determined, that is, when W(F1) and W(F2) are determined, E(F) is uniquely determined by E(F1) and E(F2). That is, E(F) can be controlled by controlling the weight ratio of component (F1) to component (F2), E(F1) and E(F2).

[0656] For example, to increase E(F), E(F1) can be increased or E(F2) can be increased. In addition, when focusing on the fact that E(F2) is higher than E(F1), it is also easy to understand that W(F1) can be reduced while W(F2) can be increased. The same applies to the opposite direction control.

[0657] Furthermore, what can actually be directly obtained as measured values ​​are E(F) and E(F1), so E(F2) is calculated using the measured values ​​of both. Therefore, when an operation to increase E(F) is performed, in the case of an operation to increase E(F2), that is, assuming that an operation to increase the amount of ethylene fed to the second polymerization step is selected as a method, what is directly confirmed as a measured value is E(F) rather than E(F2), but it is obvious that the cause of the increase in E(F) is the increase in E(F2).

[0658] Next, a method of controlling MFR(F) will be described. In the present embodiment, MFR(F2) is defined by the following formula.

[0659] MFR(F2)=exp{(log e [MFR(F)]-W(F1)×log e [MFR(F1)])÷W(F2)}

[0660] where log e It is the logarithm of the base e. MFR(F), MFR(F1) and MFR(F2) are respectively the MFR of the propylene-ethylene block copolymer (F), the MFR of the component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer, and the MFR of the component (F2) composed of a propylene-ethylene random copolymer.

[0661] This formula is a transformation of the empirical expression commonly known as the logarithmic addition rule for viscosity:

[0662] Log e [MFR(F)]=W(F1)×log e [MFR(F1)]+W(F2)×log e [MFR(F2)]

[0663] And is commonly used in this field.

[0664] Since they are defined by this formula, the weight ratio of component (F1) to component (F2), MFR(F), MFR(F1) and MFR(F2) are not independent. Therefore, in order to control MFR(F), the three factors of the weight ratio of component (F1) to component (F2), MFR(F1) and MFR(F2) are fully controlled. For example, in order to increase MFR(F), MFR(F1) may be increased or MFR(F2) may be increased. In addition, in the case where MFR(F2) is lower than MFR(F1), it is also easy to understand that MFR(F) can be increased by increasing W(F1) and decreasing W(F2). The same applies to control in the opposite direction.

[0665] Furthermore, what can actually be directly obtained as measured values ​​are MFR(F) and MFR(F1), so MFR(F2) is calculated using the measured values ​​of both. Therefore, when an operation to increase MFR(F) is performed, in the case of an operation to increase MFR(F2), that is, assuming that an operation to increase the amount of hydrogen fed to the second polymerization step is selected as a method, what is directly confirmed as a measured value is MFR(F) rather than MFR(F2), but it is obvious that the cause of the increase in MFR(F) is the increase in MFR(F2).

[0666] The polymerization method of the propylene-ethylene block copolymer can be carried out by any method of a batch method and a continuous method. In this case, a method of polymerizing in an inert hydrocarbon solvent such as hexane or heptane, a method of using propylene as a solvent without substantially using an inert solvent, a method of polymerizing in a gaseous monomer without substantially using a liquid solvent, and a method combining these methods can be adopted. In addition, in the first polymerization step and the second polymerization step, the same polymerization tank may be used or different polymerization tanks may be used.

[0667] (1) Measurement of ethylene content in copolymers

[0668] Using the propylene-ethylene block copolymer (F), each ethylene content in the copolymer was measured. That is, by analyzing the ethylene content measured by the complete proton decoupling method according to the following conditions: 13 C-NMR spectrum, the ethylene content of each of the component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer obtained upon completion of the first polymerization step and the propylene-ethylene block copolymer (F) obtained by the second polymerization step was determined.

[0669] Instrument: GSX-400 manufactured by JEOL Ltd. or equivalent (carbon nucleus resonance frequency above 100MHz)

[0670] Solvent: o-dichlorobenzene + deuterated benzene (4:1 (volume ratio))

[0671] Concentration: 100mg / mL

[0672] Temperature: 130℃

[0673] Pulse angle: 90°

[0674] Pulse interval: 15 seconds

[0675] Cumulative times: more than 5,000 times

[0676] For example, the attribution of the spectrum can be carried out with reference to Macromolecules 17, 1950 (1984). The attribution of the spectrum measured under the above conditions is shown in the table below. In Table 1, symbols such as Sαα are described according to the markings of Carman et al. (Macromolecules 10, 536 (1977)), and P, S and T represent methyl carbon, methylene carbon and methine carbon respectively.

[0677] [Table 1]

[0678] Chemical shift (ppm) Attribution 45 to 48 <![CDATA[S αα ]]> 37.8 to 37.9 <![CDATA[S αγ ]]> 37.4 to 37.5 <![CDATA[S αδ ]]> 33.1 <![CDATA[T δδ ]]> 30.9 <![CDATA[T βδ ]]> 30.6 <![CDATA[S γγ ]]> 30.2 <![CDATA[S γδ ]]> 29.8 <![CDATA[S δδ ]]> 28.7 <![CDATA[T ββ ]]> 27.4 to 27.6 <![CDATA[S βδ ]]> 24.4 to 24.7 <![CDATA[S ββ ]]> 19.1 to 22.0 P

[0679] Hereinafter, when "P" is a propylene unit in a copolymer chain and "E" is an ethylene unit, six triads PPP, PPE, EPE, PEP, PEE and EEE may be present in the chain. As described in Macromolecules, 15, 1150 (1982) etc., the concentrations of these triads are related to the peak intensity of the spectrum by the following relationships (f-1) to (f-6).

[0680] [PPP] = k × I (Tββ) ... (f-1)

[0681] [PPE] = k × I (Tβδ) ... (f-2)

[0682] [EPE] = k × I (Tδδ) ... (f-3)

[0683] [PEP] = k × I (Sββ) ... (f-4)

[0684] [PEE] = k × I (Sβδ) ... (f-5)

[0685] [EEE]=k×{I(Sδδ) / 2+I(Sγδ) / 4}...(f-6)

[0686] Here, brackets [] denote the fraction of triples, e.g., [PPP] is the fraction of PPP triples among all triples. Therefore,

[0687] [PPP]+[PPE]+[EPE]+[PEP]+[PEE]+[EEE]=1...(f-7)

[0688] In addition, k is a constant, and I represents the spectrum intensity. For example, I(Tββ) represents the intensity of the peak at 28.7 ppm attributed to Tββ. By using the above-mentioned relations (f-1) to (f-7), the score of each triad is determined, and the ethylene content is further determined according to the following formula (f-8).

[0689] Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100... (f-8)

[0690] Furthermore, conversion of the ethylene content from mol % to weight % was performed using the following formula (f-9).

[0691] Ethylene content (weight %) = (28 × X / 100) / {28 × X / 100 + 42 × (1-X / 100)} × 100 ... (f-9)

[0692] Here, X is the ethylene content in mol%.

[0693] The propylene-ethylene block copolymer (F) in the present embodiment may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of the propylene-ethylene block copolymer (F), additives, fillers, and other resin components, etc. The total amount of the additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the resin composition.

[0694] As the additive, known various additives usable for polypropylene-based resins such as an antioxidant, a neutralizer, a light stabilizer, a UV absorber, a crystallization nucleating agent, a blocking inhibitor, a lubricant, an antistatic agent, and a metal deactivator may be blended.

[0695] As antioxidants, phenolic antioxidants, phosphite antioxidants, and sulfur-containing antioxidants can be exemplified. As neutralizers, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified. As light stabilizers and UV absorbers, hindered amines, benzotriazoles, and benzophenones can be exemplified.

[0696] Examples of the crystal nucleating agent include metal salts of aromatic carboxylic acids, metal salts of aromatic phosphoric acids, sorbitol derivatives, metal salts of rosin, and amide nucleating agents. Examples of the crystal nucleating agent include aluminum p-tert-butylbenzoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a complex of bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosphaoctane-6-oxy)aluminum hydroxide and an organic compound, p-methylbenzylidene sorbitol, p-ethylbenzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[(4-propylphenyl)methylene]-nonanol, and sodium salt of rosin.

[0697] As lubricants, higher fatty acid amides such as stearic acid amide can be exemplified. As antistatic agents, fatty acid partial esters such as glycerol fatty acid monoester can be exemplified. As metal deactivators, triazines, phosphonates, epoxies, triazoles, hydrazides, and oxamides can be exemplified.

[0698] As fillers, various known fillers that can be used in polypropylene resins, such as inorganic fillers and organic fillers, can be blended. As inorganic fillers, calcium carbonate, silicon dioxide, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber can be exemplified. In addition, as organic fillers, cross-linked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, etc. can be exemplified.

[0699] As other resin components, polyethylene-based resins, polyolefins such as ethylene-based elastomers, modified polyolefins, petroleum resins, and other thermoplastic resins and the like can be exemplified.

[0700] The above-mentioned resin composition can be produced by a method of melt-kneading the propylene-ethylene block copolymer (F), additives, fillers, and other resin components, etc., a method of melt-kneading the propylene-ethylene block copolymer (F), additives, fillers, etc. and dry-blending the other resin components into the molten blend, or a method of dry-blending a masterbatch in which the additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-ethylene block copolymer (F) and other resin components.

[0701] [7. Sealing layer (I) composed of polyolefin adhesive resin (G)]

[0702] As one embodiment of the decorative film of the present invention, the decorative film further includes a sealing layer (I) (adhesive layer (I)) composed of a polyolefin adhesive resin (G), and can be strongly bonded to a substrate composed of a resin material having polarity generated by stacking the sealing layer (I) on layer (II).

[0703] The MFR (G) (230°C, 2.16 kg load) of the polyolefin adhesive resin (G) in this embodiment is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, and further preferably 20 g / 10 min or less. By controlling the MFR (G) of the polyolefin adhesive resin (G) to be below the above value, it becomes possible to laminate the sealant layer (I) composed of the polyolefin adhesive resin (G) on the layer (II) composed of the resin composition (B) containing the polypropylene resin (B) by an extrusion molding method.

[0704] The lower limit of the MFR (G) of the polyolefin adhesive resin (G) is not particularly limited, but is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. By controlling the MFR (G) of the polyolefin adhesive resin (G) to be above the above value, in the coextrusion molding of the polypropylene resin composition (B) and the polyolefin adhesive resin (G), it is possible to suppress the occurrence of problems such as interface roughness at the lamination interface and the polyolefin adhesive resin (G) not being laminated to the edge of the film.

[0705] From the viewpoint of improving the adhesiveness with the layer (II) composed of the resin composition (B) containing the polypropylene resin (B), the polyolefin adhesive resin (G) in the present invention is preferably a polyolefin resin having a polar functional group containing at least one heteroatom.

[0706] As the polar functional group having at least one hetero atom, there can be mentioned an epoxy group, a carbonyl group, an ester group, an ether group, a hydroxyl group, a carboxyl group or a metal salt thereof, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an acid anhydride group, an amino group, an imide group, an amide group, a nitrile group, a thiol group, a sulfone group, an isocyanate group, and a halogen group, etc. In particular, the polyolefin adhesive resin (G) is more preferably a polyolefin resin having at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, an imide group, an amide group, a nitrile group, a thiol group, an isocyanate group, and a halogen group.

[0707] Specific examples of such polyolefins having a polar functional group include acid-modified polypropylenes such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene or α-olefin / vinyl monomer copolymers such as ethylene / vinyl chloride copolymers, ethylene / vinylidene chloride copolymers, ethylene / acrylonitrile copolymers, ethylene / methacrylonitrile copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylamide copolymers, ethylene / methacrylamide copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / maleic acid copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / isopropyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / isobutyl acrylate copolymers, ethylene / 2-ethylhexyl acrylate copolymers, ethylene / methyl methacrylate copolymers, ethylene / ethyl methacrylate copolymers, ethylene / isopropyl methacrylate copolymers, ethylene / butyl methacrylate copolymers, ethylene / isobutyl methacrylate copolymers, ethylene / 2-ethylhexyl methacrylate copolymers, ethylene / maleic anhydride copolymers, ethylene / ethyl acrylate / maleic anhydride copolymers, ethylene / metal salts of acrylic acid (metal methacrylate) acrylate) copolymers, ethylene / methacrylate metal salt copolymers, ethylene / vinyl acetate copolymers or saponification products thereof, ethylene / vinyl propionate copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / ethyl acrylate / glycidyl methacrylate copolymers, and ethylene / vinyl acetate / glycidyl methacrylate copolymers; chlorinated polyolefins such as chlorinated polypropylene and chlorinated polyethylene; and the like.

[0708] Furthermore, these resins may be used alone or two or more thereof may be used in combination. Furthermore, if necessary, other resins or rubbers, tackifiers, and various additives and the like may be mixed.

[0709] As other resins or rubbers, for example, poly-α-olefins such as polypentene-1 and polymethylpentene-1, ethylene or α-olefin / α-olefin copolymers such as propylene / butene-1 copolymers, ethylene or α-olefin / α-olefin / diene monomer copolymers such as ethylene / propylene / 5-ethylidene-2-norbornene copolymers, polybutadiene copolymers such as polybutadiene and polyisoprene, vinyl monomer / diene monomer random copolymers such as styrene / butadiene random copolymers and styrene / isoprene random copolymers, vinyl monomer / diene monomer / vinyl monomer block copolymers such as styrene / butadiene / styrene block copolymers and styrene / isoprene / styrene block copolymers, hydrogenated (vinyl monomer / diene monomer random copolymers) such as hydrogenated (styrene / butadiene random copolymers) and hydrogenated (styrene / isoprene random copolymers). hydrogenated (styrene / isoprene random copolymer), hydrogenated (vinyl monomer / diene monomer / vinyl monomer block copolymer) such as hydrogenated (styrene / butadiene / styrene block copolymer) and hydrogenated (styrene / isoprene / styrene block copolymer), vinyl monomer / diene monomer / vinyl monomer graft copolymer such as acrylonitrile / butadiene / styrene graft copolymer and methyl methacrylate / butadiene / styrene graft copolymer, vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polystyrene, vinyl copolymers such as vinyl chloride / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer and methyl methacrylate / styrene copolymer, etc.

[0710] As the tackifier, for example, rosin resins (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleic rosin, rosin ester, etc.), terpene phenol resins, terpene resins (polymers such as α-pinene, β-pinene and limonene), aromatic hydrocarbon-modified terpene resins, petroleum resins (aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, etc.), coumarone-indene resins, styrene resins, phenol resins (alkylphenol, phenol-xylene-formaldehyde, rosin-modified phenol resins, etc.), and xylene resins, etc. can be mentioned. These resins can be used alone or two or more of them can be used in combination. Among these, rosin resins, terpene-phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferred from the viewpoint of thermal stability, and rosin resins and terpene-phenol resins are particularly preferred in view of compatibility with the modified polyolefin resin of the present invention and the ability to contribute to adhesion to polar resins.

[0711] As additives, there may be mentioned stabilizers such as antioxidants, metal deactivators, phosphorus-based processing stabilizers, UV absorbers, UV stabilizers, metal soaps, anti-acid adsorbents or crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, and fluorescent brighteners, etc. They may be added within the range that does not impair the advantages of the present invention.

[0712] Among the polyolefin resins having a polar functional group mentioned above, from the viewpoint of adhesion to layer (II), as commercially available products, "ADMER" manufactured by Mitsui Chemicals Inc., "MODIC" manufactured by Mitsubishi Chemical Corporation, "UMEX" manufactured by Sanyo Chemical Industries, Ltd., etc. can be appropriately used.

[0713] [Decorative film]

[0714] The decorative film in the present invention includes a layer (II) containing a polypropylene resin (B), and preferably further includes a sealing layer (I) containing a polypropylene resin (A). That is, the decorative film can be a single-layer film composed of layer (II), a two-layer film composed of layer (II) and a sealing layer (I), or a multilayer film having three or more layers composed of layer (II), a sealing layer (I) and other one or more layers. In addition, it can be a multilayer film having two or more layers composed of layer (II) and other one or more layers. In addition to layer (II), the decorative film can adopt various structures. In addition, the sealing layer (I) is attached along the resin molded body (substrate). In addition, the decorative film can be embossed, embossed, printed, sandblasted, and scratched, etc.

[0715] The decorative film has a large degree of freedom in shape, has an excellent appearance without seams because the edge of the decorative film is rolled up to the back of the decorative object, and can express various textures by applying embossing to the surface of the decorative film. For example, in the case of applying a texture such as embossing to a resin molded body, three-dimensional thermoforming using the decorative film to which the embossing has been applied is fully performed. Therefore, the problem in the case of forming using a forming mold to which embossing is applied, that is, the problem that a forming mold is required for each embossing pattern, and it is very difficult and expensive to provide complex embossing on a curved mold, can be solved, and thus a decorative molded body to which embossing of various patterns has been applied can be obtained.

[0716] In the multilayer film, in addition to the sealing layer (I) and the layer (II), a surface layer, a surface decoration layer, a printing layer, a light shielding layer, a coloring layer, a substrate layer, a barrier layer, and a tie layer (tie layer) that can be provided between these layers, etc. The layer (II) composed of the resin composition (B) can be any layer constituting the multilayer film except the sealing layer.

[0717] As a preferred embodiment of the decorative film, in the case of a single-layer film of layer (II), it is a film composed of a resin composition (B) having an MFR (230° C., load of 2.16 kg) of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more.

[0718] As another preferred embodiment of the decorative film, in the case of a multilayer film having two layers consisting of layer (II) and another layer, the surface layer as the surface of the decorative molded body and / or the inner layer attached to the molded body is layer (II) composed of a resin composition (B) having an MFR (230°C, a load of 2.16 kg) of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more. It is more preferred that the inner layer attached to the molded body is a layer composed of the resin composition (B).

[0719] As another preferred embodiment of the decorative film, in the case of a multilayer film having three layers consisting of layer (II) and other layers, the surface layer as the surface of the decorative molded body, the inner layer attached to the molded body and / or the intermediate layer between the surface layer and the inner layer is layer (I) composed of a resin composition (B) having an MFR (230°C, a load of 2.16 kg) of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more. More preferably, the inner layer attached to the molded body is layer (II) composed of the resin composition (B).

[0720] In a multilayer film having a more complex layer structure, similarly, at least one layer constituting the multilayer film is a layer (II) composed of a resin composition (B) having an MFR (230°C, load of 2.16 kg) of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more.

[0721] When the decorative film is a two-layer film consisting of layer (II) and sealing layer (I), it is preferred that layer (II) constitutes a surface layer opposite to the pasting surface of the resin formed body, and sealing layer (I) constitutes a sealing layer for the pasting surface of the resin formed body.

[0722] In addition, as another preferred embodiment of a multilayer film consisting of two or more layers including layer (II) and sealing layer (I), the layer other than layer (II) and sealing layer (I) is preferably a layer composed of a thermoplastic resin, more preferably a layer composed of a polypropylene resin. In the layer other than layer (II) and sealing layer (I), the MFR (230°C, load of 2.16 kg) of the polypropylene resin constituting the layer is not particularly limited as long as it can be distinguished from layer (II) and sealing layer (I). 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 resin, the complication of the layer constitution can be suppressed, and recyclability can be further improved.

[0723] When the decorative film is a multilayer film having three or more layers, the effect of suppressing scratches on the substrate surface may be reduced when other layers are interposed between the sealing layer (I) and the layer (II). Therefore, the multilayer film preferably has a structure of sealing layer (I) / layer (II) / other layers (including multiple layers) from the bonding side of the resin molded body.

[0724] Figure 1A (a) to Figure 1A (c) is an explanatory diagram schematically illustrating a cross section of an embodiment of a decorative film attached to a resin molded body in a mode in which the decorative film includes a layer (II) composed of a polypropylene-based resin composition (B). Figure 1A (a) to Figure 1A In (c), for ease of understanding, the configuration of the layer (II) is specified and described, but the layer structure of the decorative film should not be construed as being limited to these examples.

[0725] Here, reference numeral 1 in the drawings denotes a decorative film, reference numeral 2 denotes a layer (II), reference numeral 4 denotes a surface decorative layer (III), reference numeral 5 denotes a resin molded body, and reference numeral 6 denotes a decorative molded body. Figure 1A (a) is an example in which the decorative film 1 is composed of a single-layer film and the layer (II) composed of the resin composition (B) is attached to the resin molded body 5 . Figure 1A (b) and Figure 1A (c) is an example in which the decorative film consists of a multilayer film. Figure 1A The decorative film 1 of (b) is composed of a layer (II) 2 and a surface decorative layer (III) 4 , and the layer (II) 2 is pasted on the surface of a resin molded body 5 , and the surface decorative layer (III) 4 is laminated on the layer (II) 2 . Figure 1A The decorative film 1 of (c) is composed of layer (II) 2, an intermediate layer and a surface decorative layer (III) 4, and layer (II) 2 is pasted on the surface of a resin molded body 5, and the intermediate layer and the surface decorative layer (III) 4 are stacked on layer (II) 2 in sequence.

[0726] Figure 1C (a) to Figure 1C (c) is an explanatory diagram schematically illustrating a cross section of an embodiment of a decorative film in a mode in which the decorative film includes a layer (II) composed of a polypropylene-based resin composition (B) and a sealant layer (I), and Figure 1B (a) to Figure 1B (c) is an explanatory diagram schematically illustrating a cross section of an embodiment of a decorative film attached to a resin molded body. Figure 1B (a) to Figure 1B (c) illustrates an implementation method of the decorative film. Figure 1B (a) to Figure 1B In (c), for ease of understanding, the configurations of the sealing layer (I) and the layer (II) are specified and described, but the layer configuration of the decorative film should not be construed as being limited to these examples.

[0727] Reference numeral 1 in the drawings denotes a decorative film, reference numeral 2 denotes layer (II), reference numeral 3 denotes a sealing layer (I), reference numeral 4 denotes a surface decorative layer (III), reference numeral 5 denotes a resin molded body, and reference numeral 6 denotes a decorative molded body. Figure 1B (a) is an example in which the decorative film 1 is composed of two films, the sealant layer (I) 3 is attached to the resin molded body 5, and the layer (II) 2 composed of the resin composition (B) is attached to the sealant layer (I) 3. Figure 1B The decorative film 1 of (b) is composed of a sealing layer (I) 3, a layer (III) 2 and a surface layer, the sealing layer (I) 3 is adhered to the surface of the resin molded body 5 and the layer (II) 2 and the surface layer are stacked on the sealing layer (I) 3 in sequence. Figure 1B The decorative film 1 of (c) is composed of a sealing layer (I), a layer (II) and a surface decorative layer (III) composed of a polypropylene resin, the sealing layer (I) is adhered to the surface of the resin molded body 5, and the layer (II) and the surface decorative layer (III) are stacked on the sealing layer (I) in sequence.

[0728] In addition, Figure 1C (a) to Figure 1C In (c), for ease of understanding, the configuration of the sealing layer (I) and the layer (II) is specified and described, but the layer configuration of the decorative film should not be understood to be limited to these examples. Reference numeral 1 in the drawings represents a decorative film, reference numeral 2 represents layer (II), reference numeral 3 represents a sealing layer (I), and reference numeral 4 represents a surface decorative layer (III). Figure 1C (a) is an example in which the decorative film 1 is composed of two films and the layer (II) 2 composed of the resin composition (A) is laminated on the sealing layer (I). Figure 1CThe decorative film 1 of (b) is composed of a sealing layer (I) 3, a layer (II) 2 and a surface layer, and the layer (II) 2 and the surface layer are sequentially laminated on the sealing layer (I) 3. Figure 1C The decorative film 1 of (c) is composed of a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4, and the layer (II) 2 and the surface decorative layer (III) 4 are sequentially stacked on the sealing layer (I) 3.

[0729] As a preferred embodiment of the multilayer film, the layers other than the layer (II) composed of the resin composition (B) are preferably layers composed of thermoplastic resins, and more preferably layers composed of polypropylene resins other than the polypropylene resin (B). Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved. In addition, by using a polypropylene resin other than the polypropylene resin (B), the complication of the layer constitution can be suppressed, and recyclability can be further improved.

[0730] As another preferred embodiment of the decorative film, there can be mentioned a multilayer film comprising a layer (II) composed of a resin composition (B) and a surface decorative layer (III) composed of a surface decorative layer resin, wherein the surface decorative layer (III) is arranged on the side of the layer (II) opposite to the adhesive surface having the resin molded body.

[0731] The surface decoration layer resin is preferably composed of a thermoplastic resin, more preferably composed of a polypropylene resin (H). By using a polypropylene resin (H), the complication of the layer structure and the reduction of recyclability can be suppressed. In addition, by using a polypropylene resin (H) for the surface decoration layer of the decorative film, excellent solvent resistance and the like can be achieved. In addition, by using a polypropylene resin (H) for the surface decoration layer, the transferability of the surface is improved during the production and thermoforming of the decorative film, and when a mirror-shaped roller is used during thermoforming, a decorative film with higher gloss can be obtained.

[0732] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains 50 mol% or more of propylene monomer. The propylene polymer preferably does not contain a monomer unit containing a polar group. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoints of gloss and transparency (color development), propylene-α-olefin copolymers are preferred.

[0733] The polypropylene resin (H) in this embodiment has a strain hardening degree of preferably less than 1.1, more preferably less than 1.0. By controlling the strain hardening degree of the polypropylene resin (H) to less than 1.1, the appearance of the decorative molded body can be made satisfactory. The strain hardening degree of the polypropylene resin (H) is measured by the above method.

[0734] Regarding the polypropylene resin (H), MFR (H) (230°C, load of 2.16 kg) is preferably greater than 2 g / 10 min, more preferably 5 g / 10 min or more, and further preferably 9 g / 10 min or more. By controlling the MFR of the polypropylene resin (H) to the above value range, the effects obtained are that the gloss of the decorative film and the embossing transferability are improved, and a decorative molded body having a satisfactory appearance in terms of the surface form (glossy, matte, embossed, etc.) required for the molded body can be obtained.

[0735] The upper limit of the MFR of the polypropylene resin (H) is not particularly limited, but is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less. By controlling the MFR (H) to the above value range, satisfactory oil resistance, solvent resistance, scratch resistance, etc. can be exhibited.

[0736] The polypropylene resin (H) may contain additives, fillers, colorants, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, colorants, and other resin components, etc. The total amount of additives, fillers, colorants, and other resins, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0737] As the additive, additives that can be contained in the polypropylene-based resin (B) and the like can be used.

[0738] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0739] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0740] When the decorative film is a single-layer film, the ratio of the thickness of layer (II) to the total thickness of the decorative film is 100%. When the decorative film is a multilayer film, the ratio of the thickness of layer (II) to the total thickness of the decorative film is preferably 30% or more, more preferably 50% or more. The upper limit is not particularly limited, but is preferably less than 100%. When the ratio of the thickness of layer (II) to the entire decorative film is within the above value range, it is possible to avoid the thermoformability of the decorative film from becoming insufficient.

[0741] When the decorative film includes the sealing layer (I) described in [1. Sealing layer (I) composed of a polypropylene resin (A)] above, as another preferred embodiment of the decorative film, a multilayer film including a surface decorative layer (III) composed of a surface decorative layer resin is mentioned, and the surface decorative layer (III) is located on the side of the layer (II) opposite to the adhesive side having the resin molded body, and more preferably on the uppermost surface of the opposite side. The surface decorative layer resin is preferably a thermoplastic resin, and more preferably a polypropylene resin (H) having an MFR (230°C, a load of 2.16 kg) greater than 2 g / 10 minutes. That is, by additionally providing a layer (III) composed of a polypropylene resin (H) on the surface layer of the decorative film, the gloss and embossing transferability can be improved without significantly reducing the thermoformability. In addition, by using the polypropylene resin (H), the complication of the layer structure and the reduction of the recyclability can be suppressed. In addition, by using the polypropylene resin (H) for the surface decorative layer of the decorative film, the solvent resistance and the like can be made excellent. Furthermore, by using the polypropylene-based resin (H) for the surface decorative layer, the transferability of the surface is improved during production and thermoforming of the decorative film, and when a mirror-shaped roller is used during thermoforming, a decorative film with higher gloss can be obtained.

[0742] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of propylene monomer. The propylene polymer preferably does not contain a monomer unit containing a polar group. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoint of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present invention, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

[0743] The polypropylene resin (H) in this embodiment has a strain hardening degree of preferably less than 1.1, more preferably less than 1. By controlling the strain hardening degree of the polypropylene resin (H) to less than 1.1, the appearance of the decorative molded body can be made satisfactory. The strain hardening degree of the polypropylene resin (H) is measured by the above method.

[0744] Regarding the polypropylene resin (H), MFR (H) (230°C, load of 2.16 kg) is preferably greater than 2 g / 10 min, more preferably 5 g / 10 min or more, and further preferably 9 g / 10 min or more. By controlling the MFR of the polypropylene resin (H) to the above value range, the effects obtained are that the gloss of the decorative film and the embossing transferability are improved, and a decorative molded body having a satisfactory appearance in terms of the surface form (glossy, matte, embossed, etc.) required for the molded body can be obtained.

[0745] The upper limit of the MFR of the polypropylene resin (H) is not particularly limited, but is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less. By controlling the MFR within the above value range, satisfactory oil resistance, solvent resistance, scratch resistance, etc. can be exhibited.

[0746] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0747] As the additive, additives that can be contained in the polypropylene-based resin (B) and the like can be used.

[0748] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which the additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0749] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the polypropylene resin (A) constituting the sealant layer (I). In the case where the two polypropylene resin compositions are the same, the sealant layer (I) and the surface decorative layer (III) can be formed by one extruder using a feed block or the like.

[0750] 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during molding is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0751] In the decorative film of the present embodiment, the ratio of the thickness of the layer (II) to the thickness of the entire decorative film is preferably 30 to 99%, and the ratio of the thickness of the sealing layer (I) is preferably 1 to 70%. When the ratio of the thickness of the layer (II) to the thickness of the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient. When the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is within the above value range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface.

[0752] Furthermore, in a multilayer film in which a surface decorative layer (III) composed of a polypropylene-based resin (H) is provided on the uppermost surface of the decorative film, the ratio of the thickness of the surface decorative layer (III) to the thickness of the entire decorative film is preferably 30% or less.

[0753] When the decorative film includes the sealing layer (I) described in [2. Sealing layer (I) composed of a polypropylene resin (A)] above, as another more preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, the surface decorative layer (III) being located on the side of the layer (II) opposite to the adhesive surface side having the resin molded body, more preferably on the uppermost surface of the opposite side. The surface decorative layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (H).

[0754] The melt flow rate (230° C., 2.16 kg load) (MFR(H)) of the polypropylene resin (H) in this embodiment preferably satisfies the following: MFR(H)>MFR(B). By controlling the value within the above range, a more beautiful surface texture can be expressed.

[0755] As the polypropylene resin (H) of the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoints of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present invention, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

[0756] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0757] As the additive, additives that can be contained in the polypropylene-based resin (A) and the like can be used.

[0758] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0759] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the polypropylene resin (A) constituting the sealant layer (I).

[0760] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0761] In the decorative film of this embodiment, the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. When the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above value range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface. In addition, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient.

[0762] Furthermore, in the multilayer film in which the surface decorative layer (III) composed of the polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) relative to the entire decorative film is preferably 30% or less.

[0763] When the decorative film includes the sealing layer (I) described in the above [3. The sealing layer (I) is composed of a resin composition (X) comprising a polypropylene resin (A) and an ethylene-α-random copolymer (C) as main components], as another preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, wherein the surface decorative layer (III) is located on the side of the layer (II) opposite to the side to be pasted to the resin molded body, and more preferably on the uppermost surface of the opposite side.

[0764] The surface decoration layer resin is preferably a thermoplastic resin, more preferably a polypropylene-based resin (H).

[0765] The melt flow rate (230° C., 2.16 kg load) (MFR(H)) of the polypropylene resin (H) in this embodiment preferably satisfies the following: MFR(H)>MFR(B). By controlling the value within the above range, a more beautiful surface texture can be expressed.

[0766] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoint of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present embodiment, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same or different from the polypropylene resin (A) constituting the sealing layer (I).

[0767] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0768] As the additive, additives that can be contained in the resin composition (X) constituting the sealing layer (I) and the like can be used.

[0769] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0770] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the polypropylene resin (A) constituting the sealant layer (I).

[0771] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0772] In the decorative film of this embodiment, the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. When the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above value range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface. In addition, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient.

[0773] Furthermore, in the multilayer film in which the surface decorative layer (III) composed of the polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) relative to the entire decorative film is preferably 30% or less.

[0774] When the decorative film includes the sealing layer (I) described in the above [4. A sealing layer (I) composed of a resin composition comprising a polypropylene resin (A) and a thermoplastic elastomer (D) as main components], as another preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, wherein the surface decorative layer (III) is located on the side of the layer (II) opposite to the bonding side having the resin molded body, and more preferably on the uppermost surface of the opposite side.

[0775] The surface decoration layer resin is preferably a thermoplastic resin, more preferably a polypropylene-based resin (H).

[0776] The melt flow rate (230° C., 2.16 kg load) (MFR(H)) of the polypropylene resin (H) in this embodiment preferably satisfies the following: MFR(H)>MFR(B). By controlling the value within the above range, a more beautiful surface texture can be expressed.

[0777] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoint of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present embodiment, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same or different from the polypropylene resin (A) constituting the sealing layer (I).

[0778] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0779] As the additive, additives that can be contained in the resin composition (X) constituting the sealing layer (I) and the like can be used.

[0780] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0781] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the polypropylene resin (A) constituting the sealant layer (I).

[0782] 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during molding is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0783] In the decorative film of this embodiment, the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. When the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above value range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface. In addition, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient.

[0784] Furthermore, in a multilayer film in which a surface decorative layer (III) composed of a polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) is preferably 30% or less relative to the entire decorative film.

[0785] When the decorative film includes the sealing layer (I) described in the above [5. The sealing layer (I) is composed of a resin composition (X) containing a polypropylene resin (A) and a thermoplastic resin (E) as main components], as another preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, wherein the surface decorative layer (III) is located on the side of the layer (II) opposite to the bonding side having the resin molded body, and more preferably on the uppermost surface of the opposite side.

[0786] The surface decoration layer resin is preferably a thermoplastic resin, more preferably a polypropylene-based resin (H).

[0787] The melt flow rate (230° C., 2.16 kg load) (MFR(H)) of the polypropylene resin (H) in this embodiment preferably satisfies the following: MFR(H)>MFR(B). By controlling the value within the above range, a more beautiful surface texture can be expressed.

[0788] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoints of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present invention, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

[0789] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0790] As the additive, additives that can be contained in the resin composition (X) and the like can be used.

[0791] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0792] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the polypropylene resin (A) constituting the sealant layer (I).

[0793] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0794] In the decorative film of this embodiment, the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. When the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above value range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface. In addition, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient.

[0795] Furthermore, in the multilayer film in which the surface decorative layer (III) composed of the polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) relative to the entire decorative film is preferably 30% or less.

[0796] When the decorative film includes the sealing layer (I) described in [6. Sealing layer (I) composed of propylene-ethylene block copolymer (F)] above, as another preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, the surface decorative layer (III) being located on the side of the layer (II) opposite to the side to be attached to the resin molded body, more preferably on the uppermost surface of the opposite side. The surface decorative layer resin is preferably a thermoplastic resin, more preferably a polypropylene-based resin (H).

[0797] The melt flow rate (230° C., 2.16 kg load) (MFR(H)) of the polypropylene resin (H) in this embodiment preferably satisfies the following: MFR(H)>MFR(B). By controlling the value within the above range, a more beautiful surface texture can be expressed.

[0798] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene-α-olefin block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoint of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present embodiment, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same or different from the propylene-ethylene block copolymer (F) constituting the sealing layer (I).

[0799] The polypropylene resin (H) may contain additives, fillers, and other resin components. That is, it may be a resin composition (polypropylene resin composition) of the propylene polymer (H), additives, fillers, and other resin components. The total amount of additives, fillers, and other resin components is preferably 50% by weight or less relative to the polypropylene resin composition.

[0800] As the additive, additives that can be contained in the resin composition constituting the sealing layer (I) and the like can be used.

[0801] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0802] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from the polypropylene resin composition comprising the propylene-ethylene block copolymer (F) constituting the sealant layer (I).

[0803] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0804] In the decorative film of this embodiment, the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is preferably 1 to 70%, and the ratio of the thickness of the layer (II) is preferably 30 to 99%. When the ratio of the thickness of the sealing layer (I) to the entire decorative film is within the above range, sufficient bonding strength can be exhibited, and scratches of the resin molded body (substrate) can be suppressed from appearing on the surface. In addition, when the ratio of the thickness of the layer (II) to the entire decorative film is within the above range, the thermoformability of the decorative film can be prevented from becoming insufficient.

[0805] Furthermore, in the multilayer film in which the surface decorative layer (III) composed of the polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) relative to the entire decorative film is preferably 30% or less.

[0806] When the decorative film includes the sealing layer (I) described in [7. Sealing layer (I) composed of a polyolefin adhesive resin (G)] above, as another preferred embodiment of the decorative film, a multilayer film is mentioned which also includes a surface decorative layer (III) composed of a surface decorative layer resin, the surface decorative layer (III) being located on the side of the layer (II) opposite to the adhesive side of the resin molded body, more preferably on the uppermost surface of the opposite side. The surface decorative layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (H) having an MFR (230°C, a load of 2.16 kg) of more than 2 g / 10 minutes. That is, by additionally providing a surface decorative layer (III) composed of a polypropylene resin (H) on the surface layer of the decorative film, the gloss and embossing transferability can be improved without significantly reducing the thermoformability. In addition, by using the polypropylene resin (H), the complication of the layer structure and the reduction of the recyclability can be suppressed. In addition, by using the polypropylene resin (H) for the surface decorative layer of the decorative film, the solvent resistance and the like can be made excellent. Furthermore, by using the polypropylene-based resin (H) for the surface decorative layer, the transferability of the surface is improved during production and thermoforming of the decorative film, and when a mirror-shaped roller is used during thermoforming, a decorative film with higher gloss can be obtained.

[0807] As the polypropylene resin (H) in the present embodiment, one of various types of propylene polymers can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene) and propylene block copolymer (block polypropylene), or a combination thereof. The propylene polymer preferably contains more than 50 mol% of propylene monomer. The propylene polymer preferably does not contain a monomer unit containing a polar group. From the viewpoints of oil resistance, solvent resistance, and scratch resistance, the polypropylene resin (H) is preferably homopolypropylene. From the viewpoint of gloss and transparency (color rendering), propylene-α-olefin copolymers are preferred. In the present embodiment, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same or different from the polyolefin adhesive resin (G) constituting the sealing layer (I).

[0808] The polypropylene resin (H) in this embodiment has a strain hardening degree of preferably less than 1.1, more preferably less than 1.0. By controlling the strain hardening degree of the polypropylene resin (H) to less than 1.1, the appearance of the decorative molded body can be made satisfactory. The strain hardening degree of the polypropylene resin (H) is measured by the above method.

[0809] Regarding the polypropylene resin (H) in the present embodiment, the MFR (H) (230° C., load of 2.16 kg) is preferably greater than 2 g / 10 min, more preferably 5 g / 10 min or more, and further preferably 9 g / 10 min or more. By controlling the MFR of the polypropylene resin (H) to the above value range, the effects obtained are that the gloss of the decorative film and the embossing transferability are improved, and a decorative molded body having a satisfactory appearance in terms of the surface form (glossy, matte, embossed, etc.) required for the molded body can be obtained.

[0810] The upper limit of the MFR of the polypropylene resin (H) is not particularly limited, but is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less. By controlling the MFR (H) to the above value range, satisfactory oil resistance, solvent resistance, scratch resistance, etc. can be exhibited.

[0811] The polypropylene resin (H) may contain additives, fillers, and other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of a propylene polymer, additives, fillers, and other resin components, etc. The total amount of additives, fillers, and other resin components, etc. is preferably 50% by weight or less relative to the polypropylene resin composition.

[0812] As the additive, additives that can be contained in the resin composition (B) and the like can be used.

[0813] The polypropylene resin composition can be produced by a method of melt-kneading a propylene polymer, additives, fillers, and other resin components, etc., a method of melt-kneading a propylene polymer, additives, fillers, etc. and dry-blending the other resin components into the melt blend, or a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene polymer and other resin components.

[0814] The decorative film of the present embodiment 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 controlling the thickness of the decorative film to be above this value, the effect of imparting a design is improved, and the stability during forming is also improved, so that a more satisfactory 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 further preferably about 0.8 mm or less. By controlling the thickness of the decorative film to be below this value, the time required for heating during thermoforming is shortened, thereby improving productivity, and it becomes easy to trim unnecessary parts.

[0815] In the decorative film of this embodiment, the ratio of the thickness of the layer (II) to the thickness of the entire decorative film is preferably 30 to 99%, and the ratio of the thickness of the sealing layer (I) is preferably 1 to 70%. When the ratio of the thickness of the layer (II) to the thickness of the entire decorative film is within the above value range, the thermoformability of the decorative film can be prevented from becoming insufficient. In addition, when the ratio of the thickness of the sealing layer (I) to the thickness of the entire decorative film is within the above value range, sufficient bonding strength can be exhibited to a substrate composed of a polar resin material.

[0816] Furthermore, in the multilayer film in which the surface decorative layer (III) composed of the polypropylene resin (H) is provided on the uppermost surface of the decorative film, the thickness of the surface decorative layer (III) relative to the entire decorative film is preferably 30% or less.

[0817] [Production of decorative films]

[0818] The decorative film of the present invention can be produced by various known forming methods.

[0819] For example, there can be mentioned a method for extrusion molding of a layer (II) composed of a resin composition (B) containing a polypropylene resin (B), a method for co-extrusion molding of a layer (II) composed of a resin composition (B) and one or more other layers, a heat lamination method in which another layer is attached to one surface of a layer previously subjected to extrusion molding by applying heat and pressure, a dry lamination method and a wet lamination method in which a layer (II) and one or more other layers are attached via an adhesive, an extrusion lamination method in which a polypropylene resin is melt-extruded onto one surface of a layer previously subjected to extrusion molding, and a sand lamination method.

[0820] In addition, there can be mentioned any of various co-extrusion methods of a sealing layer (I) and a layer (II) composed of a resin composition (B) containing a polypropylene resin (B), a co-extrusion method of a sealing layer (I), a layer (II) and another other layer or layers, a heat lamination method in which other layers are attached to one surface of a layer previously subjected to extrusion molding by applying heat and pressure, a dry lamination method and a wet lamination method in which layers are attached via an adhesive, an extrusion lamination method in which a polypropylene resin is melt-extruded onto one surface of a layer previously subjected to extrusion molding, and a sand lamination method, etc.

[0821] As the apparatus for forming the decorative film, a known co-extrusion T-die molding machine or a known lamination molding machine can be used. Among these, a (co)extrusion T-die molding machine is preferably used from the viewpoint of productivity.

[0822] As a method of cooling the molten decorative film extruded from the die, there may be mentioned a method of bringing the molten decorative film into contact with one cooling roll by air discharged from an air knife unit or an air chamber unit and a cooling method by pressing the film by means of a plurality of cooling rolls.

[0823] In the case of imparting gloss to the decorative film of the present invention, a method of mirror-finishing the decorative film by transferring the mirror-shaped cooling roll surface to the design surface of the decorative film product is used.

[0824] In addition, the decorative film of the present invention may have an embossed shape on the surface. Such a decorative film may be produced by a method of directly pressing a molten resin extruded from a die head with a roller having a concave-convex shape and a smooth roller to transfer the concave-convex shape to the surface, a method of pressing a smooth film with a roller having a concave-convex shape and a smooth cooling roller to achieve surface transfer, and other methods. As the embossed shape, satin tone, animal skin tone, ultra-fine line tone, and carbon tone are exemplified.

[0825] The decorative film of the present invention may be subjected to heat treatment after film formation. As the heat treatment method, there may be mentioned 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 other methods.

[0826] [Decorative molding]

[0827] As the molded body to be decorated (decoration object) in the present invention, various types of resin molded bodies (hereinafter, sometimes referred to as "substrate") composed of a polypropylene resin or a polypropylene resin composition can be preferably used. The molding method of the resin molded body is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

[0828] Since polypropylene resin is non-polar, it is a polymer that is difficult to bond. However, the decorative film in the present invention includes a layer (II) composed of a resin composition (B) containing a polypropylene resin (B). Therefore, by pasting the decorative object composed of the polypropylene resin and the decorative film together, a very high bonding strength can be exhibited.

[0829] Furthermore, since the film includes one of the various sealing layers (I) and the layer (II) composed of the resin composition (B) containing the polypropylene-based resin (B), a very high bonding strength can be exhibited by pasting the decorative object composed of the polypropylene-based resin and the decorative film, and scratches formed on the surface of the decorative object can be made less noticeable.

[0830] As the base resin of the polypropylene resin and polypropylene resin composition of the molded body of the decorative object, various types of known resins using propylene monomer as the main raw material can be selected, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer and propylene block copolymer. In addition, fillers such as talc for imparting rigidity and elastomers for imparting impact resistance may be contained as long as the advantages of the present invention are not impaired. In addition, similar to the above-mentioned polypropylene resin composition that can constitute the decorative film, additive components and other resin components may be included.

[0831] In addition, as the molded body (decoration object) to be decorated in the present invention, various types of resin molded bodies composed of polar resin materials can also be used. In this case, various molded bodies composed of polar resin materials selected from polyester resins, polyamide resins, polyimide resins, polystyrene resins, acrylic resins, polyvinyl alcohol resins, polycarbonate resins, ABS resins, polyurethane resins, melamine resins, polyphenylene ether resins and their composite materials can be preferably used. In addition, additives such as reinforcing agents such as inorganic fillers, antioxidants, UV absorbers, antistatic agents, flame retardants and lubricants can be added to these resins, and these additives can be used alone or in combination. Two or more thereof. The molding method is not particularly limited, and for example, injection molding, blow molding, press molding, and extrusion molding can be mentioned.

[0832] Since non-polar polypropylene resins are difficult to bond, the above-mentioned polar resin materials are generally not thermally bonded to the resin. On the other hand, the decorative film of the present invention preferably includes a sealing layer (I) composed of a polyolefin adhesive resin (G), so that thermal bonding of the decorative object and the film becomes possible and high bonding strength can be exhibited. As the polyolefin adhesive resin (G), a modified polyolefin resin grafted with an α,β-unsaturated carboxylic acid can be preferably exemplified.

[0833] When the decorative film of the present invention is adhered to various molded bodies composed of polypropylene resins, especially various molded bodies formed into three-dimensional shapes, the VOC contained in the coating and the adhesive is significantly reduced, so the decorative molded body can be suitably used as automobile components, household appliances, vehicles (railways, etc.), building materials, and daily necessities.

[0834] [Production of Decorative Molded Articles]

[0835] The production method of the decorative film of the present invention is characterized in that it includes the steps of preparing the above-mentioned decorative film, preparing a resin molded body, placing the resin molded body and the decorative film in a decompressible cavity box, reducing the pressure in the cavity box, heating and softening the decorative film, pushing the heated and softened decorative film onto the resin molded body, and restoring the interior of the decompressed cavity box to atmospheric pressure or pressurizing the interior.

[0836] The basic steps of three-dimensional decorative thermoforming are to place the decorative object and the decorative film in a decompressible cavity box, heat and soften the decorative film under reduced pressure in the cavity box, push the softened decorative film to the decorative object, and paste the decorative film to the surface of the decorative object by returning the cavity box to atmospheric pressure or pressurizing the interior, thereby attaching the decorative film under reduced pressure. Thus, an aesthetically pleasing decorative molding can be obtained without generating bubbles. In the production method of the present invention, any known techniques can be used as long as they are facilities and conditions suitable for three-dimensional decorative thermoforming.

[0837] That is, the cavity box may be one cavity box that accommodates all of the decoration object and the decoration film, a mechanism for pressing them, a device for heating the decoration film, and the like, or may be a plurality of cavity boxes separated by the decoration film.

[0838] Furthermore, the mechanism for pressing the decorative object to the decorative film may be any type of a mechanism that transfers the decorative object, a mechanism that transfers the decorative film, and a mechanism that transfers both the decorative object and the decorative film.

[0839] More specifically, typical forming methods are exemplified below.

[0840] Hereinafter, a method of attaching a decoration film to a decoration object using a three-dimensional decoration thermoforming machine will be illustratively explained with reference to the accompanying drawings.

[0841] like Figure 2 As shown, the three-dimensional decorative thermoforming machine of this embodiment has cavity boxes 11 and 12 on the upper and lower sides, and the thermoforming of the decorative film 1 is performed inside the two cavity boxes 11 and 12. A vacuum circuit (not shown in the figure) and an air circuit (not shown in the figure) are connected to the upper and lower cavity boxes 11 and 12 through pipelines, respectively.

[0842] In addition, between the upper and lower cavity boxes 11 and 12, a clamp 13 for fixing the decorative film 1 is provided. In addition, a platform 14 capable of ascending and descending is installed in the lower cavity box 12, and a resin molded body (decoration object) 5 is placed on the platform 14 (by a clamp, etc. or directly). A heater 15 is introduced into the upper cavity box 11, and the decorative film 1 is heated by the heater 15. As the decorative object 5, a propylene resin composition may be a base.

[0843] As such a three-dimensional decoration thermoforming machine, a commercially available forming machine (for example, NGF series manufactured by Fu-se Vacuum Forming Ltd.) can be used.

[0844] like Figure 3 As shown, first, in a state where the upper and lower cavity boxes 11 and 12 are opened, the decorative object 5 is placed on the platform 14 in the lower cavity box 12, and the platform 14 is set in a lowered state. Subsequently, the decorative film 1 is placed on the fixture 13 for film fixing between the upper and lower cavity boxes 11 and 12. In the system containing the sealing layer (I), the decorative film 1 is placed so that the sealing layer (I) faces the substrate.

[0845] like Figure 4 As shown, the upper cavity box 11 is lowered, and the upper and lower cavity boxes 11 and 12 are connected to seal the interior of the cavity boxes 11 and 12. Thereafter, a vacuum suction state is achieved in the interior of each of the upper and lower cavity boxes 11 and 12, and the decorative film 1 is heated by the heater 15.

[0846] After heating and softening the decorative film 1, Figure 5 As shown, the platform 14 in the lower cavity box 12 is raised, while the interiors of the upper and lower cavity boxes 11 and 12 are kept in a vacuum suction state. The decorative film 1 is pushed onto the decorative object 5 to cover the decorative object 5. In addition, as shown in FIG. Figure 6 As shown, by opening the upper cavity box 11 under atmospheric pressure or supplying compressed air from an air pressure tank, the decoration film 1 is closely adhered to the decoration object 5 by a greater force.

[0847] Subsequently, the interiors of the upper and lower cavity boxes 11 and 12 are opened under atmospheric pressure, and the decorative molded body 6 is taken out of the lower cavity box 12. Figure 7 As shown in the example, unnecessary edges of the decorative film 1 around the decorative molded body 6 are trimmed.

[0848] [Forming conditions]

[0849] The pressure in the cavity boxes 11 and 12 may be reduced to such an extent that no bubbles are generated, and the pressure in the cavity boxes is 10 kPa or less, preferably 3 kPa or less, and more preferably 1 kPa or less.

[0850] In addition, in the two cavity boxes 11 and 12 divided into upper and lower boxes by the decorative film 1, the pressure in the cavity box on the side where the decorative object 5 and the decorative film 1 are attached is fully within the above-mentioned range, and by changing the pressure of the upper and lower cavity boxes 11 and 12, the stretching of the decorative film 1 can also be suppressed.

[0851] At this time, a film composed of a general polypropylene-based resin may be significantly deformed or broken due to a slight pressure change caused by a decrease in viscosity during heating.

[0852] However, since the decorative film 1 of the present invention includes the layer (II) composed of the resin composition (B) containing the specific polypropylene-based resin (B), the film is not only less susceptible to draping but also resistant to film deformation that may be caused by pressure changes.

[0853] The heating of the decorative film 1 is controlled by the heater temperature (output) and the heating time. Furthermore, the surface temperature of the film can also be measured on a thermometer such as a radiation thermometer and used as a measure of the appropriate conditions.

[0854] In the present invention, in order to adhere the polypropylene-based decorative film 1 to the decorative object 5 composed of a polypropylene-based resin, it is necessary to sufficiently soften or melt the surfaces of the resin molded body 5 and the decorative film 1 .

[0855] Therefore, the heater temperature should be higher than the melting temperature of the polypropylene resin constituting the decorative object 5 and the polypropylene resin constituting the decorative film 1. The heater temperature is preferably 160°C or higher, more preferably 180°C or higher, most preferably 200°C or higher.

[0856] Although the time required for heating is shortened as the heater temperature becomes higher, by the time the inside of the decorative film 1 (or the opposite surface of the heater when the heater is installed only on one side) is sufficiently heated, the temperature on the heater side becomes too high, thereby causing not only deterioration of formability but also thermal degradation of the resin. Therefore, the heater temperature is preferably 500°C or lower, more preferably 450°C or lower, and most preferably 400°C or lower.

[0857] The suitable heating time varies with the heater temperature, but if short, it is preferred to continue heating for a period of time such that the polypropylene-based decorative film is heated and tension-back called springback begins, or for a period of time longer than this period of time.

[0858] In some embodiments, the first embodiment and the second embodiment, it is preferred that heating is continued for a period of time or a period of time longer than 2 seconds after the end of the stretch recovery.

[0859] That is, the decorative film heated by the heater shows a behavior of thermal expansion by heating from the solid state, and once relaxed as the crystal melting proceeds, when the crystal melting proceeds throughout the film, a rebound is observed in which the tension is temporarily recovered by the relaxation of the molecules, and then it sags due to its own weight. After the rebound, the crystals are completely melted in the decorative film and the relaxation of the molecules is sufficient, thereby obtaining sufficient adhesive strength.

[0860] In addition, since the decorative film including the sealing layer (I) of the present invention can be unexpectedly strongly bonded to the substrate even when decorative thermoforming is performed before stretch recovery is completed, such damage to the film caused by migration of one or more additives contained in the film to the outside of the film during thermoforming can be reduced, and a great effect is also observed in suppressing the disappearance of embossing.

[0861] On the other hand, when the heating time is too long, the decorative film sags due to its own weight or deforms due to the pressure difference between the upper and lower cavity boxes, so the heating time after the rebound is completed is preferably less than 120 seconds.

[0862] In the case of decorating a molded body with a complex shape having concave and convex shapes or in the case of achieving a higher bonding force, it is preferred to supply compressed air when the decorative film is tightly bonded to the substrate. The pressure in the upper cavity box when the compressed air is introduced is preferably 150 kPa or more, more preferably 200 kPa or more, and further preferably 250 kPa or more. The upper limit is not particularly limited, but since there is a concern about damaging the device when the pressure is too high, it is suitable that the pressure is preferably 450 kPa or less, and more preferably 400 kPa or less.

[0863] Example

[0864] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention should not be construed as being limited to these examples.

[0865] 1. Measurement methods of various physical properties

[0866] (i) Melt flow rate (MFR)

[0867] It is measured according to ISO 1133:1997, Condition M, at 230°C, under a load of 2.16 kg. The unit is g / 10 minutes.

[0868] (ii) Strain hardening degree λ

[0869] The determination of strain hardening degree λ was carried out by the method mentioned 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 method. In addition, the sample used for measurement at this time was a sample formed into a flat sheet of 0.7 mm or 2 mm in thickness by pressing at a temperature of 180°C and a pressure of 10 MPa for 1 hour, and a sample with a thickness of 0.7 mm was used for the measurement of extension viscosity, and a sample with a thickness of 2 mm was used for the measurement of dynamic frequency sweep experiment.

[0870] (ii-1) Shear viscosity η*(0.01)

[0871] A dynamic frequency sweep experiment was performed using ARES manufactured by Rheometric Scientific Ltd. As the measurement geometry, a parallel circular plate with a diameter of 25 mm was used. The measurement was performed in the measurement mode of Dynamic Frequency Sweep Test using the device control software TA Orchestrator. As a sample, a pressed body with a thickness of 2 mm prepared by the above method was used. The measurement temperature was controlled to 180°C. Measurements were performed at five points of each number between the angular frequency ω of 0.01 and 100 rad / s, so as to become equal intervals on the logarithmic scale.

[0872] As an index showing the viscosity of the sample at a low shear rate, the complex viscosity coefficient η*(0.01) [unit: Pa.s] of ω=0.01 rad / s was used. In addition, the complex viscosity coefficient η* was calculated from the complex modulus G* [unit: Pa] and ω using η*=G* / ω.

[0873] (ii-2) Extensional viscosity ηe (3.5)

[0874] The measurement of extensional viscosity was performed using Extensional Viscosity Fixture manufactured by TA instruments as a measuring fixture for ARES manufactured by Rheometric Scientific Ltd. The measurement was performed in the measurement mode of Extensional Viscosity Test using the device control software TA Orchestrator. As a sample, a test sample having a thickness of 0.7 mm prepared by the above method was used. The width of the test sample was 10 mm and its length was 18 mm. The strain rate was 1.0 s -1 , the measurement temperature is 180° C. Other measurement parameters are set as follows.

[0875] Sampling mode: log

[0876] Points per region: 200

[0877] Solid density: 0.9

[0878] Melt density: 0.8

[0879] Pre-stretching rate: 0.05s -1

[0880] Relaxation after pre-stretching: 30 seconds

[0881] Under the conditions, data were collected for at least 3.7 seconds from the start of the measurement. With the aid of software, the time-dependent data of the extensional viscosity were obtained. The value of the extensional viscosity at the time point of 3.5 seconds (i.e., strain 3.5) on the obtained extensional viscosity curve was taken as ηe(3.5) [unit: Pa.s].

[0882] (iii) Melting peak temperature (melting point):

[0883] Using a differential scanning calorimeter (DSC), after the temperature was once raised to 200°C and maintained for 10 minutes, the temperature was lowered to 40°C at a temperature lowering rate of 10°C / min, and when measured again at a temperature raising rate of 10°C / min, the temperature at the top of the endothermic peak was taken as the melting peak temperature (melting point). The unit is °C.

[0884] (iv) Measurement of the branching index g' at an absolute molecular weight Mabs of 1,000,000

[0885] According to the above method, measurement is performed using a GPC equipped with a light scattering meter and a viscometer as detectors, and the branching index g' is determined based on the above analytical method.

[0886] (v) Use 13 Detection of long-chain branched structures by C-NMR:

[0887] According to the above method, use 13 C-NMR measurement was performed to measure the presence of long chain branched structures.

[0888] (vi) GPC measurement:

[0889] The GPC measurement was performed using the following equipment and conditions, and the calculation of Mw / Mn was carried out.

[0890] - Equipment: GPC manufactured by Waters Corporation (ALC / GPC 150C)

[0891] - Detector: MIRAN 1A IR detector manufactured by FOXBORO (measuring wavelength: 3.42 μm).

[0892] - Column: AD806M / S manufactured by Showa Denko KK (3 columns).

[0893] -Mobile phase solvent: o-dichlorobenzene (ODCB)

[0894] -Measurement temperature: 140℃

[0895] -Flow rate: 1.0ml / min

[0896] -Injection volume: 0.2ml

[0897] - Sample preparation: A sample was prepared as a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) dissolved at 140°C over about 1 hour.

[0898] The conversion of the retention volume obtained on the GPC measurement into the molecular weight was performed using a calibration curve previously generated using standard polystyrene (PS). The standard polystyrenes used were those of the following grades all manufactured by Tosoh Corporation.

[0899] F380,F288,F128,F80,F40,F20,F10,F4,F1,A5000,A2500,A1000

[0900] A calibration curve was prepared by injecting 0.2 mL of a solution obtained by dissolving each polystyrene in ODCB (containing 0.5 mg / mL BHT) to 0.5 mg / mL. For the calibration curve, a cubic equation obtained by least squares approximation was used.

[0901] In addition, in the viscosity expression [η]=K×Mα for conversion into molecular weight, the following numerical values ​​are used.

[0902] PS: K = 1.38 × 10 -4 , α=0.7

[0903] PP: K = 1.03 × 10 -4 , α=0.78

[0904] (vii) Density:

[0905] The density of the ethylene-α-olefin random copolymer (C) and the thermoplastic elastomer (D) is measured by the density gradient column method according to JIS K7112:1999.

[0906] (viii-1) Ethylene content [E(C)]:

[0907] The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) is obtained by the method as described above. 13 The sample preparation and measurement conditions are as follows.

[0908] 200 mg of a sample of ethylene-α-olefin random copolymer (C) and 2.4 ml of o-dichlorobenzene / deuterated bromobenzene (C 6 D 5 Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane as a reference substance for chemical shift were added to an NMR sample tube with an inner diameter of 10 mmφ, followed by dissolution.

[0909] The NMR measurement was carried out using an AV400 model NMR apparatus manufactured by Burker-Biospin KK equipped with a 10 mmφ cryoprobe.

[0910] 13 The conditions for C-NMR measurement are as follows: sample temperature of 120° C., pulse angle of 90°, pulse interval of 20 seconds, accumulation times of 512, and measurement is performed by a broadband decoupling method.

[0911] (viii-2): Calculation of ethylene content of propylene-ethylene block copolymer (F), component (F1) and component (F2):

[0912] With the help of 13 C-NMR, the ethylene contents of the propylene-ethylene block copolymer (F), the component (F1) and the component (F2) were determined by the above-mentioned method for measuring the ethylene content.

[0913] (ix) Isothermal crystallization time:

[0914] The isothermal crystallization time was measured by the above method using a differential scanning calorimeter (DSC).

[0915] In addition, in the case of measuring the isothermal crystallization time of the resin composition (X), the polypropylene resin (A) and the thermoplastic resin (E) are melt-kneaded on a twin-screw extruder to obtain pellets of the resin composition (X), and the isothermal crystallization time is measured using the pellets. As a twin-screw extruder, KZW-15 manufactured by TECHNOVEL Corporation is used, the screw rotation number is set at 400RPM, and the kneading temperature is set to 80°C, 120°C and 200°C (the same temperature as the die outlet thereafter) from below the hopper.

[0916] [1. Decorative film including layer (II) (decorative film excluding sealing layer (I))

[0917] 1-2. Materials used

[0918] (1-1) Polypropylene resin

[0919] The following polypropylene-based resins were used.

[0920] (1A-1-1): A propylene homopolymer having long chain branches, produced by a macromonomer copolymerization method, trade name "WAYMAX (registered trademark) MFX8" manufactured by Japan Polypropylene Corporation, MFR = 1.0 g / 10 min, strain hardening λ = 9.7, Tm = 154°C, branching index g' = 0.89 at an absolute molecular weight Mabs of 1,000,000,13 C-NMR measurements confirmed the presence of a long-chain branched structure.

[0921] (1A-1-2): A propylene homopolymer having long chain branches, produced by a macromonomer copolymerization method, trade name "WAYMAX (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR = 8.8 g / 10 min, strain hardening λ = 7.8, Tm = 154°C, branching index g' = 0.85 at an absolute molecular weight Mabs of 1,000,000, 13 C-NMR measurements confirmed the presence of a long-chain branched structure.

[0922] (1A-1-3): A propylene homopolymer having long chain branches, produced by a crosslinking method, trade name "Daproy (registered trademark) WB140" manufactured by Borealis AG, MFR = 2.2 g / 10 min, strain hardening λ = 10.6, Tm = 158°C, branching index g' = 0.58 at an absolute molecular weight Mabs of 1,000,000, 13 C-NMR measurements confirmed the presence of a long-chain branched structure.

[0923] (1A-1-4): A polypropylene resin composition obtained by blending 96 wt% of a polypropylene resin (1A-1-1) with 4 wt% of a black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo KK) (MFR = 1.0 g / 10 min, strain hardening degree λ = 9.3, Tm = 154°C)

[0924] (1A-2-1): A propylene homopolymer having no long chain branch (MFR = 10 g / 10 min, Tm = 161° C., strain hardening degree λ = 1.0), trade name “NOVATEC (registered trademark) FA3KM” manufactured by Japan Polypropylene Corporation, branching index g′ = 1.0 at an absolute molecular weight Mabs of 1,000,000, 13 C-NMR measurements confirmed the absence of long-chain branched structures.

[0925] (1A-2-2): A propylene homopolymer having no long chain branch (MFR = 2.4 g / 10 min, Tm = 161° C., strain hardening degree λ = 0.9), trade name “NOVATEC (registered trademark) FY6” manufactured by Japan Polypropylene Corporation, branching index g′ = 1.0 at an absolute molecular weight Mabs of 1,000,000, 13C-NMR measurements confirmed the absence of long-chain branched structures.

[0926] (1B-1): A polypropylene resin composition (MFR = 10 g / 10 min, Tm = 164° C.) obtained by blending 100 wt % of a polypropylene resin (1A-2-1) with 0.4 wt % of a nucleating agent (Millad NX8000J, a trademark manufactured by Milliken Japan, KK)

[0927] (1B-2): A propylene-α-olefin copolymer without long-chain branching by means of a metallocene-based catalyst (MFR=7 g / 10 min, Tm=125° C., Mw / Mn=2.5), trade name “WINTEC (registered trademark) WFX4M” manufactured by Japan Polypropylene Corporation, 13 C-NMR measurements confirmed the absence of long-chain branched structures.

[0928] (1B-3): A polypropylene resin composition (MFR = 7 g / 10 min, Tm = 127° C.) obtained by blending 100 wt % of the polypropylene resin (1B-2) with 0.4 wt % of a nucleating agent (trademark “Millad NX8000J” manufactured by Milliken Japan, KK)

[0929] (1B-4): A polypropylene resin composition obtained by blending 96 wt% of a polypropylene resin (1A-2-1) with 4 wt% of a white pigment MB (EPP-W-59578 manufactured by Polycol Kogyo KK, 80 wt% titanium oxide content) (MFR = 11 g / 10 min, Tm = 161°C)

[0930] (1B-5): A polypropylene resin composition obtained by blending 96 wt% of a polypropylene resin (1A-2-1) with 4 wt% of a silver pigment MB (PPCM913Y-42SILVER21X manufactured by TOYOCOLOR Co., Ltd.) (MFR = 10 g / 10 min, Tm = 161°C)

[0931] (1-2) Polypropylene resin for resin molded body

[0932] The following polypropylene-based resins were used.

[0933] (1X-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 165°C), trade name "NOVATEC (registered trademark) MA04H" manufactured by Japan Polypropylene Corporation

[0934] (1X-2): Propylene ethylene block copolymer (MFR = 30 g / 10 min, Tm = 164°C), trade name "NOVATEC (registered trademark) NBC03HR" manufactured by Japan Polypropylene Corporation

[0935] (1X-3): A polypropylene resin composition obtained by blending 60 wt% of a polypropylene resin (1X-2) having an EBR of 20% and having an MFR of 1.0 (TAFMER (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with 20 wt% of an inorganic filler (TALC P-6 manufactured by Nippon Talc Co., Ltd., average particle size 4.0 μm)

[0936] 1-3. Production of resin molded body (substrate)

[0937] Using the polypropylene-based resins (1X-1) to (1X-3), an injection-molded body (base body) was obtained by injection molding according to the following method.

[0938] Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., 100 tons of mold clamping pressure

[0939] Cylinder temperature: 200℃

[0940] Mold temperature: 40℃

[0941] Injection mold: flat plate with width × height × thickness = 120mm × 120mm × 3mm

[0942] Condition control: Maintain in a constant temperature and humidity chamber at 23°C and 50%RH for 5 days

[0943] {Example 1-1}

[0944] -Production of decorative films

[0945] The polypropylene resin (1A-1-1) was extruded using an extruder having a nozzle diameter of 40 mm (diameter) at a resin temperature of 240° C. and a discharge rate of 13 kg / h, and introduced into a single-layer T-die having a temperature controlled at 240° C., a die width of 400 mm, and a die lip opening of 0.8 mm, thereby performing melt extrusion. The melt-extruded film was cooled and solidified on a roll rotating at 80° C. at 3 m / min to obtain a single-layer unstretched film having a thickness of 200 μm. The unstretched film constitutes layer (I) of the decorative film.

[0946] -3D decorative thermoforming

[0947] As the resin molded body (substrate) 5, the injection molded body composed of the polypropylene-based resin (1X-1) obtained above was used.

[0948] As a three-dimensional decorative thermoforming equipment, "NGF-0406-SW" manufactured by Fu-se Vacuum Forming Ltd. is used. The decorative film 1 is cut into a size of 250 mm in width and 350 mm in length, and is set on a clamp 13 for film fixing with an opening size of 210 mm × 300 mm so that the length direction becomes the MD direction of the film. By "NICETACK NW-K15" manufactured by Nichiban Co., Ltd, the resin molded body (substrate) 5 is attached to a sample placement table with a height of 20 mm placed on a platform 14 located below the clamp 13 for film fixing. The clamp 13 and the platform 14 for film fixing are placed in the upper and lower cavity boxes 11 and 12, and the upper and lower cavity boxes 11 and 12 are closed so that the interior of the cavity box is in a closed state. The cavity box is divided into upper and lower cavity boxes by the decorative film 1. The upper and lower cavity boxes are vacuum-sucked, and in the state where the pressure is reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 placed on the upper cavity box 11 is turned on at 80% output to heat the decorative film 1. During the heating period, the vacuum suction is continued, and the pressure is finally reduced to 0.1 kPa. After 40 seconds from the end of the rebound phenomenon from the heating of the decorative film 1 to the temporary relaxation and subsequent stretching and recovery, the platform 14 placed in the lower cavity box 12 is conveyed upward to push the resin molded body (substrate) 5 to the decorative film 1, and then compressed air is immediately supplied so that the pressure in the upper cavity box 11 becomes 270 kPa, so that the resin molded body (substrate) 5 is tightly bonded to the decorative film 1. Thus, a three-dimensional decorative thermoformed product 6 is obtained, in which the decorative film 1 is attached to the upper surface and side surface of the resin molded body (substrate) 5.

[0949] -Physical performance evaluation

[0950] (1-1) Evaluation of the appearance of the decorative molded article

[0951] The drawn state of the decorative film at the time of three-dimensional decoration thermoforming and the attached state of the decorative film of the decorative formed body in which the decorative film had been attached to the base were visually observed and evaluated according to the criteria shown below.

[0952] O: Since contact between the base and the decorative film is simultaneously achieved over the entire contact surface without causing draping of the decorative film during three-dimensional decorative thermoforming, uneven contact does not occur and the film is evenly adhered.

[0953] Δ: Since slight draping of the decorative film occurs during the three-dimensional decorative thermoforming, contact with the decorative film starts from the center of the base, resulting in uneven contact at the edge portion of the upper surface of the base.

[0954] ×: Since the drawing down of the decorative film significantly occurred during the three-dimensional decoration thermoforming, uneven contact was formed over the entire surface of the base.

[0955] (1-2) Luster

[0956] The gloss near the center of the three-dimensional decorated thermoformed product to which the decorative film had been attached was measured at an incident angle of 60° using a Gloss Meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. The measurement method complied with JIS K7105-1981. Table 2 shows the measurement results.

[0957] (1-3) Adhesion between the resin molded body (substrate) and the decorative film

[0958] "712N Craft Tape" manufactured by Nitoms, Inc. was cut into a size of 75 mm in width and 120 mm in length, and attached to the resin molded body (substrate) within a range of 75 mm × 120 mm from the edge of the resin molded body for masking treatment (the surface exposed portion of the substrate was 45 mm in width and 120 mm in length). The resin molded body (substrate) was placed on the three-dimensional decorative thermoforming equipment NGF-0406-SW so that the masking surface of the molded body was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

[0959] Using a cutter, cut the decorative film surface of the obtained decorative molding to the substrate surface with a width of 10 mm in the vertical direction toward the length direction of the tape to prepare a test sample. In the obtained test sample, the width of the bonding surface between the substrate and the decorative film is 10 mm and the length is 45 mm. Fix it on a tensile testing machine so that the substrate part and the decorative film part of the test sample form an angle of 180°, and measure the 180° peel strength of the bonding surface at a tensile speed of 200 mm / min. Measure the maximum strength (N / 10mm) when peeling or breaking five times, and take the average strength as the bonding strength.

[0960] Table 2 shows the evaluation results of the physical properties of the obtained decorative molded products.

[0961] Since the MFR of the polypropylene-based resin (1A-1-1) is 40 g / 10 min or less and the strain hardening degree λ is 1.1 or more, the obtained decorative molded article is excellent in appearance and adhesiveness.

[0962] (1-4) Evaluation of recyclability

[0963] The obtained decorative molded body was crushed and injection molded in the same manner as in the production of the resin molded body (substrate) to prepare a regenerated molded body. The appearance of the obtained regenerated molded body was excellent (evaluation in the table: "O").

[0964] {Examples 1-2 to 1-5}

[0965] Forming and evaluation were performed in the same manner as in Example 1-1, except that in the three-dimensional decorative thermoforming of Example 1-1, the polypropylene resin (1A-1-1) was changed to each blend (resin composition (B)) of the polypropylene resins (1A-1-1) and (1A-2-1) described in Table 2. Table 2 shows the obtained results.

[0966] Since the MFR of the resin composition (B) is 40 g / 10 minutes or less and the strain hardening degree l is 1.1 or more, the obtained decorative molded body is excellent in appearance and adhesiveness. In addition, the appearance of the regenerated molded body is excellent.

[0967] {Examples 1-6}

[0968] Forming and evaluation were performed in the same manner as in Example 1-1 except that the polypropylene resin (1A-1-1) was changed to the polypropylene resin (1A-2-1) in the three-dimensional decoration thermoforming of Example 1-1. Table 2 shows the obtained results.

[0969] Since the polypropylene resin (1A-1-2) has an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more, the obtained decorative molded article has excellent appearance and adhesive strength. In addition, the regenerated molded article has excellent appearance.

[0970] {Examples 1-7 to 1-10}

[0971] Forming and evaluation were performed in the same manner as in Example 1-6, except that in the three-dimensional decorative thermoforming of Example 1-6, the polypropylene resin (1A-1-2) was changed to each blend (resin composition (B)) of the polypropylene resins (1A-1-2) and (1A-2-1) described in Table 2. Table 2 shows the obtained results.

[0972] Since the resin composition (B) has an MFR of 40 g / 10 minutes or less and a strain hardening degree λ of 1.1 or more, the obtained decorative molded body has excellent appearance and adhesive strength. In addition, the regenerated molded body has excellent appearance.

[0973] {Example 1-11}

[0974] Forming and evaluation were performed in the same manner as in Example 1-1 except that the polypropylene resin (1A-1-1) was changed to the polypropylene resin (1A-1-3) in the three-dimensional decoration thermoforming of Example 1-1. Table 2 shows the obtained results.

[0975] Since the polypropylene resin (1A-1-3) has an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more, the obtained decorative molded article has excellent appearance and adhesive strength. In addition, the regenerated molded article has excellent appearance.

[0976] {Example 1-12}

[0977] -Production of decorative films

[0978] In order to produce the decorative film, two types of 2-layer T-die having a die lip opening of 0.8 mm and a die width of 400 mm were used, which had been connected to an extruder-1 for the surface layer having a nozzle diameter of 30 mm (diameter) and an extruder-2 having a nozzle diameter of 40 mm (diameter). The polypropylene resin (1A-2-1) was charged into the extruder-1 for the surface layer, and the polypropylene resin (1A-1-1) was charged into the extruder-2, and melt extrusion was performed under the conditions of a resin temperature of 240° C., an output of the extruder-1 for the surface layer of 4 kg / h, and an output of the extruder-2 of 12 kg / h.

[0979] The melt-extruded film was cooled and solidified so that the surface layer was in contact with a cooling roll rotating at 3 m / min at 80° C., thereby obtaining a double-layer unstretched film in which a surface layer having a thickness of 50 μm and a layer having a thickness of 150 μm were stacked. The obtained unstretched film was a decorative film comprising layer (II) and layer (III) of a surface decorative layer.

[0980] Except for the above, the evaluation was carried out in the same manner as in Example 1-1. Table 2 shows the obtained results.

[0981] Since the MFR of the polypropylene resin (1A-1-1) constituting layer (II) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the obtained decorative molded body has excellent appearance and adhesive strength. In addition, since the polypropylene resin (1A-2-1) is laminated as the surface decorative layer (III) [surface layer (III)] on layer (II), excellent gloss is observed.

[0982] {Example 1-13}

[0983] Forming and evaluation were performed in the same manner as in Example 1-12, except that the composition of layer (II) was changed from polypropylene resin (1A-1-1) to polypropylene resin (1A-1-2) in the production of the decorative film of Example 1-12. Table 2 shows the results.

[0984] Since the MFR of the polypropylene resin (1A-1-2) constituting layer (II) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the obtained decorative molded body has excellent appearance and adhesive strength. In addition, since the polypropylene resin (1A-2-1) is laminated as the surface decorative layer (III) [surface layer (III)] on layer (II), excellent gloss is observed.

[0985] {Comparative Example 1-1}

[0986] Forming and evaluation were performed in the same manner as in Example 1-1, except that the polypropylene-based resin (1A-1-1) was changed to a polypropylene-based resin (1A-2-1) having no long-chain branch in the production of the decorative film of Example 1-1.

[0987] Since the strain hardening degree λ of the polypropylene resin (1A-2-1) is less than 1.1, the stability during thermoforming is poor, and significant stretching of the decorative film occurs during three-dimensional decorative thermoforming, thereby forming uneven contact over the entire surface of the substrate, resulting in significantly poor appearance of the decorative molded body.

[0988] {Comparative Example 1-2}

[0989] Forming and evaluation were performed in the same manner as in Example 1-1, except that the polypropylene-based resin (1A-1-1) was changed to a polypropylene-based resin (1A-2-2) having no long-chain branch in the production of the decorative film of Example 1-1.

[0990] Since the strain hardening degree λ of the polypropylene resin (1A-2-2) is less than 1.1, the stability during thermoforming is poor, and significant stretching of the decorative film occurs during three-dimensional decorative thermoforming, thereby forming uneven contact over the entire surface of the substrate and resulting in significantly poor appearance of the decorative molded body.

[0991] {Comparative Example 1-3 (Decorative film including a polyurethane layer)}

[0992] -Production of decorative films

[0993] A pre-solution was obtained by mixing and stirring 70 g of a water-dispersible polycarbonate polyurethane (trade name "R-986" (manufactured by DSM)) and 6.5 g of a polycarbodiimide crosslinking agent CARBODILITE (trade name "V-02" (manufactured by Nisshinbo Chemical Inc.)). The pre-solution was applied to a PET film having a thickness of 75 μm using a bar coater, dried at 90° C. for 3 minutes in a box-type hot air oven, and then further dried and cured at 120° C. for 15 minutes to obtain a PET (polyethylene terephthalate) / polyurethane laminated film. The thickness of the polyurethane resin layer was 30 μm.

[0994] Next, 80 g of a polyurethane adhesive (trade name "NIPPOLAN 3124" (manufactured by Tosoh Corporation)) and 4 g of an adhesive crosslinking agent (trade name "Coronate HL" (manufactured by Tosoh Corporation)) were mixed and stirred to obtain a pre-solution. The cooling roll contact surface of the unstretched film obtained in Comparative Example 1-1 was subjected to a corona treatment (wetting index was 40 mN / m), and the pre-solution was applied to the corona-treated surface of the polypropylene unstretched film using a rod coater, and dried at 80°C for 3 minutes in a box-type hot air oven to obtain a polypropylene unstretched film / polyurethane adhesive laminated film. The thickness of the polyurethane adhesive layer was 10 μm.

[0995] Subsequently, the PET / polyurethane laminated film and the polypropylene unstretched film / polyurethane adhesive laminated film were laminated so that the polyurethanes were in contact with each other, and after aging at 40° C. for 3 days, the PET film was removed to obtain a polyurethane / polypropylene laminated film.

[0996] -3D decorative thermoforming

[0997] Evaluation was performed in the same manner as in Example 1-1, except that the film was set to a jig for film fixing so that the polypropylene surface was in contact with the substrate in the three-dimensional decorative thermoforming of Example 1-1.

[0998] Since the polyurethane layer was included, the appearance and adhesiveness of the obtained decorative molded body were excellent even though the polypropylene film had no strain hardening property. However, in terms of recyclability, since polyurethane is a thermosetting resin and does not redissolve, it was dispersed as a foreign matter in the polypropylene melt during injection molding, resulting in a large number of fish eyes in the injection piece, and thus a significantly poor appearance was observed (evaluation: ×).

[0999] {Examples 1-14}

[1000] Evaluation was performed in the same manner as in Example 1-1, except that the base was changed to an injection-molded body using the resin (1X-2) in the three-dimensional decorative thermoforming of Example 1-1. Table 3 shows the obtained results.

[1001] Since the resin composition (1A-1-1) has an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more, the obtained decorative molded article has excellent appearance and adhesive strength. In addition, the regenerated molded article has excellent appearance.

[1002] {Example 1-15}

[1003] Evaluation was performed in the same manner as in Example 1-1, except that the base was changed to an injection-molded body using the resin (1X-3) in the three-dimensional decorative thermoforming of Example 1-1. Table 3 shows the obtained results.

[1004] Since the resin composition (1A-1-1) has an MFR of 40 g / 10 min or less and a strain hardening degree λ of 1.1 or more, the obtained decorative molded article has excellent appearance and adhesive strength. In addition, the regenerated molded article has excellent appearance.

[1005] {Example 1-16}

[1006] Evaluation was performed in the same manner as in Example 1-12, except that the polypropylene resin (1A-2-1) used for the surface layer was changed to the polypropylene resin (1B-1) in the production of the decorative film of Example 1-12. Table 3 shows the obtained results.

[1007] Since the MFR of the resin composition (1A-1-1) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the appearance and adhesive strength of the obtained decorative molded body are excellent. In addition, the appearance of the regenerated molded body is excellent. In addition, the polypropylene resin (1B-1) to which the nucleating agent has been added is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so that the result of excellent gloss is observed.

[1008] {Example 1-17}

[1009] Evaluation was performed in the same manner as in Example 1-12, except that the polypropylene resin (1A-2-1) used for the surface layer was changed to the polypropylene resin (1B-2) in the production of the decorative film of Example 1-12. Table 3 shows the obtained results.

[1010] Since the MFR of the resin composition (1A-1-1) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the appearance and adhesive strength of the obtained decorative molded body are excellent. In addition, the appearance of the regenerated molded body is excellent. In addition, the polypropylene resin (1B-2) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so that the result of excellent gloss is observed.

[1011] {Example 1-18}

[1012] Evaluation was performed in the same manner as in Example 1-12, except that the polypropylene resin (1A-2-1) used for the surface layer was changed to the polypropylene resin (1B-3) in the production of the decorative film of Example 1-12. Table 3 shows the obtained results.

[1013] Since the MFR of the resin composition (1A-1-1) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the appearance and adhesive force of the obtained decorative molded body are excellent. In addition, the appearance of the regenerated molded body is excellent. In addition, the polypropylene resin (1B-3) to which the nucleating agent has been added is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so that the result of excellent gloss is observed.

[1014] {Example 1-19}

[1015] Evaluation was performed in the same manner as in Example 1-12, except that the polypropylene resin (1A-2-1) used for the surface layer was changed to the polypropylene resin (1B-4) in the production of the decorative film of Example 1-12. Table 3 shows the obtained results.

[1016] Since the MFR of the resin composition (1A-1-1) is 40 g / 10 minutes or less and its strain hardening degree λ is 1.1 or more, the appearance and adhesive force of the obtained decorative molded body are excellent. In addition, the appearance of the regenerated molded body is excellent. In addition, the surface decorative layer (III) [surface layer (III)] with excellent gloss is colored white, so the appearance is excellent.

[1017] {Example 1-20}

[1018] Evaluation was performed in the same manner as in Example 1-12, except that the polypropylene resin (1A-1-1) was changed to the polypropylene resin (1A-1-4) in the production of the decorative film of Example 1-12. Table 3 shows the obtained results.

[1019] Since the MFR of the resin composition (1A-1-4) is less than 40g / 40 minutes and its strain hardening degree λ is more than 1.1, the appearance and bonding strength of the obtained decorative molding are excellent. In addition, the appearance of the regenerated molding is excellent. In addition, since the layer (II) is colored black, the appearance is excellent. In addition, the polypropylene resin (1A-2-1) is laminated as the surface decoration layer (III) [surface layer (III)] on the outermost surface side, and therefore the result of excellent gloss is observed.

[1020] {Example 1-21}

[1021] Evaluation was performed in the same manner as in Example 1-20, except that the polypropylene resin (1A-2-1) used for the surface layer was changed to the polypropylene resin (1B-5) in the production of the decorative film of Example 1-20. Table 3 shows the obtained results.

[1022] Since the MFR of the resin composition (1A-1-4) is less than 40g / 40 minutes and its strain hardening degree λ is more than 1.1, the appearance and adhesive force of the obtained decorative molding are excellent. In addition, the appearance of the regenerated molding is excellent. In addition, the polypropylene resin (1B-5) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so the result of excellent gloss is observed. In addition, since the layer (II) is colored black and the surface layer (III) is colored silver, the film becomes a metallic film and has an excellent appearance.

[1023]

[1024] [Table 3]

[1025]

[1026] [2. Decorative film comprising a sealing layer (I) composed of a polypropylene resin (A) having an MFR (A) of more than 2 g / 10 min]

[1027] 2-2. Materials used

[1028] (2-1) Polypropylene resin

[1029] The following polypropylene-based resins were used.

[1030] (2A-1-1): A propylene homopolymer having long chain branches, produced by a macromonomer copolymerization method, trade name "WAYMAX (registered trademark) MFX8" manufactured by Japan Polypropylene Corporation, MFR = 1.0 g / 10 min, strain hardening λ = 9.7, Tm = 154°C, branching index g' = 0.89 at an absolute molecular weight Mabs of 1,000,000,13 C-NMR measurements confirmed the presence of a long-chain branched structure.

[1031] (2A-1-2): A propylene homopolymer having long chain branches, produced by a macromonomer copolymerization method, trade name "WAYMAX (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR = 8.8 g / 10 min, strain hardening λ = 7.8, Tm = 154°C, branching index g' = 0.85 at an absolute molecular weight Mabs of 1,000,000, 13 C-NMR measurements confirmed the presence of a long-chain branched structure.

[1032] (2A-1-3): A polypropylene resin composition obtained by blending 96 wt% of a polypropylene resin (2A-1-1) with 4 wt% of a black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo KK) (MFR = 1.0 g / 10 min, strain hardening degree λ = 9.3, Tm = 154°C)

[1033] (2A-2-1): A propylene homopolymer having no long chain branch (MFR = 10 g / 10 min, Tm = 161° C., strain hardening degree λ = 1.0), trade name “NOVATEC (registered trademark) FA3KM” manufactured by Japan Polypropylene Corporation, 1,000,000 absolute molecular weight Mabs, branching index g′ = 1.0, 13 C-NMR measurements confirmed the absence of long-chain branched structures.

[1034] (2A-2-2): A propylene homopolymer having no long chain branch (MFR = 2.4 g / 10 min, Tm = 161° C., strain hardening degree λ = 0.9), trade name “NOVATEC (registered trademark) FY6” manufactured by Japan Polypropylene Corporation, branching index g′ = 1.0 at an absolute molecular weight Mabs of 1,000,000, 13 C-NMR measurements confirmed the absence of long-chain branched structures.

[1035] (2B-1): A polypropylene resin composition (MFR = 10 g / 10 min, Tm = 164° C.) obtained by blending 100 wt % of a polypropylene resin (2A-2-1) with 0.4 wt % of a nucleating agent (Millad NX8000J, a trademark manufactured by Milliken Japan, KK)

[1036] (2B-2): A propylene-α-olefin copolymer without long-chain branching catalyzed by a metallocene catalyst (MFR=7 g / 10 min, Tm=125° C., Mw / Mn=2.5), trade name “WINTEC (registered trademark) WFX4M” manufactured by Japan Polypropylene Corporation, 13 C-NMR measurements confirmed the absence of long-chain branched structures.

[1037] (2B-3): A polypropylene resin composition obtained by blending 100 wt% of a polypropylene resin (2B-2) with 0.4 wt% of a nucleating agent (Millad NX8000J, a trademark manufactured by Milliken Japan, KK) (MFR = 7 g / 10 min, Tm = 127°C)

[1038] (2B-4): A polypropylene resin composition obtained by blending 96 wt% of a polypropylene resin (2A-2-1) with 4 wt% of a white pigment MB (EPP-W-59578 manufactured by Polycol Kogyo KK, 80 wt% titanium oxide content) (MFR = 11 g / 10 min, Tm = 161°C)

[1039] (2B-5): A polypropylene resin composition (MFR = 10 g / 10 min, Tm = 161° C.) obtained by blending 96 wt % of a polypropylene resin (2A-2-1) and 4 wt % of a silver pigment MB (PPCM913Y-42SILVER21X manufactured by TOYOCOLOR Co., Ltd.)

[1040] (2C-1): Propylene-α-olefin copolymer without long-chain branching (MFR=5.0 g / 10 min, Tm=127° C.), trade name “NOVATEC (registered trademark) FX4G” manufactured by Japan Polypropylene Corporation

[1041] (2C-2): Propylene-α-olefin copolymer without long-chain branching (MFR=7.0 g / 10 min, Tm=146° C.), trade name “NOVATEC (registered trademark) FW3GT” manufactured by Japan Polypropylene Corporation

[1042] 2-3. Production of resin molded body (substrate)

[1043] Using the following polypropylene resins (2X-1) to (2X-3), injection molded bodies (base bodies) were obtained by the following method.

[1044] (2X-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 165°C), trade name "NOVATEC (registered trademark) MA04H" manufactured by Japan Polypropylene Corporation

[1045] (2X-2): Propylene-ethylene block copolymer (MFR = 30 g / 10 min, Tm = 164° C.), trade name "NOVATEC (registered trademark) NBC03HR" manufactured by Japan Polypropylene Corporation

[1046] (2X-3): A polypropylene resin composition obtained by blending 60 wt% of a polypropylene resin (2X-2) having an MFR of 1.0 and 20% of an EBR (TAFMER (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) and 20 wt% of an inorganic filler (TALC P-6 manufactured by Nippon Talc Co., Ltd., average particle size 4.0 μm)

[1047] Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., 100 tons of mold clamping pressure

[1048] Cylinder temperature: 200℃

[1049] Mold temperature: 40℃

[1050] Injection mold: flat plate with width × height × thickness = 120mm × 120mm × 3mm

[1051] Condition control: Maintain in a constant temperature and humidity chamber at 23°C and 50%RH for 5 days

[1052] Furthermore, the obtained injection molded body was scratched by the following method to obtain a resin molded body (base body).

[1053] Processing for scratch evaluation: 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), the above-mentioned injection molded body was scratched at a scratching speed of 100 mm / min under a load of 15N using a scratching tip that had been processed for shape (0.5mm radius of curvature, spherical).

[1054] When the scratches formed on the surface of the resin molded body (substrate) were measured by a shape measuring laser microscope ("VX-X200" manufactured by KEYENCE Corporation), the depth of the scratches was 13 μm. In addition, the scratches became whitened scratches.

[1055] {Example 2-1}

[1056] -Production of decorative films

[1057] Two types of two-layer T-die with a die lip opening of 0.8 mm and a die width of 400 mm were used, which had been connected to an extruder-1 for the sealing layer (I) with a nozzle diameter of 30 mm (diameter) and an extruder-2 with a nozzle diameter of 40 mm (diameter). The polypropylene resin (2A-2-1) was loaded into the extruder-1 for the sealing layer (I), and the polypropylene resin (2A-1-1) was loaded into the extruder-2, and melt extrusion was carried out under the conditions of a resin temperature of 240°C, an output of 4 kg / h of the extruder-1 for the sealing layer, and an output of 12 kg / h of the extruder-2. The melt-extruded film was cooled and solidified, and at the same time, it was pushed to the first roller rotating at 3 m / min at 80°C with an air knife so that the sealing layer (I) reached the outside, thereby obtaining a double-layer unstretched film in which a sealing layer (I) with a thickness of 50 μm and a layer (II) with a thickness of 150 μm were laminated.

[1058] -3D decorative thermoforming

[1059] As the resin molded body (substrate) 5, the injection molded body composed of the polypropylene-based resin (2X-1) obtained above was used.

[1060] As a three-dimensional decorative thermoforming equipment, "NGF-0406-SW" manufactured by Fu-se Vacuum Forming Ltd. is used. The decorative film 1 is cut into a size of 250 mm in width and 350 mm in length, and is placed on a clamp 13 for film fixing having an opening size of 210 mm × 300 mm so that the length direction becomes the MD direction of the film. The resin molded body (substrate) 5 is mounted on a sample placement table with a height of 20 mm on a platform 14 located below the clamp 13 for film fixing by "NICETACK NW-K15" manufactured by Nichiban Co., Ltd. The clamp 13 and the platform 14 for film fixing are placed in the upper and lower cavity boxes 11 and 12, and the upper and lower cavity boxes 11 and 12 are closed so that the interior of the cavity box is in a closed state. The cavity box is divided into upper and lower cavity boxes by the decorative film 1. The upper and lower cavity boxes 11 and 12 are vacuum-sucked, and in a state where the pressure is reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa, the far-infrared heater 15 placed on the upper cavity box 11 is turned on at 80% output to heat the decorative film 1. During the heating, the vacuum suction is continued, and the pressure is finally reduced to 0.1 kPa. 20 seconds after the rebound phenomenon from the heating of the decorative film 1 to the temporary relaxation and subsequent stretching and recovery ends, the platform 14 placed in the lower cavity box 12 is conveyed upward to push the resin molded body (substrate) 5 to the decorative film 1, and then compressed air is immediately supplied so that the pressure in the upper cavity box 11 becomes 270 kPa, so that the resin molded body (substrate) 5 is tightly bonded to the decorative film 1. Thus, a three-dimensional decorative thermoformed product 6 is obtained, in which the decorative film 1 is attached to the upper surface and side surface of the resin molded body (substrate) 5.

[1061] -Physical performance evaluation

[1062] (2-1) Evaluation of the appearance of the decorative molded article (effect of making scratches less noticeable)

[1063] The scratch depth of the portion where the scratch exists on the three-dimensional decorative thermoformed product of the resin molded body (substrate) which has been scratched under a load of 15 N was measured by a shape measuring laser microscope ("VX-X200" manufactured by KEYENCE Corporation). The number of measurements was 5 times (n=5), and their average value was taken as the scratch depth (μm).

[1064] Furthermore, evaluation was performed by visually judging whether or not whitening scratches on a molded body (substrate) that had been scratched under a load of 15 N were made less noticeable by the decorative film according to the following criteria.

[1065] O: The traces of whitening scratches are not noticeable and the appearance is excellent.

[1066] ×: Whitened scratches remain and the appearance is poor.

[1067] (2-2) Evaluation of hot formability

[1068] The drawn-down state of the decorative film at the time of three-dimensional decoration thermoforming and the attached state of the decorative film of the decorative formed body in which the decorative film had been attached to the base were visually observed and evaluated by the criteria shown below.

[1069] O: Since contact between the base and the decorative film is simultaneously achieved over the entire surface of the contact face without causing draping of the decorative film during three-dimensional decorative thermoforming, uneven contact is not produced and the film is uniformly adhered.

[1070] ×: Since the drawing down of the decorative film significantly occurred during the three-dimensional decoration thermoforming, uneven contact was formed over the entire surface of the base.

[1071] (2-3) Adhesion between the resin molded body (substrate) and the decorative film

[1072] "712N Craft Tape" manufactured by Nitoms, Inc. was cut into a size of 75 mm in width and 120 mm in length, and attached to the resin molded body (substrate) within a range of 75 mm × 120 mm from the edge of the resin molded body for masking (the surface exposed portion of the substrate was 45 mm in width and 120 mm in length). The resin molded body (substrate) was placed on the three-dimensional decorative thermoforming equipment NGF-0406-SW so that the masking surface of the molded body was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

[1073] Use a cutter to cut the decorative film surface of the obtained decorative molding to the substrate surface with a width of 10 mm in the vertical direction toward the length direction of the tape to prepare a test sample. In the obtained test sample, the width of the bonding surface between the substrate and the decorative film is 10 mm and the length is 45 mm. Fix it on a tensile testing machine so that the substrate and the decorative film of the test sample form an angle of 180°, and measure the 180° peel strength of the bonding surface at a tensile speed of 200 mm / min. Measure the maximum strength (N / 10mm) when peeling or breaking five times, and take the average strength as the bonding strength.

[1074] Table 4 shows the evaluation results of the physical properties of the obtained decorative molded products.

[1075] Since the MFR of the polypropylene resin (2A-1-1) is less than 40 g / 10 min, its strain hardening degree λ is greater than 1.1, and the MFR of the polypropylene resin (2A-2-1) constituting the sealing layer (I) is greater than 2 g / 10 min, the obtained decorative molded body has excellent appearance and adhesion, and traces of scratches become less noticeable.

[1076] (2-4) Luster

[1077] The gloss near the center of the decorative molded body to which the decorative film had been attached was measured at an incident angle of 60° using a Gloss Meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. The measurement method was in accordance with JIS K7105-1981. Table 4 shows the measurement results.

[1078] (2-5) Evaluation of recyclability

[1079] The obtained decorative molded body was crushed and injection molded by the same method as in the production of the resin molded body (substrate) to obtain a regenerated molded body. The appearance of the obtained regenerated molded body was excellent (evaluation in the table: "O").

[1080] {Examples 2-2 to 2-4}

[1081] Except that in the production of the decorative film of Example 2-1, the polypropylene resin (2A-1-1) was changed to each blend (resin composition (B)) of the polypropylene resins (2A-1-1) and (2A-2-1) described in Table 4, molding and evaluation were performed in the same manner as in Example 2-1. Table 4 shows the evaluation results.

[1082] Since the MFR of the resin composition (B) is 40 g / 10 minutes or less, its strain hardening degree l is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1083] {Example 2-5}

[1084] The molding and evaluation were performed in the same manner as in Example 2-1, except that the polypropylene resin (2A-1-1) was changed to the polypropylene resin (2A-1-2) in the production of the decorative film of Example 2-1. Table 4 shows the evaluation results.

[1085] Since the MFR of the polypropylene resin (2A-1-2) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1086] {Examples 2-6 to 2-8}

[1087] Except that in the production of the decorative film of Example 2-5, the polypropylene resin (2A-1-2) was changed to each blend (resin composition (B)) of the polypropylene resins (2A-1-2) and (2A-2-1) described in Table 4, molding and evaluation were performed in the same manner as in Example 2-5. Table 4 shows the evaluation results.

[1088] Since the MFR of the polypropylene resin (2A-1-2) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1089] {Example 2-9}

[1090] The molding and evaluation were performed in the same manner as in Example 2-5, except that the polypropylene resin used for the sealant layer was changed to (2C-1) in the production of the decorative film of Example 2-5. Table 4 shows the evaluation results.

[1091] Since the MFR of the polypropylene resin (2A-1-2) is 40 g / 10 min or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2C-1) constituting the sealant layer (I) is greater than 2 g / 10 min, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1092] {Example 2-10}

[1093] The molding and evaluation were performed in the same manner as in Example 2-5, except that the polypropylene resin used for the sealant layer was changed to (2C-2) in the production of the decorative film of Example 2-5. Table 4 shows the evaluation results.

[1094] Since the MFR of the polypropylene resin (2A-1-2) is 40 g / 10 minutes or less, the strain hardening degree λ thereof is 1.1 or more, and the MFR of the polypropylene resin (2C-2) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1095] {Example 2-11}

[1096] In the production of the decorative film of Example 2-1, three kinds of three-layer T-die having a die lip opening of 0.8 mm and a die width of 400 mm were used, which had been connected to an extruder-1 for a sealing layer having a nozzle diameter of 30 mm (diameter), an extruder-2 having a nozzle diameter of 40 mm (diameter), and an extruder-3 for a surface layer having a nozzle diameter of 30 mm (diameter). The polypropylene-based resin (2A-2-1) was charged into the extruder-1 for the sealing layer, the polypropylene-based resin (2A-1-1) was charged into the extruder-2, and the polypropylene-based resin (2A-2-1) was charged into the extruder-3 for the surface layer, and melt extrusion was performed under the conditions of a resin temperature of 240° C., a discharge amount of 4 kg / h of the extruder-1 for the sealing layer, a discharge amount of 8 kg / h of the extruder-2, and a discharge amount of 4 kg / h of the extruder-3 for the surface layer.

[1097] The melt-extruded film is cooled and solidified so that the surface decorative layer contacts a cooling roll rotating at 3 m / min at 80°C, thereby obtaining a three-layer unstretched film having a surface decorative layer (III) having a thickness of 50 μm, a layer (II) having a thickness of 100 μm, and a sealing layer (I) having a thickness of 50 μm.

[1098] The evaluation was performed in the same manner as in Example 2-1 except that the unstretched film obtained in the production of the decorative film was used. Table 4 shows the evaluation results.

[1099] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealing layer (I) is greater than 2 g / 10 minutes, the appearance and adhesion of the obtained decorative molded body are excellent, and the traces of scratches become less noticeable. In addition, the polypropylene resin (2A-2-1) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so that the result of excellent gloss is observed. In addition, the appearance of the regenerated molded body is excellent.

[1100] {Example 2-12}

[1101] The molding and evaluation were performed in the same manner as in Example 2-11 except that the polypropylene resin (2A-1-1) was changed to the polypropylene resin (2A-1-2) in the production of the decorative film of Example 2-11. Table 4 shows the evaluation results.

[1102] Since the MFR of the polypropylene resin (2A-1-2) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the appearance and adhesion of the obtained decorative molded body are excellent, and the traces of scratches become less noticeable. In addition, the polypropylene resin (2A-2-1) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, so that the result of excellent gloss is observed. In addition, the appearance of the regenerated molded body is excellent.

[1103] {Comparative Example 2-1}

[1104] Evaluation was performed in the same manner as in Example 2-1 except that the polypropylene resin (2A-1-1) used for layer (II) was changed to a polypropylene resin (2A-2-1) having no long chain branch in the production of the decorative film of Example 2-1. Table 4 shows the evaluation results.

[1105] Since the strain hardening degree λ of the polypropylene resin (2A-2-1) is less than 1.1, the stability during thermoforming is poor, and significant stretching of the decorative film occurs during three-dimensional decorative thermoforming, thereby producing uneven contact over the entire surface of the substrate, resulting in significantly poor appearance of the decorative molded body.

[1106] {Comparative Example 2-2}

[1107] Evaluation was performed in the same manner as in Example 2-1 except that the polypropylene resin (2A-1-1) used for layer (II) was changed to a polypropylene resin (2A-2-2) having no long chain branch in the production of the decorative film of Example 2-1. Table 4 shows the evaluation results.

[1108] Since the strain hardening degree λ of the polypropylene resin (2A-2-2) is less than 1.1, the stability during thermoforming is poor, and significant stretching of the decorative film occurs during three-dimensional decorative thermoforming, resulting in uneven contact over the entire surface of the substrate, resulting in significantly poor appearance of the decorative molded body.

[1109] {Reference Example 2-3}

[1110] The polypropylene resin (2A-1-1) was extruded using an extruder having a nozzle diameter of 40 mm (diameter) at a resin temperature of 240° C. and a discharge rate of 13 kg / h, and introduced into a single-layer T-die controlled at a temperature of 240° C., a die width of 400 mm, and a die lip opening of 0.8 mm, thereby performing melt extrusion. The melt-extruded film was cooled and solidified on a cooling roll rotating at 80° C. at 3 m / min to obtain a single-layer unstretched film having a thickness of 200 μm. The film was used as a decorative film.

[1111] Forming and evaluation were performed in the same manner as in Example 2-1 except that a decorative film having no sealant layer (I) was used. Table 4 shows the evaluation results.

[1112] Since a decorative film without a sealant layer (I) was used, the adhesive force was smaller than that of Example 2-1, and obvious scratch marks were observed.

[1113] {Example 2-13}

[1114] Evaluation was performed in the same manner as in Example 2-1, except that the base was changed to an injection-molded body using the resin (2X-2) in the three-dimensional decorative thermoforming of Example 2-1. Table 5 shows the obtained results.

[1115] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 min or less, the strain hardening degree λ thereof is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 min, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1116] {Example 2-14}

[1117] Evaluation was performed in the same manner as in Example 2-1, except that the base was changed to an injection-molded body using the resin (2X-3) in the three-dimensional decorative thermoforming of Example 2-1. Table 5 shows the obtained results.

[1118] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 min or less, the strain hardening degree λ thereof is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 min, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, the appearance of the recycled molded body is excellent.

[1119] {Example 2-15}

[1120] Evaluation was performed in the same manner as in Example 2-11 except that the polypropylene resin (2A-2-1) charged into the extruder-3 for the surface layer was changed to the polypropylene resin (2B-1) in the production of the decorative film of Example 2-11. Table 5 shows the obtained results.

[1121] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, since the polypropylene resin (2B-1) to which the nucleating agent has been added is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, excellent gloss is observed.

[1122] {Example 2-16}

[1123] Evaluation was performed in the same manner as in Example 2-11 except that the polypropylene resin (2A-2-1) charged to the extruder-3 for the surface layer was changed to the polypropylene resin (2B-2) in the production of the decorative film of Example 2-11. Table 5 shows the obtained results.

[1124] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, since the polypropylene resin (2B-2) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, excellent gloss is observed.

[1125] {Example 2-17}

[1126] Evaluation was performed in the same manner as in Example 2-11 except that the polypropylene resin (2A-2-1) charged into the extruder-3 for the surface layer was changed to the polypropylene resin (2B-3) in the production of the decorative film of Example 2-11. Table 5 shows the obtained results.

[1127] Since the MFR of the polypropylene resin (2A-1-1) is 40 g / 10 minutes or less, its strain hardening degree λ is 1.1 or more, and the MFR of the polypropylene resin (2A-2-1) constituting the sealant layer (I) is greater than 2 g / 10 minutes, the obtained decorative molded body has excellent appearance and adhesive strength, and scratch marks become less noticeable. In addition, since the polypropylene resin (2B-3) to which the nucleating agent has been added is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, excellent gloss is observed.

[1128] {Example 2-18}

[1129] Evaluation was performed in the same manner as in Example 2-11 except that the polypropylene resin (2A-2-1) charged into the extruder-4 for the surface layer was changed to the polypropylene resin (2B-4) in the production of the decorative film of Example 2-11. Table 5 shows the obtained results.

[1130] Since the MFR of the polypropylene resin (2A-1-1) is less than 40 g / 10 minutes, its strain hardening degree λ is more than 1.1, and the MFR of the polypropylene resin (2A-2-1) constituting the sealing layer (I) is greater than 2 g / 10 minutes, the appearance and adhesion of the obtained decorative molding are excellent. In addition, in combination with the decorative film pasted with white coloring, the scratches are fully concealed to the extent that the scratch position cannot be identified. Therefore, the scratch depth was not measured. In addition, since the surface decorative layer (III) [surface layer (III)] with excellent gloss is colored white, the appearance is excellent.

[1131] {Example 2-19}

[1132] Evaluation was performed in the same manner as in Example 2-11, except that the polypropylene-based resin (2A-1-1) was changed to the polypropylene-based resin (2A-1-3) in the production of the decorative film of Example 2-11. Table 5 shows the obtained results.

[1133] Since the MFR of the polypropylene resin (2A-1-3) is less than 40g / 10 minutes, its strain hardening degree λ is more than 1.1, and the MFR of the polypropylene resin (2A-2-1) constituting the sealing layer (I) is greater than 2g / 30 minutes, the appearance and adhesion of the obtained decorative molding are excellent. In addition, in combination with the decorative film pasted with black coloring, the scratches are fully concealed to the extent that the scratch position cannot be identified. Therefore, the scratch depth is not measured. In addition, since the layer (II) is colored black, the appearance is excellent. In addition, the polypropylene resin (2A-2-1) is laminated as the surface decorative layer (III) [surface layer (III)] on the outermost surface side, and therefore the result of excellent gloss is observed.

[1134] {Example 2-20}

[1135] Evaluation was performed in the same manner as in Example 2-19, except that the polypropy...

Claims

1. Application of a decorative film pasted on a resin molded body by thermoforming, The decorative film comprises a layer (II) comprising a resin composition (B), the resin composition (B) being composed of a polypropylene resin (B) alone or a blend of a polypropylene resin (B) and another polypropylene resin, and the resin composition (B) meets the following requirements (b1) and (b2): (b1) a melt flow rate (MFR) (B) of 40 g / 10 min or less at 230° C. and a load of 2.16 kg, and (b2) The strain hardening degree λ is 1.1 or more, The polypropylene resin (B) is a polypropylene resin (B-1) having a long-chain branched structure. The polypropylene resin (B-1) is a propylene homopolymer, The decorative film further includes a sealant layer (I) comprising a polypropylene-based resin (A), and the polypropylene-based resin (A) has an MFR (A) of greater than 2 g / 10 min at 230° C. and a load of 2.16 kg.

2. The use according to claim 1, wherein the polypropylene-based resin (A) satisfies the following requirements (a1) to (a4), and the polypropylene-based resin (B) further satisfies the following requirement (b3): (a1) the polypropylene resin (A) is a metallocene catalyst-based propylene polymer, (a2) MFR (A) at 230°C and a load of 2.16 kg is greater than 0.5 g / 10 min, (a3) the melting peak temperature (Tm) (A) is lower than 150°C, (a4) a molecular weight distribution (Mw / Mn) (A) measured by GPC is 1.5 to 3.5, and (b3) Tm(B) satisfies the following relation (b-3) with respect to the above Tm(A): Tm(B)>Tm(A)...Formula (b-3).

3. The use according to claim 1, wherein the sealing layer (I) comprises a resin composition (X) containing a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) as main components, the weight ratio of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) being 97:3 to 5:95, and The polypropylene resin (A) satisfies the following requirement (a2) and the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3): (a2) MFR (A) at 230°C and a load of 2.16 kg is greater than 0.5 g / 10 min, (c1) an ethylene content [E(C)] of 65% by weight or more, (c2) Density 0.850 to 0.950 g / cm 3 ,and (c3) MFR (C) at 230°C and a load of 2.16 kg is from 0.1 to 100 g / 10 min.

4. The use according to claim 1, wherein the sealing layer (I) comprises a resin composition (X) containing a polypropylene-based resin (A) and a thermoplastic elastomer (D) as main components, the weight ratio of the polypropylene-based resin (A) to the thermoplastic elastomer (D) being 97:3 to 5:95, and The polypropylene resin (A) satisfies the following requirement (a2) and the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d3): (a2) MFR (A) at 230°C and a load of 2.16 kg is greater than 0.5 g / 10 min, (d1) the thermoplastic elastomer is a thermoplastic elastomer in which at least one of propylene and butene is a main component, (d2) Density 0.850 to 0.950 g / cm 3 ,and (d3) MFR (D) at 230° C. and a load of 2.16 kg is from 0.1 to 100 g / 10 min.

5. The use according to claim 1, wherein the sealing layer (I) comprises a resin composition (X) containing a polypropylene-based resin (A) and a thermoplastic resin (E) as main components, the weight ratio of the polypropylene-based resin (A) to the thermoplastic resin (E) being 97:3 to 5:95, and The polypropylene-based resin (A) satisfies the following requirement (a2), the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X) satisfies the following requirement (x1): (a2) MFR (A) at 230°C and a load of 2.16 kg is greater than 0.5 g / 10 min, (e1) the thermoplastic resin (E) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and (x1) The isothermal crystallization time (t) measured by differential scanning calorimetry (DSC) satisfies the following formula (x-1): t(X)≥1.5×t(A)...Formula (x-1) wherein t(A) represents the isothermal crystallization time of the polypropylene based resin (A) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A), and t(X) is the isothermal crystallization time of the resin composition (X) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene based resin (A), The unit of the isothermal crystallization time is seconds.

6. The use according to claim 1, The sealing layer (I) comprises a propylene-ethylene block copolymer (F), and the propylene-ethylene block copolymer (F) meets the following requirements (f1) to (f3): (f1) the propylene-ethylene block copolymer (F) contains 5 to 97 wt% of a component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and 3 to 95 wt% of a component (F2) consisting of a propylene-ethylene random copolymer having an ethylene content greater than that of the component (F1), (f2) an MFR (F) of greater than 0.5 g / 10 min at 230°C and a load of 2.16 kg, and (f3) The melting peak temperature (Tm) (F) is 110 to 170°C.

7. The use according to claim 1, The sealing layer (I) contains a polyolefin adhesive resin (G), which is a polyolefin resin having a polar functional group containing at least one heteroatom, and has an MFR (G) of 100 g / 10 min or less at 230° C. and a load of 2.16 kg.

8. The use according to any one of claims 1 to 7, The resin composition (B) satisfies the following requirements (b1') and (b2'): (b1') (MFR)(B) at 230°C and a load of 2.16 kg is 20 g / 10 min or less, and (b2′) The degree of strain hardening λ is 1.8 or more.

9. The use according to any one of claims 1 to 7, The resin composition (B) satisfies the following requirements (b1") and (b2"): (b1″) (MFR)(B) at 230°C and a load of 2.16 kg is 12 g / 10 min or less, and (b2”) The strain hardening degree λ is greater than 2.

3.

10. The use according to any one of claims 1 to 7, The polypropylene resin (B-1) is a polypropylene resin with less gel, which is produced by a method other than a crosslinking method.

11. The use according to any one of claims 1 to 7, wherein the decorative film comprises a surface decorative layer (III) composed of a surface decorative layer resin, and the surface decorative layer (III) is located on the side of the layer (II) opposite to the bonding side having the resin molded body.

12. The use according to claim 11, The surface decoration layer resin contains a polypropylene-based resin (H), and the polypropylene-based resin (H) has a strain hardening degree λ of 1 or less.

13. The use according to claim 2, wherein the polypropylene-based resin (A) is a propylene-α-olefin copolymer.

14. The use according to claim 2 or 13, The above-mentioned Tm(A) is 140°C or lower.

15. The use according to claim 3, The ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4): (c4) The melting peak temperature (Tm) (C) is 30 to 130°C.

16. The use according to claim 3 or 15, The ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c5): (c5) The ethylene-α-olefin random copolymer (C) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

17. The use according to claim 4, The thermoplastic elastomer (D) is a propylene-ethylene copolymer having an ethylene content of less than 50 wt%, a butene-ethylene copolymer having an ethylene content of less than 50 wt%, a propylene-ethylene-butene copolymer having an ethylene content of less than 50 wt%, a propylene-butene copolymer or a butene homopolymer.

18. The use according to claim 4 or 17, The thermoplastic elastomer (D) further meets the following requirement (d4): (d4) The melting peak temperature (Tm) (D) is 30 to 170°C.

19. The use according to claim 5, The thermoplastic resin (E) is a styrene elastomer.

20. The use according to claim 5, The thermoplastic resin (E) is an alicyclic hydrocarbon resin.

21. The use according to claim 6, The propylene-ethylene block copolymer (F) further satisfies the following requirement (f4): (f4) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.

22. The use according to claim 6 or 21, The propylene-ethylene block copolymer (F) further satisfies the following requirement (f5): (f5) The ethylene content of the component (F1) is in the range of 0 to 6% by weight.

23. The use according to claim 6 or 21, The propylene-ethylene block copolymer (F) further satisfies the following requirement (f6): (f6) The ethylene content of the component (F2) is in the range of 5 to 90% by weight.

24. A method for producing a decorative shaped body, comprising: preparing a decorative film, preparing a resin molded body, The resin molded body and the decorative film are placed in a decompressible cavity box. reducing the pressure in the cavity box, The decorative film is heated to soften, pressing the heated and softened decorative film onto the resin molded body, and Return the interior of the decompression chamber box to atmospheric pressure or pressurize the interior. The decorative film comprises a layer (II) comprising a resin composition (B), the resin composition (B) being composed of a polypropylene resin (B) alone or a blend of a polypropylene resin (B) and another polypropylene resin, and the resin composition (B) meets the following requirements (b1) and (b2): (b1) a melt flow rate (MFR) (B) of 40 g / 10 min or less at 230° C. and a load of 2.16 kg, and (b2) The strain hardening degree λ is 1.1 or more, The polypropylene resin (B) is a polypropylene resin (B-1) having a long-chain branched structure. The polypropylene resin (B-1) is a propylene homopolymer, The decorative film further includes a sealant layer (I) comprising a polypropylene-based resin (A), and the polypropylene-based resin (A) has an MFR (A) of greater than 2 g / 10 min at 230° C. and a load of 2.16 kg. 25 . The method for producing a decorative molded body according to claim 24 , wherein the resin molded body comprises a propylene-based resin composition.

26. The method for producing a decorative molded body according to claim 24, wherein the sealing layer (I) comprises a polyolefin adhesive resin (G), the polyolefin adhesive resin (G) being a polyolefin resin having a polar functional group containing at least one heteroatom, and having an MFR (G) of 100 g / 10 min or less at 230° C. and a load of 2.16 kg, and The resin molded body includes a polar resin material containing at least one selected from the following: polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, polyurethane resin, melamine resin, polyphenylene ether resin and their composite materials.

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