JP2019116090A - Decorative film and manufacturing method of decorative molded body using the same - Google Patents

Abstract

To provide a decorative film excellent in heat moldability without irregular contact, good in weather resistance and adhesive force, suppressing reduction of weather resistance before and after heat molding, excellent in recycling property and capable of being used for three-dimensional decorative heat molding, and a manufacturing method of a decorative molded body using the same.SOLUTION: There is provided a decorative film for sticking on a resin molded body by thermoforming, the decorative film containing a hindered amine-based photostabilizer and/or an ultraviolet absorber, and including a seal layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), in which the polypropylene resin (A) satisfies a following requirement (a1), and the polypropylene resin (B) satisfies a following requirement (b1). (a1) melt flow rate (230°C, 2.16 kg load) (MFR(A)) is over 0.5 g/10 min. (b1) melt flow rate (230°C, 2.16 kg load) (MFR(B)) and the MFR(A) satisfy a relational formula (b-1). MFR(B)<MFR(A) Formula (b-1).SELECTED DRAWING: None

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a decorative film for pasting on a resin molded body by thermoforming and a method of manufacturing a decorative molded body using the decorative film. Specifically, a decorative film for sticking by thermoforming on a resin molded body which can suppress wrinkles and breakage of a film at the time of thermoforming and can exhibit sufficient adhesive strength to the resin molded body and The present invention relates to a method for producing a decorative molded article using the decorative film. Furthermore, there is no contact unevenness, it is excellent in thermoforming property, is excellent in weatherability and adhesion, and is used for three-dimensional decorative thermoforming in which the deterioration of the weatherability is suppressed before and after thermoforming and is excellent in recyclability. The present invention relates to a decorative film that can be used and a method of manufacturing a decorative formed body using the decorative film.

  In recent years, the demand for a decoration technology to replace painting has been increasing due to the demand for reduction of VOC (volatile organic compound), etc., and various proposals for decoration technology have been made.

  In particular, a technique for forming a decorative molded product in which the decorative film and the molded body are integrated by proposing a decorative film replacing the coating film to the molded body by vacuum pressure forming or vacuum forming is proposed (for example, Patent Document 1) See.) In recent years, it has come to be particularly noted.

  Compared with other decorative molding such as insert molding, vacuum forming and vacuum forming have greater freedom in shape, and the end face of the decorative film is joined by being wound up to the back side of the object to be decorated Since it is excellent in appearance because it does not occur, and can be thermoformed at relatively low temperature and low pressure, reproducibility of emboss etc. on the surface of the decorated molded body can be obtained by applying emboss etc on the surface of the decorated film Have the advantage of being superior to

  When attaching a decorative film and a molded product in such vacuum pressure air forming and decorative forming by vacuum forming, the decorative film may be broken or wrinkled, or the adhesion of the decorative film to the molded object There is a problem that the strength can not be obtained sufficiently. The use of adhesives and tackifiers has also been proposed as a layer for improving adhesive strength, but it is expensive, the layer structure is extremely complicated, and the solvent resistance and heat resistance are insufficient. , Etc. have problems.

  With respect to such a problem, the decorative film and the molded body are heat-sealed by applying a decorative film including an adhesive layer containing the polypropylene resin to a substrate (molded body) made of a polypropylene resin. Has been proposed (see, for example, Patent Documents 2 and 3). The inventions disclosed in Patent Documents 2 and 3 use a polypropylene-based resin as the adhesive layer of the decorative film, but substantially further, it is possible to use acrylic on the surface layer, adhesive layer and bulk layer on the adhesive layer. It is necessary to provide a layer of resin, polyurethane resin, polycarbonate or the like. By combining different types of raw materials in this manner, thermoforming properties such as drawdown properties are expressed, and in the case of a decorative film made of a polypropylene-based resin that does not contain these different types of raw materials, it is possible to ensure thermoformability. It was not possible, and holes, wrinkles, and air entrapment tended to occur on the surface of the molded product to which it was attached, and furthermore, film breakage occurred, and a decorative molded product having an excellent appearance could not be obtained. In particular, when a polyurethane resin is contained as a dissimilar raw material, the polyurethane resin which is a thermosetting resin does not melt at the time of heating and thus easily maintains the form of the film and greatly enhances thermoforming, but has the problem of extremely low recyclability. The

  That is, the decorative films described in Patent Documents 2 and 3 contain different raw materials in order to ensure thermoforming properties such as adhesiveness and appearance, and the layer structure is complicated and their production requires many steps. In addition, there is a problem that it is difficult to recycle a decorative film in which different types of raw materials are combined.

Japanese Patent Application Laid-Open No. 2002-67137 Japan JP 2013-14027 Japanese Patent Application Laid-Open No. 2014-124940

  In order to provide the decorative film with weather resistance, hindered amine light stabilizers or ultraviolet light absorbers may be added. However, a decorative film containing such a hindered amine light stabilizer or ultraviolet light absorber has a problem that the weatherability is significantly impaired after three-dimensional decorative molding.

  In the prior art, a decorative film composed of a propylene-based resin which is easy to recycle, has both excellent adhesion and appearance, and has a small decrease in weather resistance even after decorative molding has been achieved. Absent. In view of the above problems, the object of the present invention is to prevent contact unevenness and to be excellent in thermoforming properties, to be excellent in weatherability and adhesion, to suppress deterioration in weatherability before and after thermoforming, and to be excellent in recyclability. An object of the present invention is to provide a decorative film that can be used for three-dimensional decorative thermoforming and a method for producing a decorative molded body using the same.

In three-dimensional decorative thermoforming, in order to stick a decorative film in a solid state to a resin molding in a solid state, it is necessary that the surface of the molded body and the film be sufficiently softened or melted. Therefore, it is important to apply a heat amount necessary for softening or melting of the surface of the molded product and the film, or to use a molded product and a film which are easily softened or melted. On the other hand, when the film is heated too much, the film has a reduced viscosity, and the film is broken or swayed by the pushing up of the molded product in the three-dimensional decorative thermoforming process or the inflow of air when the vacuum chamber is returned to atmospheric pressure. Leads to poor appearance. As a result of paying attention to the mechanism in which the appearance defect occurs, the present inventors have found that a decorative film including a layer made of a specific polypropylene-based resin can solve the problem.
Furthermore, in the process of heating the decorative film under decorative molding conditions, that is, under vacuum, it is found that the hindered amine light stabilizer or the ultraviolet light absorber added to the resin to impart weatherability is significantly volatilized. The The inventors of the present invention, by including a seal layer having good adhesiveness, enable decoration molding at a low temperature and in a short time, and perform decoration molding before volatilization of the hindered amine light stabilizer and the ultraviolet light absorber. By making it complete, it discovers that a weather-resistant fall can be suppressed and came to complete this invention.

  That is, the present invention includes the following.

(1) A decorative film containing a hindered amine light stabilizer and / or an ultraviolet light absorber for adhering on a resin molded body by thermoforming, wherein the decorative film is a polypropylene resin (A) And a layer (II) containing a polypropylene resin (B), the polypropylene resin (A) satisfies the following requirement (a1), and the polypropylene resin (B) contains A decorative film satisfying the requirement (b1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) and MFR (A) satisfy the relational expression (b-1).
MFR (B) <MFR (A) formula (b-1)

(2) The polypropylene-based resin (A) further satisfies the following requirements (a2) to (a4), and the polypropylene-based resin (B) further satisfies the following requirement (b2): Decorative film.
(A2) A metallocene catalyst based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B2) The melting peak temperature (Tm (B)) and Tm (A) satisfy the relational expression (b-2).
Tm (B)> Tm (A) Formula (b-2)

(3) The polypropylene-based resin (A) further satisfies the following requirement (a5), and the polypropylene-based resin (B) further satisfies the following requirement (b3): (1) or (2) Decorative film.
(A5) The crystallization temperature (Tc (A)) is less than 100 ° C.
(B3) The crystallization temperature (Tc (B)) and Tc (A) satisfy the relational expression (b-3).
Tc (B)> Tc (A) .. Formula (b-3)

(4) The resin composition (X3) in which the weight ratio of the polypropylene-based resin (A) to the ethylene-α-olefin random copolymer (C) is 97: 3 to 5:95 in the seal layer (I) The decorative film according to any one of (1) to (3), wherein the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3).
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min.

(5) The sealing layer (I) contains a resin composition (X4) in which the weight ratio of the polypropylene resin (A) to the thermoplastic elastomer (D) is 97: 3 to 5:95, and the thermoplastic resin The decoration film as described in any one of (1)-(3) which an elastomer (D) satisfy | fills the following requirements (d1)-(d4).
(D1) A thermoplastic elastomer comprising as a main component at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile modulus of elasticity is smaller than that of the polypropylene resin (A).

(6) The sealing layer (I) contains a resin composition (X5) in which the weight ratio of the polypropylene resin (A) to the thermoplastic resin (E) is 97: 3 to 5:95, and the thermoplastic resin Resin (E) satisfy | fills the following requirements (e1), The decorative film as described in any one of (1)-(3) which the said resin composition (X5) satisfy | fills the following requirements (x1).
(E1) At least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group is contained.
(X1) The isothermal crystallization time (t (X5)) (seconds) of the resin composition (X5) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) .. Formula (x-1)
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t (X 5) It is isothermal crystallization time (second) of the resin composition (X5) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A).)

(7) The polypropylene-based resin (A) described in any one of (1) to (6), which is a propylene-ethylene block copolymer (F) satisfying the following requirements (f1) and (f2) Decorative film.
(F1) The melting peak temperature (Tm (F)) is 110 to 170 ° C.
(F2) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, a component consisting of a propylene-ethylene random copolymer having an ethylene content higher than that of the component (F1) 3 to 95% by weight of F2).

(8) The decorative film according to any one of (1) to (6), wherein the polypropylene resin (A) is a propylene-α-olefin copolymer.

(9) The decorative film according to any one of (2) to (8), wherein the Tm (A) is 140 ° C. or less.

(10) The ethylene-α-olefin random copolymer (C) further satisfies at least one of the following requirements (c4) and (c5), of (4) and (7) to (9): The decorating film as described in any one.
(C4) The melting peak temperature (Tm (C)) is 30 to 130 ° C.
(C5) A random copolymer of ethylene and an α-olefin of 3 to 20 carbon atoms.

(11) 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%, an ethylene content of less than 50 wt% Any one of (5) and (7) to (9), which is at least one copolymer selected from the group consisting of a propylene-ethylene-butene copolymer, a propylene-butene copolymer, and a butene homopolymer. Decorative film described in one.

(12) The decorative film according to any one of (5), (7) to (9) and (11), wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(D5) The melting peak temperature (Tm (D)) is 30 to 170 ° C.

(13) The decorative film according to any one of (6) to (9), wherein the thermoplastic resin (E) is a styrene-based elastomer.

(14) The decorative film according to any one of (6) to (9), wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin.

(15) Any one of (7) and (9) to (14), wherein the propylene-ethylene block copolymer (F) further satisfies at least one of the following requirements (f3) to (f5): The decorative film described in one.
(F3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.
(F4) The ethylene content of the component (F1) is in the range of 0 to 6% by weight.
(F5) The ethylene content of the component (F2) is in the range of 5 to 90% by weight.

(16) A step of preparing the decorative film according to any one of (1) to (15), a step of preparing a resin molded body, the resin molded body and the decoration in a depressurizable chamber box The step of setting the film, the step of depressurizing the inside of the chamber box, the step of heating and softening the decorative film, the step of pressing the decorative film against the resin molded body, and the atmospheric pressure in the depressurized chamber box The manufacturing method of the decorating molded object containing the step to return or press.

(17) The method for producing a decorated molded product according to (16), wherein the resin molded product comprises a propylene-based resin composition.

  According to the present invention, there is no contact unevenness, excellent thermoforming properties, good weatherability and adhesiveness, a decrease in weatherability before and after thermoforming, and excellent recyclability, three-dimensional decorative heat The decorative film which can be used for shaping | molding, and the manufacturing method of a decorating molded object using the same can be provided.

  According to the method for producing a decorative molded article of the present invention, there is no air entrapment between the decorative film and the resin molded article, and it is possible to obtain a beautiful decorative molded article with good reproducibility of texture such as emboss and the like. it can. The decorative molded body thus obtained is a polypropylene-based resin for the decorative film and does not need to contain the thermosetting resin layer, so it does not need to contain the thermosetting resin layer. The decrease in performance is small and the recyclability is high.

Fig.1 (a)-FIG.1 (c) are figures which show an example of the laminated constitution of the decorating film of this invention. FIG. 2 is a schematic cross-sectional view for explaining an outline of an apparatus used for the method of manufacturing a decorated formed body of the present invention. FIG. 3 is a schematic cross-sectional view for explaining how a resin molded body and a decorative film are set in the apparatus of FIG. FIG. 4 is a schematic cross-sectional view for explaining how the inside of the apparatus of FIG. 2 is heated and depressurized. FIG. 5 is a schematic cross-sectional view for explaining how the decorative film is pressed against the resin molding in the apparatus of FIG. 6 is a schematic cross-sectional view for explaining how the inside of the apparatus of FIG. 2 is returned to atmospheric pressure or pressurized. FIG. 7 is a schematic cross-sectional view for explaining how an edge of an unnecessary decorative film is trimmed in the obtained decorative molded body. Fig.8 (a)-FIG.8 (c) are figures which show an example of the laminated constitution of the obtained decorative molded object.

  In the present specification, a decorative film refers to a film for decorating a formed body. Decorative molding refers to molding in which a decorative film and a molded body are attached. Three-dimensional decorative thermoforming is a process of adhering a decorative film and a molded body, and has a step of thermoforming the decorative film along the adhering surface of the molded body and simultaneously attaching it. In this process, in order to suppress air being trapped between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), and the heated decorative film is attached to the molded body, and pressure is applied. It refers to molding, which is a process of bringing into close contact by releasing (pressurizing).

  Moreover, in this specification, the measurement of each MFR of a polypropylene resin and a polypropylene resin composition was measured on 230 degreeC and the conditions of 2.16 kg load based on ISO1133: 1997 ConditionsM. The unit is g / 10 minutes.

  In addition, Mn and Mw of polypropylene resins are described in “Basics of Polymer Chemistry” (edited by Polymer Society, edited by Tokyo Kagaku Dojin, 1978) and the like, and are values calculated from molecular weight distribution curves by GPC.

  Also, as used herein, the unit "wt%" means wt%.

  Hereinafter, modes for carrying out the present invention will be described in detail.

The decorative film of the present invention is a decorative film containing a hindered amine light stabilizer and / or an ultraviolet light absorber for adhering on a resin molded body by thermoforming, and the decorative film is a polypropylene based film A sealing layer (I) containing a resin (A) and a layer (II) containing a polypropylene resin (B), wherein the polypropylene resin (A) satisfies the following requirement (a1), and the polypropylene resin B) is characterized by satisfying the following requirement (b1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) and MFR (A) satisfy the relational expression (b-1).
MFR (B) <MFR (A) formula (b-1)

In the first embodiment, the polypropylene resin (A) preferably further satisfies the following requirements (a2) to (a4), and the polypropylene resin (B) preferably further satisfies the following requirement (b2): .
(A2) A metallocene catalyst based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B2) The melting peak temperature (Tm (B)) and Tm (A) satisfy the relational expression (b-2).
Tm (B)> Tm (A) Formula (b-2)

In the second embodiment, the polypropylene resin (A) preferably further satisfies the following requirement (a5), and the polypropylene resin (B) preferably further satisfies the following requirement (b3).
(A5) The crystallization temperature (Tc (A)) is less than 100 ° C.
(B3) The crystallization temperature (Tc (B)) and Tc (A) satisfy the relational expression (b-3).
Tc (B)> Tc (A) .. Formula (b-3)

In the third embodiment, the seal layer (I) is a resin in which the weight ratio of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) is 97: 3 to 5:95. It is preferable that the ethylene-α-olefin random copolymer (C) contains the composition (X3) and the following requirements (c1) to (c3) be satisfied.
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min.

In the fourth embodiment, the sealing layer (I) is formed of a resin composition (X4) in which the weight ratio of the polypropylene resin (A) to the thermoplastic elastomer (D) is 97: 3 to 5:95. It is preferable that the thermoplastic elastomer (D) contains the following requirements (d1) to (d4).
(D1) A thermoplastic elastomer comprising as a main component at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile modulus of elasticity is smaller than that of the polypropylene resin (A).

In the fifth embodiment, the sealing layer (I) is a resin composition (X5) in which the weight ratio of the polypropylene resin (A) to the thermoplastic resin (E) is 97: 3 to 5:95. It is preferable that the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X5) satisfies the following requirement (x1).
(E1) At least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group is contained.
(X1) The isothermal crystallization time (t (X5)) (seconds) of the resin composition (X5) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) .. Formula (x-1)
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t (X 5) It is isothermal crystallization time (second) of the resin composition (X5) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A).)

In the sixth embodiment, the polypropylene-based resin (A) is preferably a propylene-ethylene block copolymer (F) satisfying the following requirements (f1) and (f2).
(F1) The melting peak temperature (Tm (F)) is 110 to 170 ° C.
(F2) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, a component consisting of a propylene-ethylene random copolymer having an ethylene content higher than that of the component (F1) 3 to 95% by weight of F2).

[Hindered amine light stabilizers and UV absorbers]
In the present specification, a material capable of enhancing the weather resistance of a resin by blending a hindered amine light stabilizer and an ultraviolet light absorber (hereinafter both may be collectively referred to as "weathering agent") with a resin or the like. It is.
The weathering agent is volatile before forming the weathering agent by volatilizing the weathering agent by including the seal layer (I) which is easily volatilized under decoration forming conditions, that is, forming conditions of heating under vacuum, but exerts good adhesion. Can be completed and the decrease in weather resistance can be suppressed.

  Specific examples of the hindered amine light stabilizer used in the present invention include, for example, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, bis (2,2 6,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-) Piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene Diamine, bis (2, 2 6,6-Tetramethyl-4-piperidyl) .di (tridecyl) butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butane tetracarboxylate, 3 , 9-Bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [5,5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl ] -2,4,8,10-Tetraoxaspiro [5,5] undecane, 1,5,8,12-tetrakis [4,6-bis {N- (2,2,7) , 6-Tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2, 2,6,6-Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2,6,6 -Tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate, 2,2,6 , 6-Tetramethyl-4-hydroxypiperidine-N-oxyl, bis (2,2,6,6-tetramethyl-4-oxylpiperidine) sebacate, tetrakis (2,2,6,6-tetrame) Tyl-4-oxylpiperidyl) butane-1,2,3,4-tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 3,9-bis (1,1-dimethyl-2- (tris (2 2,2,6,6-Tetramethyl-N-oxylpiperidyl-4-oxycarbonyl) butylcarbonyloxy) ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Among them, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4 diyl] [(2,2,6 is particularly preferable. , 6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, 3,9-bis [1,1-dimethyl-2- { Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis (2,2 6,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate.

  Examples of commercially available products include LA-68 (registered trademark) and LA-57 (registered trademark) manufactured by ADEKA Corporation, Tinuvin 770 (registered trademark) manufactured by BASF Corporation, Tinuvin 765 (registered trademark), Chimassorb 944 (registered trademark), and the like. Tinuvin 622 (registered trademark) and the like.

  The hindered amine light stabilizers can be used alone or in combination of two or more.

  The amount of the hindered amine light stabilizer added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0 parts by weight with respect to 100 parts by weight of the resin constituting the layer containing the light stabilizer. It is .50 parts by weight. When the addition amount is in the above-mentioned range, a decorative film and a decorative molded article with good weather resistance can be obtained.

  Specific examples of the ultraviolet light absorber used in the present invention include, for example, [2-hydroxy-4- (octyloxy) phenyl] (phenyl) methanone, 2- (5-chloro-2H-benzotriazol-2-yl)- 6-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-) Yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, etc. It can be mentioned.

  Examples of commercially available products include Adekastab LA-36 (registered trademark), Adekastab 1413 (registered trademark), Adekastab LA-31G (registered trademark), Adekastab LA-46 (registered trademark), Adekastab LA-F70 (trade name) manufactured by ADEKA Corporation. And registered trademark) and Tinuvin 326 (registered trademark) manufactured by BASF Corporation.

  The ultraviolet absorbers can be used alone or in combination of two or more.

  The amount of the ultraviolet absorber added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50, based on 100 parts by weight of the resin constituting the layer containing the ultraviolet absorber. It is a weight part. When the addition amount is in the above-mentioned range, a decorative film and a decorative molded article with good weather resistance can be obtained.

  Further, both a hindered amine light stabilizer and an ultraviolet light absorber may be contained, in which case the total amount of both weathering agents is 0 with respect to 100 parts by weight of the resin constituting the layer containing the weathering agent. The range of .002 to 2.00 parts by weight is preferable, and more preferably 0.01 to 1.00 parts by weight.

  By setting the content ratio of the hindered amine light stabilizer and the ultraviolet light absorber in a specific range, higher effects can be exhibited. The blending ratio of the two weathering agents is preferably 1/5 to 5/1 and more preferably 1/4 to 4/1 of the hindered amine light stabilizer / ultraviolet absorber. By including both of the weathering agents, it is possible to obtain a decorative film and a decorated molded body with better weatherability by the synergistic effect of the weathering agents.

  The hindered amine light stabilizer and / or the ultraviolet light absorber may be contained in the entire layer of the decorative film, but may be contained only in the surface layer of the decorative film, which is the surface of the decorative molded article good. In particular, since deterioration by light proceeds from the surface of the molded product, it is more preferable that the surface layer of the decorative film contains a weathering agent. For example, in the case of a two-layered decorative film consisting of the seal layer (I) and the layer (II), the layer (II) preferably contains a hindered amine light stabilizer and / or a UV absorber. Furthermore, when the surface decoration layer (III) which is an optional layer is laminated on the layer (II), the surface decoration layer (III) contains a hindered amine light stabilizer and / or a UV absorber. It is preferable to contain.

[Seal layer (I)]
The decorative film of the present invention includes a seal layer (I) comprising a resin composition (X) containing a polypropylene resin (A). The seal layer (I) is a layer in contact with the resin molded body (base) during three-dimensional decorative thermoforming. By providing the seal layer (I), good adhesion is expressed even if the molding time of three-dimensional decorative thermoforming is shortened, so the molding is completed before the weathering agent is volatilized, and the weather resistance is lowered. It becomes possible to suppress.
Hereinafter, the configuration of the seal layer (I) will be specifically described by taking the above-described basic embodiment and the first to sixth embodiments as examples.

<Basic embodiment>
In a basic embodiment, the sealing layer (I) contains a polypropylene resin (A). In the basic embodiment, the polypropylene resin (A) is preferably a resin that is easy to relax. By providing the seal layer (I) containing such a polypropylene-based resin (A), good adhesion is developed even if the molding time of three-dimensional decorative thermoforming is shortened, and therefore the weathering agent evaporates. It is possible to complete the molding before and to suppress the decrease in weatherability.

<< Polypropylene resin (A) >>
1. Melt flow rate (MFR (A)): (a1)
In a basic embodiment, the melt flow rate (230 ° C., 2.16 kg load) MFR (A) of the polypropylene resin (A) needs to exceed 0.5 g / 10 min, preferably 1 g / It is 10 minutes or more, more preferably 2 g / 10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Resin Composition The polypropylene-based resin (A) of the basic embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst based propylene polymer or a metallocene catalyst based propylene polymer.

  The polypropylene resin (A) in the basic embodiment is various types such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene) and the like. The propylene-based polymer of (1) or a combination thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

First Embodiment
In the first embodiment, the seal layer (I) is made of a resin composition (X1) containing a polypropylene resin (A). In the first embodiment, the polypropylene resin (A) is preferably a resin that is easy to melt and relax. By providing the seal layer (I) comprising the resin composition (X1) containing such a polypropylene-based resin (A), good adhesiveness is exhibited even if the molding time of three-dimensional decorative thermoforming is shortened. Therefore, the molding can be completed before the weathering agent evaporates, and the decrease in the weather resistance can be suppressed.

<< Polypropylene resin (A) >>
1. Melt flow rate (MFR (A)): (a1)
In the first embodiment, the melt flow rate (230 ° C., 2.16 kg load) MFR (A) of the polypropylene resin (A) needs to exceed 0.5 g / 10 min, preferably 1 g / 10 It is more than 2 minutes, more preferably more than 2 g / 10 minutes. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Molecular weight distribution (Mw / Mn (A)): (a4)
The Mw / Mn of the polypropylene resin (A) is preferably 1.5 to 3.5, and more preferably 2 to 3. It is preferable that the above-mentioned range is obtained because the component having a relatively long relaxation time is few and the resin can be easily relaxed sufficiently.

3. Melting peak temperature (Tm (A)): (a3)
The melting peak temperature of the polypropylene resin (A) (DSC melting peak temperature, sometimes referred to herein as "melting point") (Tm (A)) is preferably less than 150 ° C, more preferably It is at most 145 ° C., more preferably at most 140 ° C., particularly preferably at most 130 ° C. Sufficient adhesive strength can be exhibited as it is the above-mentioned range. If the Tm (A) is too low, the heat resistance may be lowered, which may cause problems in the use of the molded product, so the temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher.

4. Resin composition: (a2)
The polypropylene resin (A) of the first embodiment is preferably a so-called metallocene catalyst based propylene polymer polymerized by a metallocene catalyst. Since the metallocene catalyst has a single active point, the propylene polymer polymerized by the metallocene catalyst has a narrow molecular weight distribution and crystalline distribution and is easy to melt / relax, so it does not add much heat. It becomes possible to fuse with

  The polypropylene-based resin (A) in the first embodiment is various types of polypropylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), etc. Propylene-based polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

The polypropylene-based resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of adhesiveness. Propylene-α-olefin copolymers generally have a lower crystallization temperature as the melting point lowers than propylene homopolymers, so it is good even if the molding time of three-dimensional decorative thermoforming is shortened Adhesion is likely to develop.
As the α-olefin, one or a combination of two or more selected from ethylene and an α-olefin having 3 to 8 carbon atoms can be used.

Second Embodiment
In the second embodiment, the seal layer (I) is made of a resin composition (X2) containing a polypropylene resin (A). In the second embodiment, the polypropylene resin (A) is preferably a resin having a slow onset of crystallization. By providing the seal layer (I) comprising the resin composition (X2) containing such a polypropylene resin (A), good adhesiveness is exhibited even if the molding time of three-dimensional decorative thermoforming is shortened. Therefore, the molding can be completed before the weathering agent evaporates, and the decrease in the weather resistance can be suppressed.

<< Polypropylene resin (A) >>
1. Melt flow rate (MFR (A)): (a1)
In the second embodiment, the melt flow rate (230 ° C., 2.16 kg load) MFR (A) of the polypropylene resin (A) needs to exceed 0.5 g / 10 min, preferably 1 g / 10 It is more than 2 minutes, more preferably more than 2 g / 10 minutes. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Molecular weight distribution (Mw / Mn (A))
The Mw / Mn of the polypropylene resin (A) is preferably 3.5 to 10, and more preferably 3.7 to 7. Within the above range, surface roughness is less likely to occur during film formation, and the surface appearance is excellent, which is preferable.

3. Crystallization temperature (Tc (A)): (a5)
The crystallization temperature Tc (A) of the polypropylene resin (A) is preferably less than 100 ° C., more preferably 97 ° C. or less, and still more preferably 93 ° C. or less. When it is in the above range, sufficient adhesive strength is exhibited. If Tc (A) is too low, the heat resistance may be lowered, which may cause problems in the use of the molded product. Therefore, the temperature is preferably 65 ° C. or higher, more preferably 75 ° C. or higher.

4. Resin Composition The polypropylene-based resin (A) of the second embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst based propylene polymer or a metallocene catalyst based propylene polymer.

  The polypropylene resin (A) in the second embodiment is various types of polypropylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), and the like. Propylene-based polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

The polypropylene-based resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of adhesiveness. Propylene-α-olefin copolymers generally have a lower crystallization temperature than propylene homopolymers, and good adhesion is easily expressed even if the molding time of three-dimensional decorative thermoforming is shortened. It is possible to complete the molding before the weathering agent evaporates, and to suppress the deterioration of the weatherability.
As the α-olefin, one or a combination of two or more selected from ethylene and an α-olefin having 3 to 8 carbon atoms can be used.

Third Embodiment
In the third embodiment, the seal layer (I) contains a resin composition (X3) containing a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C). By providing the seal layer (I) containing such a resin composition (X3), sufficient adhesive strength is developed even if the film heating time at the time of three-dimensional decorative thermoforming is short.

<< Polypropylene resin (A) >>
The polypropylene resin (A) in the third embodiment is various types of polypropylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), etc. Propylene-based polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

1. Melt flow rate (MFR (A)): (a1)
The melt flow rate (230 ° C, 2.16 kg load) MFR (A) of the polypropylene resin (A) contained in the seal layer (I) needs to exceed 0.5 g / 10 min, preferably 1 g It is at least 10 minutes, more preferably at least 2 g / 10 minutes. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Melting peak temperature (Tm (A))
The melting peak temperature (Tm (A)) of the polypropylene resin (A) is preferably 110 ° C. or more, more preferably 115 ° C. or more, and still more preferably 120 ° C. or more. The formability at the time of three-dimensional decorative thermoforming is favorable in it being the said range. Although the upper limit of the melting peak temperature is not limited, it is preferably 170 ° C. or less, and within the above range, sufficient adhesive strength can be exhibited.

3. Resin Composition The polypropylene resin (A) in the third embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst based propylene polymer or a metallocene catalyst based propylene polymer.

<< Ethylene-α-olefin random copolymer (C) >>
The ethylene-α-olefin random copolymer (C) used in the seal layer (I) of the third embodiment has the following requirements (c1) to (c3), preferably further the requirements (c4) to (c5) It is possessed.

1. Ethylene content [E (C)]: (c1)
The ethylene content [E (C)] of the ethylene-α-olefin random copolymer (C) of the third embodiment is preferably 65% by weight or more, more preferably 68% by weight or more, and still more preferably 70 % By weight or more. Within the above range, sufficient adhesive strength can be exhibited at the time of three-dimensional decorative 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.

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

(Calculation method 1 (binary system))
First, a method of calculating the ethylene content [E (C)] in a binary copolymer composed of two types of repeating units will be described. In this case, the ethylene content of the ethylene-α-olefin binary copolymer can be determined by (Expression-1).
Ethylene content (mol%) = IE × 100 / (IE + IX) (Equation 1)
Ethylene content (% by 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]

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

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

  Below, the integral intensity | strength used for (Formula 2) and (Formula 3) is demonstrated for every alpha-olefin of ethylene- alpha-olefin binary copolymer.

<In the case of ethylene-propylene copolymer>
When the α-olefin is propylene, the following integrated strength values are substituted into (Formula 2) and (Formula 3) to determine the ethylene content [E (C)].
_I ββ = I _25.0-24.2
I _{γ γ} = I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _48.0-43.9
I _αγ + I _αδ = I _39.0-36.2

Here, I indicates the integrated intensity, and the subscript index value of I on the right side indicates the range of chemical shift. For example, I _39.0-36.2 shows the integrated intensity of the ¹³ C signal detected between 39.0 ppm and 36.2 ppm.
The chemical shifts set the ¹³ C signal of hexamethyldisiloxane to 1.98 ppm, and the chemical shifts of the other ¹³ C signals are referenced to it. The ethylene-1-butene copolymer, the ethylene-1-hexene copolymer, and the ethylene-1-octene copolymer are also described below, similarly to the ethylene-propylene copolymer.

<In the case of ethylene-1-butene copolymer>
When the α-olefin is 1-butene, the following integrated strength values are substituted into (Formula 2) and (Formula 3) to determine the ethylene content [E (C)].
_I ββ = I _24.6-24.4
I γγ = I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ = I _30.5-30.2
I _δδ = I _30.2-28.0
I αα = I _39.3-38.1
I _{alpha gamma} + I _{alpha delta} = I _34.5-33.8

<In the case of ethylene-1-hexene copolymer>
When the α-olefin is 1-hexene, the following integrated strength values are substituted into (Formula 2) and (Formula 3) to determine the ethylene content [E (C)].
_I ββ = I _24.5-24.4
I γγ = I _31.0-30.8
I _βδ = I _27.5-27.0
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _40.0-39.0
I _{alpha gamma} + I _{alpha delta} = I _35.0-34.0

<In the case of ethylene-1-octene copolymer>
When the α-olefin is 1-octene, the βδ signal and the αγ + αδ signal overlap the 1-octene-based methylene carbon of the hexyl branch (5B6 and 6B6 in the following structural formulas).
_I βδ + I 5B6 ₌ I _27.6-26.7
I _αγ + I _αδ + I _6B6 = I _35.0-34.0

Therefore, I _βδ corrected for the overlap of 5B6 and 6B6 and I _αγ + I _αδ are substituted, and the integrated intensities shown below are substituted into (Expression-2) and (Expression-3) to _obtain ethylene content [E (C (C) )].
_I ββ = I _{24.7-24.2
I γγ + I γδ + I δδ} = I 32.0-28.0
I _{β δ} = 2/3 × I _27.6-26.7
I αα = I _40.8-39.6
I _αγ + I _αδ = I _βδ + 2 × I _ββ

(Calculation method 2 (ternary system))
Next, a method of calculating the ethylene content [E (C)] in a ternary copolymer composed of three types of repeating units will be described. For example, the ethylene content of the ethylene-propylene-butene ternary copolymer can be determined by the following (Formula 4).
Ethylene content (mol%) = IE × 100 / (IE + IP + IB) (Equation 4)
Ethylene content (wt%) = [ethylene content (mol%) x ethylene molecular weight] x 100 / [ethylene content (mol%) x ethylene molecular weight + propylene content (mol%) x propylene molecular weight + butene content (mol% ) Molecular weight of butene]
Here, IE, IP and IB are integrated strengths for ethylene, propylene and butene, respectively, and can be determined by (Equation-5), (Equation-6) and (Equation-7).
_{IE = (I ββ + I γγ} + I βδ + I γδ + I δδ) / 2 + (I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B)) / 4 ··· ( wherein -5)
IP = 1/3 × [I _CH 3 _(P) + I _{CH (P)} + I _{α α (PP)} + 1/2 x (I _{α α (PB)} + I _{α γ (P)} + I _{α δ (P)} )] 6)
IB = 1⁄4 × [(I _{CH 3 (B)} + I _{CH (B)} + I _{2 B 2} + I _{α α (BB)} ) + 1/2 × (I _{α α (PB)} + I _{α γ (B)} + I _{α δ (B)} )] -(Formula 7)
Here, the subscript (P) means that it is a signal based on a methyl group branch derived from propylene, and similarly, (B) means that a signal based on an ethyl group branch derived from butene.
Also, αα (PP) means a signal of methylene carbon based on propylene chain, and similarly αα (BB) is a signal of methylene carbon based on butene chain, and αα (PB) is a methylene carbon based on propylene-butene chain Means the signal of

Here, since the γγ signal overlaps with the tail of the central methine carbon CH (PPE) signal in line with propylene-propylene-ethylene, it is difficult to separate the γγ signal.
The γγ signal appears in structural formula (c) having two ethylene chains, and the integrated strength of ethylene-derived γγ and the integrated strength of βδ in structural formula (c) hold (formula 8).
I _{β δ} (Structural formula (c)) = 2 × I _{γ γ} (Equation 8)
In addition, βδ appears in structural formula (d) having three or more ethylene chains, and the integrated intensity of βδ in structural formula (d) is equal to the integrated intensity of γδ (formula 9).
_I βδ (structural formula _{(d)) = I γδ ···} ( formula -9)
Therefore, βδ based on the structural formula (c) and the structural formula (d) can be obtained by (formula-10).
_I βδ = I βδ (structural formula _(c)) + I βδ (structural formula (d)) = 2 × I γγ + I γδ
... (equation-10)
_{That, I γγ = (I βδ -I} γδ) / 2 ··· ( wherein -10 ')
Therefore, when (Equation-10 ') is substituted into (Equation-5), IE can be replaced with (Equation-11).
_{IE = (I ββ + I δδ} ) / 2 + (I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B) + 3 × I βδ + I γδ) / 4 ··· ( wherein -11)
Here, the βδ signal corrects the overlap of ethyl branches based on 1-butene and becomes (formula 12).
I _βδ = I _{αγ (P)} + I _{αδ (P)} + I _{αγ (B)} + I _{αδ (B)} -2 × I _{β β} (12)
IE becomes (formula 13) from (formula 11) and (formula 12).
_{IE = I δδ / 2 + I} γδ / 4-I ββ + I αγ (P) + I αδ (P) + I αγ (B) + I αδ (B) ··· ( wherein -13)
The following is substituted into (Equation -13), (Equation -6) and (Equation -7) to determine the ethylene content.
_I ββ = I _25.2-23.8
I _γδ = I _30.4-30.2
I _δδ = I _30.2-29.8
I _{αγ (P)} + I _{αδ (P)} = I _39.5-37.3
I _{alpha gamma (B)} + I _{alpha delta (B)} = I _34.6-33.9
I _{CH 3 (P)} = I _{22.6 to 19.0}
I _{CH (P)} = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I _{alpha alpha (PP)} = I _48.0-45.0
I _{CH 3 (B)} = I _11.4-10.0
I _{CH (B)} = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
I _{alpha alpha (BB)} = I _40.3-40.0
I _{αα (PB)} = I _44.2-42.0
I _{2 B 2} = I _26.7-26.4

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

  Even if the α-olefin of the ethylene-α-olefin random copolymer is a case other than the above, the ethylene content can be determined in the same manner as described above by assigning each signal.

2. Density: (c2)
The density of the ethylene -α- olefin random copolymer (C) is preferably 0.850~0.950g / cm ^3, more preferably 0.855~0.900g / cm ^3, more preferably 0 It is .860 to 0.890 g / cm ³ . Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, and film formability is also good.

3. Melt flow rate (MFR (C)): (c3)
The melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) of the ethylene-α-olefin random copolymer (C) is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, more preferably 1 to 30 g / 10 min. Even if it is the said range, even if it shortens the shaping | molding time of three-dimensional decoration thermoforming, favorable adhesiveness will be expressed.

4. Melting peak temperature (Tm (C)): (c4)
The melting temperature peak (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 Is 40-110 ° C. Sufficient adhesive strength can be exhibited at the time of three-dimensional decoration thermoforming as it is the above-mentioned range.

5. Kind of ethylene-α-olefin random copolymer (C): (c5)
The ethylene-α-olefin random copolymer (C) is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specifically as said C3-C20 alpha-olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Among these, in particular, propylene, 1-butene, 1-hexene and 1-octene are preferably used.

  Such ethylene-alpha-olefin random copolymer (C) is manufactured by copolymerizing each monomer in the presence of a catalyst. Specifically, the ethylene-α-olefin random copolymer (C) is a gas phase method, a solution method, a high pressure method, using a catalyst such as Ziegler catalyst, Phillips catalyst, metallocene catalyst as a polymerization catalyst of olefin. It can be produced by copolymerizing ethylene and an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene or the like by a process such as a slurry method.

In addition, the ethylene-α-olefin random copolymer (C) used in the seal layer (I) of the third embodiment may be used singly or in combination of two or more, as long as the effects of the present invention are not impaired. it can.
As commercially available products of such ethylene-α-olefin random copolymer, Kernel series made by Nippon Polyethylene Co., Ltd., Tafmer P series made by Mitsui Chemical Co., Ltd., Tafmer A series, Engage EG series made by DuPont Dow, etc. Can be mentioned.

<< Resin composition (X3) >>
In the third embodiment, the resin composition (X3) constituting the seal layer (I) contains a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) as main components, It may be a mixture of a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) or a melt-kneaded product, and the polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) And a sequential polymerization product thereof.

1. Weight ratio of polypropylene resin (A) and ethylene-α-olefin random copolymer (C) In the resin composition (X3), polypropylene resin (A) and ethylene-α-olefin random copolymer (C) The weight ratio ((A) :( C)) is preferably selected in the range of 97: 3 to 5:95, more preferably 95: 5 to 10:90, still more preferably 93: 7 to 20: It is 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 seal layer (I) and the layer (II) is good. is there.

Fourth Embodiment
In the fourth embodiment, the seal layer (I) contains a resin composition (X4) containing a polypropylene resin (A) and a thermoplastic elastomer (D) as main components. By providing the seal layer (I) containing such a resin composition (X4), good adhesion is developed even if the molding time of three-dimensional decorative thermoforming is shortened, so before the weathering agent evaporates It is possible to complete the molding and to suppress the decrease in weather resistance.

<< Polypropylene resin (A) >>
1. Melt flow rate (MFR (A)): (a1)
The melt flow rate (230 ° C, 2.16 kg load) MFR (A) of the polypropylene resin (A) contained in the seal layer (I) needs to exceed 0.5 g / 10 min, preferably 1 g It is at least 10 minutes, more preferably at least 2 g / 10 minutes. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Melting peak temperature (Tm (A))
The melting peak temperature (Tm (A)) of the polypropylene resin (A) is preferably 110 ° C. or more, more preferably 115 ° C. or more, and still more preferably 120 ° C. or more. The formability at the time of three-dimensional decorative thermoforming is favorable in it being the said range. Although the upper limit of the melting peak temperature is not limited, it is preferably 170 ° C. or less, and within the above range, sufficient adhesive strength can be exhibited.

3. Resin Composition The polypropylene-based resin (A) in the fourth embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst based propylene polymer or a metallocene catalyst based propylene polymer.

  The polypropylene resin (A) in the fourth embodiment is various types of polypropylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), etc. Propylene-based polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

<< Thermoplastic Elastomer (D) >>
The thermoplastic elastomer (D) used in the seal layer (I) of the fourth embodiment satisfies the following requirements (d1) to (d4), and preferably has the requirement (d5).

1. Composition: (d1)
The thermoplastic elastomer (D) of the present invention is a thermoplastic elastomer based on at least one of propylene and butene. Here, “a thermoplastic elastomer mainly composed of at least one of propylene and butene” is (i) a thermoplastic elastomer mainly composed of propylene, (ii) a thermoplastic elastomer mainly composed of butene, (Iii) The thermoplastic elastomer which has as a main component the component which totaled propylene and butene is included.

The content of propylene or butene in the thermoplastic elastomer (D) is not particularly limited, but is preferably 30 wt% or more, more preferably 40 wt% or more, and still more preferably 50 wt% or more. For example, the thermoplastic elastomer (D) can contain more than 35 wt% of propylene or butene.
Also, the thermoplastic elastomer (D) may contain both propylene and butene, in which case the component of the total of propylene and butene is the main component of the thermoplastic elastomer (D), and the total content of propylene and butene is It is preferably 30 wt% or more, more preferably 40 wt% or more, and still more preferably 50 wt% or more. When both propylene and butene are contained, for example, the thermoplastic elastomer (D) can contain propylene and butene in total in excess of 35 wt%. Within the above range, sufficient adhesive strength can be exhibited at the time of three-dimensional decorative thermoforming, and the heating time of the film can be shortened.

2. Density: (d2)
Preferably the density of the thermoplastic elastomer (D) is 0.850~0.950g / cm ^3, more preferably 0.855~0.940g / cm ^3, more preferably 0.860～0.930G / cm ³ When it is in the above-mentioned range, sufficient adhesive strength is exhibited at the time of three-dimensional decorative thermoforming, and the film formability also becomes good.

3. Melt flow rate (MFR (D)): (d3)
The melt flow rate (230 ° C., 2.16 kg load) MFR (D) of the thermoplastic elastomer (D) is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min More preferably, it is 1 to 30 g / 10 min. Even if it is the said range, even if it shortens the shaping | molding time of three-dimensional decoration thermoforming, favorable adhesiveness will be expressed.

4. Tensile modulus: (d4)
The tensile modulus of elasticity of the thermoplastic elastomer (D) is preferably smaller than that of the polypropylene resin (A). More preferably, the tensile elastic modulus of the thermoplastic elastomer (D) is 500 MPa or less, more preferably 450 MPa or less. Sufficient adhesive strength can be exhibited at the time of three-dimensional decoration thermoforming as it is the above-mentioned range.

5. Melting peak temperature (Tm (D)): (d5)
The melting peak temperature (Tm (D)) of the thermoplastic elastomer (D) is preferably 30 to 170 ° C., more preferably 35 to 168 ° C., and still more preferably 40 to 165 ° C. or more. Sufficient adhesive strength can be exhibited at the time of three-dimensional decoration thermoforming as it is the above-mentioned range.

  The thermoplastic elastomer (D) of the present invention can be appropriately selected and used if it satisfies the above requirements (d1) to (d4), but a propylene-ethylene copolymer having an ethylene content of less than 50 wt% And 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.

6. Ethylene content [E (D)]
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, still more preferably 40 wt% or less, and the above range When it is, sufficient adhesive strength can be exhibited at the time of three-dimensional decoration thermoforming.

(Calculation method of ethylene content [E (D)])
When the thermoplastic elastomer (D) is an elastomer containing ethylene, the ethylene content [E (D)] of the thermoplastic elastomer (D) can be determined from the integrated strength obtained by ¹³ C-NMR measurement.
The calculation method is the “calculation method 1 (two-component system)” cited in the calculation method of the ethylene content [E (C)] of the ethylene-α-olefin random copolymer (C) described in the third embodiment. And “Calculation method 2 (ternary system)”.

  In addition, the thermoplastic elastomer (D) may be a copolymer of propylene and an α-olefin other than butene, as long as the effects of the present invention are not impaired. Specific examples of the α-olefin include ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-eikosen etc. are mentioned. These α-olefins can be used alone or in combination. Among these, 1-hexene and 1-octene are particularly preferably used.

  The thermoplastic elastomer (D) is produced by copolymerizing the respective monomers in the presence of a catalyst. Specifically, propylene, 1-butene, etc. are used in processes such as gas phase method, solution method, high pressure method and slurry method using catalysts such as Ziegler catalyst, Phillips catalyst, metallocene catalyst as polymerization catalyst of olefin. And optionally, it can be produced by copolymerizing α-olefins such as ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

The thermoplastic elastomer (D) selectively used in the seal layer (I) of the fourth embodiment can be used alone or in combination of two or more, as long as the effects of the present invention are not impaired.
As such thermoplastic elastomers, commercially available products include Tafmer XM series, Tafmer BL series, Tafmer PN series manufactured by Mitsui Chemicals, Inc., VISTAMAXX series manufactured by ExxonMobil Chemical Co., and the like.

<< Resin composition (X4) >>
In the fourth embodiment, the resin composition (X4) constituting the seal layer (I) contains a polypropylene resin (A) and a thermoplastic elastomer (D). The resin composition (X4) may be a mixture or a melt-kneaded product of a polypropylene resin (A) and a thermoplastic elastomer (D), or the polypropylene resin (A) and a thermoplastic elastomer (D). Or a sequential polymerization product of

1. Weight ratio of polypropylene resin (A) to thermoplastic elastomer (D) In the resin composition (X4), the weight ratio ((A): (D)) of the polypropylene resin (A) to the thermoplastic elastomer (D) is , 97: 3 to 5:95, more preferably 95: 5 to 10:90, still 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 adhesion between the seal layer (I) and the layer (II) is good. Become.

Fifth Embodiment
In the fifth embodiment, the seal layer (I) contains a resin composition (X5) containing a polypropylene resin (A) and a thermoplastic resin (E). By providing the seal layer (I) containing such a resin composition (X5), good adhesion is developed even if the molding time of three-dimensional decorative thermoforming is shortened, so before the weathering agent evaporates It is possible to complete the molding and to suppress the decrease in weather resistance.

<< Polypropylene resin (A) >>
The polypropylene-based resin (A) in the fifth embodiment is various types of polypropylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), and the like. Propylene-based polymers or combinations thereof can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer.

1. Melt flow rate (MFR (A)): (a1)
The melt flow rate (230 ° C, 2.16 kg load) MFR (A) of the polypropylene resin (A) contained in the seal layer (I) needs to exceed 0.5 g / 10 min, preferably 1 g It is at least 10 minutes, more preferably at least 2 g / 10 minutes. Within the above range, relaxation at the time of three-dimensional decorative thermoforming proceeds sufficiently, and sufficient adhesive strength can be exhibited. Although the upper limit of MFR (A) is not limited, it is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

2. Melting peak temperature (Tm (A))
The melting peak temperature (Tm (A)) of the polypropylene resin (A) is preferably 110 ° C. or more, more preferably 115 ° C. or more, and still more preferably 120 ° C. or more. The formability at the time of three-dimensional decorative thermoforming is favorable in it being the said range. Although the upper limit of the melting peak temperature is not limited, it is preferably 170 ° C. or less, and within the above range, sufficient adhesive strength can be exhibited.

3. Resin Composition The polypropylene-based resin (A) in the fifth embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst based propylene polymer or a metallocene catalyst based propylene polymer.

<< Thermoplastic resin (E) >>
The thermoplastic resin (E) used in the seal layer (I) of the fifth embodiment is a component having a function of delaying the crystallization of the polypropylene resin (A) by containing the polypropylene resin (A). . By slowing the crystallization rate of the polypropylene resin (A), the seal layer resin is crystallized (solidified) before the seal layer (I) and the substrate surface are thermally fused in the case of decoration molding. Adhesion can be prevented. As a result, even if the heating time of the decorative film is short, strong adhesion is developed. About the effect which delays crystallization of this polypropylene resin (A), it evaluated by the isothermal crystallization time of the resin composition (X5) mentioned later.

1. Resin composition: (e1)
The thermoplastic resin (E) in the present invention preferably contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group. By the thermoplastic resin (E) having the above-mentioned features, when mixed with the polypropylene resin (A), the effect of delaying the crystallization of the polypropylene resin (A) is developed, and the adhesion to the substrate and the substrate It is highly effective in making the scratches on the surface less noticeable. Specifically, examples of the alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and their substituent derivatives, a fused cyclized product, a crosslinked structure and the like. It is preferable to contain a cyclopentyl group or a cyclohexyl group, in particular. Examples of the aromatic hydrocarbon group include phenyl group, methylphenyl group, biphenyl group, indenyl group, fluorenyl group and their derivative derivatives and condensed cyclic compounds, etc., among which phenyl group, biphenyl group and indenyl group are contained. Is preferred. Moreover, an alicyclic hydrocarbon group may be obtained by hydrogenating the aromatic hydrocarbon group contained in resin.

  In addition, as thermoplastic resin (E), although the above-mentioned requirement (e1) is satisfied, it can select suitably and it can be used, but using styrene system elastomer or alicyclic hydrocarbon resin especially suitably Yes, both may be included.

As styrene-based elastomers, 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 Tajien butylene - styrene copolymer elastomer (SBBS) or the like can be exemplified, those hydrogenated can be particularly preferably used.
Examples of commercially available products include Dynaron series manufactured by JSR Corporation, Clayton G series manufactured by Kraton Polymer Japan KK, Tuftec series manufactured by Asahi Kasei Corporation, and the like.

  Examples of alicyclic hydrocarbon resins include hydrocarbons obtained by polymerizing a mixture of one or two or more kinds of dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc. as a main raw material Resin, hydrogenated coumarone / indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, etc., and commercially available A product can be used, and specifically, Alcon series manufactured by Arakawa Chemical Co., Ltd. can be mentioned.

<< Resin composition (X5) >>
In the fifth embodiment, the resin composition (X5) constituting the seal layer (I) contains a polypropylene resin (A) and a thermoplastic resin (E) as main components, and the polypropylene resin (A) And a thermoplastic resin (E), or may be a melt-kneaded product.

1. Weight ratio of polypropylene resin (A) to thermoplastic resin (E) In the resin composition (X5), the weight ratio ((A): (E)) of the polypropylene resin (A) to the thermoplastic resin (E) is Preferably, it is selected in the range of 97: 3 to 5:95, more preferably 95: 5 to 10:90, still more preferably 93: 7 to 20:80. Here, a plurality of types of polypropylene resin (A) or thermoplastic resin (E) may be contained, and for example, in the case of containing a thermoplastic resin (E1) and a thermoplastic resin (E2), a thermoplastic resin ( Let the total of E1) and a thermoplastic resin (E2) be the weight of a thermoplastic resin (E). Within the above range, sufficient adhesive strength can be exhibited at the time of three-dimensional decorative thermoforming, and the heating time of the film can be shortened. Furthermore, the adhesion between the seal layer (I) and the layer (II) is good.

2. Isothermal crystallization time (t (X5)): (x1)
In the resin composition (X5), the isothermal crystallization time (t (X5)) (seconds) of the resin composition (X5) determined by differential thermal scanning calorimeter (DSC) is represented by the following formula (x-1) It is preferable to satisfy the above, more preferably the formula (x-2), still more preferably (x-3).
t (X5) 1.5 1.5 x t (A) ... Formula (x-1)
t (X5) 2.0 2.0 x t (A) ... Formula (x-2)
t (X5) 2.5 2.5 x t (A) ... Formula (x-3)
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t (X 5) It is isothermal crystallization time (second) of the resin composition (X5) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A).)
Until the isothermal crystallization time (t (X5)) of the resin composition (X5) falls within the above-mentioned range, the seal layer (I) of the decorative film and the substrate surface are thermally fused at the time of decorative molding It is possible to earn time for the development of high adhesion.
The upper limit of the isothermal crystallization time (t (X5)) is not particularly limited, but the formability of the film is good when 30t (A) 成形 t (X5).

(Measurement of isothermal crystallization time by differential scanning calorimeter (DSC))
The isothermal crystallization time in the present invention is a value measured using a differential scanning calorimeter (DSC), and conforms to JIS-K 7121 (2012) “Method for measuring transition temperature of plastic”.

  Specifically, 5 mg of a sample of the polypropylene-based resin (A) is placed in an aluminum holder, and the temperature is raised from 40 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere. After holding at 200 ° C. for 10 minutes, crystallization is performed at a cooling rate of 10 ° C./minute up to 40 ° C., and the crystallization start temperature is measured and calculated from the DSC curve at this time.

Next, 5 mg of a sample of a polypropylene resin (A) or a resin composition (X5) is placed in an aluminum holder, heated from 40 ° C. to 200 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere and held for 10 minutes. Melt the sample. Subsequently, it is cooled at a rate of 40 ° C./min to a temperature (hereinafter referred to as “measurement temperature”) higher by 10 ° C. than the crystallization start temperature of the polypropylene resin (A) determined by the method described above The temperature is maintained and the behavior of the sample crystallized and heated is measured. The time from when the temperature of the sample reaches the measurement temperature until the exothermic peak time is taken as isothermal crystallization time. Here, it is conceivable that the adhesion is greatly reduced only by the slight crystallization of the seal layer (I) of the decorative film at the time of decoration molding, so that there are two or more exothermic peaks in the isothermal crystallization measurement In this case, the time until the first exothermic peak time is taken as isothermal crystallization time.
Further, depending on the type of polypropylene resin (A), the isothermal crystallization time of the polypropylene resin (A) is extremely short (for example, 120 seconds or less) or long even at a temperature higher by 10 ° C. than the crystallization start temperature. A case may occur (for example, 3000 seconds or more). In that case, the isothermal crystallization time may be measured at a temperature 10 ± 2 ° C. higher than the crystallization start temperature. However, when such measurement is performed, the isothermal crystallization time of the resin composition (X5) must also be measured in accordance with the measurement temperature of the polypropylene resin (A).

Sixth Embodiment
In the sixth embodiment, a resin composition (X6) containing a propylene-ethylene block copolymer (F) is used as the polypropylene resin (A) of the seal layer (I). By providing such a seal layer (I), good adhesion is expressed even if the molding time of three-dimensional decorative thermoforming is shortened, so that the molding is completed before the weathering agent evaporates, and the weather resistance is improved Can be suppressed.

<< Propylene-Ethylene block copolymer (F) >>
The propylene-ethylene block copolymer (F) used in the sixth embodiment contains a component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer, and ethylene more than the component (F1). The component (F2) which consists of a propylene ethylene random copolymer is included. The adhesive strength with a resin molding (base | substrate) improves by the component (F2) which is a rubber component in a propylene ethylene block copolymer (F). The propylene-ethylene block copolymer (F) is obtained by (co) polymerizing a component (F1) consisting of propylene alone or a propylene-ethylene random copolymer in the first polymerization step, and from the component (F1) in the second polymerization step It is obtained by sequentially copolymerizing a component (F2) consisting of a propylene-ethylene random copolymer containing a large amount of ethylene.

1. Ratio of component (F1) and component (F2): (f2)
The compounding ratio of the component (F1) and the component (F2) constituting the propylene-ethylene block copolymer (F) in the sixth embodiment is 5 to 97% by weight of the component (F1) and 3 to 3 of the component (F2) It is preferably 95% by weight. More preferably, the component (F1) is 30 to 95% by weight and the component (F2) is 5 to 70% by weight, and further preferably, the component (F1) is 52 to 92% by weight and the component (F2) is 8 to 8 It is 48% by weight. Sufficient adhesive strength can be exhibited as the ratio of a component (F1) and a component (F2) is said range. Moreover, a film is not sticky in it being the said range, and film formability is favorable.

2. Melt flow rate (MFR (F)): (a1)
The melt flow rate (230 ° C, 2.16 kg load) MFR (F) of the propylene-ethylene block copolymer (F) is required to exceed 0.5 g / 10 min, preferably 1 g / 10 min or more More preferably, it is 2 g / 10 minutes or more. When the MFR (F) is in the above range, the relaxation of the propylene-ethylene block copolymer (F) can be sufficiently advanced at the time of three-dimensional decorative thermoforming, and sufficient adhesive strength can be exhibited. The upper limit of MFR (F) is not limited, but is preferably 100 g / 10 min or less. Within the above range, deterioration of the adhesive strength due to the reduction of the physical properties does not occur.

3. Melting peak temperature (Tm (F)): (f1)
The melting point (melting peak temperature) Tm (F) of the propylene-ethylene block copolymer (F) is preferably 110 to 170 ° C. More preferably, it is 113-169 degreeC, More preferably, it is 115-168 degreeC. When Tm (F) is in the above-mentioned range, the formability at the time of three-dimensional decorative thermoforming is good. The melting peak temperature is mainly derived from the component (F1) having a low ethylene content, that is, the component (F1) having high crystallinity, and the melting peak temperature can be changed by the content of ethylene to be copolymerized.

4. Ethylene content (E (F)) in propylene-ethylene block copolymer (F): (f3)
The ethylene content (hereinafter referred to as "E (F)") in the propylene-ethylene block copolymer (F) is preferably 0.15 to 85% by weight. More preferably, it is 0.5 to 75% by weight, still more preferably 2 to 50% by weight. Sufficient adhesive strength can be exhibited as E (F) is the above-mentioned range, and adhesiveness with layer (II) of a decoration film is good, and is excellent also in film formability.

5. Ethylene content (E (F1)) of component (F1): (f4)
Component (F1) is a propylene homopolymer or a propylene-ethylene random copolymer having a relatively high melting point and an ethylene content (hereinafter referred to as "E (F1)") in the range of 0 to 6% by weight Is preferred. More preferably, it is 0 to 5% by weight. When E (F1) is in the above range, the formability at the time of three-dimensional decorative thermoforming is good, and the film is less sticky and the film formability is also excellent.

6. Ethylene content (E (F2)) of component (F2): (f5)
Component (F2) has an ethylene content (hereinafter referred to as "E (F2)") higher than that of component (F1). Moreover, it is preferable that it is a propylene ethylene random copolymer which has E (F2) in the range of 5 to 90 weight%. E (F2) is more preferably 7 to 80% by weight, still more preferably 9 to 50% by weight. Sufficient adhesive strength can be exhibited as E (F2) is the above-mentioned range.

(Method for producing propylene-ethylene block copolymer (F))
Component (F1) consisting of a propylene-ethylene block copolymer (F) used in the present invention and a propylene homopolymer or propylene-ethylene random copolymer constituting the same and component (F2) consisting of a propylene-ethylene random copolymer Can be preferably produced by the following raw materials and polymerization methods. The method for producing the propylene-ethylene block copolymer (F) used in the present invention will be described below.

· Raw materials used As a catalyst used when producing the propylene-ethylene block copolymer (F) used in the present invention, magnesium, halogen, titanium, magnesium supported catalyst using an electron donor as a catalyst component, trichloride A catalyst comprising a solid catalyst component catalyzed by titanium and an organoaluminum, or a metallocene catalyst can be used. Although the specific method for producing the catalyst is not particularly limited, the Ziegler catalyst disclosed in Japanese Patent Laid-Open Publication No. 2007-254671 or the metallocene catalyst disclosed in Japanese Patent Laid-Open Publication No. 2010-105197 as an example Can be illustrated.

  Also, the raw material olefins to be polymerized are propylene and ethylene, and if necessary, other olefins that do not impair the object of the present invention, for example, 1-butene, 1-hexene, 1-octene, 4-methyl-1 -Pentenes can also be used.

Polymerization Step The polymerization step performed in the presence of the catalyst comprises multiple steps of a first polymerization step for producing the component (F1) and a second polymerization step for producing the component (F2).

First polymerization step In the first polymerization step, propylene alone or a mixture of propylene / ethylene is supplied to a polymerization system to which the catalyst is added to produce a propylene homopolymer or a propylene-ethylene random copolymer to obtain total weight. In this step, the component (F1) is formed to an amount corresponding to 5 to 97% by weight of the combined amount.

  The MFR of the 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 the component (F1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and the adjustment is extremely easy for those skilled in the art. When the component (F1) is a propylene-ethylene random copolymer, it is convenient to use a method of controlling the amount of ethylene supplied to the polymerization tank as a means of controlling the ethylene content. Specifically, the ethylene content of the component (F1) is increased by increasing the amount ratio of ethylene to propylene (ethylene supply amount / propylene supply amount) supplied to the polymerization tank. The reverse is also true. Although the relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the component (F1) varies depending on the type of catalyst used, the component having the target ethylene content by adjusting the supply ratio appropriately Obtaining (F1) is extremely easy for those skilled in the art.

Second polymerization step In the second polymerization step, a propylene / ethylene mixture is further introduced subsequently to the first polymerization step to produce a propylene-ethylene random copolymer, to 3 to 95% by weight of the total polymer amount. This is a step of forming the component (F2) in a corresponding amount.

  MFR of the 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 the component (F1). As a means for controlling the ethylene content of the component (F2), it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank. The specific control method is the same as in the case where the component (F1) is a propylene-ethylene random copolymer.

Next, the control method of the index of a propylene ethylene block copolymer (F) is explained.
First, a method of controlling the weight ratio of the component (F1) to the component (F2) will be described. The weight ratio of the component (F1) to the component (F2) is controlled by the production amount in the first polymerization step for producing the component (F1) and the production amount in the second polymerization step for producing the component (F2). For example, in order to increase the amount of component (F1) and reduce the amount of component (F2), it is sufficient to reduce the amount of production of the second polymerization step while maintaining the amount of production of the first polymerization step. The residence time of the polymerization step may be shortened or the polymerization temperature may be lowered. Moreover, it can control also by adding a polymerization inhibitor, such as ethanol and oxygen, or, when originally added, increasing the addition amount. The reverse is also true.

Usually, the weight ratio of the component (F1) to the component (F2) is defined by the production amount in the first polymerization step for producing the component (F1) and the production amount in the second polymerization step for producing the component (F2). The formula is shown below.
Weight of component (F1): Weight of component (F2) = W (F1): W (F2)
W (F1) = production amount of first polymerization step ÷ (production amount of first polymerization step + production amount of second polymerization step) × 100
W (F 2) = production amount of second polymerization step ÷ (production amount of first polymerization step + production amount of second polymerization step) × 100
W (F1) + W (F2) = 100
(Here, W (F1) and W (F2) are respectively a weight ratio (percentage) of the component (F1) to the component (F2) in the propylene-ethylene block copolymer (F).)

  In an industrial production facility, it is usual to determine the production amount from the heat balance and material balance of each polymerization tank. In addition, when the crystallinity of the component (F1) and the component (F2) is sufficiently different, the two may be separated and identified using an analysis method such as TREF (Temperature Elevated Temperature Fractionation) to determine the quantitative ratio. Techniques for evaluating the crystallinity distribution of polypropylene by TREF measurement are well known to those skilled in the art, see G. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990); Wild, Adv. Polym. Sci. 98, 1-47 (1990), J.M. B. P. Soares, A .; E. Detailed measurement methods are shown in the literature such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

Next, the control method of ethylene content is demonstrated. The propylene-ethylene block copolymer (F) is a mixture of a component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and a component (F2) consisting of a propylene-ethylene random copolymer. The following relationship is established between the ethylene content of
E (F) = E (F1) × W (F1) / 100 + E (F2) × W (F2) / 100
(Here, E (F), E (F1) and E (F2) are each a propylene-ethylene block copolymer (F), a component consisting of a propylene homopolymer or a propylene-ethylene random copolymer (F1) And ethylene content of the component (F2) consisting of a propylene-ethylene random copolymer, and W (F1) and W (F2) are the same as above.)

This equation shows the material balance in terms of ethylene content.
Therefore, if the weight ratio of component (F1) to component (F2) is determined, that is, if W (F1) and W (F2) are determined, then E (F) is unique by E (F1) and E (F2). It becomes decided. That is, E (F) can be controlled by controlling three factors of the weight ratio of component (F1) to component (F2), E (F1) and E (F2). For example, in order to increase E (F), E (F1) may be increased, or E (F2) may be increased. Also, it can be easily understood that W (F1) may be reduced to increase W (F2), provided that E (F2) is higher than E (F1). The control method in the reverse direction is also the same.

  In addition, it is E (F) and E (F1) that can actually obtain a measured value directly, and will calculate E (F2) using both measured value. Therefore, if an operation to increase E (F2) is performed when performing an operation to increase E (F), that is, an operation to increase the amount of ethylene supplied to the second polymerization step is selected as a means, it is directly used as a measured value. Although E (F) and not E (F2) can be confirmed, it is self-evident that E (F) becomes high because E (F2) becomes high.

Finally, the control method of MFR (F) will be described. In the present application, MFR (F2) is defined by the following equation.
MFR (F2) = exp {(loge [MFR (F)]-(W (F1) / 100) x
loge [MFR (F1)] ÷ (W (F2) / 100)}
(Here, loge is a logarithm based on e. MFR (F), MFR (F 1) and MFR (F 2) are respectively a propylene-ethylene block copolymer (F), a propylene homopolymer or a propylene- Component (F1) consisting of ethylene random copolymer and MFR of component (F2) consisting of propylene-ethylene random copolymer, and W (F1) and W (F2) are the same as above.)

This equation is generally an empirical equation loge [MFR (F)] = (W (F1) / 100) × loge [MFR (F1)] + (W (F2) / 100) × loge [loge [MFR (F)] MFR (F2)]
And are routinely used in the industry.

  As 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), three factors of the weight ratio of component (F1) to component (F2), MFR (F1) and MFR (F2) may be controlled. For example, to increase MFR (F), MFR (F1) may be increased, or MFR (F2) may be increased. In addition, if MFR (F2) is lower than MFR (F1), it can be easily understood that MFR (F) can be increased even if W (F1) is increased and W (F2) is decreased. . The control method in the reverse direction is also the same.

  In addition, it is MFR (F) and MFR (F1) that can actually obtain a measured value directly, and it will calculate MFR (F2) using both measured value. Therefore, when performing an operation to increase MFR (F) temporarily, an operation to increase MFR (F 2), that is, an operation to increase the amount of hydrogen supplied to the second polymerization step is selected as a means, it is directly used as a measured value. Although it is MFR (F) that can be confirmed but not MFR (F2), it is obvious that the cause of the increase in MFR (F) is the increase in MFR (F2).

  The polymerization process of the propylene-ethylene block copolymer can be carried out by either a batch system or a continuous system. At this time, a method of conducting polymerization in an inert hydrocarbon solvent such as hexane, heptane, etc., a method of using propylene as a solvent substantially without using an inert solvent, a gaseous state substantially without using a liquid solvent A method of conducting polymerization in a monomer, and a method combining these can be adopted. Further, the first polymerization step and the second polymerization step may use the same polymerization tank or separate polymerization tanks.

(1) Measurement of Ethylene Content in Copolymer Using a propylene-ethylene block copolymer (F), each ethylene content in this copolymer was measured. That is, a component (F1) comprising a propylene homopolymer or a propylene-ethylene random copolymer obtained at the end of the first polymerization step, and a propylene-ethylene block copolymer (F) obtained through the second polymerization step Each ethylene content in was determined by analyzing a ¹³ C-NMR spectrum measured according to the following conditions by a proton complete decoupling method.
Model: Japan Electronics Co., Ltd. GSX-400 or equivalent device (carbon nuclear resonance frequency 100 MHz or more)
Solvent: o-dichlorobenzene + heavy benzene (4: 1 (volume ratio))
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration number: 5,000 or more The assignment of spectra may be performed, for example, with reference to Macromolecules 17, 1950 (1984) or the like. The attribution of the spectrum measured under the above conditions is as shown in the following table. In the table, symbols such as Sαα and the like follow the notation of Carman et al. (Macromolecules 10, 536 (1977)), P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.

Hereinafter, when "P" is a propylene unit in a copolymer chain and "E" is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules 15, 1150 (1982), etc., the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (Tββ) (1)
[PPE] = k × I (Tβδ) (2)
[EPE] = k × I (Tδδ) (3)
[PEP] = k × I (Sββ) (4)
[PEE] = k × I (Sβδ) (5)
[EEE] = k × {I (Sδδ) / 2 + I (Sγδ) / 4} (6)
Here, parentheses [] indicate fractions of triads, for example, [PPP] is a fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1
(7)
It is. Also, k is a constant, I indicates a spectral intensity, for example, I (Tββ) means the intensity of a 28.7 ppm peak attributed to Tββ. By using the above-mentioned relational expressions (1) to (7), the fraction of each triad is determined, and the ethylene content is further determined by the following equation.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
In addition, conversion from mol% to weight% of ethylene content is performed using the following formula | equation.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1-X / 100)} × 100
Here, X is ethylene content in mol%.

[Other components of seal layer (I)]
In the above-described basic embodiment and the first to sixth embodiments, the resin composition (X) (resin compositions (X1) to (X6)) constituting the seal layer (I) As long as the effects of the invention are not impaired, additives containing a hindered amine light stabilizer or ultraviolet light absorber, fillers, other resin components, etc. may be contained. However, the total amount of the additive, the filler, the other resin component and the like is preferably 50% by weight or less with respect to the resin composition.

  When resin composition (X) consists of polypropylene resin (A), it is preferable that resin composition (X) has the characteristic of said polypropylene resin (A).

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

  Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, and thio-based antioxidants. As the neutralizing agent, higher fatty acid salts such as calcium stearate and zinc stearate can be exemplified.

  Examples of nucleating agents include metal salts of aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives, nonitol derivatives, amide compounds, metal salts of rosin and the like. Among these nucleating agents, aluminum p-tert-butylbenzoate, phosphate 2,2'-methylenebis (4,6-di-tert-butylphenyl) sodium, phosphate 2,2'-methylenebis (4 , 6-di-t-butylphenyl) aluminum, bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphospho A complex of aluminum (6-hydroxyl) hydroxide and an organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6: 5,7-bis- [ Examples are (4-propylphenyl) methylene] -nonitol, sodium salts of rosin and the like.

  As the lubricant, higher fatty acid amides such as stearic acid amide can be exemplified. As the antistatic agent, fatty acid partial esters such as glycerin fatty acid monoester can be exemplified. Examples of the metal deactivator include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

  As the filler, various known fillers that can be used for polypropylene resins such as inorganic fillers and organic fillers can be blended. Examples of the inorganic filler include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber and carbon fiber. Further, as the organic filler, crosslinked rubber fine particles, thermosetting resin fine particles, thermosetting resin hollow fine particles, and the like can be exemplified.

  Examples of other resin components include elastomers such as modified polyolefins and ethylene-α-olefin copolymers, low density polyethylene, high density polyethylene, petroleum resins, and other thermoplastic resins.

  The method for producing the resin composition (X) comprises a polypropylene-based resin (A) (in the case of the basic embodiment and the first and second embodiments), a polypropylene-based resin (A) and an ethylene-α-olefin random copolymer. Polymer (C) (in the case of the third embodiment), polypropylene resin (A) and thermoplastic elastomer (D) (in the case of the fourth embodiment), polypropylene resin (A) and thermoplastic resin (E) (in the case of the fourth embodiment) In the case of the fifth embodiment), or a method of melt-kneading the propylene-ethylene block copolymer (F) (in the case of the sixth embodiment) and additives, fillers, other resin components and the like, the third to the third In the fifth embodiment, the ethylene-.alpha.-olefin random copolymer (C), thermoplastic elast to a melt-kneaded polypropylene resin (A) and additives, fillers, other resin components, etc. A method of dry blending a mer (D) or a thermoplastic resin (E), or a polypropylene resin (A) with an ethylene-α-olefin random copolymer (C), a thermoplastic elastomer (D) or a thermoplastic resin (E) In addition to the above, it can be manufactured by a method such as dry blending of a master batch in which additives, fillers, other resin compositions and the like are dispersed in a carrier resin at a high concentration.

[Layer (II)]
The layer (II) contained in the decorative film of the present invention is composed of a resin composition (Y) containing a polypropylene resin (B). By providing the layer (II) on the decorative film, it is possible to suppress the occurrence of appearance defects due to breakage or runaway of the film during three-dimensional decorative thermoforming. Thereby, a decoration film does not need to contain the thermosetting resin layer which is excellent in the thermoforming property for improving a thermoforming property.

<< Polypropylene resin (B) >>
Next, the polypropylene resin (B) constituting the layer (II) will be described. The polypropylene resin (B) is preferably a resin that is more difficult to melt and relax than the polypropylene resin (A) described above.

1. Melt flow rate (MFR (B)): (b1)
The melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) of the polypropylene resin (B) needs to be lower than the MFR (A) of the polypropylene resin (A). That is, the following relational expression (b-1) is satisfied.
MFR (B) <MFR (A) formula (b-1)

  MFR (B) / MFR (A) which is a ratio of MFR between the polypropylene resin (B) and the polypropylene resin (A) is less than 1 (that is, MFR (B) <MFR (A)), which is preferable. Is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less, and particularly preferably 0.25 or less. When the MFR (B) / MFR (A) is in the above range, the thermoformability becomes good. Although the lower limit of MFR (B) / MFR (A) is not limited, it is preferably 0.01 or more.

  MFR (B) is not particularly limited as long as it is in the above range, but is preferably 0.1 g / 10 min or more, more preferably 0.2 g / 10 min or more. The spreadability of a decoration film is favorable in the case of thermoforming as it is the said range. Further, MFR (B) is preferably 20 g / 10 min or less, more preferably 15 g / 10 min or less.

2. Melting peak temperature (Tm (B)): (b2)
The melting peak temperature Tm (B) in the DSC measurement of the polypropylene resin (B) is not particularly limited, but is preferably 150 ° C. or more, more preferably 155 ° C. or more. When the Tm (B) is in the above range, the heat resistance, scratch resistance, and solvent resistance become good.

The melting peak temperature (Tm (B)) of the polypropylene resin (B) is preferably higher than the melting peak temperature (Tm (A)) of the polypropylene resin (A), and the following relational expression (b-2) Meet).
Tm (B)> Tm (A) Formula (b-2)
When it is in the above range, the thermoformability becomes good.

3. Crystallization temperature (Tc (B)): (b3)
The crystallization temperature (Tc (B)) in DSC measurement of the polypropylene resin (B) is preferably higher than the crystallization temperature (Tc (A)) of the polypropylene resin (A), and the following relational expression (b- Meet 3).
Tc (B)> Tc (A) .. Formula (b-3)
When it is in the above range, the thermoformability becomes good.
Tc (B) is not particularly limited as long as it is in the above range, but is preferably 95 ° C. or more, more preferably 100 ° C. or more.

4. Resin Composition The polypropylene resin (B) can be selected from a metallocene catalyst-based propylene polymer, a Ziegler-Natta catalyst-based propylene polymer, and the like. Ziegler-Natta catalyst-based propylene polymers are preferred.

  The polypropylene-based resin (B) in the present invention is various, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene-α-olefin block copolymer (block polypropylene), etc. Types of propylene-based polymers, or combinations thereof, can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer.

In the present invention, preferred combinations with the seal layer (I) are as follows.
In the first embodiment, the layer (II) preferably satisfies the requirements (b1) and (b2), and in the second embodiment, the layer (II) satisfies the requirements (b1) and (b3). In the third to sixth embodiments, the layer (II) satisfies the above requirement (b1).

[Other components of layer (II)]
In the resin composition (Y) constituting the layer (II), in addition to the polypropylene resin (B), an additive containing a hindered amine light stabilizer or an ultraviolet absorber, a filler, a colorant, other resin components, etc. May be included. That is, it may be a resin composition (polypropylene resin composition) containing a propylene polymer (polypropylene resin (B)), additives, fillers, colorants, other resin components, and the like. The total amount of additives, fillers, colorants, other resin components and the like is preferably 50% by weight or less based on the polypropylene resin composition.

  As an additive, an additive etc. which may be contained in resin composition (X) which constitutes the above-mentioned seal layer (I) can be used.

  Resin composition (Y) is a method of melt-kneading a propylene-based polymer and additives, fillers, other resin components, etc., and other resin components to a melt-kneaded propylene-based polymer, additives, fillers, etc. It can be manufactured by a method of dry blending, a method of dry blending a master batch in which additives, fillers and the like are dispersed at a high concentration in a carrier resin in addition to a propylene polymer and other resin components.

  When resin composition (Y) consists of polypropylene resin (B), it is preferable that resin composition (Y) has the characteristic of said polypropylene resin (B).

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

  When the decorated molded body of the present invention is molded as a colored molded body, a coloring agent may be used only for the decorating film, and therefore, the use of an expensive coloring agent as compared to the case of coloring the entire resin molded body It is possible to suppress In addition, it is possible to suppress the change in physical properties associated with the blending of the colorant.

[Decorated film]
The decorative film in the present invention includes a seal layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B). The decorative film can have various configurations in addition to the sealing layer (I) and the layer (II). That is, even if the decorative film is a two-layer film comprising the seal layer (I) and the layer (II), it is a multilayer film of three or more layers comprising the seal layer (I) and the layer (II) and other layers. It may be. In addition, seal layer (I) adheres along a resin molding (base | substrate). In addition, the decorative film may have emboss, emboss, print, sandplast, scratch, etc. on its surface.

  Three-dimensional decorative thermoforming has a high degree of freedom in the shape of the object to be decorated, and since the end face of the decorative film is wound up to the back side of the object to be decorated, a seam does not occur, and the decorative film is excellent. Various textures can be expressed by applying emboss and the like to the surface. For example, in the case of applying a texture such as embossing to a resin molded body, three-dimensional decorative thermoforming may be performed using the embossed decorative film. For this reason, the problem in the case of molding with a molded body mold to which embossing is applied, that is, the molded body mold is required for each embossing pattern, it is very difficult and expensive to complexly emboss a curved mold. It is possible to solve the problem of being, and to obtain a decorated molded body to which embossing of various patterns is easily imparted. Moreover, if a mirror-like cooling roll is surface-transferred and mirror processing is given to a decorating film, a higher gloss decorative film can be obtained.

  In addition to the seal layer (I) and the layer (II), the multilayer film is provided between the surface layer, the surface decoration layer (III), the printing layer, the light shielding layer, the colored layer, the base layer, the barrier layer, and these layers Can include tie layer layers etc. The layer (II) containing the polypropylene resin (B) may be any layer other than the seal layer among the layers constituting the multilayer film.

  In the multilayer film, layers other than the seal layer (I) and the layer (II) are preferably layers made of a thermoplastic resin, and more preferably layers made of a polypropylene resin. As long as layers other than the seal layer (I) and the layer (II) can be distinguished from the seal layer (I) and the layer (II), MFR (230 ° C., 2.16 kg) of the polypropylene resin constituting the layer The load is not particularly limited. Each layer is preferably a layer not containing a thermosetting resin. By using a thermoplastic resin, the recyclability is improved, and by using a polypropylene resin, it is possible to suppress the complication of the layer structure, and the recyclability is further improved.

  When the decorative film is a two-layer film, the seal layer (I) constitutes the adhesion surface to the resin molding, and the layer (II) is the surface layer opposite to the adhesion surface to the resin molding Configure. In this case, the layer (II) preferably contains a hindered amine light stabilizer and / or a UV absorber.

  Fig.1 (a)-FIG.1 (c) are explanatory drawings which illustrate typically the cross section of embodiment of a decorating film. In FIG. 1 (a) to FIG. 1 (c), the arrangement of the seal layer (I) and the layer (II) is specified and described for ease of understanding, but the layer configuration of the decorative film is illustrated in these examples. It is not to be interpreted as limited. In the present specification, reference numeral 1 in the drawings indicates a decorative film, reference numeral 2 indicates a layer (II), reference numeral 3 indicates a seal layer (I), and reference numeral 4 indicates a surface decorative layer (III). FIG. 1 (a) is an example in which the decorative film 1 is a two-layer film, and the layer (II) 2 is laminated on the seal layer (I) 3. The decorative film 1 of FIG. 1 (b) comprises a seal layer (I) 3, a layer (II) 2 and a surface layer, and the layer (II) and the surface layer are laminated in this order on the seal layer (I). The decorative film 1 of FIG. 1 (c) comprises a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4 and has a layer (II) and a surface coating on the sealing layer (I). The decorative layer (III) is laminated in this order.

  FIG. 8A to FIG. 8C are explanatory views schematically illustrating the cross section of the embodiment of the decorative molded body 6 in which the decorative film 1 is attached to the resin molded body 5. In FIGS. 8 (a) to 8 (c), the arrangement of the seal layer (I) and the layer (II) is specified and described for ease of understanding. It should not be interpreted as limited to FIG. 8 (a) is an example in which the decorative film 1 is a two-layer film, and the seal layer (I) 3 is adhered to the resin molded body 5 and the layer (II) is formed on the seal layer (I). Two stacks. The decorative film 1 of FIG. 8 (b) comprises a seal layer (I) 3, a layer (II) 2 and a surface layer, and the seal layer (I) is adhered to the surface of the resin molded body 5 to form a seal layer (I). Layer (II) and the surface layer are laminated in this order on the The decorative film 1 of FIG. 8 (c) comprises a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4, and the sealing layer (I) is adhered to the surface of the resin molded body 5. Layer (II) and the surface decoration layer (III) are laminated in this order on the seal layer (I).

  As another preferable embodiment of the decorative film, a multilayer film including a surface decorative layer (III) comprising a surface decorative layer resin on the outermost surface opposite to the surface to which the resin molded body is attached is mentioned Be

  The surface decoration layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (H). In addition, it is preferable that the surface decoration layer (III) contains a hindered amine light stabilizer and / or a UV absorber.

  The melt flow rate (230 ° C., 2.16 kg load) (MFR (H)) of the polypropylene resin (H) in the present invention preferably satisfies MFR (H)> MFR (B). By setting the above values, more beautiful surface gloss and texture can be expressed.

  The polypropylene-based resin (H) in the present invention is various, such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene-α-olefin block copolymer (block polypropylene), etc. Types of propylene-based polymers, or combinations thereof, can be selected. The propylene-based polymer preferably contains 50 mol% or more of a polymerization unit derived from a propylene monomer. The propylene-based polymer is preferably one that does not contain a polymerization unit derived from a polar group-containing monomer. The polypropylene resin (H) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance and the like. In addition, from the viewpoint of gloss (gloss) and transparency (coloring property), a propylene-α-olefin copolymer is preferable. In the present invention, the polypropylene resin (H) constituting the surface decoration layer (III) may be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

  The polypropylene resin (H) may contain an additive containing a hindered amine light stabilizer and / or a UV absorber, a filler, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) comprising a propylene polymer, an additive, a filler, another resin component, and the like. The total amount of additives, fillers, other resin components and the like is preferably 50% by weight or less based on the polypropylene resin composition.

  As an additive, an additive etc. which may be contained in resin composition (X) which constitutes the above-mentioned seal layer (I) can be used.

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

  When the polypropylene resin (H) constituting the surface decoration layer (III) is a polypropylene resin composition, this polypropylene resin composition comprises the polypropylene resin (A) constituting the seal layer (I) It may be the same as or different from the polypropylene resin composition to be used.

  The decorative film of the present invention preferably has a thickness of about 20 μm or more, more preferably about 50 μm or more, and still more preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of providing the designability is improved, the stability at the time of molding is also improved, and it becomes possible to obtain a better decorated molded body. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, and still more preferably about 0.8 mm or less. By making the thickness of the decorative film equal to or less than this value, the time required for heating at the time of thermoforming is shortened, the productivity is improved, and it becomes easy to trim unnecessary portions.

  In the decorative film of the present invention, the ratio of the thickness of the seal 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 It is 99%. If the ratio of the thickness of the seal layer (I) to the entire decorative film is within the above range, sufficient adhesive strength can be exhibited, and the scratch of the resin molded body (substrate) floats on the surface. Can be suppressed. Moreover, if the ratio of the thickness of layer (II) occupied to the whole decoration film is a range of said value, it can avoid that the thermoforming property of a decoration film becomes inadequate.

  In the multilayer film in which the surface decoration layer (III) made of polypropylene resin (H) is provided on the outermost surface of the decoration film, the ratio of the thickness of the surface decoration layer (III) in the decoration film is , Preferably 30% or less.

[Production of decorative film]
The decorative film of the present invention can be produced by various known molding methods.
For example, a method of coextrusion of the seal layer (I) comprising the resin composition (X) and the layer (II) comprising the resin composition (Y), the seal layer (I) and the layer (II) A method of co-extrusion with a layer, a thermal lamination method in which the other layer is bonded by applying heat and pressure onto one surface of one of the layers previously extruded, and a dry lamination method in which bonding is performed via an adhesive And a wet lamination method, an extrusion lamination method in which a polypropylene resin is melt-extruded on one surface of one layer extruded in advance, a sand lamination method, and the like. As an apparatus for forming a decoration film, a well-known co-extrusion T-die molding machine and a well-known lamination molding machine can be used. Among these, from the viewpoint of productivity, a co-extrusion T-die molding machine is preferably used.

  As a method of cooling a molten decorative film extruded from a die, a method of bringing a molten decorative film into contact with one cooling roll via air discharged from an air knife unit or an air chamber unit, The method of pressure-bonding and cooling by several cooling rolls is mentioned.

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

  Furthermore, the surface of the decorative film of the present invention may have an embossed shape. Such a decorative film is a method of directly pressing the molten resin extruded from a die with a roll having a concavo-convex shape and a smooth roll to transfer the concavo-convex shape, a smooth film having a concavo-convex shape It can manufacture by the method etc. of pressure-contacting with the heating roll and the smooth cooling roll which were given. Examples of the emboss shape include satin, animal skin tone, hairline tone, carbon tone and the like.

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

[Decorated molded body]
As a molded object (decorated object) to be decorated in the present invention, it is preferable to use various resin molded products (hereinafter sometimes referred to as "substrate") made of a polypropylene resin or a polypropylene resin composition. it can. The molding method of the resin molded product is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

  The polypropylene-based resin is a non-adhesive polymer because it is nonpolar, but the decorative film in the present invention is a seal layer (I) comprising the resin composition (X), and a resin composition (Y) By including layer (II) which consists of, the very high adhesive strength is exhibited by sticking the decoration object and decoration film which consist of polypropylene resin, and adhering.

  As a base resin of a polypropylene resin and a polypropylene resin composition of a molded object to be decorated, a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, or a propylene block copolymer, etc. It is possible to select various types based on various known propylene monomers as main raw materials. Further, unless the effect of the present invention is impaired, a filler such as talc may be contained to impart rigidity, or an elastomer may be contained to impart impact resistance. Moreover, you may also contain an additive component and the other resin component similarly to the polypropylene resin composition which can comprise the decoration film mentioned above.

  The decorative molded body in which the decorative film according to the present invention is attached to various molded bodies formed in a three-dimensional shape made of a polypropylene-based resin has a large reduction of VOC contained in the coating and the adhesive. They can be suitably used as home appliances, vehicles (such as railways), construction materials, daily goods, and the like.

[Manufacturing of a decorated molded body]
In the method of manufacturing a decorated molded body according to the present invention, the step of preparing the above-mentioned decorated film, the step of preparing a resin molded body, and the step of setting the resin molded body and the decorated film in a depressurizable chamber box. Step: decompressing the inside of the chamber box, heating and softening the decorative film, pressing the decorative film against the resin molded body, and returning or pressurizing the decompressed chamber to atmospheric pressure It is characterized by including a step.

  In three-dimensional decoration thermoforming, the decoration target and the decoration film are set in a depressurizable chamber box, the film is heated and softened in a state where the pressure in the chamber box is reduced, and the film is pressed against the decoration target It has a basic process of sticking a decoration film on the surface of decoration object by returning the inside of a chamber box to atmospheric pressure, or pressurizing, and pastes a film under pressure reduction. This makes it possible to obtain a beautifully decorated molded body free of air stagnation. In the manufacturing method of the present invention, any known device can be used as long as it is an apparatus suitable for three-dimensional decorative thermoforming, under the conditions.

  That is, the chamber box may contain all of the object to be decorated, the decoration film, the mechanism for pressing it, the device for heating the decoration film, etc. It may be a plurality of divided ones.

The mechanism for pressing the decoration target and the decoration film may be any type that moves the decoration target, moves the decoration film, or moves both.
More specific representative forming methods will be exemplified below.

  Hereinafter, the method of sticking a decoration film on a decoration object using a three-dimensional decoration thermoforming machine is demonstrated illustratively, referring a figure.

  As shown in FIG. 2, the three-dimensional decorative thermoforming machine of this embodiment comprises chamber boxes 11 and 12 at the top and bottom, and performs thermoforming of the decorative film 1 in the two chamber boxes 11 and 12. It is like that. A vacuum circuit (not shown) and an air circuit (not shown) are connected to the upper and lower chamber boxes 11 and 12, respectively.

  In addition, a jig 13 for fixing the decorative film 1 is provided between the upper and lower chamber boxes 11 and 12. Further, a table 14 capable of being raised and lowered is installed in the lower chamber box 12, and the resin molded body (target for decoration) 5 is set on this table 14 (via a jig or the like or directly). Ru. A heater 15 is incorporated in the upper chamber box 11, and the decorative film 1 is heated by the heater 15. The decoration target 5 can use a propylene-based resin composition as a base.

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

  As shown in FIG. 3, first, with the upper and lower chamber boxes 11 and 12 open, the object to be decorated 5 is placed on the table 14 in the lower chamber box 12 and the table 14 is lowered. Subsequently, the decorative film 1 is set in the film fixing jig 13 between the upper and lower chamber boxes 11 and 12 so that the seal layer (I) faces the base, ie, the object to be decorated 5.

  As shown in FIG. 4, the upper chamber box 11 is lowered, the upper and lower chamber boxes 11 and 12 are joined to make the inside of the box closed, and then the insides of the respective chamber boxes 11 and 12 are vacuum suctioned. Heating of the decorative film 1 is performed.

  After the decorative film 1 is heated and softened, as shown in FIG. 5, the table 14 in the lower chamber box 12 is raised with the inside of the upper and lower chamber boxes 11 and 12 in the vacuum suction state. The decorative film 1 is pressed against the object to be decorated 5 to cover the object to be decorated 5. Further, as shown in FIG. 6, the upper chamber box 11 is opened at atmospheric pressure or compressed air is supplied from a pressurized air tank, thereby bringing the decorative film 1 into close contact with the object 5 to be decorated with a greater force.

  Subsequently, the interiors of the upper and lower chamber boxes 11 and 12 are opened to atmospheric pressure, and the decorated formed body 6 is removed from the lower chamber box 12. Finally, as illustrated in FIG. 7, the edges of the unnecessary decorative film 1 around the decorative formed body 6 are trimmed.

[Molding condition]
The pressure reduction in the chamber boxes 11 and 12 may be such that no air accumulation occurs, and the pressure in the chamber box is 10 kPa or less, preferably 3 kPa or less, more preferably 1 kPa or less.

  Moreover, in the two chamber boxes 11 and 12 divided up and down by the decoration film 1, the pressure in the chamber box on the side to which the decoration object 5 and the decoration film 1 are to be attached should be in the above range. The drawdown of the decorative film 1 can also be suppressed by changing the pressure of the chamber boxes 11 and 12.

  At this time, a film made of a general polypropylene-based resin may be largely deformed and ruptured by a slight pressure fluctuation due to a decrease in viscosity at the time of heating.

  The decorative film 1 of the present invention is not only difficult to draw down, but also resistant to film deformation due to pressure fluctuation.

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

  In the present invention, in order to attach the polypropylene-based decorative film 1 to the decorative object 5 made of a polypropylene-based resin, it is necessary that the surface of the resin molded body 5 and the decorative film 1 be sufficiently softened or melted.

  Therefore, it is necessary that the heater temperature is higher than the melting temperature of the polypropylene-based resin constituting the object to be decorated 5 and the polypropylene-based resin constituting the decorative film 1. The heater temperature is preferably 160 ° C. or more, more preferably 180 ° C. or more, and most preferably 200 ° C. or more.

  The higher the heater temperature, the shorter the time required for heating, but the heater side is sufficient to heat the interior of the decorative film 1 (or the surface opposite to the heater if the heater is installed on only one side). Since the resin is thermally deteriorated as well as the moldability is deteriorated due to the temperature of the resin becoming too high, the heater temperature is preferably 500.degree. C. or less, more preferably 450.degree. C. or less, most preferably 400.degree. It is below.

Although the appropriate heating time varies depending on the heater temperature, it is preferable that the polypropylene-based decorative film be heated even if it is short, for a time called springback, or a time until retension starts to be initiated. In the basic mode, the first embodiment, and the second embodiment, it is preferable that heating be performed for two seconds or more after the end of the recoil.
That is, the decorative film heated by the heater is thermally expanded by being heated from the solid state, and once stretched along with crystal melting, the spring back temporarily recoils by relaxation of the molecules as the crystal melting progresses to the whole. Is observed and then hangs down under its own weight, but after springback, the film is completely melted in crystals, and sufficient adhesion strength is obtained because molecular relaxation is sufficient.
Furthermore, since the decorative film of the present invention is surprisingly capable of strongly adhering to the substrate even by decorative thermoforming before recoiling is completed, the time of thermoforming can be shortened. The shaping can be completed before the hindered amine light stabilizer and / or the ultraviolet light absorber contained in the decorative film is volatilized.

  On the other hand, if the heating time is too long, the film sags due to its own weight or deforms due to the pressure difference between the upper and lower chamber boxes. Therefore, the heating time is preferably less than 30 seconds after the end of spring back.

  It is preferable to supply compressed air when the decorative film is brought into close contact with the substrate, in the case of decorating a molded article having a complicated shape having asperities or when achieving higher adhesion. The pressure in the upper chamber box when compressed air is introduced is 150 kPa or more, preferably 200 kPa or more, and more preferably 250 kPa or more. The upper limit is not particularly limited, but if the pressure is too high, there is a risk of damaging the device, so 450 kPa or less, preferably 400 kPa or less is good.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

Test Examples 1 and 2
(Method of measuring and evaluating physical properties)
1. Measurement method of various physical properties (i) Melt flow rate (MFR)
In accordance with ISO 1133: 1997 Conditions M, it was measured at 230 ° C. under a 2.16 kg load. The unit is g / 10 minutes.

(Ii) melting peak temperature (melting point)
Using a differential scanning calorimeter (DSC), raise the temperature to 200 ° C and hold for 10 minutes, and then drop the temperature to 40 ° C at a temperature drop rate of 10 ° C / min, and again at a temperature rise rate of 10 ° C / min The temperature of the endothermic peak top at the time of measurement was taken as the melting peak temperature (melting point). The unit is ° C.

(Iii) Crystallization temperature Using a differential scanning calorimeter (DSC), a sheet sample piece is packed in a 5 mg aluminum pan and heated from 50 ° C. to 200 ° C. at a heating rate of 100 ° C./min. After holding for a minute, crystallization was performed by lowering the temperature to 40 ° C. at 10 ° C./min. The crystallization maximum peak temperature at this time was taken as the crystallization temperature (Tc).

(Iv) GPC measurement GPC measurement was performed under the following apparatus and conditions to calculate Mw / Mn.
Equipment: GPC (ALC / GPC 150C) manufactured by Waters
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
・ Column: Showa Denko AD 806 M / S (3)
Mobile phase solvent: ortho-dichlorobenzene (ODCB)
・ Measurement temperature: 140 ° C
・ Flow rate: 1.0 ml / min
Injection volume: 0.2 ml
Preparation of sample: A sample was prepared using ODCB (containing 0.5 mg / mL BHT) to prepare a 1 mg / mL solution and dissolved at 140 ° C. for about 1 hour.

The conversion from the retention volume obtained by GPC measurement to the molecular weight was performed using a calibration curve with standard polystyrene (PS) prepared in advance. The standard polystyrenes used are all of the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is generated by injecting 0.2 mL of a solution of ODCB (containing 0.5 mg / mL BHT) to 0.5 mg / mL each. The calibration curve used the cubic equation obtained by approximating by the least squares method.
In addition, the following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(V) Density The density of the ethylene-α-olefin random copolymer (C) and the thermoplastic elastomer (D) was measured according to the density gradient tube method of JIS K7112 (1999).

(Vi) Tensile elastic modulus The tensile elastic modulus of the thermoplastic elastomer (D) was measured according to ASTM D 638, using ASTM-IV injection specification, 23 ° C., and a tensile speed of 50 mm / min.

(Vii) Ethylene content [E (C)] and [E (D)]
The ethylene content [E (C)] of the ethylene-α-olefin random copolymer (C) and the ethylene content [E (D)] of the thermoplastic elastomer (D) are measured by ¹³ C-NMR based on the method described above It calculated | required from the integral intensity obtained by these. The sample preparation and measurement conditions are as follows.
O-Dichlorobenzene / deuterated brominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio of 200 mg of ethylene-α-olefin random copolymer (C) or thermoplastic elastomer (D) as a sample 2.) It was placed in an NMR sample tube with an inner diameter of 10 mmφ and dissolved with 2.4 ml and hexamethyldisiloxane which is a standard substance of chemical shift.
^{The 13} C-NMR measurement was carried out using an AV400 NMR apparatus manufactured by Bruker Biospin Ltd. equipped with a 10 mmφ cryoprobe.
^{The 13} C-NMR measurement was performed by a broadband decoupling method with a sample temperature of 120 ° C., a pulse angle of 90 °, a pulse interval of 20 seconds, and an integration count of 512.

(Viii): Calculation of ethylene content of propylene-ethylene block copolymer (F), component (F1) and component (F2) Propylene-ethylene block copolymer (F), component (F1) and component (F2) The ethylene content was measured using the method of measuring ethylene content by ¹³ C-NMR described above.

(Ix) Isothermal crystallization time The isothermal crystallization time was measured by the above-mentioned method using a differential scanning calorimeter (DSC).
When measuring the isothermal crystallization time of the polypropylene resin (A) and the resin composition (X5), the polypropylene resin (A) and the resin composition (X5) are respectively melt-kneaded by a twin screw extruder. The pellet of polypropylene resin (A) and a resin composition (X5) was obtained, and the isothermal crystallization time was measured using it. KZW-15 manufactured by Technobel Co., Ltd. was used as a twin-screw extruder, and the screw rotation speed was set to 400 RPM, and the kneading temperature was set to 80 ° C., 120 ° C. and 200 ° C. .

2. Physical property evaluation of a decorative molded body (1) Evaluation of thermoforming property Drawdown state of a decorative film at the time of three-dimensional decorative thermoforming, and a decorative film of a decorative molded body having a decorative film attached to a substrate The sticking state was visually observed and evaluated by the criteria shown below.
Good: At the time of three-dimensional decorative thermoforming, since the contact between the base and the decorative film was simultaneously made on the entire contact surface without drawdown of the decorative film, contact unevenness does not occur, and adhesion is uniformly performed. ing.
[Delta]: Because the decorative film was slightly drawn down during three-dimensional decorative thermoforming, contact with the decorative film from the center of the substrate occurs, and contact unevenness occurs at the upper surface end of the substrate.
×: At the time of three-dimensional decorative thermoforming, since the decorative film was drawn down largely, contact unevenness occurs on the entire surface of the substrate.

(2) Adhesive force between resin molded body (substrate) and decorative film "Kraft adhesive tape No. 712 N" manufactured by NITOMS CORPORATION is cut out to 75 mm in width and 120 mm in length, and from the end of the resin molded body (substrate) It was stuck to a resin molding (substrate) in the range of 75 mm × 120 mm and subjected to masking treatment (substrate surface exposed portion is 45 mm wide and 120 mm long). It installed in three-dimensional decoration thermoforming apparatus NGF-0406-SW so that the masking surface of a resin molding (substrate) might contact with a decoration film, and performed three-dimensional decoration thermoforming.

  The decorative film surface of the resulting decorative molded body was cut to a substrate surface with a width of 10 mm in a direction perpendicular to the longitudinal direction of the pressure-sensitive adhesive tape, using a cutter, to prepare a test piece. In the obtained test piece, the adhesion surface of the base and the decoration film is 10 mm wide × 45 mm long. Attach to a tensile tester so that the base part of the test piece and the decorative film part become 180 °, and measure the 180 ° peel strength of the adhesive surface at a tensile speed of 200 mm / min. Maximum strength at peeling or breaking The (N / 10 mm) was measured five times, and the average strength was taken as the adhesive strength. The test was performed at 23 ° C. and 50% RH.

(3) Weatherability A flat plate sample after three-dimensional decorative thermoforming is held at 23 ° C. and 50% RH for 48 hours, and then a test piece is cut out of the flat plate to a length of 30 mm and a width of 70 mm. At the black panel temperature of 89 ° C., humidity of 50%, and irradiance of 100 W / m ² , 504 MJ of xenon arc lamp light was irradiated to the decorative film side of the decorative formed body. The irradiation time is as follows.
Irradiation time (1). When the decoration film contains only a hindered amine light stabilizer: 400 hr
Irradiation time (2). When the decoration film contains only UV absorber: 200 hr
Irradiation time (3). When the decorative film contains both a hindered amine light stabilizer and a UV absorber: 600 hours
After irradiation, the surface of the test piece was observed by magnifying 20 times with a microscope and evaluated. The evaluation criteria are as follows.
Good: No change is observed on the irradiated surface, or slight stains are observed.
X: fine cracks are observed on the irradiated surface.

(4) Evaluation of Recyclability The obtained decorated molded body was crushed, and a recycled molded body was obtained by injection molding in the same manner as production of a resin molded body (substrate), and the appearance was visually evaluated. A product excellent in appearance was designated as "○".

(Production of resin molded body (substrate))
1. Polypropylene-Based Resin Used for Resin Molded Body The following polypropylene-based resin was used.
(Z-1): Propylene homopolymer (MFR = 40 g / 10 min, Tm = 165 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name "Novatec (registered trademark) MA04H"
(Z-2): Propylene ethylene block copolymer (MFR = 30 g / 10 min, Tm = 164 ° C.), manufactured by Nippon Polypro Co., Ltd., trade name “Novatec (registered trademark) NBC 03 HR”
(Z-3): Polypropylene resin (Z-2) 60 wt%, MFR = 1.0 EBR (Mitsui Chemical Co., Ltd. Tafmar (registered trademark) A0550S) 20 wt%, inorganic filler (Japan) Polypropylene resin composition in which 20% by weight of Talc P-6, Talc P-6, average particle diameter 4.0 μm) is blended

2. Production of Resin Molded Body (Substrate) An injection molded body was obtained by the following method using polypropylene resins (Z-1) to (Z-3).
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., clamping pressure 100 tons cylinder temperature: 200 ° C.
Mold temperature: 40 ° C
Injection mold: Width × height × thickness = 120 mm × 120 mm × 3 mm flat plate adjustment: Hold for 5 days in a constant temperature and humidity room with a temperature of 23 ° C and a humidity of 50% RH

(Test Example 1)
[Material used]
(1) Polypropylene Based Resin The following polypropylene based resin was used.
(A-1): Propylene-α-olefin copolymer catalyzed by metallocene (MFR = 7.0 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Nippon Polypropylene Corporation, trade name "Wintec (registered trademark) WFX4M"
(A-2): Propylene-α-olefin copolymer catalyzed by metallocene (MFR = 25 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.4), manufactured by Japan Polypropylene Corp., trade name “Wynn” Tech (registered trademark) WSX03 "
(A-3): Propylene-α-olefin copolymer catalyzed by metallocene (MFR = 7.0 g / 10 min, Tm = 135 ° C., Mw / Mn = 2.3), manufactured by Nippon Polypropylene Corporation, trade name "Wintec (registered trademark) WFW4M"
(A-4): Propylene-α-olefin copolymer catalyzed by metallocene (MFR = 30 g / 10 min, Tm = 145 ° C., Mw / Mn = 2.4), manufactured by Nippon Polypropylene Corporation, trade name “Wind Tech (registered trademark) WMG03 "

(B-1): Propylene homopolymer based on Ziegler-Natta catalyst (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C., Mw / Mn = 4.9), manufactured by Nippon Polypropylene Corporation , Trade name "Novatec (registered trademark) EA9"
(B-2): Ziegler-Natta catalyzed propylene homopolymer (MFR = 2.4 g / 10 min, Tm = 161 ° C., Tc = 112 ° C.), manufactured by Nippon Polypropylene Corporation, trade name “Novatec (registered trademark) ) FY6 "
(B-1-1): Polypropylene resin composition in which 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin 770") is blended with 100 parts by weight of a polypropylene resin (B-1) Product (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-2): Polypropylene resin composition in which 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Chimassorb 944") is blended with 100 parts by weight of a polypropylene resin (B-1) Product (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-3): Polypropylene resin composition obtained by blending 0.2 weight parts of hindered amine light stabilizer (made by ADEKA, trade name "LA57") with 100 weight parts of polypropylene resin (B-1) Product (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-4): Polypropylene resin composition obtained by blending 0.2 weight parts of hindered amine light stabilizer (made by ADEKA, trade name "LA 52") with 100 weight parts of polypropylene resin (B-1) Product (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-5): Polypropylene resin composition obtained by blending 0.2 parts by weight of an ultraviolet light absorber (made by ADEKA, trade name "Adeka stub 1413") with 100 parts by weight of polypropylene resin (B-1) (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-6): To 100 parts by weight of a polypropylene resin (B-1), 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corp., trade name "Tinuvin 770"), and an ultraviolet absorber ( A polypropylene-based resin composition (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.) obtained by blending 0.2 parts by weight of trade name “ADEKA STAB 1413” manufactured by ADEKA CORPORATION
(B-2-1): Polypropylene resin composition in which 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin 770") is blended with 100 parts by weight of a polypropylene resin (B-2) Product (MFR = 2.4 g / 10 min, Tm = 161 ° C, Tc = 114 ° C)

(H-1): Propylene homopolymer (MFR = 10 g / 10 min, Tm = 161 ° C., Tc = 116 ° C., tensile elastic modulus = 1600 MPa), manufactured by Nippon Polypropylene Corp., trade name “Novatec (registered trademark)” FA3KM "
(H-1-1): Polypropylene resin composition in which 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin 770") is blended with 100 parts by weight of a polypropylene resin (A-1) Object (MFR = 10 g / 10 min, Tm = 161 ° C.)

Example 1-1
-Manufacture of a decoration film The lip opening degree 0.8 mm to which extruder 1 for seal layer (I) of diameter 30 mm (diameter) and extruder 2 for layer (II) of diameter 40 mm (diameter) were connected A two-kind two-layer T-die with a die width of 400 mm was used. The polypropylene resin (A-1) is charged into the extruder 1 for the seal layer (I), and the polypropylene resin (B-1-1) is charged into the extruder 2 for the layer (II), and the resin temperature is 240 ° C. The melt extrusion was performed under the conditions of 4 kg / h for the discharge amount of the extruder for sealing layer (I) and 12 kg / h for the discharge amount of the extruder for layer (II).

  The melt-extruded film is cooled and solidified so that the seal layer (I) is in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and a 50 μm thick seal layer (I) and a 150 μm thick layer ( An unstretched film of 2 layers in which II) was laminated was obtained.

Three-Dimensional Decoration Thermoforming As the resin molded body (base) 5, an injection molded body made of the polypropylene resin (Z-1) obtained as described above was used.
As a three-dimensional decorative thermoforming apparatus, "NGF-0406-SW" manufactured by NUSHIYAKU SEIKO CO., LTD. As shown in FIGS. 2 to 7, the decorative film 1 is 250 mm wide × 350 mm long so that the seal layer (I) faces the substrate (the resin molded body 5) and the longitudinal direction is the MD direction of the film. The film was cut out and set in a film fixing jig 13 having an opening size of 210 mm × 300 mm. The resin molded body 5 is pasted via a “Nystack NW-K15” manufactured by Nichiban Co., Ltd. on a 20 mm high sample installation table installed on the table 14 positioned below the jig 13 The The jig 13 and the table 14 were placed in the upper and lower chamber boxes 11 and 12, and the upper and lower chamber boxes 11 and 12 were closed to seal the inside of the chamber box. The chamber box is divided up and down via the decorative film 1. The upper and lower chamber boxes 11 and 12 are vacuum-sucked, and the far-infrared heater 15 installed on the upper chamber box 11 is started with an output of 80% with the pressure being reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa. The decoration film 1 was heated. During heating, vacuum suction was continued, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated and temporarily sags, and then, 5 seconds after the end of the springback phenomenon, the table 14 installed in the lower chamber box 12 is moved upward, and the resin molding 5 is finished. Immediately after this, compressed air was fed so that the pressure in the upper chamber box 11 became 270 kPa, and the resin molded body 5 and the decorative film 1 were brought into close contact with each other. Thus, a three-dimensional decorative thermoformed article (decorative molded body 6) in which the decorative film 1 was attached to the upper surface and the side surface of the resin molded body 5 was obtained. The evaluation results are shown in Table 2-1. In addition, evaluation of the weather resistance was performed on the conditions of irradiation time (1).

Example 1-2
Example 1- 1 except that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-2) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 2-1.

Example 1-3
Example 1- 1 except that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-3) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 2-1.

Example 1-4
Example 1- 1 except that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-4) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 2-1.

Example 1-5
In the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 1-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 2-1.

Example 1-6
Example 1- 1 except that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-2-1) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 2-1.

Example 1-7
Production of the decorative film of Example 1-1 is the same as Example 1-1 except that the polypropylene resin (A-1) of the seal layer (I) is changed to the polypropylene resin (A-2). Molded and evaluated. The evaluation results are shown in Table 2-1.

Example 1-8
Production of the decorative film of Example 1-1 is the same as Example 1-1 except that the polypropylene resin (A-1) of the seal layer (I) is changed to the polypropylene resin (A-3). Molded and evaluated. The evaluation results are shown in Table 2-1.

Example 1-9
Production of the decorative film of Example 1-1 is the same as Example 1-1 except that the polypropylene resin (A-1) of the seal layer (I) is changed to a polypropylene resin (A-4). Molded and evaluated. The evaluation results are shown in Table 2-1.

Example 1-10
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. Polypropylene resin (A-1) for extruder 1 for sealing layer (I), polypropylene resin (B-1-1) for extruder 2 for layer (II), surface decoration layer (III) The polypropylene resin (H-1-1) is put into the extruder 3 for each, the resin temperature is 240 ° C., the discharge amount of the extruder 1 is 4 kg / h, and the discharge amount of the extruder 2 is 8 kg / h, Melt extrusion was carried out under the condition of 4 kg / h for the discharge amount of the extruder 3.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 1-1, and evaluation was performed. The evaluation results are shown in Table 2-2.

Example 1-11
In the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 1-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 2-2.

Example 1-12
In the three-dimensional decorative thermoforming of Example 1-1, molding and evaluation were performed in the same manner as in Example 1-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 2-2.

Example 1-13
In the three-dimensional decorative thermoforming of Example 1-1, molding and evaluation were performed in the same manner as in Example 1-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 2-2.

Comparative Example 1-1
Example 1-1 with the exception that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1) It molded similarly and evaluated. The evaluation results are shown in Table 2-2.

Comparative Example 1-2
Example 1-1 with the exception that in the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (H-1) It molded similarly and evaluated. The evaluation results are shown in Table 2-2.

Comparative Example 1-3
Production of the decorative film of Example 1-1 is the same as Example 1-1 except that the polypropylene resin (A-1) of the seal layer (I) is changed to the polypropylene resin (B-1). Molded and evaluated. The evaluation results are shown in Table 2-2.

Comparative Example 1-4
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the seal layer (I) is changed to a polypropylene resin (B-1), and spring back in three-dimensional decorative thermoforming Molding and evaluation were performed in the same manner as in Example 1-1 except that molding was performed 40 seconds after the phenomenon was completed. The evaluation results are shown in Table 2-2.

Comparative Example 1-5
In the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the sealing layer (I) is used. The polypropylene resin (A-1) is changed to the polypropylene resin (B-1), and molding is performed 40 seconds after the end of the spring back phenomenon in three-dimensional decorative thermoforming, and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 1-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 2-2.

  The decorative molded body obtained from the decorative film of Examples 1-1 to 1-13 contains a hindered amine light stabilizer and / or a UV absorber in any of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) )) Was smaller than MFR (A), there was no contact unevenness, the thermoforming properties were excellent, and the adhesion was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 1-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 1-2 where MFR (B) is larger than MFR (A), the decorative film is drawn down during three-dimensional decorative thermoforming, and the thermoformability is inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted. In Comparative Example 1-3 in which MFR (A) was 0.5 g / 10 min or less and the hindered amine light stabilizer was blended in layer (II), molding was performed 5 seconds after the end of the spring back phenomenon. In the case, since the heating time of three-dimensional decoration molding was short, favorable adhesiveness was not expressed. In Comparative Example 1-4 in which molding was performed 40 seconds after the end of the spring back phenomenon using the same decorative film as Comparative Example 1-3, the heating time of the three-dimensional decorative molding was extended by Although the adhesiveness was developed, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior as compared with Example 1-1. MFR (A) is 0.5 g / 10 minutes or less, and Comparative Example 1-5 which mix | blended the ultraviolet absorber with layer (II) has adhesiveness by lengthening the heating time of three-dimensional decoration molding. Although it expressed, the added ultraviolet absorber volatilized, and the weather resistance was inferior as compared with Example 1-5.

(Test Example 2)
[Material used]
The following polypropylene resins were used in addition to the polypropylene resins used in (Test Example 1).
(A-6): Propylene-α-olefin copolymer (MFR = 5.0 g / 10 min, Tc = 86 ° C., Mw / Mn = 4.0), manufactured by Nippon Polypropylene Corp., trade name “Novatec Registered trademark) FX4G "
(A-7): Propylene-α-olefin copolymer (MFR = 7.0 g / 10 min, Tc = 96 ° C., Mw / Mn = 3.9), manufactured by Nippon Polypropylene Corporation, trade name “Novatec Registered trademark) FW4B "
(B-1-7): Polypropylene resin composition obtained by blending 0.2 parts by weight of an ultraviolet light absorber (made by ADEKA, trade name "LA-31G") with 100 parts by weight of polypropylene resin (B-1) Product (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.)
(B-1-8): To 100 parts by weight of a polypropylene resin (B-1), 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Chimassorb 944"), and an ultraviolet absorber ( Polypropylene resin composition (MFR = 0.4 g / 10 min, Tm = 161 ° C., Tc = 114 ° C.) blended with 0.2 parts by weight of trade name “LA-31G”) manufactured by ADEKA Co., Ltd.

Example 2-1
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the seal layer (I) is changed to a polypropylene resin (A-6), and spring back in three-dimensional decorative thermoforming The molding and evaluation were performed in the same manner as in Example 1-1 except that molding was performed 10 seconds after the phenomenon ended. The evaluation results are shown in Table 3-1.

Example 2-2
Example 2-Example 2-2 except that polypropylene-based resin (B-1-1) of layer (II) is changed to polypropylene-based resin (B-1-2) in the production of the decorative film of Example 2-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 3-1.

Example 2-3
Example 2-Example 2-2 except that polypropylene-based resin (B-1-1) of layer (II) is changed to polypropylene-based resin (B-1-3) in the production of the decorative film of Example 2-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 3-1.

Example 2-4
Example 2- With the exception of changing the polypropylene resin (B-1-1) of the layer (II) to a polypropylene resin (B-1-4) in the production of the decorative film of Example 2-1, It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 3-1.

Example 2-5
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 2-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 3-1.

Example 2-6
Example 2- (2), except that the polypropylene resin (B-1-1) of the layer (II) was changed to a polypropylene resin (B-2-1) in the production of the decorative film of Example 2-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 3-1.

Example 2-7
Production of the decorative film of Example 2-1 is the same as Example 2-1 except that the polypropylene resin (A-6) of the seal layer (I) is changed to the polypropylene resin (A-7). Molded and evaluated. The evaluation results are shown in Table 3-1.

Example 2-8
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. Polypropylene resin (A-6) for extruder 1 for seal layer (I), polypropylene resin (B-1-1) for extruder 2 for layer (II), surface decoration layer (III) The polypropylene resin (H-1-1) is put into the extruder 3 for each, the resin temperature is 240 ° C., the discharge amount of the extruder 1 is 4 kg / h, and the discharge amount of the extruder 2 is 8 kg / h, Melt extrusion was carried out under the condition of 4 kg / h for the discharge amount of the extruder 3.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 2-1, and evaluation was performed. The evaluation results are shown in Table 3-1.

Example 2-9
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 2-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 3-1.

Example 2-10
In the three-dimensional decorative thermoforming of Example 2-1, molding and evaluation were performed in the same manner as in Example 2-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 3-2.

Example 2-11
In the three-dimensional decorative thermoforming of Example 2-1, molding and evaluation were performed in the same manner as in Example 2-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 3-2.

Example 2-12
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-7), and the evaluation of the weather resistance is the irradiation time It shape | molded and evaluated similarly to Example 2-1 except having performed on the conditions of (2). The evaluation results are shown in Table 3-2.

Example 2-13
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-8), and the evaluation of the weather resistance is the irradiation time It shape | molded and evaluated similarly to Example 2-1 except having performed on the conditions of (3). The evaluation results are shown in Table 3-2.

Comparative Example 2-1
Example 2-1 and Example 2-1 except that in the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (B-1) It molded similarly and evaluated. The evaluation results are shown in Table 3-2.

Comparative Example 2-2
Example 2-1 and Example 2-1 except that in the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (H-1) It molded similarly and evaluated. The evaluation results are shown in Table 3-2.

Comparative Example 2-3
In production of a decoration film of Example 2-1, it is the same as that of Example 2-1 except having changed polypropylene system resin (A-6) of seal layer (I) into polypropylene system resin (B-1). Molded and evaluated. The evaluation results are shown in Table 3-2.

Comparative Example 2-4
In the production of the decorative film of Example 2-1, the polypropylene resin (A-6) of the seal layer (I) is changed to a polypropylene resin (B-1), and spring back in three-dimensional decorative thermoforming Molding and evaluation were performed in the same manner as in Example 2-1 except that molding was performed 40 seconds after the phenomenon was completed. The evaluation results are shown in Table 3-2.

Comparative Example 2-5
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the sealing layer (I) is used. The polypropylene resin (A-6) is changed to the polypropylene resin (B-1), and molding is performed 40 seconds after the end of the spring back phenomenon in three-dimensional decorative thermoforming, and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 2-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 3-2.

  The decorative molded article obtained from the decorative film of Examples 2-1 to 2-13 contains a hindered amine light stabilizer and / or a UV absorber in one of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) ) Is smaller than MFR (A), and furthermore, the crystallization temperature (Tc (A)) of the polypropylene resin in the seal layer (I) is less than 100 ° C., and the polypropylene resin in layer (II) Because the crystallization temperature (Tc (B)) of the above was higher than Tc (A), there was no contact unevenness, the thermoforming properties were excellent, and the adhesion was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 2-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 2-2 in which MFR (B) is larger than MFR (A), the decorative film was drawn down during three-dimensional decorative thermoforming, and the thermoformability was inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted. In Comparative Example 2-3 in which MFR (A) was 0.5 g / 10 min or less and the hindered amine light stabilizer was blended in layer (II), molding was performed 10 seconds after the end of the spring back phenomenon. In the case, since the heating time of three-dimensional decoration molding was short, favorable adhesiveness was not expressed. In Comparative Example 2-4, in which the same decorative film as Comparative Example 2-3 was used and the molding was performed 40 seconds after the end of the spring back phenomenon, the heating time of the three-dimensional decorative molding was extended, Although the adhesiveness was developed, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior as compared with Example 2-1. MFR (A) is 0.5 g / 10 minutes or less, and Comparative Example 2-5 which mix | blended the ultraviolet absorber with layer (II) is the adhesiveness by lengthening the heating time of three-dimensional decoration molding Although it expressed, the added ultraviolet absorber volatilized, and the weather resistance was inferior as compared with Example 2-5.

(Test Example 3)
[Material used]
The following resins were used in addition to the resin used in (Test Example 1).
(A-5): Propylene-α-olefin copolymer (MFR = 7.0 g / 10 min, Tm = 146 ° C., Tc = 115 ° C., Mw / Mn = 4.0, tensile modulus) using Ziegler-Natta catalyst = 1200MPa), manufactured by Nippon Polypropylene Corporation, trade name "Novatec (registered trademark) FW3GT"

Ethylene-α-olefin random copolymer The following ethylene-α-olefin random copolymer was used.
(C-1): Ethylene-butene random copolymer (MFR = 6.8 g / 10 min, Tm = 66 ° C., density = 0.885 g / cm ³ , ethylene content = 84% by weight): Mitsui Chemical Co., Ltd. Product name "Toughmer A 4085S"
(C-2): Ethylene-butene random copolymer (MFR = 7.0 g / 10 min, Tm = 47 ° C., density = 0.860 g / cm ³ , ethylene content = 73% by weight): Mitsui Chemical Co., Ltd. Product name "Tafmar A4050S"
(C-3): ethylene-octene random copolymer (MFR = 2.0 g / 10 min, Tm = 77 ° C., density = 0.885 g / cm ³ , ethylene content = 85 wt%): manufactured by DuPont Dow, Product Name "Engage EG 8003"
(C-4): ethylene-octene random copolymer (MFR = 2.0 g / 10 min, Tm = 38 ° C., density = 0.860 g / cm ³ , ethylene content = 75% by weight): manufactured by DuPont Dow, Product Name "Engage EG8842"
(C-5): ethylene-hexene random copolymer (MFR = 3.5 g / 10 min, Tm = 60 ° C., density = 0.880 g / cm ³ , ethylene content = 76% by weight): Nippon Polyethylene Co., Ltd. Product name "Kernel KS340T"
(C-6): Ethylene-propylene random copolymer (MFR = 7.0 g / 10 min, Tm = 38 ° C., density = 0.860 g / cm ³ , ethylene content = 73% by weight): Mitsui Chemical Co., Ltd. Product name "Tafmar P0280"

Example 3-1
In the production of the decorative film of Example 1-1, the polypropylene-based resin (A-1) of the seal layer (I) was treated with the polypropylene-based resin (A-5) and the ethylene-α-olefin random copolymer (C-). Change 1) to a blend of 85: 15 in weight ratio, and immediately after springback phenomenon is finished in three-dimensional decorative thermoforming (that is, the heating time after springback is 0 seconds) Molding and evaluation were performed in the same manner as in Example 1-1 except for the above. The evaluation results are shown in Table 4-1.

Example 3-2
Example 3-l except that in the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-2) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 4-1.

Example 3-3
Example 3-l except that in the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-3) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 4-1.

Example 3-4
Example 3-l except that in the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-4) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 4-1.

Example 3-5
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 3-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 4-1.

Example 3-6
Example 3-l except that in the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-2-1) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 4-1.

Example 3-7
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the seal layer (I) was replaced with the ethylene-α-olefin random copolymer (C-2) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was changed to The evaluation results are shown in Table 4-1.

Example 3-8
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the seal layer (I) was replaced with the ethylene-α-olefin random copolymer (C-3) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was changed to The evaluation results are shown in Table 4-1.

Example 3-9
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the seal layer (I) is replaced with an ethylene-α-olefin random copolymer (C-4) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was changed to The evaluation results are shown in Table 4-1.

Example 3-10
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the seal layer (I) was replaced with the ethylene-α-olefin random copolymer (C-5) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was changed to The evaluation results are shown in Table 4-2.

Example 3-11
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the seal layer (I) is replaced with an ethylene-α-olefin random copolymer (C-6) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was changed to The evaluation results are shown in Table 4-2.

Example 3-12
In the production of the decorative film of Example 3-1, the compounding ratio of the resin of the seal layer (I) was changed to a polypropylene resin (A-5): ethylene-α-olefin random copolymer (C-1) = 70: It shape | molded and evaluated similarly to Example 3-1 except having set it as 30. The evaluation results are shown in Table 4-2.

Example 3-13
In the production of the decorative film of Example 3-1, the compounding ratio of the resin of the seal layer (I) was changed to a polypropylene resin (A-5): ethylene-α-olefin random copolymer (C-1) = 30: Molding and evaluation were performed in the same manner as in Example 3-1 except that 70 was used. The evaluation results are shown in Table 4-2.

Example 3-14
Example 3-1 except that in the production of the decorative film of Example 3-1, the polypropylene resin (A-5) used for the seal layer (I) is changed to a polypropylene resin (H-1) It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 4-2.

Example 3-15
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. A blend of a polypropylene resin (A-5) and an ethylene-α-olefin random copolymer (C-1) in a weight ratio of 85:15 in an extruder 1 for a seal layer (I) Add polypropylene-based resin (B-1-1) to extruder (2) for layer (II) and polypropylene-based resin (H-1-1) to extruder 3 for surface decorative layer (III) Melt extrusion was performed under the conditions of a resin temperature of 240 ° C., a discharge amount of extruder 1 of 4 kg / h, a discharge amount of extruder 2 of 8 kg / h, and a discharge amount of extruder 3 of 4 kg / h.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 3-1, and evaluation was performed. The evaluation results are shown in Table 4-2.

Example 3-16
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 3-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 4-2.

Example 3-17
In the three-dimensional decorative thermoforming of Example 3-1, molding and evaluation were performed in the same manner as in Example 3-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 4-2.

Example 3-18
In the three-dimensional decorative thermoforming of Example 3-1, molding and evaluation were performed in the same manner as in Example 3-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 4-2.

Comparative Example 3-1
Example 3-1 and Example 3-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1) in the production of the decorative film of the example 3-1 It molded similarly and evaluated. The evaluation results are shown in Table 4-3.

Comparative Example 3-2
Example 3-1 and Example 3-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (H-1) in the production of the decorative film of the example 3-1 It molded similarly and evaluated. The evaluation results are shown in Table 4-3.

Comparative Example 3-3
In the production of the decorative film of Example 3-1, molding and evaluation were performed in the same manner as in Example 3-1 except that the resin of the seal layer (I) was changed to only the polypropylene resin (B-1). The The evaluation results are shown in Table 4-3.

Comparative Example 3-4
In the production of the decorative film of Example 3-1, the resin of the seal layer (I) is changed to the polypropylene resin (B-1) only, and after the spring back phenomenon is finished in the three-dimensional decorative thermoforming Molding and evaluation were performed in the same manner as in Example 3-1 except that molding was performed after 40 seconds. The evaluation results are shown in Table 4-3.

Comparative Example 3-5
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the sealing layer (I) is obtained. Resin is changed to only polypropylene resin (B-1), and molding is performed 40 seconds after the springback phenomenon is finished in three-dimensional decorative thermoforming, and the weatherability evaluation is the condition of irradiation time (2) The molding and evaluation were performed in the same manner as in Example 3-1 except that the above was performed. The evaluation results are shown in Table 4-3.

The decorative molded article obtained from the decorative film of Examples 3-1 to 3-18 contains a hindered amine light stabilizer and / or a UV absorber in one of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) ) Is smaller than MFR (A), and further, the seal layer (I) has a weight ratio of polypropylene resin (A) to ethylene-α-olefin random copolymer (C) of 97: 3 to 5:95. And the ethylene-.alpha.-olefin random copolymer (C), wherein the (c1) ethylene content [E (C)] is at least 65% by weight, and the (c2) density is 0.850. ~ 0.950 g / cm ³ , (c3) Melt flow rate (MFR (C)) was 0.1 to 100 g / 10 min, so there was no contact unevenness, the thermoformability was excellent, and the adhesive strength was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 3-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 3-2 in which MFR (B) is larger than MFR (A), the decorative film was drawn down during three-dimensional decorative thermoforming, and the thermoformability was inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted. Comparative Example 3-3 in which MFR (A) is 0.5 g / 10 min or less and the hindered amine light stabilizer is blended in the layer (II) is a third order when molding is performed immediately after the spring back phenomenon is completed. Good adhesion was not expressed because the heating time of the primary decoration molding was short. In Comparative Example 3-4, in which the same decorative film as Comparative Example 3-3 was used, and the molding was performed 40 seconds after the end of the spring back phenomenon, the heating time of the three-dimensional decorative molding was extended, Although the adhesiveness was developed, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior as compared with Example 3-1. MFR (A) is 0.5 g / 10 minutes or less, and Comparative Example 3-5 which mix | blended the ultraviolet absorber with layer (II) has adhesiveness by lengthening the heating time of three-dimensional decoration molding. Although it expressed, the added ultraviolet absorber volatilized, and the weather resistance was inferior as compared with Example 3-5.

(Test Example 4)
[Material used]
Polypropylene-Based Resin The polypropylene-based resin used in (Test Example 1) and (Test Example 3) was used.

Thermoplastic elastomer (D)
The following thermoplastic elastomers were used.
(D-1): Propylene-butene random copolymer mainly composed of propylene (MFR = 7.0 g / 10 min, Tm = 75 ° C., density = 0.885 g / cm ³ , tensile modulus of elasticity = 290 MPa, propylene Content = 69% by weight, butene content = 31% by weight, ethylene content [E] = 0% by weight): Mitsui Chemicals Co., Ltd., trade name "Tafmer XM 7070"
(D-2): butene homopolymer (MFR = 5.0 g / 10 min, Tm = 125 ° C., density = 0.915 g / cm ³ , tensile modulus = 430 MPa, ethylene content [E] = 0 wt%) : Mitsui Chemicals Co., Ltd., trade name "Tafmer BL4000"
(D-3): Propylene-ethylene-butene random copolymer (MFR = 6.0 g / 10 min, Tm = 160 ° C., density = 0.868 g / cm ³ , tensile elastic modulus = 50 MPa) Propylene content = 84% by weight, ethylene content [E] = 9% by weight, butene content = 7% by weight): manufactured by Mitsui Chemicals, Inc., trade name "Tafmer PN2060"
(D-4): Propylene-ethylene random copolymer mainly composed of propylene (MFR = 8.0 g / 10 min, Tm = 61 ° C., density = 0. 871 g / cm ³ , tensile modulus of elasticity = 45 MPa, propylene Content = 89 wt%, ethylene content [E] = 11 wt%): Exxon Mobil Chemical Co., Ltd., trade name "VISTAMAXX 3000"

Example 4-1
In production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (A-1) of the seal layer (I) to the polypropylene resin (A-5) and the thermoplastic elastomer (D-1) The molding and evaluation were performed in the same manner as in Example 1-1 except that the blend ratio was changed to 85:15. The evaluation results are shown in Table 5-1.

Example 4-2
Example 4- (4) Example of production of the decoration film of Example 4-1 except changing the polypropylene resin (B-1-1) of layer (II) into a polypropylene resin (B-1-2) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 5-1.

Example 4-3
Example 4- (4) Example of production of the decoration film of Example 4-1 except changing the polypropylene resin (B-1-1) of layer (II) into a polypropylene resin (B-1-3) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 5-1.

Example 4-4
Example 4- (4) Example of production of the decoration film of Example 4-1 except changing the polypropylene resin (B-1-1) of layer (II) into a polypropylene resin (B-1-4) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 5-1.

Example 4-5
In the production of the decorative film of Example 4-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 4-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 5-1.

Example 4-6
Example 4- (4) Example of production of the decoration film of Example 4-1 except changing the polypropylene resin (B-1-1) of layer (II) into a polypropylene resin (B-2-1). It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 5-1.

Example 4-7
Example 4-1 except that the thermoplastic elastomer (D-1) used for the seal layer (I) is changed to the thermoplastic elastomer (D-2) in the production of the decorative film of Example 4-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 5-1.

Example 4-8
Example 4-1 except that the thermoplastic elastomer (D-1) used for the seal layer (I) is changed to the thermoplastic elastomer (D-3) in the production of the decorative film of Example 4-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 5-1.

Example 4-9
Example 4-1 except that the thermoplastic elastomer (D-1) used for the seal layer (I) is changed to the thermoplastic elastomer (D-4) in the production of the decorative film of Example 4-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 5-1.

Example 4-10
In the production of the decorative film of Example 4-1, the compounding ratio of the resin of the seal layer (I) is set to polypropylene resin (A-5): thermoplastic elastomer (D-1) = 70:30. Molding and evaluation were performed in the same manner as in Example 4-1. The evaluation results are shown in Table 5-1.

Example 4-11
In the production of the decorative film of Example 4-1, the compounding ratio of the resin of the seal layer (I) is set to polypropylene resin (A-5): thermoplastic elastomer (D-1) = 30: 70. Molding and evaluation were performed in the same manner as in Example 4-1. The evaluation results are shown in Table 5-1.

Example 4-12
Example 4-1 except that in the production of the decorative film of Example 4-1, the polypropylene resin (A-5) used for the seal layer (I) is changed to a polypropylene resin (H-1) It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 5-2.

Example 4-13
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. What is obtained by blending a polypropylene resin (A-5) and a thermoplastic elastomer (D-1) so that the weight ratio is 85:15 in the extruder 1 for the seal layer (I) is for the layer (II) The polypropylene resin (B-1-1) is put into the extruder 2, and the polypropylene resin (H-1-1) is put into the extruder 3 for the surface decoration layer (III), and the resin temperature is 240 ° C, The melt extrusion was performed under the conditions of 4 kg / h for the discharge amount of the extruder-1, 8 kg / h for the discharge amount of the extruder-2, and 4 kg / h for the discharge amount of the extruder-3.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 4-1, and evaluation was performed. The evaluation results are shown in Table 5-2.

Example 4-14
In the production of the decorative film of Example 4-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 4-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 5-2.

Example 4-15
In the three-dimensional decorative thermoforming of Example 4-1, molding and evaluation were performed in the same manner as in Example 4-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 5-2.

Example 4-16
In the three-dimensional decorative thermoforming of Example 4-1, molding and evaluation were performed in the same manner as in Example 4-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 5-2.

Comparative Example 4-1
Example 4-1 and Example 4-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (B-1) in the production of the decorative film of the example 4-1 It molded similarly and evaluated. The evaluation results are shown in Table 5-2.

Comparative Example 4-2
Example 4-1 and Example 4-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (H-1) in the production of the decorative film of the example 4-1 It molded similarly and evaluated. The evaluation results are shown in Table 5-2.

Comparative Example 4-3
In the production of the decorative film of Example 4-1, molding and evaluation were performed in the same manner as in Example 4-1 except that the resin of the seal layer (I) was changed to only the polypropylene resin (B-1). The The evaluation results are shown in Table 5-2.

Comparative Example 4-4
In the production of the decorative film of Example 4-1, the resin of the seal layer (I) is changed to only the polypropylene resin (B-1), and after the spring back phenomenon is finished in the three-dimensional decorative thermoforming Molding and evaluation were performed in the same manner as in Example 4-1 except that molding was performed after 40 seconds. The evaluation results are shown in Table 5-2.

Comparative Example 4-5
In the production of the decorative film of Example 4-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the sealing layer (I) is used. Resin is changed to only polypropylene resin (B-1), and molding is performed 40 seconds after the springback phenomenon is finished in three-dimensional decorative thermoforming, and the weatherability evaluation is the condition of irradiation time (2) The molding and evaluation were carried out in the same manner as in Example 4-1 except that the above was carried out. The evaluation results are shown in Table 5-2.

The decorative molded article obtained from the decorative film of Examples 4-1 to 4-16 contains a hindered amine light stabilizer and / or a UV absorber in one of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) A resin composition wherein the weight ratio of the sealing layer (I) to the polypropylene resin (A) and the thermoplastic elastomer (D) is 97: 3 to 5:95. The thermoplastic elastomer (D) is a thermoplastic elastomer containing X4) and having at least one of (d1) propylene and butene as a main component, and (d2) density is 0.850 to 0.950 g / cm. ³ (D3) Melt flow rate (MFR (D)) is 0.1 to 100 g / 10 min and (d4) tensile elastic modulus is smaller than that of polypropylene resin (A). And the adhesion was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 4-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 4-2 in which MFR (B) is larger than MFR (A), the decorative film was drawn down during three-dimensional decorative thermoforming, and the thermoformability was inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted. In Comparative Example 4-3 in which MFR (A) was 0.5 g / 10 min or less and the hindered amine light stabilizer was blended in layer (II), molding was performed 5 seconds after the end of the spring back phenomenon. In the case, since the heating time of three-dimensional decoration molding was short, favorable adhesiveness was not expressed. In Comparative Example 4-4, in which the same decorative film as Comparative Example 4-3 was used, and the molding was performed 40 seconds after the end of the spring back phenomenon, the heating time of the three-dimensional decorative molding was extended by Although the adhesiveness was developed, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior as compared with Example 4-1. MFR (A) is 0.5 g / 10 minutes or less, and Comparative Example 4-5 which blended the ultraviolet absorber into layer (II) has adhesiveness by lengthening the heating time of three-dimensional decoration molding Although it expressed, the added ultraviolet absorber volatilized, and the weather resistance was inferior as compared with Example 4-5.

Test Example 5
[Material used]
Polypropylene-Based Resin The following polypropylene-based resin was used as the polypropylene-based resin of the seal layer (I).
(A-1): Propylene-α-olefin copolymer (MFR = 7.0 g / 10 min, Tm = 125 ° C., crystallization start temperature = 97 ° C., isothermal crystallization time (t) = 570 seconds (107 ° C.) Measured by the Japan Polypropylene Corporation), trade name “Wintec (registered trademark) WFX4M”
(A-5): Propylene-α-olefin copolymer (MFR = 7.0 g / 10 min, Tm = 146 ° C., crystallization start temperature = 111 ° C., isothermal crystallization time (t) = 263 seconds (121 ° C. Measured by the Japan Polypropylene Corporation), trade name "Novatec (registered trademark) FW3GT"
(A-8): Propylene block copolymer (MFR = 6.0 g / 10 min, Tm = 135 ° C., crystallization onset temperature = 99 ° C., isothermal crystallization time (t) = 478 seconds (measured at 109 ° C.) ), Japan Polypropylene Corp., trade name “Welnex® RFG4VA”
(H-1): Propylene homopolymer (MFR = 10 g / 10 min, Tm = 161 ° C., crystallization onset temperature = 123 ° C., isothermal crystallization time (t) = 613 seconds (measured at 133 ° C.), Japan Polypro Co., Ltd., trade name "Novatec (registered trademark) FA3KM"

  The polypropylene resin used in (Test Example 1) was used for the layer (II) and the surface decoration layer (III).

Thermoplastic resin (E)
The following thermoplastic resin was used.
(E-1): Hydrogenated styrenic elastomer (HSBR): manufactured by JSR Corporation, trade name "Dynalon 1320P"
(E-2): Styrene-based elastomer (SEBS): manufactured by Kraton Polymer Japan Co., Ltd., trade name "Clayton G1645"
(E-3): Alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name "Alcon-P125"

Example 5-1
In production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (A-1) of the seal layer (I) to the polypropylene resin (A-5) and the thermoplastic resin (E-1) Except that the blend was changed so as to be 50:50, and molding was performed immediately after the springback phenomenon ended in three-dimensional decoration thermoforming (that is, the heating time after springback is 0 seconds), Molding and evaluation were performed in the same manner as in Example 1-1. The evaluation results are shown in Table 6-1.

Example 5-2
Example 5- (5), except that the polypropylene resin (B-1-1) of the layer (II) was changed to a polypropylene resin (B-1-2) in the production of the decorative film of Example 5-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 6-1.

Example 5-3
Example 5- (5), except that the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-3) in the production of the decorative film of Example 5-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 6-1.

Example 5-4
Example 5- (5), except that polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-4) in the production of the decorative film of Example 5-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 6-1.

Example 5-5
In the production of the decorative film of Example 5-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 5-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 6-1.

Example 5-6
Example 5- (5), except that the polypropylene resin (B-1-1) of the layer (II) was changed to a polypropylene resin (B-2-1) in the production of the decorative film of Example 5-1 It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 6-1.

Example 5-7
Example 5-1 except that the thermoplastic resin (E-1) used for the seal layer (I) is changed to the thermoplastic resin (E-2) in the production of the decorative film of Example 5-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 6-1.

Example 5-8
In the production of the decorative film of Example 5-1, the thermoplastic resin (E-1) used for the seal layer (I) is changed to a thermoplastic resin (E-3), and a polypropylene resin (A-5) The molding and evaluation were performed in the same manner as in Example 5-1 except that the compounding ratio of the thermoplastic resin (E-3) and the thermoplastic resin (E-3) was 85:15. The evaluation results are shown in Table 6-1.

Example 5-9
In the production of the decorative film of Example 5-1, the compounding ratio of the resin in the seal layer (I) is set to polypropylene resin (A-5): thermoplastic resin (E-1) = 70: 30. Molding and evaluation were performed in the same manner as in Example 5-1. The evaluation results are shown in Table 6-1.

Example 5-10
In the production of the decorative film of Example 5-1, the compounding ratio of the resin of the seal layer (I) is set to polypropylene resin (A-5): thermoplastic resin (E-1) = 30: 70. Molding and evaluation were performed in the same manner as in Example 5-1. The evaluation results are shown in Table 6-1.

Example 5-11
Example 5-1 other than having changed the polypropylene resin (A-5) used for seal layer (I) into polypropylene resin (H-1) in manufacture of the decoration film of Example 5-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 6-2.

Example 5-12
Example 5-1 other than having changed into a polypropylene resin (A-1) the polypropylene resin (A-5) used for seal layer (I) in manufacture of the decoration film of Example 5-1 It was molded and evaluated in the same manner as in. The evaluation results are shown in Table 6-2.

Example 5-13
In the production of the decorative film of Example 5-1, the polypropylene resin (A-5) used for the seal layer (I) is changed to a polypropylene resin (A-8), and a polypropylene resin (A-8) Molding and evaluation were carried out in the same manner as in Example 5-1 except that the compounding ratio of the thermoplastic resin (E-1) and the thermoplastic resin (E-1) was 70:30. The evaluation results are shown in Table 6-2.

Example 5-14
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. What is obtained by blending a polypropylene resin (A-5) and a thermoplastic resin (E-1) so that the weight ratio is 50:50 in the extruder 1 for the seal layer (I) is for the layer (II) The polypropylene resin (B-1-1) is put into the extruder 2, and the polypropylene resin (H-1-1) is put into the extruder 3 for the surface decoration layer (III), and the resin temperature is 240 ° C, The melt extrusion was performed under the conditions of 4 kg / h for the discharge amount of the extruder-1, 8 kg / h for the discharge amount of the extruder-2, and 4 kg / h for the discharge amount of the extruder-3.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 5-1, and evaluation was performed. The evaluation results are shown in Table 6-2.

Example 5-15
In the production of the decorative film of Example 5-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 5-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 6-2.

Example 5-16
In the three-dimensional decorative thermoforming of Example 5-1, molding and evaluation were performed in the same manner as in Example 5-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 6-2.

Example 5-17
In the three-dimensional decorative thermoforming of Example 5-1, molding and evaluation were performed in the same manner as in Example 5-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 6-2.

Comparative Example 5-1
Example 5-1 and production of the decorative film of Example 5-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (B-1) It molded similarly and evaluated. The evaluation results are shown in Table 6-2.

Comparative Example 5-2
Example 5-1 and Example 5-1 except that the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (H-1) in the production of the decorative film of the example 5-1 It molded similarly and evaluated. The evaluation results are shown in Table 6-2.

  The decorative molded article obtained from the decorative film of Examples 5-1 to 5-17 contains a hindered amine light stabilizer and / or a UV absorber in one of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) A resin composition in which the weight ratio of the sealing layer (I) to the polypropylene resin (A) and the thermoplastic resin (E) is 97: 3 to 5:95. And X5), wherein the thermoplastic resin (E) contains at least one of (e1) alicyclic hydrocarbon group and aromatic hydrocarbon group, and isothermal crystal of (x1) resin composition (X5) Time (t (X5)) (seconds) Since system resin (A) isothermal crystallization time (t (A)) is at least 1.5 times (in seconds), is excellent in thermoformability without contact unevenness, the adhesive strength was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 5-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 5-2 in which MFR (B) is larger than MFR (A), the decorative film was drawn down during three-dimensional decorative thermoforming, and the thermoformability was inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted.

(Test Example 6)
[Material used]
The following polypropylene resins were used in addition to the polypropylene resins used in (Test Example 1).

Production of Propylene-Ethylene Block Copolymer (F) Propylene-Ethylene Block Copolymer Obtained by the Following Preparation Example as Propylene-Ethylene Block Copolymer (F) Used for Seal Layer (I) of Decorative Film (F-1) to (F-4) were used. The polymerization conditions and the polymerization results are shown in Table 7-1, and the results of the polymer analysis are shown in Table 7-2.

Preparation Example F-1 Preparation of Propylene-Ethylene Block Copolymer (F-1)
Analysis of Catalyst Composition Ti Content: The sample was accurately weighed, hydrolyzed and measured using a colorimetric method. For the samples after prepolymerization, the content was calculated using the weight excluding the prepolymerization polymer.
Silicon Compound Content: The sample was accurately weighed and decomposed with methanol. The concentration of silicon compound in the obtained methanol solution was determined by comparison with a standard sample using gas chromatography. From the concentration of silicon compound in methanol and the weight of the sample, the content of silicon compound contained in the sample was calculated. For the samples after prepolymerization, the content was calculated using the weight excluding the prepolymerization polymer.

Preparation of Prepolymerization Catalyst (1) Preparation of Solid Catalyst A 10 L autoclave equipped with a stirrer was fully purged with nitrogen, and 2 L of purified toluene was introduced. At this temperature, 200 g of magnesium diethoxide [Mg (OEt) ₂ ] was added at room temperature, and 1 L of titanium tetrachloride (TiCl ₄ ) was slowly added. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. and reaction was performed for 3 hours. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 liters. At room temperature, 1 L of TiCl ₄ was added, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Then, purified toluene was introduced to adjust the total liquid volume to 2 liters. At room temperature, 1 L of TiCl ₄ was added, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Further, toluene was replaced with n-heptane using purified n-heptane to obtain a slurry of solid components. A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component was 2.7% by weight.

Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the above solid component slurry was introduced as a solid component. The purified n-heptane was introduced to adjust the concentration of the solid component to 25 g / L. 50 ml of silicon tetrachloride (SiCl ₄ ) was added, and the reaction was performed at 90 ° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane.

Thereafter, purified n-heptane was introduced to adjust the liquid level to 4 liters. To this, 30 ml of dimethyldivinylsilane, 30 ml of diisopropyldimethoxysilane [i-Pr ₂ Si (OMe) ₂ ], and 80 g of a diluted solution of triethylaluminum (Et ₃ Al) in n-heptane as Et ₃ Al are added at 40 ° C. The reaction was performed for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A portion of the resulting solid catalyst slurry was sampled, dried and analyzed. The solid catalyst contained 1.2 wt% of Ti and 8.9 wt% of i-Pr ₂ Si (OMe) ₂ .

(2) Prepolymerization The prepolymerization was performed according to the following procedure using the solid catalyst obtained above. The purified n-heptane was introduced into the above slurry to adjust the concentration of the solid catalyst to 20 g / L. After cooling the slurry to 10 ° C., 10 g of Et ₃ Al in n-heptane diluted solution as Et ₃ Al was added, and 280 g of propylene was fed over 4 hours. The reaction was continued for another 30 minutes after the propylene supply was over. Then, the gas phase was thoroughly replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was withdrawn from the autoclave and vacuum dried to obtain a prepolymerization catalyst. The prepolymerized catalyst contained 2.5 grams of polypropylene per gram of solid catalyst. As a result of analysis, the prepolymerization catalyst portion excluding the polypropylene contained 1.0% by weight of Ti and 8.3% by weight of i-Pr ₂ Si (OMe) ₂ .
Production of a propylene-ethylene block copolymer (F) was carried out according to the following procedure using this prepolymerization catalyst.

(3) Production of Propylene-Ethylene Block Copolymer (F) Propylene-Ethylene Block Copolymer (F) Using a Two-But Continuous Polymerization System in which Two Fluidized Bed Type Polymerization Tanks with an Internal Volume of 2 m ³ are Connected in Series Production of The production conditions of the propylene-ethylene block copolymer (F-1) are as described in 6A-1 of Table 7-1. The propylene, ethylene, hydrogen and nitrogen used were those purified using a general purification catalyst. The production amount of the component (F1) in the first polymerization tank and the production amount of the component (F2) in the second polymerization tank were determined from the value of the cooling water temperature of the heat exchanger used for temperature control of the polymerization tank.

First Polymerization Step: Production of Component (F1) Composed of Propylene Homopolymer Propylene was homopolymerized using a first polymerization tank. The polymerization temperature was 65 ° C., the total pressure was 3.0 MPaG (gauge pressure, the same applies hereinafter), and the powder hold amount was 40 kg. Propylene, hydrogen and nitrogen were continuously supplied to the polymerization tank, and the concentrations of propylene and hydrogen were adjusted to 70.83 mol% and 0.92 mol%, respectively. As a co-catalyst, Et ₃ Al was continuously fed at a rate of 5.0 g / hour. The prepolymerized catalyst obtained above was continuously supplied to the polymerization tank such that the production amount of the component (F1) in the first polymerization tank was 20.0 kg / hour. The component (F1) thus produced was continuously withdrawn, and adjusted so that the powder hold amount was constant at 40 kg. The component (F1) withdrawn from the first polymerization tank was continuously supplied to the second polymerization tank, and the production of the component (F2) consisting of a propylene-ethylene random copolymer was continued.

Second polymerization step: Production of propylene-ethylene random copolymer component (F2) In the second polymerization tank, random copolymerization of propylene and ethylene was performed. The polymerization temperature was 65 ° C., the total pressure was 2.0 MPaG, and the powder hold amount was 40 kg. Propylene, ethylene, hydrogen and nitrogen were continuously fed to the polymerization tank, and the concentrations of propylene, ethylene and hydrogen were adjusted to 54.29 mol%, 17.14 mol% and 0.41 mol%, respectively. . By continuously feeding ethanol which is a polymerization inhibitor, the production amount of the propylene-ethylene random copolymer component (F2) in the second polymerization tank was adjusted to 6.7 kg / h. The propylene-ethylene block copolymer (F) thus produced was continuously withdrawn, and was adjusted so that the powder hold amount was constant at 40 kg. The propylene-ethylene block copolymer (F) withdrawn from the second polymerization tank was further transferred to a drier and sufficiently dried.

  When a part of the produced propylene-ethylene block copolymer (F) was analyzed, the MFR (F) was 7.0 g / 10 min, and the ethylene content E (F) was 9.5 wt%. Where the weight ratio W (F1) of the component (F1) and the weight ratio W (F2) of the component (F2) were determined from the production amount of the first polymerization step and the production amount of the second polymerization step, 75 weight% each , 25% by weight.

The ethylene content E (F2) of the propylene-ethylene random copolymer component (F2) was calculated from W (F1), W (F2) and E (F) thus obtained.
The following formula was used for calculation.
E (F2) = {E (F) -E (F1) × W (F1) / 100} ÷
(W (F2) / 100)
(Here, since the component (F1) is a propylene homopolymer, E (F1) is 0% by weight. Further, the above-mentioned formulas are the same as those described for E (F) described above and are rearranged for E (F2). It is
The ethylene content E (F2) was 38.0% by weight.

Preparation Examples F-2 and F-3: Preparation of Propylene-Ethylene Block Copolymers (F-2) and (F-3)
A propylene-ethylene block copolymer (the same as in the production example of the propylene-ethylene block copolymer (F-1) except that the conditions described in 6A-2 and 6A-3 of Table 7-1 were respectively used Production of F-2) and (F-3) was performed.

Preparation Example F-4 Preparation of Propylene-Ethylene Block Copolymer F-4)
Preparation of Prepolymerization Catalyst (1) Chemical Treatment of Silicate Into a 10-liter glass separable flask equipped with a stirring blade, 3.75 liters of distilled water and then 2.5 kg of concentrated sulfuric acid (96%) were slowly added. did. At 50 ° C., 1 kg of montmorillonite (Benclay SL manufactured by Mizusawa Chemical; average particle diameter = 25 μm, particle size distribution = 10-60 μm) was further dispersed, and the temperature was raised to 90 ° C. and maintained for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover a cake. To this cake, 7 liters of distilled water was added, reslurried and filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried overnight at 110 ° C. under a nitrogen atmosphere. The weight after drying was 707 g.

(2) Drying of silicate The previously chemically treated silicate was dried by a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, internal diameter 50 mm, temperate zone 550 mm (electric furnace)
Speed with pick-up wings: 2 rpm
Inclination angle: 20/520
Silicate feed rate: 2.5 g / min Gas flow rate: nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(3) Preparation of catalyst An autoclave having an internal volume of 16 liters and equipped with a stirrer and a temperature controller was sufficiently replaced with nitrogen. Here, 200 g of dry silicate was introduced, 1,160 ml of mixed heptane, and further 840 ml of a heptane solution (0.60 M) of triethylaluminum were added, and the mixture was stirred at room temperature. After 1 hour, it was washed with mixed heptane, and a silicate slurry was prepared to 2,000 ml. Next, 9.6 ml of a heptane solution (0.71 M) of triisobutylaluminum was added to the previously prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, 870 ml of mixed heptane with 2, 180 mg (0.3 mM) of (r) -dichloro [1,1'-dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium and mixed heptane Add 33.1 ml of a solution of triisobutylaluminum in heptane (0.71 M), add the mixture reacted at room temperature for 1 hour to the silicate slurry, stir for 1 hour, add mixed heptane and add 5,000 ml Prepared.

(4) Prepolymerization / Washing Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the propylene supply was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped, and after standing for about 10 minutes, the supernatant was decanted into 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M) and 5600 ml of mixed heptanes were further added, and the mixture was stirred at 40 ° C. for 30 minutes and allowed to stand for 10 minutes. This operation was further repeated three times. The final component analysis of the supernatant showed that the concentration of the organoaluminum component was 1.23 mmol / l, the concentration of zirconium (Zr) was 8.6 × 10 ^-6 g / L, and the supernatant relative to the preparation amount The present amount of is 0.016%. Subsequently, after 170 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, drying under reduced pressure was performed at 45 ° C. A prepolymerized catalyst was obtained containing 2.0 g of polypropylene per gram of catalyst.

(5) Production of Propylene-Ethylene Block Copolymer (F) First Polymerization Step: Production of Component (F1) Consisting of Propylene-Ethylene Random Copolymer Horizontal Reactor with Agitated Blade (L / D = 6, Content The product (100 liters) was sufficiently dried and the inside was thoroughly replaced with nitrogen gas. In the presence of a polypropylene powder bed, while stirring at a rotation speed of 30 rpm, 0.444 g / hour of triisobutylaluminum (as a solid catalyst amount excluding the prepolymerized powder) prepared as the prepolymerized catalyst in the upstream part of the reactor It was continuously fed at 15.0 mmol / hour. The monomer mixture gas is continuously reacted such that the reactor temperature is kept at 65 ° C., the pressure is kept at 2.00 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.058 and the hydrogen concentration is 150 ppm. The mixture was circulated in the vessel to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the powder bed volume in the reactor became constant. At this time, the amount of polymer withdrawn at the steady state was 10.0 kg / hour.
The analysis of the propylene-ethylene random copolymer obtained in the first polymerization step revealed that the ethylene content was 1.7% by weight.

Second polymerization step: Production of component (F2) comprising propylene-ethylene random copolymer Propylene extracted from the first polymerization step in a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade The ethylene copolymer was fed continuously. While stirring at a rotational speed of 25 rpm, keep the temperature of the reactor at 70 ° C. and the pressure at 1.88 MPaG, and so that the ethylene / propylene molar ratio in the gas phase in the reactor is 0.450 and the hydrogen concentration is 300 ppm. The monomer mixed gas was continuously flowed into the reactor to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously withdrawn from the downstream part of the reactor so that the powder bed volume in the reactor became constant. At this time, oxygen was supplied as an activity inhibitor so that the polymer withdrawal amount was 18.0 kg / hour, and the polymerization reaction amount in the second polymerization step was controlled.
When the propylene ethylene block copolymer (F-4) obtained in this way was analyzed, MFR was 7.0 g / 10 minutes and ethylene content was 6.3 weight%.

  The results of polymer analysis of the propylene-ethylene block copolymers (F-1) to (F-4) are shown in Table 7-2.

Pelletization of propylene-ethylene block copolymer (F) With respect to 100 parts by weight of each propylene-ethylene block copolymer (F) obtained in Production Examples F-1 to F-4, (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] 0.05 parts by weight of methane, 0.10 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, calcium stearate 0.05 parts by weight of each is mixed with a tumbler and homogenized, and the obtained mixture is melt-kneaded at 230 ° C. with a 35 mm diameter twin screw extruder to obtain propylene-ethylene block copolymers F-1 to F-4. Each pellet was obtained.

Example 6-1
In the production of the decorative film of Example 1-1, the polypropylene-based resin (A-1) of the seal layer (I) is changed to a propylene-ethylene block copolymer (F-1) to obtain a three-dimensional heat of decoration The molding and evaluation were performed in the same manner as in Example 1-1 except that molding was performed immediately after the spring back phenomenon ended in molding (that is, the heating time after spring back was 0 seconds). The evaluation results are shown in Table 8-1.

Example 6-2
Example 6-6 in the production of the decorative film of Example 6-1, except that the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-2) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 8-1.

Example 6-3
Example 6- 6 except that in the production of the decorative film of Example 6-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-3). It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 8-1.

Example 6-4
Example 6 Example 6 was repeated except that the polypropylene resin (B-1-1) of the layer (II) was changed to a polypropylene resin (B-1-4) in the production of the decorative film of Example 6-1. It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 8-1.

Example 6-5
In the production of the decorative film of Example 6-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the evaluation of the weather resistance is irradiated. Molding and evaluation were performed in the same manner as in Example 6-1 except that the process was performed under the condition of time (2). The evaluation results are shown in Table 8-1.

Example 6-6
Example 6-6 in the manufacture of the decorative film of Example 6-1, except that the polypropylene resin (B-1-1) of the layer (II) is changed to the polypropylene resin (B-2-1) It shape | molded and evaluated similarly to 1. The evaluation results are shown in Table 8-1.

Example 6-7
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the seal layer (I) was changed to a propylene-ethylene block copolymer (F-2) Molding and evaluation were performed in the same manner as in Example 6-1 except for the following. The evaluation results are shown in Table 8-1.

Example 6-8
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the seal layer (I) was changed to a propylene-ethylene block copolymer (F-3) Molding and evaluation were performed in the same manner as in Example 6-1 except for the following. The evaluation results are shown in Table 8-1.

Examples 6-9
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the seal layer (I) was changed to a propylene-ethylene block copolymer (F-4) Molding and evaluation were performed in the same manner as in Example 6-1 except for the following. The evaluation results are shown in Table 8-1.

Example 6-10
-Manufacture of a decoration film Extruder 1 for seal layer (I) of diameter 30 mm (diameter), Extruder 2 for layer (II) of diameter 40 mm (diameter), and surface decoration of diameter 30 mm (diameter) A three-kind three-layer T-die with a lip opening degree of 0.8 mm and a die width of 400 mm, to which an extruder 3 for layer (III) was connected, was used. Propylene-ethylene block copolymer (F-1) for extruder 1 for seal layer (I), polypropylene resin (B-1-1) for extruder 2 for layer (II), surface decoration Polypropylene resin (H-1-1) is put into each of extruder (3) for layer (III), resin temperature 240 ° C., discharge amount of extruder 1 4 kg / h, discharge amount of extruder 2 Melt extrusion was performed under the conditions of 8 kg / h and a discharge amount of extruder 3 of 4 kg / h.

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

  Using the unstretched film obtained in the above-mentioned decorative film production, three-dimensional decorative thermoforming was performed in the same manner as in Example 6-1, and evaluation was performed. The evaluation results are shown in Table 8-2.

Example 6-11
In the production of the decorative film of Example 6-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-6), and the evaluation of weatherability is irradiated. Molding and evaluation were performed in the same manner as in Example 6-1 except that the process was performed under the condition of time (3). The evaluation results are shown in Table 8-2.

Example 6-12
In the three-dimensional decorative thermoforming of Example 6-1, molding and evaluation were performed in the same manner as in Example 6-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-2). The evaluation results are shown in Table 8-2.

Example 6-13
In the three-dimensional decorative thermoforming of Example 6-1, molding and evaluation were performed in the same manner as in Example 6-1 except that the substrate was changed to an injection-molded article made of a polypropylene resin (Z-3). The evaluation results are shown in Table 8-2.

Comparative Example 6-1
Example 6-1 with the exception of changing the polypropylene resin (B-1-1) of the layer (II) to a polypropylene resin (B-1) in the production of the decorative film of the example 6-1 It molded similarly and evaluated. The evaluation results are shown in Table 8-2.

Comparative Example 6-2
Example 6-1 with the exception of changing the polypropylene resin (B-1-1) of the layer (II) to the polypropylene resin (H-1) in the production of the decorative film of the example 6-1 It molded similarly and evaluated. The evaluation results are shown in Table 8-2.

Comparative Example 6-3
Example 6 except that the propylene-ethylene block copolymer (F-1) of the seal layer (I) is changed to a polypropylene resin (B-1) in the production of the decorative film of Example 6-1 It shape | molded and evaluated like -1. The evaluation results are shown in Table 8-2.

Comparative Example 6-4
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) of the seal layer (I) is changed to a polypropylene resin (B-1), and the three-dimensional decorative heat is obtained Molding and evaluation were performed in the same manner as in Example 6-1 except that molding was performed 40 seconds after the end of the spring back phenomenon in molding. The evaluation results are shown in Table 8-2.

Comparative Example 6-5
In the production of the decorative film of Example 6-1, the polypropylene resin (B-1-1) of the layer (II) is changed to a polypropylene resin (B-1-5), and the sealing layer (I) is obtained Propylene-ethylene block copolymer (F-1) is changed to polypropylene resin (B-1), and molding is performed 40 seconds after the end of springback phenomenon in three-dimensional decorative thermoforming, and weather resistance The molding and evaluation were performed in the same manner as in Example 6-1 except that the evaluation of was performed under the condition of the irradiation time (2). The evaluation results are shown in Table 8-2.

  The decorative molded article obtained from the decorative film of Examples 6-1 to 6-13 contains a hindered amine light stabilizer and / or a UV absorber in one of the layers, and the seal layer (I) The melt flow rate (MFR (A)) of the polypropylene resin (A) in the solution exceeds 0.5 g / 10 min, and the melt flow rate (MFR (B) of the polypropylene resin (B) in the layer (II) ) Is smaller than MFR (A), and further, the polypropylene-based resin (A) is a propylene-ethylene block copolymer (F), and in the copolymer (F), (f1) melting peak temperature (Tm (Tm (T)) F)) at 110 to 170 ° C., (f2) 5-97% by weight of component (F1) consisting of propylene homopolymer or propylene-ethylene random copolymer, ethylene content being higher than that of component (F1) There propylene - to containing components comprising an ethylene random copolymer (F2) from 3 to 95 wt%, uneven contact is excellent in thermoformability without adhesion was good. Moreover, since it was decoration heat-forming for a short time, volatilization of a hindered amine light stabilizer and / or a ultraviolet absorber can be reduced, and it was excellent in the weather resistance also after thermoforming. Furthermore, the obtained molded product was excellent in recyclability.

  On the other hand, the decorative film of Comparative Example 6-1 in which none of the layers contained the hindered amine light stabilizer and / or the ultraviolet light absorber was inferior in the weather resistance of the decorative film. In the decorative film of Comparative Example 6-2 in which MFR (B) is larger than MFR (A), the decorative film was drawn down during three-dimensional decorative thermoforming, and the thermoformability was inferior. The resulting decorative molded product was inferior in appearance, and no evaluation of adhesive strength and weatherability was conducted. In Comparative Example 6-3 in which MFR (A) is 0.5 g / 10 min or less and the hindered amine light stabilizer is blended in layer (II), when molding is performed immediately after the end of the spring back phenomenon, the third order Good adhesion was not expressed because the heating time of the primary decoration molding was short. In Comparative Example 6-4 in which molding was performed 40 seconds after the end of the spring back phenomenon using the same decorative film as in Comparative Example 6-3, the heating time of the three-dimensional decorative molding was extended by: Although the adhesiveness was developed, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior compared to Example 6-1. In Comparative Example 6-5 where MFR (A) is 0.5 g / 10 min or less and the ultraviolet light absorber is blended in layer (II), the adhesiveness is improved by prolonging the heating time of the three-dimensional decoration molding. Although it developed, the added ultraviolet absorber volatilized, and the weather resistance was inferior as compared with Example 6-5.

  The decorative film of the present invention and the method for producing a decorative molded article using the same can be used for a three-dimensional decorative molded article and its production.

1 Decorative film 2 layers (II)
3 Seal layer (I)
4 surface decoration layer (III)
5 Resin moldings (deterioration target, substrate)
6 Decoration molding 11 upper chamber box 12 lower chamber box 13 jig 14 table 15 heater

Claims (17)

A decorative film containing a hindered amine light stabilizer and / or an ultraviolet light absorber for adhering on a resin molded body by thermoforming, the decorative film containing a polypropylene resin (A) A sealing layer (I) and a layer (II) containing a polypropylene resin (B),
The said polypropylene resin (A) satisfy | fills the following requirements (a1), and the said polypropylene resin (B) is a decorative film which satisfy | fills the following requirements (b1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 0.5 g / 10 min.
(B1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (B)) and MFR (A) satisfy the relational expression (b-1).
MFR (B) <MFR (A) formula (b-1) The decorative film according to claim 1, wherein the polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the polypropylene resin (B) further satisfies the following requirement (b2).
(A2) A metallocene catalyst based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B2) The melting peak temperature (Tm (B)) and Tm (A) satisfy the relational expression (b-2).
Tm (B)> Tm (A) Formula (b-2) The decorative film according to claim 1 or 2, wherein the polypropylene resin (A) further satisfies the following requirement (a5), and the polypropylene resin (B) further satisfies the following requirement (b3).
(A5) The crystallization temperature (Tc (A)) is less than 100 ° C.
(B3) The crystallization temperature (Tc (B)) and Tc (A) satisfy the relational expression (b-3).
Tc (B)> Tc (A) .. Formula (b-3) The seal layer (I) contains a resin composition (X3) in which the weight ratio of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) is 97: 3 to 5:95,
The decorative film according to any one of claims 1 to 3, wherein the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3).
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min. The seal layer (I) contains a resin composition (X4) in which the weight ratio of the polypropylene resin (A) to the thermoplastic elastomer (D) is 97: 3 to 5:95,
The decorative film according to any one of claims 1 to 3, wherein the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d4).
(D1) A thermoplastic elastomer comprising as a main component at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile modulus of elasticity is smaller than that of the polypropylene resin (A). The seal layer (I) contains a resin composition (X5) in which the weight ratio of the polypropylene resin (A) to the thermoplastic resin (E) is 97: 3 to 5:95,
The decorative film according to any one of claims 1 to 3, wherein the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X5) satisfies the following requirement (x1).
(E1) At least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group is contained.
(X1) The isothermal crystallization time (t (X5)) (seconds) of the resin composition (X5) determined by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) .. Formula (x-1)
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t (X 5) It is isothermal crystallization time (second) of the resin composition (X5) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A).) The decorative film according to any one of claims 1 to 6, wherein the polypropylene resin (A) is a propylene-ethylene block copolymer (F) satisfying the following requirements (f1) and (f2).
(F1) The melting peak temperature (Tm (F)) is 110 to 170 ° C.
(F2) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, a component consisting of a propylene-ethylene random copolymer having an ethylene content higher than that of the component (F1) 3 to 95% by weight of F2).   The decorative film according to any one of claims 1 to 6, wherein the polypropylene resin (A) is a propylene-α-olefin copolymer.   The decorative film according to any one of claims 2 to 8, wherein the Tm (A) is 140 ° C or less. The ethylene-α-olefin random copolymer (C) according to any one of claims 4 and 7 to 9, further satisfying at least one of the following requirements (c4) and (c5): Decorative film.
(C4) The melting peak temperature (Tm (C)) is 30 to 130 ° C.
(C5) A random copolymer of ethylene and an α-olefin of 3 to 20 carbon atoms.   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 having an ethylene content of less than 50 wt% The decorative film according to any one of claims 5 and 7 to 9, which is at least one copolymer selected from the group consisting of a copolymer, a propylene-butene copolymer, and a butene homopolymer. . The decorative film according to any one of claims 5, 7 to 9 and 11, wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(D5) The melting peak temperature (Tm (D)) is 30 to 170 ° C.   The decorative film according to any one of claims 6 to 9, wherein the thermoplastic resin (E) is a styrene-based elastomer.   The decorative film according to any one of claims 6 to 9, wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin. The decoration according to any one of claims 7 and 9 to 14, wherein the propylene-ethylene block copolymer (F) further satisfies at least one of the following requirements (f3) to (f5): the film.
(F3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.
(F4) The ethylene content of the component (F1) is in the range of 0 to 6% by weight.
(F5) The ethylene content of the component (F2) is in the range of 5 to 90% by weight. Preparing the decorative film according to any one of claims 1 to 15,
Preparing a resin molding,
Setting the resin molded body and the decorative film in a depressurizable chamber box;
Decompressing the inside of the chamber box;
Heat-softening the decorative film;
A method for producing a decorated formed body, comprising the steps of: pressing the decorative film against the resin molded body; and returning or pressurizing the interior of the chamber box that has been depressurized to atmospheric pressure.   The method for producing a decorated formed body according to claim 16, wherein the resin formed body is made of a propylene-based resin composition.