JP7192545B2 - DECORATION FILM AND METHOD FOR MANUFACTURING DECORATION MOLDED PRODUCT USING IT - Google Patents

Description

The present invention relates to a decorative film to be adhered onto a resin molded article by thermoforming, and a method for producing a decorated molded article using the decorative film. Specifically, it is a decorative film that can suppress wrinkles and breakage of the film during thermoforming and can exhibit sufficient adhesive strength to the resin molded body, and is to be attached to the resin molded body by thermoforming. The present invention relates to a method for manufacturing a decorative molded article using the decorative film. Furthermore, it has excellent thermoformability without uneven contact, good weather resistance and adhesion, suppresses deterioration of weather resistance before and after thermoforming, and has excellent recyclability, and is used for three-dimensional decorative thermoforming. The present invention relates to a decorative film and a method for producing a decorative molded article using the decorative film.

In recent years, demand for decoration techniques to replace painting has increased due to demands for reduction of VOCs (volatile organic compounds), etc., and various decoration techniques have been proposed.

Among them, a technique has been proposed in which a decorative film (decorative sheet) instead of a coating film is applied to a molded product by vacuum pressure forming or vacuum forming to form a decorative molded product in which the decorative film and the molded product are integrated ( See, for example, Patent Document 1), which has recently attracted particular attention.

Decoration molding by vacuum pressure molding and vacuum molding has a greater degree of freedom in shape than other decoration molding represented by insert molding. The appearance is excellent because it does not occur, and furthermore, it can be thermoformed at a relatively low temperature and low pressure. It has the advantage of excellent reproducibility.

In such decorative molding by vacuum pressure forming and vacuum forming, when the decorative film and the molded article are adhered, the decorative film may be broken or wrinkled, or the adhesion between the decorative film and the molded article may occur. There was a problem that sufficient strength could not be obtained. Also, the use of adhesives, tackifiers, etc. has been proposed as a layer for improving the adhesive strength, but they are expensive, the layer structure is extremely complicated, and the solvent resistance and heat resistance are insufficient. etc.

To solve this problem, a decorative film including an adhesive layer containing a polypropylene resin is applied to a substrate (molded body) made of a polypropylene resin, so that the decorative film and the molded body are heat-sealed. has been proposed (see Patent Documents 2 and 3, for example). The inventions disclosed in Patent Documents 2 and 3 use a polypropylene-based resin as the adhesive layer of the decorative film. It is necessary to provide a layer of resin, polyurethane resin, polycarbonate or the like. By combining different kinds of raw materials in this way, thermoformability such as drawdown property is expressed, and it is possible to ensure thermoformability in a decorative film made of a polypropylene-based resin that does not contain these different kinds of raw materials. Can not. As a result, holes, wrinkles, air entrainment, and film rupture occurred on the surface of the molded product to which the decorative film was adhered, making it impossible to obtain a decorative molded product with excellent appearance. . In addition, when polyurethane resin is included as a different raw material, polyurethane resin, which is a thermosetting resin, does not melt when heated, so it is easy to maintain the shape of the film and greatly improves thermoformability, but there is a problem that recyclability is extremely low. there were.

That is, the decorative films described in Patent Documents 2 and 3 contain different raw materials in order to ensure thermoformability such as adhesiveness and appearance, have a complicated layer structure, and require many steps for their production. Another problem is that it is difficult to recycle decorative films in which different kinds of raw materials are combined.

Automobile parts, home appliance parts and building material parts include polyester resins, polyamide resins, polyimide resins, polystyrene resins, acrylic resins, polyvinyl alcohol resins, polycarbonate resins, ABS resins, urethane resins, melamine resins and polyphenylene ether resins. Resin moldings made of polar resin materials are often used. Since these polar resin materials are inferior in water resistance and chemical resistance, it is expected to improve the water resistance and chemical resistance by adhering a decorative film.

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

Hindered amine light stabilizers and UV absorbers are sometimes added to impart weather resistance to the decorative film. However, decorative films containing such hindered amine light stabilizers and UV absorbers have a problem that their weather resistance is significantly impaired after three-dimensional decorative molding.

Conventional technologies have yet to achieve decorative films made from propylene-based resins that are easy to recycle, have both excellent adhesiveness and appearance, and exhibit minimal deterioration in weather resistance even after decorative molding. No. In view of the above-mentioned problems, the problem of the present invention is to provide an excellent thermoformability without contact unevenness, good weather resistance and adhesive strength, suppressed deterioration of weather resistance before and after thermoforming, and excellent recyclability. , to provide a decorative film that can be used for three-dimensional decorative thermoforming and a method for producing a decorative molded article using the same.

In three-dimensional decorative thermoforming, it is necessary that the surface of the molded body and the film are sufficiently softened or melted in order to adhere the solid decorative film to the solid resin molded body. Therefore, it is important to apply heat necessary for softening or melting the surface of the molded article and the film, or to use a molded article and film that are easily softened or melted. On the other hand, if the film is heated too much, the viscosity of the film will decrease, and the film will break or run wild due to the push-up of the molded product in the three-dimensional decoration thermoforming process and the inflow of air when returning the vacuum chamber to atmospheric pressure. It leads to poor appearance. The inventors of the present invention focused on the mechanism that causes the above-described poor appearance and, as a result, found that a decorative film containing a layer made of a specific polypropylene-based resin could solve the above-described problems.
Furthermore, it was found that the hindered amine light stabilizer and ultraviolet absorber added to the resin to impart weather resistance volatilized significantly during the process of heating the decorative film under vacuum conditions for the decorative molding. rice field. The present inventors have found that by including a sealing layer with good adhesiveness, it is possible to perform decorative molding at a low temperature in a short period of time, and decorative molding is performed before the hindered amine light stabilizer and ultraviolet absorber volatilize. The inventors have found that the deterioration of weather resistance can be suppressed by completing the process, and have completed the present invention.

That is, the present invention includes the following.

(1) A decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber for adhering to a resin molded article by thermoforming, the decorative film comprising a polypropylene resin (A) Including a layer (II) containing a resin composition (B') containing a sealing layer (I) and a polypropylene resin (B) containing,
A decorative film in which the polypropylene-based resin (A) satisfies the following requirement (a1), and the resin composition (B') satisfies the following requirements (b1) and (b2).
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 min.
(b1) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 40 g/10 minutes or less.
(b2) The strain hardening degree λ is 1.1 or more.

(2) The polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the resin composition (B') further satisfies the following requirement (b3), according to (1) decorative film.
(a2) Metallocene-catalyzed 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.
(b3) The melting peak temperature (Tm(B')) and Tm(A) satisfy the relational expression (b-3).
Tm(B')>Tm(A) Formula (b-3)

(3) The sealing layer (I) is a resin composition (X3) in which the weight ratio of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95. including
The decorative film according to (1) or (2), wherein the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3).
(c1) Ethylene content [E(C)] is 65% by weight or more.
(c2) 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 minutes.

(4) The seal layer (I) contains a resin composition (X4) in which the weight ratio of the polypropylene resin (A) and the thermoplastic elastomer (D) is 97:3 to 5:95,
The decorative film according to (1) or (2), wherein the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d4).
(d1) A thermoplastic elastomer containing at least one of propylene and butene as a main component.
(d2) 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 minutes.
(d4) The tensile elastic modulus is smaller than the tensile elastic modulus of the polypropylene-based resin (A).

(5) The seal layer (I) contains a resin composition (X5) in which the weight ratio of the polypropylene resin (A) and the thermoplastic resin (E) is 97:3 to 5:95,
The decorative film according to (1) or (2), wherein the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X5) satisfies the following requirement (x1).
(e1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group;
(x1) The isothermal crystallization time (t(X5)) (seconds) obtained by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t(X5)≧1.5×t(A) Expression (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 initiation temperature of the polypropylene resin (A), and t ( X5) is the isothermal crystallization time (seconds) of the resin composition (X5) measured at a temperature 10°C higher than the crystallization initiation temperature of the polypropylene resin (A).)

(6) Any one of (1) and (3) to (5), wherein the polypropylene-based resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following requirements (f1) and (f2): 1. The decorative film according to 1.
(f1) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, and a component (F1) consisting of a propylene-ethylene random copolymer having a higher ethylene content than the component (F1) F2) is contained in an amount of 3 to 95% by weight.
(f2) Melting peak temperature (Tm(F)) is 110 to 170°C.

(7) A decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber for adhering to a resin molded product by thermoforming, the decorative film comprising a polyolefin adhesive resin (G) and a layer (II) containing a resin composition (B') containing a sealing layer (I) containing a polypropylene resin (B),
A decorative film in which the polyolefin adhesive resin (G) satisfies the following requirements (g1) and (g2), and the resin composition (B') satisfies the following requirements (b1) and (b2).
(g1) A polyolefin resin having a polar functional group containing at least one heteroatom.
(g2) Melt flow rate (230° C., 2.16 kg load) (MFR(G)) is 100 g/10 minutes or less.
(b1) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 40 g/10 minutes or less.
(b2) The strain hardening degree λ is 1.1 or more.

(8) The decorative film according to any one of (1) to (7), wherein the resin composition (B') satisfies the following requirements (b1') and (b2').
(b1′) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 20 g/10 minutes or less.
(b2′) The strain hardening degree λ is 1.8 or more.

(9) The decorative film according to any one of (1) to (7), wherein the resin composition (B') satisfies the following requirements (b1'') and (b2'').
(b1″) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 12 g/10 minutes or less.
(b2'') The strain hardening degree λ is 2.3 or more.

(10) The decorative film according to any one of (1) to (9), wherein the polypropylene resin (B) is a polypropylene resin (BL) having a long-chain branched structure.

(11) The decorative film according to (10), wherein the polypropylene-based resin (BL) is a low-gel polypropylene-based resin produced by a method other than a cross-linking method.

(12) The decorative film according to any one of (1) to (5) and (8) to (11), wherein the polypropylene resin (A) is a propylene/α-olefin copolymer.

(13) The decorative film according to any one of (1) to (5) and (8) to (12), wherein the Tm(A) is 140°C or less.

(14) The decorative film according to (3), wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4).
(c4) Melting peak temperature (Tm(C)) is 30 to 130°C.

(15) The decorative film according to (3) or (14), wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c5).
(c5) A random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

(16) The thermoplastic elastomer (D) is a propylene-ethylene copolymer with an ethylene content of less than 50% by weight, a butene-ethylene copolymer with an ethylene content of less than 50% by weight, or an ethylene content of 50% by weight. The decorative film according to (4), which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer, which is less than.

(17) The decorative film according to (4) or (16), wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(d5) The melting peak temperature (Tm(D)) is 30-170°C.

(18) The decorative film according to (5), wherein the thermoplastic resin (E) is a styrene elastomer.

(19) The decorative film according to (5), wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin.

(20) The decorative film according to (6), wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f3).
(f3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.

(21) The decorative film according to (6) or (20), wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f4).
(f4) The ethylene content of component (F1) is in the range of 0 to 6% by weight.

(22) The decorative film according to (6), (20) or (21), wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f5).
(f5) The ethylene content of component (F2) is in the range of 5 to 90% by weight.

(23) preparing the decorative film according to any one of (1) to (22); preparing a resin molded body; a step of setting a film, a step of reducing the pressure in the chamber box, a step of heat softening the decorative film, a step of pressing the heat-softened decorative film against the resin molding, and a step of depressurizing the chamber box A method for manufacturing a decorative molded article including a step of returning to atmospheric pressure or pressurizing.

(24) The method for producing a decorated molded article according to (23), wherein the resin molded article is made of a propylene-based resin composition.

(25) The decorative film is the decorative film according to any one of (7) to (11), and the resin molding is polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin. , polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, polyphenylene ether resin, and a polar resin material containing at least one selected from composite materials thereof. manufacturing method.

According to the present invention, there is no contact unevenness, excellent thermoformability, good weather resistance and adhesion, suppression of deterioration in weather resistance before and after thermoforming, and excellent recyclability, three-dimensional decorative heat It is possible to provide a decorative film that can be used for molding and a method for producing a decorative molded article using the same.

FIGS. 1A(a) to 1A(c) are cross-sectional schematic diagrams illustrating embodiments of a decorative molded body in which the decorative film of the present invention is adhered to a resin molded body. This is an example with a different configuration. FIGS. 1B(a) to 1B(c) are diagrams showing examples of the layer structure of the decorative film of the present invention. FIG. 2 is a schematic cross-sectional view for explaining the outline of an apparatus used in the method for producing a decorative molded article of the present invention. FIG. 3 is a schematic cross-sectional view for explaining how the resin molding and the decorative film are set in the apparatus of FIG. FIG. 4 is a schematic cross-sectional view illustrating how the inside of the apparatus of FIG. 2 is heated and decompressed. 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. 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 the edge of the unnecessary decorative film is trimmed in the obtained decorative molded article.

As used herein, a decorative film refers to a film for decorating a molded article. Decorative molding refers to molding in which a decorative film and a molded body are adhered together. Three-dimensional decorative thermoforming is a process of adhering a decorative film to a molded body, and includes a step of thermoforming the decorative film along the adhering surface of the molded body and simultaneously adhering it, In this step, thermoforming is performed under reduced pressure (vacuum) in order to prevent air from being entrained between the decorative film and the molded article, the heated decorative film is adhered to the molded article, and pressure is applied. It refers to molding, which is the process of bringing into close contact by releasing (pressurizing). In addition, "~" indicating a numerical range is used to include the numerical values described before and after it as a lower limit and an upper limit.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments 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-based light stabilizer and/or an ultraviolet absorber to be adhered onto a resin molding by thermoforming, and the decorative film is a polypropylene-based The sealing layer (I) containing the resin (A) and the layer (II) containing the resin composition (B') containing the polypropylene resin (B) are included, and the polypropylene resin (A) satisfies the following requirements (a1 ), and the resin composition (B′) satisfies the following requirements (b1) and (b2).
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 min.
(b1) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 40 g/10 minutes or less.
(b2) The strain hardening degree λ is 1.1 or more.

The decorative film of the present invention uses a layer (II) containing a resin composition (B') containing a polypropylene resin (B) having a specific melt flow rate (MFR) and a specific strain hardness, Even if the thermosetting resin layer is not included, it is possible to obtain a decorated molded article having excellent thermoformability during three-dimensional decorative thermoforming and a good product appearance.
Furthermore, the decorative film contains a hindered amine light stabilizer and / or an ultraviolet absorber, and a seal layer (adhering layer) (I) containing a polypropylene resin having a specific melt flow rate (MFR) By including it, it is possible to attach it to the resin molding (substrate) in a short heating time, so that the decorative molding is completed before the added hindered amine light stabilizer and / or ultraviolet absorber volatilizes, and the weather resistance is improved. It is possible to obtain a decorative molded article with high weather resistance by suppressing deterioration of properties.
Depending on the structure of the sealing layer (I), a decorative film can be attached to a substrate having polarity, and a decorative molded article produced from a substrate made of a decorative film and a polar resin material is particularly water resistant. and excellent chemical resistance.

According to the method for producing a decorative molded article of the present invention, there is no hole or wrinkle on the surface of the molded article, there is no entrainment of air between the decorative film and the resin molded article, and the deterioration of weather resistance is suppressed, resulting in a beautiful decoration. A molded body can be obtained. Furthermore, the decorative molded article obtained in this manner has the decorative film composed of the polypropylene resin (A) and the polypropylene resin (B), and does not or does not contain a thermosetting resin layer. Since it does not need to be removed, there is little deterioration in appearance and performance during recycling, and it is highly recyclable.

[Hindered amine light stabilizer and UV absorber]
In this specification, a hindered amine light stabilizer and an ultraviolet absorber (hereinafter both may be collectively referred to as a "weather resistant agent") are materials that can improve the weather resistance of a resin or the like by being blended into the resin. is.
The weathering agent tends to volatilize under decorative molding conditions, i.e., heating under vacuum. can be completed, and deterioration of weather resistance can be suppressed.

Specific examples of hindered amine light stabilizers used in the present invention include 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-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-tetraoxaspiro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxy carbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,5,8,12-tetrakis[4,6-bis{N-(2,2 ,6,6-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-tetramethyl Chill-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-butane tetracarboxylate, 3,9-bis(1,1-dimethyl-2-(tris(2 , 2,6,6-tetramethyl-N-oxylpiperidyl-4-oxycarbonyl)butylcarbonyloxy)ethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane and the like. Among these, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4diyl][(2,2,6 ,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-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, Tinuvin770 (registered trademark), Tinuvin765 (registered trademark) and Chimassorb944 (registered trademark) manufactured by BASF Corporation. and Tinuvin622 (registered trademark).

The hindered amine light stabilizers may be used alone or in appropriate 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 0.00 parts by weight, per 100 parts by weight of the resin constituting the layer containing the light stabilizer. .50 parts by weight. When the addition amount is within the above range, it is possible to obtain a decorative film and a decorative molded article with good weather resistance.

Specific examples of the ultraviolet 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. 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 (registered trademark) manufactured by ADEKA Corporation. registered trademark) and Tinuvin326 (registered trademark) manufactured by BASF Corporation.

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

The amount of the ultraviolet absorber to be added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50, per 100 parts by weight of the resin constituting the layer containing the ultraviolet absorber. weight part. When the addition amount is within the above range, it is possible to obtain a decorative film and a decorative molded article with good weather resistance.

Also, both the hindered amine light stabilizer and the ultraviolet absorber may be contained, in which case the total amount of both weathering agents is 0 per 100 parts by weight of the resin constituting the layer containing the weathering agent. A range of 0.002 to 2.00 parts by weight is preferred, more preferably 0.01 to 1.00 parts by weight.

A higher effect can be exhibited by setting the content ratio of the hindered amine light stabilizer and the ultraviolet absorber within a specific range. The mixing ratio of both weathering agents is preferably 1/5 to 5/1, more preferably 1/4 to 4/1, of hindered amine light stabilizer/ultraviolet absorber. By including both weathering agents, the synergistic effect of the weathering agents makes it possible to obtain a decorative film and a decorated molded article with better weather resistance.

The hindered amine light stabilizer and/or ultraviolet absorber may be contained in all layers of the decorative film, or may be contained only in the surface layer of the decorative film, which is the surface of the decorative molded product. good. In particular, since deterioration due to light progresses from the surface of the molded article, it is more preferable that the surface layer of the decorative film contains a weather resistant agent. For example, in the case of a two-layer decorative film consisting of a sealing layer (I) and a layer (II), it is preferred that the layer (II) contains a hindered amine light stabilizer and/or an ultraviolet absorber. Furthermore, when the surface decorative layer (III), which is an optional layer, is laminated on the layer (II), the surface decorative layer (III) contains a hindered amine light stabilizer and/or an ultraviolet absorber. It preferably contains

<Layer (II)>
The layer (II) contained in the decorative film in the present invention contains a resin composition (B') containing a polypropylene-based resin (B), and the resin composition (B') is a requirement (b1) described later. It is characterized by having a specific melt flow rate (MFR (B')) that satisfies and a strain hardening degree in elongational viscosity measurement that satisfies the requirement (b2) described later.

By providing the layer (II), it is possible to suppress the occurrence of poor appearance due to film breakage or roughening during (three-dimensional decoration) thermoforming. As a result, the thermoformability of the decorative film is improved, so there is no need to include a thermosetting resin layer with excellent thermoformability, and recyclability can be improved.
Furthermore, by improving the moldability of the resin composition (B′) containing the polypropylene resin (B), it can be used as a decorative film with an extremely simple structure of lamination of the layer (II) and the seal layer (I). With such a configuration, it is possible to manufacture a decorative film by (co)extrusion.

[Resin composition (B') containing polypropylene resin (B)]
The decorative film includes a layer (II) containing a resin composition (B') containing a polypropylene resin (B). The layer (II) can be composed only of the polypropylene resin (B), can be composed of a plurality of polypropylene resins including the polypropylene resin (B), or can be composed of the polypropylene resin (B) and other It is also possible to compose with blends of polypropylene-based resins.

The resin composition (B') satisfies both requirements (b1) and (b2) described later, but when the resin composition (B') is composed only of the polypropylene-based resin (B), the polypropylene-based resin (B) satisfies the requirements (b1) and (b2). Further, when the resin composition (B') is composed of a blend of the polypropylene-based resin (B) and another polypropylene-based resin, in addition to the resin composition (B'), the polypropylene-based resin (B) also contains the requirements ( It is preferable to satisfy b1) and (b2). The blending of the polypropylene resin (B) and other polypropylene resins is not particularly limited, and may be pellet and/or powder mixing, melt blending, solution blending, or a combination thereof.

In the present invention, the resin composition (B') containing the polypropylene resin (B) cannot obtain sufficient molding stability if the viscosity is too low. Must have viscosity. In the present invention, melt flow rate (MFR) (230° C., 2.16 kg load) is defined as an index of this viscosity.

In this specification, the MFR (230° C., 2.16 kg load) of the resin composition (B′) containing the polypropylene resin (B) is defined as MFR (B′). MFR (B') satisfies the following requirement (b1), preferably satisfies requirement (b1'), and more preferably satisfies requirement (b1''). By setting the MFR (B') of the resin composition (B') to the following value or less, it is possible to obtain a decorative molded article having a good appearance.
(b1) MFR (B') is 40 g/10 minutes or less.
(b1') MFR (B') is 20 g/10 minutes or less.
(b1'') MFR (B') is 12 g/10 minutes or less.

Although the lower limit of MFR (B') of the resin composition (B') is not particularly limited, it is preferably 0.1 g/10 minutes or more, more preferably 0.3 g/10 minutes or more. By setting the MFR (B') to the above value or more, the formability of the decorative film is improved, and the appearance defects called sharkskin and interface roughness can be suppressed from occurring on the film surface.

In this specification, each MFR of the polypropylene-based resin and the resin composition was measured according to ISO 1133:1997 Conditions M under the conditions of 230° C. and 2.16 kg load. The unit is g/10 minutes.

The strain hardening degree λ of the resin composition (B') containing the polypropylene resin (B) satisfies the following requirement (b2), preferably satisfies the requirement (b2'), more preferably satisfies the requirement (b2'') meet. By setting the strain hardening degree of the resin composition (B′) to a value within the range below, it is possible to obtain a decorated molded product with good moldability during decorative thermoforming and good appearance.
(b2) The strain hardening degree λ is 1.1 or more.
(b2′) The strain hardening degree λ is 1.8 or more.
(b2'') The strain hardening degree λ is 2.3 or more.

Although the upper limit of the strain hardening degree of the resin composition (B') is not particularly limited, it is preferably 50 or less, more preferably 20 or less. By setting the strain hardening degree to a value within the above range, the appearance of the decorative film can be improved.

The degree of strain hardening of the resin composition (B') is obtained based on strain hardening measurement in elongational viscosity measurement. Regarding the strain hardening property (nonlinearity) of elongational viscosity, refer to "Lecture/Rheology" edited by Japan Rheology Society, Kobunshi Publishing Association, 1992, pp. 221-222, and in this specification, the strain hardening degree λ shall be calculated by a method according to the method of determination shown in Figures 7-20 of the same document, and the shear viscosity value Using η ^* (0.01) and ηe (3.5) as the elongational viscosity value, the strain hardening degree λ is defined by the following formula (b-1).
λ=ηe(3.5)/{3×η ^* (0.01)} Expression (b-1)
In the above formula (b-1), η ^* (0.01) is the complex viscosity at a measurement temperature of 180 ° C. and an angular frequency of ω = 0.01 rad / s [unit: Pa ·s], and the complex viscosity η ^* is calculated from the complex elastic modulus G ^* [unit: Pa] and the angular frequency ω by η ^* =G ^* /ω. ηe(3.5) is the elongational viscosity measured by elongational viscosity measurement at a measurement temperature of 180° C., a strain rate of 1.0 s ⁻¹ and a strain amount of 3.5.

Usually, the data obtained by these viscoelasticity measurements are collections of numerical values such as elastic modulus and viscosity at discrete frequencies or measurement time intervals. Therefore, when the measurement is performed with an apparatus and conditions different from those used in the present invention, the complex viscosity η ^* (0.01) at the angular frequency ω = 0.01 and the elongation at strain 3.5 will not necessarily There may be cases where there is no data for the viscosity ηe (3.5), but in that case, it is impossible to estimate the value by performing interpolation such as linear interpolation or spline interpolation using the data before and after that. forgiven. When performing interpolation, it is common practice to use logarithmic scales for stress and time.

At this time, if the sample does not have strain hardening (nonlinearity) in elongational viscosity, the strain hardening degree λ exhibits a value of about 1 (for example, 0.9 or more and less than 1.1) or a smaller value, strain hardening (nonlinear The value of the strain hardening degree λ increases as the strength) increases.

Ordinary crystalline polypropylene is a linear polymer and usually does not have strain hardening properties. On the other hand, the polypropylene-based resin (B) used in the present invention is preferably a polypropylene-based resin (BL) having a long-chain branched structure, whereby the resin composition containing the polypropylene-based resin (B) The product (B') can exhibit better strain hardening properties.

The long-chain branched structure in the present invention is a branched molecular chain having a carbon skeleton (main chain of the branch) that constitutes the branch and has several tens or more carbon atoms and a molecular weight of several hundred or more in order to express strain hardening properties. Say structure. This long-chain branched structure is distinguished from short-chain branches formed by copolymerization with α-olefins such as 1-butene.

Methods for introducing a long-chain branched structure into a polypropylene-based resin include a method of irradiating a polypropylene having no long-chain branched structure with high-energy ionizing radiation (Japanese Patent Laid-Open No. 62-121704), and a method of long-chain branching. A method of reacting an organic peroxide with polypropylene having no structure (Japanese Patent Publication No. 2001-524565), or producing a macromonomer having a terminal unsaturated bond using a metallocene catalyst having a specific structure, There is a method of forming a long-chain branched structure by copolymerizing it with propylene (Japanese Patent Publication No. 2001-525460). Curing degree can be greatly improved.

The polypropylene-based resin (BL) having a long-chain branched structure is not particularly limited as long as it has a long-chain branched structure, but it must be a polypropylene-based resin produced by a method other than a cross-linking method. are preferred, and those obtained by a method using a macromer copolymerization method in which a long-chain branched structure is formed during polymerization are preferred. Examples of such methods include, for example, Japanese Patent Publication No. 2001-525460, Japanese Patent Publication No. 10-338717, Japanese Patent Publication No. 2002-523575, Japanese Patent Publication No. 2009-57542. Japanese Patent No. 05027353 and Japanese Patent Laid-Open No. 10-338717. In particular, the macromer copolymerization method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 is suitable for the present invention because it does not generate gels and allows obtaining a polypropylene resin containing long chain branches.

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

The branching index g' is known as a direct index for long-chain branched structures. A detailed description is given in "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983), and the definition of the branching index g' is as follows.
Branching index g′=[η]br/[η]lin
[η]br: Intrinsic viscosity of polymer (br) having a long-chain branched structure [η]lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br) As is clear from the above definition, the branching index g′ is If it takes a value smaller than 1, it is determined that a long-chain branched structure exists, and the value of the branching index g' decreases as the number of long-chain branched structures increases.

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

{analysis method}
In determining the absolute molecular weight (Mabs), the root mean square radius of gyration (Rg) obtained from the multi-angle laser light scattering detector (MALLS), and the intrinsic viscosity ([η]) obtained from the Viscometer, the data processing provided with MALLS was used. Using the software ASTRA (version 4.73.04), calculation is performed with reference to the following literature.
References:
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004)
3. Macromolecules, 33, 2424-2436 (2000)
4. Macromolecules, 33, 6945-6952 (2000)

In the decorative film of the present invention, if the polypropylene-based resin (B) contains a gel, the appearance of the film deteriorates. Therefore, it is preferable to use a resin composition (B') that does not contain a gel. In particular, the polypropylene-based resin (BL) having the above-mentioned long-chain branched structure, which is produced by a method other than a cross-linking method and is less gelled, is preferable. More preferred is one produced by a method of producing a macromonomer having an unsaturated bond and copolymerizing it with propylene to form a long-chain branched structure.
In particular, those satisfying the following branching index g′ at an absolute molecular weight Mabs of 1,000,000 of 0.3 or more and less than 1.0 are preferable, more preferably 0.55 or more and 0.98 or less, and still more preferably 0.55 or more and 0.98 or less. 75 or more and 0.96 or less, most preferably 0.78 or more and 0.95 or less.
In the present invention, the term "low gel content" means that the branching index g' of the polypropylene-based resin at an absolute molecular weight Mabs of 1,000,000 is within the above range. When the branching index g' is within this range, highly crosslinked components are not formed, and no or very little gel is formed. Does not deteriorate the appearance when the layer (II) containing comprises the surface of the product.

{ ¹³ C-NMR}
¹³ C-NMR can distinguish between short and long chain branched structures, as described above. Macromol. Chem. Phys. 2003, vol. 204, 1738, a summary of which is as follows.

A polypropylene-based resin having a long-chain branched structure has a specific branched structure as represented by the following structural formula (1). In Structural Formula (1), C _a , C _b and C _c represent the methylene carbons adjacent to the branch carbon, C _br represents the methine carbon at the base of the branched chain, and P ¹ , P ² and P ³ , indicates a propylene-based polymer residue.

The propylene-based polymer residues P ¹ , P ² , and P ³ may themselves contain a branched carbon (C _br ) different from the C _br described in Structural Formula (1). obtain.

Such branched structures are identified by ¹³ C-NMR analysis. The assignment of each peak is according to Macromolecules, Vol. 35, No. 10. 2002, pp. 3839-3842 can be referred to. That is, a total of three methylene carbons (C _a , C _b and C _c ) were observed, one each at 43.9-44.1 ppm, 44.5-44.7 ppm and 44.7-44.9 ppm, A methine carbon (C _br ) is observed at 31.5-31.7 ppm. The methine carbon observed at 31.5 to 31.7 ppm may hereinafter be abbreviated as branched methine carbon (C _br ).

The ¹³ C-NMR spectrum of a polypropylene-based resin having a long-chain branched structure is characterized by the observation that the three methylene carbons close to the branched methine carbon _Cbr are diastereotopically non-equivalently divided into three. is.

Such a branched chain assigned by ¹³ C-NMR indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the polypropylene-based resin, and the branch having 4 or less carbon atoms is a branched carbon Therefore, in the present invention, the presence or absence of a long-chain branched structure can be determined by confirming the peak of this branched methine carbon.
The method for measuring ¹³ C-NMR in the present invention is as follows.

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

In the ¹³ C-NMR spectrum of the polypropylene-based resin (BL) having a long-chain branched structure, the amount of long-chain branches quantified from the peak near 44 ppm is preferably 0.01/1000 total propylene or more, It is more preferably 0.03/1000 total propylene or more, still more preferably 0.05/1000 total propylene or more. If this value is too large, it may cause appearance defects such as gels and fish eyes. .30 pieces/1000 total propylene or less.

The polypropylene-based resin (BL) having such a long-chain branched structure is included in a resin composition (B') containing the polypropylene-based resin (B) in an amount sufficient to impart strain hardening properties. as long as it is The polypropylene resin (BL) having a long-chain branched structure is contained in an amount of preferably 1 to 100% by weight, more preferably 5% by weight or more, based on 100% by weight of the resin composition (B').

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

The polypropylene-based resin (B) in the present invention preferably has high crystallinity from the viewpoint of heat resistance, scratch resistance, and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene resin (B) is preferably 130° C. or higher, more preferably 140° C. or higher, still more preferably 140 to 170° C., even more preferably 145 to 170° C., even more preferably 150-168°C. The polypropylene resin (B) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, even if the melting point is high, if it contains a low-crystalline component, the scratch resistance and solvent resistance will decrease, so the polypropylene resin (B) has an ethylene content of 50 to 70% by weight. It is preferably free of copolymers.

The peak melting temperature (Tm(B')) of the polypropylene resin (B) in DSC measurement is preferably higher than the peak melting temperature (Tm(A)) of the polypropylene resin (A) in DSC measurement. That is, it is preferable to satisfy the following requirement (b3).
(b3) Tm(B') satisfies the following relational expression (b-3) with respect to Tm(A).
Tm(B′)>Tm(A) Formula (b-3)
Within the above range, the thermoformability is improved.

The resin composition (B′) containing the polypropylene resin (B) may contain additives including the hindered amine light stabilizer or ultraviolet absorber, fillers, colorants, other resin components, and the like. . At this time, the total amount of additives, fillers, colorants, other resin components, etc. is 50% by weight or less with respect to the resin composition (B') containing the polypropylene resin (B) including these. preferable.

When the decorative molded article of the present invention is molded as a colored molded article, it is sufficient to use the coloring agent only in the decorative film, so the use of an expensive coloring agent compared to the case of coloring the entire resin molded article. can be suppressed. In addition, it is possible to suppress changes in physical properties that accompany the addition of a colorant.

As additives, antioxidants, neutralizers, light stabilizers, ultraviolet absorbers, nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc., can be used in polypropylene resins. Various known additives can be blended.

Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, thio-based antioxidants, and the like. Examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate.

Examples of light stabilizers and ultraviolet absorbers include the aforementioned hindered amine light stabilizers and ultraviolet absorbers.

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 are aluminum pt-butylbenzoate, 2,2′-methylenebis(4,6-di-t-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 syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[ (4-Propylphenyl)methylene]-nonitol, rosin sodium salt and the like can be exemplified.

Examples of lubricants include higher fatty acid amides such as stearamide. Examples of antistatic agents include fatty acid partial esters such as glycerin fatty acid monoester. Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

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

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

Moreover, it can be colored to impart a design property, and various coloring agents such as inorganic pigments, organic pigments, and dyes can be used for coloring. In addition, it is also possible to use luster materials such as aluminum flakes, titanium oxide flakes, and (synthetic) mica.

The resin composition (B') containing the polypropylene resin (B) is obtained by melt-kneading the polypropylene resin and additives, fillers, other resin components, etc., and melt-kneading the polypropylene resin, additives, fillers, etc. It can be manufactured by a method of dry-blending other resin components into a product, a method of dry-blending a master batch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to polypropylene resin and other resin components. can.

<Seal layer (I)>
[1. Seal layer (I) containing polypropylene resin (A)]
The decorative film of the present invention includes a seal layer (I) containing a polypropylene-based resin (A) that satisfies requirement (a1) below.
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 minutes.
By including the seal layer (I) containing the polypropylene resin (A) on the surface to be adhered to the resin molded body (substrate), sufficient adhesion is achieved even when the film is heated for a short time during three-dimensional decorative thermoforming. Since strength is developed, molding can be completed before the weathering agent volatilizes, and deterioration of weather resistance can be suppressed.

The melt flow rate (230° C., 2.16 kg load) (MFR(A)) of the polypropylene resin (A) must exceed 2.0 g/10 min, preferably 3.0 g/10 min or more. , more preferably 4.0 g/10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming progresses sufficiently, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

The MFR of the polypropylene resin (A) and the resin composition containing the same was measured according to ISO 1133:1997 Conditions M under the conditions of 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

The polypropylene-based resin (A) includes various types of propylene-based polymers such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), propylene block copolymer (block polypropylene), Or a combination thereof can be selected. The polypropylene-based resin (A) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (A) preferably does not contain polymerized units derived from a polar group-containing monomer.

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

The polypropylene-based resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties. As a result, the crystallization temperature is also lowered, so the adhesiveness is good even with short-time heating in three-dimensional decorative molding.

In addition, the polypropylene resin (A) may contain additives including the hindered amine light stabilizer or UV absorber, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene-based resin composition) of a polypropylene-based resin, an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the polypropylene resin composition.

As additives, antioxidants, neutralizers, light stabilizers, ultraviolet absorbers, nucleating agents, antiblocking agents, lubricants, antistatic agents, metal deactivators, etc., can be used in polypropylene resins. Various known additives can be blended.

Examples of antioxidants include phenol-based antioxidants, phosphite-based antioxidants, thio-based antioxidants, and the like. Examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate.

Examples of light stabilizers and ultraviolet absorbers include the aforementioned hindered amine light stabilizers and ultraviolet absorbers.

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 are aluminum pt-butylbenzoate, 2,2′-methylenebis(4,6-di-t-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 syn-6-oxide) complex of aluminum hydroxide salt and organic compound, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-[ (4-Propylphenyl)methylene]-nonitol, rosin sodium salt and the like can be exemplified.

Examples of lubricants include higher fatty acid amides such as stearamide. Examples of antistatic agents include fatty acid partial esters such as glycerin fatty acid monoester. Examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like.

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

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

The resin composition (polypropylene-based resin composition) is a method of melt-kneading a polypropylene-based resin and additives, a filler, other resin components, etc., a method of melt-kneading a polypropylene-based resin, additives, a filler, etc. It can be produced by a method of dry blending resin components, a method of dry blending a master batch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to polypropylene resin and other resin components.

[2. Seal layer (I) containing polypropylene resin (A)]
As one aspect of the decorative film of the present invention, the polypropylene-based resin (A) satisfies the following requirements (a2) to (a4) in addition to the above requirements (a1), and contains the polypropylene-based resin (B). Composition (B') preferably further satisfies the following requirement (b3).
(a2) Metallocene-catalyzed 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.
(b3) Tm(B') satisfies the following relational expression (b-3) with respect to Tm(A).
Tm(B′)>Tm(A) Formula (b-3)

The sealing layer (I) containing the polypropylene-based resin (A) in this embodiment is a layer that comes into contact with the resin molding (substrate) during three-dimensional decorative thermoforming. The polypropylene-based resin (A) is preferably a resin that is easily melted and relaxed. By providing the sealing layer (I), even if the film is heated for a short period of time during three-dimensional decorative thermoforming, sufficient adhesive strength is exhibited. can be suppressed.

Melt flow rate (MFR (A)): (a1)
The melt flow rate (230° C., 2.16 kg load) (MFR(A)) of the polypropylene resin (A) must exceed 2.0 g/10 min, preferably 3.0 g/10 min or more. , more preferably 4.0 g/10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming progresses sufficiently, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

In this embodiment, the MFR of the polypropylene-based resin (A) and the resin composition containing the same was measured according to ISO 1133:1997 Conditions M under the conditions of 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

Molecular weight distribution (Mw/Mn (A)): (a4)
Mw/Mn (A) of the polypropylene resin (A) is preferably 1.5 to 3.5 (requirement (a4)), more preferably 2.0 to 3.0. Within the above range, the content of the component having a relatively long relaxation time is small, the relaxation is sufficiently easy, surface roughness is less likely to occur during film formation, and the surface appearance is excellent, which is preferable.
Mn and Mw are described in "Koubunshi Kagaku no Kiso" (Kobunshi Kagaku no Kiso) (Edited by Kobunshi Gakkai, Tokyo Kagaku Dojin, 1978), etc., and are values calculated from a molecular weight distribution curve by GPC.

Melting peak temperature (Tm (A)): (a3)
The melting point Tm (A) (DSC melting peak temperature) of the polypropylene resin (A) is preferably less than 150°C (requirement (a3)), more preferably 145°C or less, more preferably 140°C or less, especially It is preferably 130° C. or less. Sufficient adhesive strength can be exhibited as it is the said range. If the Tm (A) is too low, the heat resistance may be lowered and problems may arise in the use of the molded article.

In addition, the melting peak temperature (Tm (B')) in DSC measurement of the resin composition (B') containing the polypropylene resin (B) must be higher than Tm (A), and Tm (B') >Tm(A) (requirement (b3)). Within the above range, the thermoformability is improved.
The melting point (Tm(B')) (melting peak temperature in DSC measurement) of the resin composition (B') is preferably 140°C or higher, more preferably 145 to 170°C, still more preferably 150 to 168°C. The polypropylene resin (B) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, even if the melting point is high, if it contains a low-crystalline component, the scratch resistance and solvent resistance will decrease. It is preferred not to contain an olefin copolymer.

Resin composition: (a2)
The polypropylene-based resin (A) is preferably a so-called metallocene-catalyzed propylene-based polymer polymerized by a metallocene catalyst (requirement (a2)). Since the metallocene catalyst has a single active site, the polypropylene resin polymerized by the metallocene catalyst has a narrow molecular weight distribution and crystallinity distribution, and is easy to melt and relax. can be fused.

The polypropylene-based resin (A) in the present embodiment includes various types of propylene-based resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof can be selected. The polypropylene-based resin (A) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (A) preferably does not contain polymerized units derived from a polar group-containing monomer.

The polypropylene-based resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties. Since the crystallization temperature is also lowered, sufficient adhesive strength is developed even if the film heating time during three-dimensional decorative thermoforming is short. It becomes possible to suppress the decrease.
As the α-olefin, one or a combination of two or more selected from ethylene and α-olefins having 3 to 8 carbon atoms can be used.

In addition, the polypropylene resin (A) may contain additives including the hindered amine light stabilizer and ultraviolet absorber, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene-based resin composition) of a polypropylene-based resin, an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the polypropylene resin composition.

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

When the polypropylene-based resin (A) contains additives, fillers, other resin components, etc., the resin composition containing the polypropylene-based resin (A) may have the properties of the polypropylene-based resin (A). preferable.

Polypropylene-based resin compositions are produced by melt-kneading polypropylene-based resin, additives, fillers, other resin components, etc., and dry-blending other resin components into melt-kneaded polypropylene-based resins, additives, fillers, etc. method, a method of dry-blending a master batch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the polypropylene resin and other resin components.

[3. Seal layer (I) containing a resin composition (X3) in which the weight ratio of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95]
As one aspect of the decorative film of the present invention, the seal layer (I) has a weight ratio of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) of 97:3 to 5:95. A certain resin composition (X3) is contained, the polypropylene resin (A) satisfies the following requirements (a1), and the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3). is preferred.
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 minutes.
(c1) Ethylene content [E(C)] is 65% by weight or more.
(c2) 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 minutes.

The seal layer (I) in this embodiment is a layer that comes into contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. By providing the sealing layer (I), even if the film is heated for a short period of time during three-dimensional decorative thermoforming, sufficient adhesive strength is exhibited. can be suppressed.

{Polypropylene resin (A)}
The polypropylene-based resin (A) in the present embodiment includes various types of propylene-based resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof can be selected. The polypropylene-based resin (A) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (A) preferably does not contain polymerized units derived from a polar group-containing monomer.

Melt flow rate (MFR (A)): (a1)
The melt flow rate (230° C., 2.16 kg load) (MFR(A)) of the polypropylene resin (A) must exceed 2.0 g/10 min, preferably 3.0 g/10 min or more. , more preferably 4.0 g/10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming progresses sufficiently, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

In this embodiment, the polypropylene resin (A), the ethylene-α-olefin random copolymer (C), and the resin composition containing these are measured for MFR in accordance with ISO 1133:1997 Conditions M, at 230°C, 2 .Measured under the condition of 16 kg load. The unit is g/10 minutes.

Melting peak temperature (Tm (A))
The melting peak temperature (DSC melting peak temperature, sometimes referred to herein as the “melting point”) (Tm (A)) of the polypropylene resin (A) is preferably 110° C. or higher, and is preferably 115° C. or higher. and more preferably 120° C. or higher. Within the above range, the moldability during three-dimensional decorative thermoforming is good. Although the upper limit of the melting peak temperature is not limited, it is preferably 170° C. or less.

The polypropylene-based resin (A) in this embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene-based 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 this embodiment has the following properties (c1) to (c3), preferably further (c4) and/or (c5 ).
(c1) Ethylene content [E(C)] is 65% by weight or more.
(c2) 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 minutes.
(c4) Melting peak temperature (Tm(C)) is 30 to 130°C.
(c5) A random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

Ethylene content [E (C)]: (c1)
The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) of the present embodiment is 65% by weight or more with respect to the total amount of the ethylene-α-olefin random copolymer (C). is preferred, 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 during three-dimensional decorative thermoforming, and the heating time of the film can be shortened. Although the upper limit of the ethylene content [E(C)] is not particularly limited, it 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 for 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 (formula c1-1) and (formula c1-2).
Ethylene content (mol%) = IE × 100 / (IE + IX) (formula c1-1)
Ethylene content [E (C)] (% by weight) = [ethylene content (mol%) x molecular weight of ethylene] x 100/[ethylene content (mol%) x molecular weight of ethylene + α-olefin content (mol%) x α- Molecular weight of olefin] (Formula c1-2)

Here, IE and IX are integral intensities for ethylene and α-olefin, respectively, and can be obtained by the following (formula c-2) and (formula c-3).
IE=(I _ββ +I _γγ +I _βδ +I _γδ +I _δδ )/2+(I _αγ +I _αδ )/4 (formula c-2)
IX= _Iαα +( _Iαγ + _Iαδ )/2 (formula c-3)
Here, the subscripts of I on the right side represent carbons described in structural formulas (a) to (d) below. For example, αα indicates the methylene carbon based on the α-olefin chain, and I _αα represents the integrated intensity of the signal of the methylene carbon based on the α-olefin chain.

In Structural Formula (d), n represents an odd number of 1 or more.

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

(In the case of ethylene-propylene copolymer)
When the α-olefin is propylene, the ethylene content [E(C)] is obtained by substituting the following integrated intensity values into (formula c-2) and (formula c-3).
I _ββ =I _25.0-24.2
I _γγ =I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ =I _30.6-30.2
I _δδ = I _30.2-28.0
I _αα =I _48.0-43.9
I _αγ +I _αδ =I _39.0-36.2

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

(In the case of ethylene-1-butene copolymer)
When the α-olefin is 1-butene, the ethylene content [E(C)] is obtained by substituting the following integrated intensity values into (formula c-2) and (formula c-3).
I _ββ =I _24.6-24.4
I _γγ =I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ =I _30.5-30.2
I _δδ = I _30.2-28.0
I _αα =I _39.3-38.1
I _αγ +I _αδ =I _34.5−33.8

(In the case of ethylene-1-hexene copolymer)
When the α-olefin is 1-hexene, the ethylene content [E(C)] is obtained by substituting the following integrated intensity values into (formula c-2) and (formula c-3).
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 _αγ +I _αδ =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 are superimposed on the methylene carbon of the hexyl branch based on 1-octene (5B6 and 6B6 in the structural formulas below).
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 overlapping of 5B6 and 6B6 and I _αγ + I _αδ are substituted, and the integrated intensity shown below is substituted into (formula c-2) and (formula c-3), and the ethylene content [E (C)].
I _ββ =I _24.7-24.2
I _γγ +I _γδ +I _δδ =I _32.0-28.0
I _βδ = 2/3 x 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 for calculating the ethylene content [E(C)] in a terpolymer composed of three types of repeating units will be described.
For example, the ethylene content of the ethylene-propylene-butene terpolymer can be determined by the following (formula c4-1) and (formula c4-2).
Ethylene content (mol%) = IE × 100 / (IE + IP + IB) (formula c4-1)
Ethylene content [E (C)] (% by weight) = [ethylene content (mol%) x molecular weight of ethylene] x 100/[ethylene content (mol%) x molecular weight of ethylene + propylene content (mol%) x molecular weight of propylene + butene content (mol%) × molecular weight of butene] (formula c4-2)
Here, IE, IP and IB are integrated intensities for ethylene, propylene and butene, respectively, and can be obtained by (formula c-5), (formula c-6) and (formula c-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 (equation c-5)
IP=1/3×[ _ICH3 (P)+ICH(P ₎ +Iαα _(PP) +1/2×(Iαα _(PB) + _Iαγ(P) + _Iαδ(P) )] (Formula c -6)
IB=1/4×[( _ICH3 (B)+ICH(B ₎ + _I2B2 +Iαα _(BB) )+1/2×(Iαα _(PB) + _Iαγ(B) + _Iαδ(B) )]...・(Formula c-7)

Here, the subscript (P) means a signal based on propylene-derived methyl group branching, and similarly (B) means a signal based on butene-derived ethyl group branching.
Also, αα(PP) means a methylene carbon signal based on a propylene linkage, similarly αα(BB) refers to a methylene carbon signal based on a butene linkage, and αα(PB) refers to a methylene carbon signal based on a propylene-butene linkage. means a signal of

Here, the γγ signal overlaps with the tail of the central propylene methine carbon CH(PPE) signal aligned with propylene-propylene-ethylene, making it difficult to separate the γγ signal.
The γγ signal appears in structural formula (c) with two ethylene chains, and the integrated intensity of γγ derived from ethylene and the integrated intensity of βδ in structural formula (c) satisfy (formula c-8).
I _βδ (structural formula (c))=2×I _γγ (formula c-8)

Also, 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 c-9).
I _βδ (structural formula (d))=I _γδ (formula c-9)
Therefore, βδ based on Structural Formula (c) and Structural Formula (d) is obtained by (Formula c-10).
I _βδ = I _βδ (structural formula (c)) + I _βδ (structural formula (d)) = 2 x I _γγ + I _γδ (formula c-10)
i.e.
I _γγ = (I _βδ −I _γδ )/2 (formula c-10′)

Therefore, by substituting (formula c-10') into (formula c-5), IE can be replaced with (formula c-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 (equation c-11)
Here, the βδ signal is corrected for the overlap of ethyl branches based on 1-butene, resulting in (equation c-12).
I _βδ = I _{αγ (P)} + I _{α δ (P)} + I _{α γ (B)} + I _{α δ (B)} −2 × I _{β β} (formula c-12)

From (formula c-11) and (formula c-12), IE becomes (formula c-13).
IE=I _δδ /2+I _γδ /4−I _ββ +I _αγ(P) +I _αδ(P) +I _αγ(B) +I _αδ(B) (Formula c-13)
Substitute the following into (formula c-13), (formula c-6) and (formula c-7) to obtain the ethylene content.
I _ββ =I _25.2-23.8
I _γδ =I _30.4-30.2
I _δδ = I _30.2-29.8
I _αγ(P) + I _αδ(P) = I _39.5-37.3
I _αγ(B) +I _αδ(B) =I _34.6-33.9
I _CH3(P) = I _22.6-19.0
I _CH(P) = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I αα _(PP) =I _48.0-45.0
I _CH3(B) = I _11.4-10.0
I _CH(B) = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
Iαα _(BB) =I _40.3-40.0
Iαα _(PB) =I _{44.2-42.0
I2B2} = _I26.7-26.4

For the assignment of each signal, the following five documents were referred to.
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 other than the above, each signal is assigned and the ethylene content [E(C)] can be determined in the same manner as described above.

Density: (c2)
The density of the ethylene-α-olefin random copolymer (C) is preferably 0.850 to 0.950 g/cm ³ , more preferably 0.855 to 0.900 g/cm ³ , still more preferably 0 0.860 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.

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 minutes, more preferably 1 to 30 g/10 minutes. Within the above range, good adhesiveness is exhibited even if the molding time for three-dimensional decorative thermoforming is shortened.

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, even more preferably. is 40-110°C. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

Type 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. Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Among these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferred.

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

The ethylene-α-olefin random copolymer (C) used in the sealing layer (I) of the present embodiment can be used singly or in combination of two or more as long as the effects of the present invention are not impaired.
Commercial products of such ethylene-α-olefin random copolymer (C) include Kernel series manufactured by Japan Polyethylene Co., Ltd., Toughmer P series and Toughmer A series manufactured by Mitsui Chemicals, Inc., and Engage manufactured by DuPont Dow. EG series and the like.

{Resin composition (X3)}
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, and the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) may be a mixture or melt-kneaded product, or a sequential polymer of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) may be

In the resin composition (X3) constituting the seal layer (I), the weight ratio ((A):(C)) of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) was 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 adhesiveness between the sealing layer (I) and the layer (II) is good. be.

The resin composition (X3) may contain additives including the hindered amine light stabilizer and ultraviolet absorber, fillers, other resin components, and the like, as long as the effects of the present invention are not impaired. However, the total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition (X3).

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

The method for producing the resin composition (X3) comprises melt-kneading the polypropylene resin (A), the ethylene-α-olefin random copolymer (C), additives, fillers, other resin components, etc. A method of dry blending an ethylene-α-olefin random copolymer (C) with a melt-kneaded polypropylene resin (A), additives, fillers, other resin components, etc. - It can be produced by a method such as dry blending a masterbatch in which additives, fillers, other resin compositions, etc. are dispersed in a carrier resin in addition to the α-olefin random copolymer (C) at a high concentration.

[4. Seal layer (I) containing a resin composition (X4) in which the weight ratio of the polypropylene resin (A) and the thermoplastic elastomer (D) is 97:3 to 5:95]
As one aspect of the decorative film of the present invention, the sealing layer (I) is a resin composition (X4 ), the polypropylene resin (A) preferably satisfies the following requirements (a1), and the thermoplastic elastomer (D) preferably satisfies the following requirements (d1) to (d4).
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 minutes.
(d1) A thermoplastic elastomer containing at least one of propylene and butene as a main component.
(d2) 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 minutes.
(d4) Tensile modulus is smaller than polypropylene resin (A).

The seal layer (I) in this embodiment is a layer that comes into contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. By providing the sealing layer (I), even if the film is heated for a short period of time during three-dimensional decorative thermoforming, sufficient adhesive strength is exhibited. can be suppressed.

{Polypropylene resin (A)}
The polypropylene-based resin (A) in the present embodiment includes various types of propylene-based resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof can be selected. The polypropylene-based resin (A) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (A) preferably does not contain polymerized units derived from a polar group-containing monomer.

Melt flow rate (MFR (A)): (a1)
The melt flow rate (230° C., 2.16 kg load) (MFR(A)) of the polypropylene resin (A) must exceed 2.0 g/10 min, preferably 3.0 g/10 min or more. , more preferably 4.0 g/10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming progresses sufficiently, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

In the present embodiment, the polypropylene resin (A), the thermoplastic elastomer (D), and the resin composition containing these are measured for MFR in accordance with ISO 1133:1997 Conditions M under the conditions of 230° C. and a load of 2.16 kg. It was measured. The unit is g/10 minutes.

Melting peak temperature (Tm (A))
The melting peak temperature (DSC melting peak temperature, sometimes referred to herein as the “melting point”) (Tm (A)) of the polypropylene resin (A) is preferably 110° C. or higher, and is preferably 115° C. or higher. and more preferably 120° C. or higher. Within the above range, the moldability during three-dimensional decorative thermoforming is good. Although the upper limit of the melting peak temperature is not limited, it is preferably 170° C. or less.

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

{Thermoplastic elastomer (D)}
The thermoplastic elastomer (D) used in the sealing layer (I) of the present embodiment has the following properties (d1) to (d4), preferably further (d5) and/or (d6). .
(d1) A thermoplastic elastomer containing at least one of propylene and butene as a main component.
(d2) 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 minutes.
(d4) Tensile modulus is smaller than polypropylene resin (A).
(d5) Melting peak temperature (Tm) (D) is 30 to 170°C.
(d6) The ethylene content [E(D)] is less than 50% by weight.

Composition: (d1)
The thermoplastic elastomer (D) used in the seal layer (I) of this embodiment is a thermoplastic elastomer containing propylene and/or butene as a main component. Here, the "thermoplastic elastomer containing propylene and/or butene as the main component" means (i) a thermoplastic elastomer containing propylene as a main component, (ii) a thermoplastic elastomer containing butene as a main component, and (iii) ) Thermoplastic elastomers based on the combined components of propylene and butene. In addition, in this specification, the unit "wt%" means weight%.

The content of propylene or butene in the thermoplastic elastomer (D) is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably 50% by weight or more. For example, thermoplastic elastomer (D) can contain more than 35% by weight of propylene or butenes.
Further, the thermoplastic elastomer (D) may contain both propylene and butene, in which case the total component 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% by weight or more, more preferably 40% by weight or more, and still more preferably 50% by weight or more. When both propylene and butene are included, for example, the thermoplastic elastomer (D) can contain more than 35% by weight of propylene and butene in total. In addition, the thermoplastic elastomer (D) can also be a single component of propylene or butene.

Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, and the heating time of the film can be shortened.

Density: (d2)
The thermoplastic elastomer (D) preferably has a density of 0.850 to 0.950 g/cm ³ , more preferably 0.855 to 0.940 g/cm ³ , still more preferably 0.860 to 0.930 g/cm 3 . ^cm3 . Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, and film moldability is also improved.

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. 10 minutes, more preferably 1.0 to 30 g/10 minutes. Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming.

Tensile modulus: (d4)
The tensile modulus of the thermoplastic elastomer (D) is preferably smaller than the tensile modulus of the polypropylene resin (A). More preferably, the thermoplastic elastomer (D) has a tensile modulus of 500 MPa or less, more preferably 450 MPa or less. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

Melting peak temperature (Tm (D)): (d5)
The melting temperature peak (DSC melting peak temperature) (Tm(D)) of the thermoplastic elastomer (D) is preferably 30 to 170°C, more preferably 35 to 168°C, still more preferably 40 to 165°C or higher. is. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

Ethylene content [E (D)]: (d6)
The thermoplastic elastomer (D) of the present embodiment can be appropriately selected and used as long as it satisfies the above properties (d1) to (d4). coalesced, butene-ethylene copolymers with an ethylene content of less than 50% by weight, propylene-ethylene-butene copolymers with an ethylene content of less than 50% by weight, propylene-butene copolymers, or butene homopolymers is preferred.

The ethylene content [E(D)] of the propylene-ethylene copolymer, butene-ethylene copolymer or propylene-ethylene-butene copolymer is more preferably 45% by weight or less, more preferably 40% by weight or less. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative 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 intensity obtained by ¹³ C-NMR measurement.

(Calculation method 1 (binary system))
The ethylene content [E(D)] in binary elastomers (propylene-ethylene copolymers, butene-ethylene copolymers, etc.) composed of two types of repeating units will be described. The ethylene content of the ethylene-α-olefin binary elastomer can be determined by (formula d1-1) and (formula d1-2).
Ethylene content (mol%) = IE × 100 / (IE + IX) (formula d1-1)
Ethylene content [E (D)] (% by weight) = [ethylene content (mol%) x molecular weight of ethylene] x 100/[ethylene content (mol%) x molecular weight of ethylene + α-olefin content (mol%) x α- Molecular weight of olefin] (Formula d1-2)

Here, IE and IX are integral intensities for ethylene and α-olefin, respectively, and can be obtained by the following (formula d-2) and (formula d-3).
IE=(I _ββ +I _γγ +I _βδ +I _γδ +I _δδ )/2+(I _αγ +I _αδ )/4 (formula d-2)
IX= _Iαα +( _Iαγ + _Iαδ )/2 (formula d-3)
Here, the subscripts of I on the right side represent carbons described in structural formulas (a) to (d) below. For example, αα indicates the methylene carbon based on the α-olefin chain, and I _αα represents the integrated intensity of the signal of the methylene carbon based on the α-olefin chain.

In Structural Formula (d), n represents an odd number of 1 or more.

The integrated intensities used in (formula d-2) and (formula d-3) are described below.
In the case of a propylene-ethylene copolymer, the ethylene content [E(D)] is obtained by substituting the following integrated intensity into (formula d-2) and (formula d-3).
I _ββ =I _25.0-24.2
I _γγ =I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ =I _30.6-30.2
I _δδ = I _30.2-28.0
I _αα =I _48.0-43.9
I _αγ +I _αδ =I _39.0-36.2

Here, I indicates integrated intensity, and the numerical value subscripted to I on the right side indicates the range of chemical shift. For example, I _39.0-36.2 indicates the integrated intensity of the ¹³ C signal detected between 39.0 ppm and 36.2 ppm.
The chemical shift was set to 1.98 ppm for the ¹³ C signal of hexamethyldisiloxane and the chemical shifts of the other ¹³ C signals were referenced to this.
In the case of a butene-ethylene copolymer, the ethylene content [E(D)] is obtained by substituting the following integrated intensity values into (formula d-2) and (formula d-3).
I _ββ =I _24.6-24.4
I _γγ =I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ =I _30.5-30.2
I _δδ = I _30.2-28.0
I _αα =I _39.3-38.1
I _αγ +I _αδ =I _34.5−33.8

(Calculation method 2 (ternary system))
Next, the ethylene content [E(D)] in the ternary elastomer composed of three types of repeating units will be described. The ethylene content of the propylene-ethylene-butene ternary elastomer can be obtained by the following (formula d4-1) and (formula d4-2).
Ethylene content (mol%) = IE × 100 / (IE + IP + IB) (formula d4-1)
Ethylene content [E (D)] (% by weight) = [ethylene content (mol%) x molecular weight of ethylene] x 100/[ethylene content (mol%) x molecular weight of ethylene + propylene content (mol%) x molecular weight of propylene + butene content (mol%) x molecular weight of butene] (formula d4-2)
Here, IE, IP and IB are integrated intensities for ethylene, propylene and butene, respectively, and can be obtained by (formula d-5), (formula d-6) and (formula d-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 (Formula d-5)
IP=1/3×[ _ICH3 (P)+ICH(P ₎ +Iαα _(PP) +1/2×(Iαα _(PB) + _Iαγ(P) + _Iαδ(P) )] (Formula d -6)
IB=1/4×[( _ICH3 (B)+ICH(B ₎ + _I2B2 +Iαα _(BB) )+1/2×(Iαα _(PB) + _Iαγ(B) + _Iαδ(B) )]...・(Formula d-7)

Here, the subscript (P) means a signal based on propylene-derived methyl group branching, and similarly (B) means a signal based on butene-derived ethyl group branching.
Also, αα(PP) means a methylene carbon signal based on a propylene linkage, similarly αα(BB) refers to a methylene carbon signal based on a butene linkage, and αα(PB) refers to a methylene carbon signal based on a propylene-butene linkage. means a signal of

Here, the γγ signal overlaps with the tail of the central propylene methine carbon CH(PPE) signal aligned with propylene-propylene-ethylene, making it difficult to separate the γγ signal.
The γγ signal appears in structural formula (c) with two ethylene chains, and (formula d-8) holds for the integrated intensity of γγ derived from ethylene and the integrated intensity of βδ in structural formula (c).
I _βδ (structural formula (c))=2×I _γγ (formula d-8)

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 d-9).
I _βδ (structural formula (d))=I _γδ (formula d-9)
Therefore, βδ based on Structural Formula (c) and Structural Formula (d) is obtained by (Formula d-10).
I _βδ = I _βδ (structural formula (c)) + I _βδ (structural formula (d)) = 2 x I _γγ + I _γδ (formula d-10)
i.e.
I _γγ = (I _βδ −I _γδ )/2 (formula d-10′)

Therefore, by substituting (formula d-10') into (formula d-5), IE can be replaced with (formula d-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 (formula d-11)
Here, the βδ signal is corrected for the overlap of ethyl branches based on 1-butene, resulting in (equation d-12).
I _βδ =I _αγ(P) +I _αδ(P) +I _αγ(B) +I _αδ(B) −2×I _ββ (formula d-12)

From (formula d-11) and (formula d-12), IE becomes (formula d-13).
IE=I _δδ /2+I _γδ /4−I _ββ +I _αγ(P) +I _αδ(P) +I _αγ(B) +I _αδ(B) (Formula d-13)
Substitute the following into (formula d-13), (formula d-6) and (formula d-7) to obtain the ethylene content.
I _ββ =I _25.2-23.8
I _γδ =I _30.4-30.2
I _δδ = I _30.2-29.8
I _αγ(P) + I _αδ(P) = I _39.5-37.3
I _αγ(B) +I _αδ(B) =I _34.6-33.9
I _CH3(P) = I _22.6-19.0
I _CH(P) = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I αα _(PP) =I _48.0-45.0
I _CH3(B) = I _11.4-10.0
I _CH(B) = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
Iαα _(BB) =I _40.3-40.0
Iαα _(PB) =I _{44.2-42.0
I2B2} = _I26.7-26.4

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

The thermoplastic elastomer (D) may also be a copolymer of propylene and an α-olefin other than butene as long as it does not impair the effects of the present invention. Specific α-olefins include ethylene, 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. These α-olefins can be used alone or in combination. Among these, 1-hexene and 1-octene are particularly preferred.

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

The thermoplastic elastomer (D) used in the sealing layer (I) of the present embodiment can be used singly or in combination of two or more as long as the effects of the present invention are not impaired.
Commercially available products of such thermoplastic elastomer (D) include Toughmer XM series, Toughmer BL series and Toughmer PN series manufactured by Mitsui Chemicals, Inc., and VISTAMAXX series manufactured by ExxonMobil Chemical.

{Resin composition (X4)}
The resin composition (X4) constituting the sealing layer (I) contains a polypropylene resin (A) and a thermoplastic elastomer (D) as main components. The resin composition (X4) may be a mixture or melt-kneaded product of the polypropylene resin (A) and the thermoplastic elastomer (D), or the polypropylene resin (A) and the thermoplastic elastomer (D) may be a sequential polymer of

In the resin composition (X4) constituting the sealing layer (I), the weight ratio ((A):(D)) of the polypropylene resin (A) and 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 adhesiveness between the seal layer (I) and the layer (II) can be improved. Become.

The resin composition (X4) may contain additives including the hindered amine light stabilizer and ultraviolet absorber, fillers, other resin components, and the like, as long as the effects of the present invention are not impaired. However, the total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition (X4).

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

The method for producing the resin composition (X4) is a method of melt-kneading the polypropylene resin (A), the thermoplastic elastomer (D), additives, fillers, other resin components, etc., and the polypropylene resin (A). A method of dry blending a thermoplastic elastomer (D) into a melt-kneaded product obtained by melt-kneading additives, fillers and other resin components, a polypropylene resin (A) is added to the thermoplastic elastomer (D), additives, fillers, etc. It can be produced by a method such as dry blending a masterbatch in which the resin composition or the like is dispersed in a carrier resin at a high concentration.

[5. Seal layer (I) containing a resin composition (X5) in which the weight ratio of the polypropylene resin (A) and the thermoplastic resin (E) is 97:3 to 5:95]
As one aspect of the decorative film of the present invention, the sealing layer (I) is a resin composition (X5 ), the polypropylene resin (A) satisfies the following requirement (a1), the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X5) satisfies the following requirement (x1) is preferred.
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 minutes.
(e1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group;
(x1) The isothermal crystallization time (t(X5)) (seconds) obtained by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t(X5)≧1.5×t(A) Expression (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 (X5) is the isothermal crystallization time (seconds) of the resin composition (X5) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene resin (A).)

The seal layer (I) in this embodiment is a layer that comes into contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. By providing the sealing layer (I), even if the film is heated for a short period of time during three-dimensional decorative thermoforming, sufficient adhesive strength is exhibited. can be suppressed.

{Polypropylene resin (A)}
The polypropylene-based resin (A) in the present embodiment includes various types of propylene-based resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof can be selected. The polypropylene-based resin (A) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (A) preferably does not contain polymerized units derived from a polar group-containing monomer.

Melt flow rate (MFR (A)): (a1)
The melt flow rate (230° C., 2.16 kg load) (MFR(A)) of the polypropylene resin (A) must exceed 2.0 g/10 min, preferably 3.0 g/10 min or more. , more preferably 4.0 g/10 minutes or more. Within the above range, relaxation at the time of three-dimensional decorative thermoforming progresses sufficiently, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(A), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

In this embodiment, the MFR of the polypropylene resin (A), the thermoplastic resin (E), and the resin composition containing these is measured according to ISO 1133:1997 Conditions M, at 230° C. under a load of 2.16 kg. It was measured. The unit is g/10 minutes.

Melting peak temperature (Tm (A))
The melting peak temperature (DSC melting peak temperature, sometimes referred to herein as the “melting point”) (Tm (A)) of the polypropylene resin (A) is preferably 110° C. or higher, and is preferably 115° C. or higher. and more preferably 120° C. or higher. Within the above range, the moldability during three-dimensional decorative thermoforming is good. Although the upper limit of the melting peak temperature is not limited, it is preferably 170° C. or less.

The polypropylene-based resin (A) in this embodiment can be a resin polymerized by a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene-based 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 present embodiment is a component having a function of delaying crystallization of the polypropylene resin (A) by being contained in the polypropylene resin (A). By retarding the crystallization speed of the polypropylene-based resin (A), the resin of the sealing layer (I) crystallizes before the sealing layer (I) and the substrate surface are heat-sealed during decorative molding. It is possible to prevent (solidification) from lowering the adhesive force. As a result, even if the decorative film is heated for a short period of time, it exhibits a strong adhesive force. The effect of delaying the crystallization of the polypropylene-based resin (A) was evaluated based on the isothermal crystallization time of the resin composition (X5) described later.

(e1) Resin Composition The thermoplastic resin (E) in the present embodiment preferably contains an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group. By having the thermoplastic resin (E) having the above characteristics, when mixed with the polypropylene resin (A), the effect of retarding the crystallization of the polypropylene resin (A) is exhibited, and the adhesive strength with the substrate is improved. do.

Specifically, the alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and substituent derivatives, condensed cyclized bodies, and crosslinked structures thereof. It is particularly preferable to contain a cyclopentyl group or a cyclohexyl group.
Examples of the aromatic hydrocarbon group include phenyl group, methylphenyl group, biphenyl group, indenyl group, fluorenyl group, and substituent derivatives and condensed cyclized products thereof. preferably. Also, the alicyclic hydrocarbon group may be obtained by hydrogenating an aromatic hydrocarbon group contained in the resin.

The thermoplastic resin (E) can be appropriately selected and used as long as it satisfies the above requirement (e1), but a styrene elastomer or an alicyclic hydrocarbon resin is particularly preferably used. Yes, both may be included.

Styrene-based elastomers include styrene/butadiene/styrene triblock copolymer elastomer (SBS), styrene/isoprene/styrene triblock copolymer elastomer (SIS), styrene-ethylene/butylene copolymer elastomer (SEB), styrene - ethylene-propylene copolymer elastomer (SEP), styrene-ethylene-butylene-styrene copolymer elastomer (SEBS), styrene-ethylene-butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene-butadiene elastomer (HSBR) ), styrene-ethylene/propylene-styrene copolymer elastomer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer elastomer (SEEPS), styrene-butadiene/butylene-styrene copolymer elastomer (SBBS), etc. For example, a hydrogenated one can be particularly preferably used.
Commercially available products include the Dynalon series manufactured by JSR Corporation, the Kraton G series manufactured by Kraton Polymer Japan, and the Tuftec series manufactured by Asahi Kasei Corporation.

Examples of alicyclic hydrocarbon resins include hydrocarbons obtained by polymerizing one or a mixture of two or more dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene as a main raw material. resins, hydrogenated coumarone-indene resins, hydrogenated C9 petroleum resins, hydrogenated C5 petroleum resins, C5/C9 copolymer petroleum resins, hydrogenated terpene resins, hydrogenated rosin resins, etc., and commercially available Products can be used, and specific examples include the Alcon series manufactured by Arakawa Chemical Co., Ltd., and the like.

{Resin composition (X5)}
The resin composition (X5) constituting the sealing layer (I) contains a polypropylene resin (A) and a thermoplastic resin (E) as main components, and the polypropylene resin (A) and the thermoplastic resin (E ), or may be a melt-kneaded product.

In the resin composition (X5) constituting the sealing layer (I), the weight ratio ((A):(E)) of the polypropylene resin (A) and the thermoplastic resin (E) is 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 included, for example, when thermoplastic resin (E1) and thermoplastic resin (E2) are included, the thermoplastic The total weight of the resin (E1) and the thermoplastic resin (E2) is taken as the weight of the thermoplastic resin (E). Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, and the heating time of the film can be shortened.

Isothermal crystallization time (t(X5)): (x1)
The resin composition (X5) preferably has an isothermal crystallization time (t(X5)) (seconds) determined by a differential scanning calorimeter (DSC) that satisfies the following relational expression (x-1), It more preferably satisfies the relational expression (x-2), and still more preferably satisfies the relational expression (x-3).
t(X5)≧1.5×t(A) Expression (x−1)
t(X5)≧2.0×t(A) Expression (x−2)
t(X5)≧2.5×t(A) Expression (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 (X5) is the isothermal crystallization time (seconds) of the resin composition (X5) measured at a temperature 10°C higher than the crystallization start temperature of the polypropylene resin (A).)

When the isothermal crystallization time (t(X5)) of the resin composition (X5) is within the above range, the seal layer (I) of the decorative film and the substrate surface are heat-sealed during decorative molding. time can be gained, and high adhesive strength is expressed.
Although the upper limit of the isothermal crystallization time (t(X5)) is not particularly limited, the formability of the film is good when the relational expression 30×t(A)≧t(X5) is satisfied.

(Measurement of isothermal crystallization time by differential scanning calorimeter (DSC))
The isothermal crystallization time in this embodiment is a value measured using a differential scanning calorimeter (DSC) and conforms to JIS-K7121: 2012 "Method for measuring transition temperature of plastics".

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

Next, 5 mg of a sample of polypropylene resin (A) or resin composition (X5) was placed in an aluminum holder and heated from 40° C. to 200° C. at a rate of 10° C./min under a nitrogen atmosphere and held for 10 minutes. Thaw the sample. Subsequently, it is cooled at a rate of 40° C./min to a temperature 10° C. higher than the crystallization start temperature of the polypropylene resin (A) obtained by the method described above (hereinafter sometimes referred to as “measurement temperature”), and then measured. The temperature is maintained and the behavior of the sample to crystallize and exotherm is measured. The isothermal crystallization time is defined as the time from when the temperature of the sample reaches the measurement temperature to when the exothermic peak occurs. Here, since it is conceivable that even a slight crystallization of the sealing layer (I) of the decorative film during decorative molding causes a large decrease in adhesive strength, there are two or more exothermic peaks in the isothermal crystallization measurement. In this case, the isothermal crystallization time is the time until the first exothermic peak.

In addition, depending on the type of polypropylene resin (A), the isothermal crystallization time of polypropylene resin (A) is extremely short (e.g., 120 seconds or less) or long even when measured at a temperature 10°C higher than the crystallization start temperature. (for example, 3000 seconds or more) may occur. 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 a measurement is performed, the isothermal crystallization time of the resin composition (X5) must also be measured according to the measurement temperature of the polypropylene resin (A).

The resin composition (X5) may contain additives including the hindered amine light stabilizer and/or UV absorber, fillers, other resin components, etc., as long as the effects of the present invention are not impaired. However, the total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition (X5).

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

The method for producing the resin composition (X5) includes melt-kneading the polypropylene-based resin (A), the thermoplastic resin (E), additives, fillers, other resin components, etc., and the polypropylene-based resin (A). A method of dry blending a thermoplastic resin (E) with a melt-kneaded product of additives, fillers and other resin components, a method of adding a polypropylene resin (A) to a thermoplastic resin (E) and adding additives, fillers, etc. It can be produced by a method such as dry blending a masterbatch in which the resin composition or the like is dispersed in a carrier resin at a high concentration.

[6. Seal layer (I) made of propylene-ethylene block copolymer (F)]
As one aspect of the decorative film of the present invention, the sealing layer (I) contains a propylene-ethylene block copolymer (F) as the polypropylene-based resin (A), and the propylene-ethylene block copolymer (F) is , the following requirements (a1), (f1) and (f2) are preferably satisfied, more preferably the propylene-ethylene block copolymer (F) further satisfies (f3), (f4) and/or (f5) .
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(F)) exceeds 2.0 g/10 minutes.
(f1) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, and a component (F1) consisting of a propylene-ethylene random copolymer having a higher ethylene content than the component (F1) F2) is contained in an amount of 3 to 95% by weight.
(f2) Melting peak temperature (Tm(F)) is 110 to 170°C.
(f3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.
(f4) The ethylene content of component (F1) is in the range of 0 to 6% by weight.
(f5) The ethylene content of component (F2) is in the range of 5 to 90% by weight.

The seal layer (I) in this embodiment is a layer that comes into contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. By providing the sealing layer (I), even if the film is heated for a short period of time during three-dimensional decorative thermoforming, sufficient adhesive strength is exhibited. can be suppressed.

{Propylene-ethylene block copolymer (F)}
The propylene-ethylene block copolymer (F) of the present embodiment comprises a component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer and a propylene-ethylene containing more ethylene than the component (F1). It contains a component (F2) consisting of a random copolymer. The component (F2), which is a rubber component in the propylene-ethylene block copolymer (F), improves the adhesive strength to the resin molding (substrate). In addition, the component (F2) has a highly uniform dispersion form in propylene, thereby improving the adhesiveness.
The propylene-ethylene block copolymer (F) is obtained by (co)polymerizing the component (F1) consisting of propylene alone or a propylene-ethylene random copolymer in the first polymerization step, and then the component (F1) in the second polymerization step. obtained by successive copolymerization of the component (F2) comprising a propylene-ethylene random copolymer containing a large amount of ethylene.

Ratio of component (F1) and component (F2): (f1)
The ratio of the component (F1) and the component (F2) constituting the propylene-ethylene block copolymer (F) in the present embodiment is 5 to 97% by weight for the component (F1) and 3 to 95% by weight for the component (F2). is preferably More preferably, component (F1) is 30 to 95% by weight and component (F2) is 5 to 70% by weight, and more preferably component (F1) is 52 to 92% by weight and component (F2) is 8 to 48% by weight. % by weight.
When the ratio of component (F1) and component (F2) is within the above range, sufficient adhesive strength can be exhibited. Moreover, when it is within the above range, the film is not sticky and the film formability is good.

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) must exceed 2.0 g/10 min, preferably 3.0 g. /10 minutes or more, more preferably 4.0 g/10 minutes or more. When the MFR (F) is within the above range, relaxation of the propylene-ethylene block copolymer (F) proceeds sufficiently during three-dimensional decorative thermoforming, and sufficient adhesive strength can be exhibited. Although there is no upper limit for MFR(F), it is preferably 100 g/10 minutes or less. Within the above range, deterioration in adhesive strength due to deterioration in physical properties does not occur.

In this embodiment, the MFR of the propylene-ethylene block copolymer (F) and the resin composition containing the same was measured according to ISO 1133:1997 Conditions M under conditions of 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

Melting peak temperature (Tm (F)): (f2)
The melting point (melting peak temperature) (hereinafter referred to as “Tm (F)”) of the propylene-ethylene block copolymer (F) is preferably from 110 to 170°C, more preferably from 113 to 169°C, and further preferably from 113 to 169°C. It is preferably 115 to 168°C. When Tm(F) is within the above range, moldability during three-dimensional decorative thermoforming is good. The peak melting temperature is mainly derived from the component (F1) with a low ethylene content, that is, the component (F1) with high crystallinity, and the peak melting temperature can be changed depending on the content of ethylene to be copolymerized.

Propylene-ethylene content in ethylene block copolymer (F) [E (F)]: (f3)
The ethylene content in the propylene-ethylene block copolymer (F) in the present embodiment (hereinafter referred to as "E(F)") is preferably 0.15 to 85% by weight. More preferably 0.5 to 75% by weight, still more preferably 2 to 50% by weight. When E(F) is within the above range, a sufficient adhesive strength can be exhibited, and the adhesiveness to the layer (II) of the decorative film is good, resulting in excellent film moldability.

Ethylene content of component (F1) [E(F1)]: (f4)
Component (F1) is a propylene homopolymer or 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 0 to 5% by weight. When E(F1) is within the above range, the moldability during three-dimensional decoration thermoforming is good, and the film is less sticky and excellent in film moldability.

Ethylene content of component (F2) [E(F2)]: (f5)
The ethylene content of component (F2) (hereinafter referred to as "E(F2)") is higher than the ethylene content E(F1) of component (F1). Further, it is preferably a propylene-ethylene random copolymer in which E(F2) is in the range of 5 to 90% by weight. E(F2) is more preferably 7 to 80% by weight, more preferably 9 to 50% by weight. Sufficient adhesive strength can be exhibited as E(F2) is within the above range.

{Method for producing propylene-ethylene block copolymer (F)}
The propylene-ethylene block copolymer (F) used in the present embodiment, the component (F1) comprising a propylene homopolymer or a propylene-ethylene random copolymer constituting it, and the component (F2) comprising a propylene-ethylene random copolymer ) can be preferably produced by the following raw materials and polymerization method. A method for producing the propylene-ethylene block copolymer (F) used in the present invention is described below.

(Raw materials used)
The catalyst used in the production of the propylene-ethylene block copolymer (F) used in the present embodiment includes magnesium, halogen, titanium, a magnesium-supported catalyst containing an electron donor as a catalyst component, and titanium trichloride as a catalyst. A catalyst consisting of a solid catalyst component and an organoaluminum, or a metallocene catalyst can be used. Specific catalyst production methods are not particularly limited, but examples include the Ziegler catalyst disclosed in Japanese Patent Application Laid-Open No. 2007-254671 and the metallocene catalyst disclosed in Japanese Patent Application Laid-Open No. 2010-105197. can be exemplified.

The raw material olefins to be polymerized are propylene and ethylene, and if necessary, other olefins such as 1-butene, 1-hexene, 1-octene, 4-methyl-1 - It is also possible to use pentene or the like.

(Polymerization process)
The polymerization step carried out in the presence of the catalyst consists of 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 propylene/ethylene mixture is supplied to a polymerization system to which the catalyst is added to produce a propylene homopolymer or a propylene-ethylene random copolymer. In this step, component (F1) is formed in an amount corresponding to 5 to 97% by weight of the polymer amount.

The MFR of component (F1) (hereinafter referred to as "MFR (F1)") can be adjusted by using hydrogen as a chain transfer agent. Specifically, increasing the concentration of hydrogen, which is a chain transfer agent, increases the MFR (F1) of the component (F1). The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, the amount of hydrogen supplied to the polymerization tank can be increased, and adjustment is extremely easy for those skilled in the art. Further, 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 reactor as means for controlling the ethylene content. Specifically, the ethylene content of the component (F1) is increased by increasing the ratio of ethylene to propylene supplied to the polymerization reactor (ethylene supply amount/propylene supply amount). The same is true vice versa. The relationship between the amount ratio of propylene and ethylene supplied to the polymerization reactor and the ethylene content of the component (F1) varies depending on the type of catalyst used, but the component having the desired ethylene content can be obtained by appropriately adjusting the supply amount ratio. Obtaining (F1) is very easy for those skilled in the art.

Second polymerization step In the second polymerization step, following the first polymerization step, a propylene/ethylene mixture is further introduced to produce a propylene-ethylene random copolymer, and the amount of the total polymer is 3 to 95% by weight. It is a step of forming the component (F2) so as to have an amount corresponding to .

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

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

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

In industrial manufacturing facilities, it is common to obtain the production amount from the heat balance and material balance of each polymerization tank. Further, when the crystallinity of the component (F1) and the component (F2) are sufficiently different, the two may be separated and identified using an analysis method such as TREF (temperature rising elution fractionation method) and the quantitative ratio may be obtained. Techniques for evaluating the crystallinity distribution of polypropylene by TREF measurement are well known to those skilled in the art. Glokner, J.; Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L.; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J. Am. B. P. Soares, A.; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995) and other literatures show detailed measurement methods.

Next, a method for controlling the ethylene content will be described. Propylene-ethylene block copolymer (F) is a mixture of component (F1) consisting of propylene homopolymer or propylene-ethylene random copolymer and component (F2) consisting of propylene-ethylene random copolymer. The following relational expression holds between the ethylene contents of
E(F)=E(F1)×W(F1)/100+E(F2)×W(F2)/100
(Here, E (F), E (F1) and E (F2) are the component (F1) consisting of a propylene-ethylene block copolymer (F), a propylene homopolymer or a propylene-ethylene random copolymer, respectively. , and the ethylene content of the component (F2) consisting of a propylene-ethylene random copolymer.)

This formula shows the material balance with respect to ethylene content.
Therefore, if the weight ratio of component (F1) and component (F2) is determined, that is, if W(F1) and W(F2) are determined, E(F) is uniquely defined by E(F1) and E(F2). Determined by In other words, E(F) can be controlled by controlling the weight ratio of component (F1) and component (F2), and the three factors E(F1) and E(F2).
For example, to increase E(F), E(F1) may be increased, or E(F2) may be increased. Also, keeping in mind that E(F2) is higher than E(F1), it can be easily understood that W(F1) may be decreased and W(F2) increased. The control method in the reverse direction is also the same.

It should be noted that it is E(F) and E(F1) that can actually obtain the measured values directly, and E(F2) is calculated using the measured values of both. Therefore, if an operation to increase E (F) is performed, if an operation to increase E (F2), that is, an operation to increase the amount of ethylene supplied to the second polymerization step is selected as a means, the measured value is directly What can be confirmed is E(F), not E(F2), but it is obvious that the reason for the increase in E(F) is the increase in E(F2).

Next, a method for controlling MFR(F) will be described. In this embodiment, MFR(F2) is defined by the following formula.
MFR(F2)=exp{(log _e [MFR(F)]−(W(F1)/100)×log _e [MFR(F1)])÷(W(F2)/100)}
(where log _e is the logarithm to the base e. MFR (F), MFR (F1) and MFR (F2) are propylene-ethylene block copolymer (F), propylene homopolymer or propylene -MFR of component (F1) consisting of ethylene random copolymer and component (F2) consisting of propylene-ethylene random copolymer.)

This formula is an empirical formula generally called log addition rule of viscosity log _e [MFR (F)] = (W (F1) / 100) × log _e [MFR (F1)] + (W (F2) / 100) × log _e [MFR(F2)]
and is routinely used in the industry.

Due to the definition in this formula, the weight ratios of component (F1) to component (F2), MFR(F), MFR(F1) and MFR(F2) are not independent. Therefore, in order to control MFR(F), the weight ratio of component (F1) and component (F2), MFR(F1) and MFR(F2) should be controlled. For example, in order to increase MFR(F), MFR(F1) may be increased, or MFR(F2) may be increased. Also, it can be easily understood that when MFR(F2) is lower than MFR(F1), MFR(F) can be increased by increasing W(F1) and decreasing W(F2). . The control method in the reverse direction is also the same.

It is to be noted that MFR(F) and MFR(F1) can actually be obtained directly, and MFR(F2) is calculated using both measured values. Therefore, if an operation to increase the MFR (F) is performed, if an operation to increase the MFR (F2), that is, an operation to increase the amount of hydrogen supplied to the second polymerization step is selected as a means, the measured value is directly What can be confirmed is MFR(F), not MFR(F2), but it is obvious that the cause of the increase in MFR(F) is the increase in MFR(F2).

The propylene-ethylene block copolymer polymerization process can be carried out by either a batchwise method or a continuous method. 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 without substantially using an inert solvent, a method of using a gaseous solvent without substantially using a liquid solvent. A method of polymerizing in a monomer and a method of combining these methods can be employed. Moreover, the same polymerization tank may be used for the first polymerization step and the second polymerization step, or separate polymerization tanks may be used.

(1) Measurement of Ethylene Content in Copolymer Using the propylene-ethylene block copolymer (F), each ethylene content in this copolymer was measured. That is, the component (F1) composed of the propylene homopolymer or propylene-ethylene random copolymer obtained at the end of the first polymerization step, and the propylene-ethylene block copolymer (F) obtained through the second polymerization step. Each ethylene content in was obtained by analyzing the ¹³ C-NMR spectrum measured according to the following conditions by the proton complete decoupling method.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 100 MHz or higher)
Solvent: o-dichlorobenzene + deuterated benzene (4:1 (volume ratio))
Concentration: 100 mg/mL
Temperature: 130°C
Pulse angle: 90°
Pulse interval: 15 seconds Accumulation times: 5,000 times or more Spectral attribution may be performed with reference to, for example, Macromolecules, 17, 1950 (1984). The attribution of the spectrum measured under the above conditions is as shown in the table below. Symbols such as Sαα in Table 1 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 the propylene unit in the copolymer chain and "E" is the ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE can 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 related by the following relational expressions (f-1) to (f-6).

[PPP]=k×I(Tββ) (f−1)
[PPE]=k×I(Tβδ) (f−2)
[EPE]=k×I(Tδδ) (f−3)
[PEP]=k×I(Sββ) (f−4)
[PEE]=k×I(Sβδ) (f−5)
[EEE]=k×{I(Sδδ)/2+I(Sγδ)/4} (f−6)

where brackets [ ] indicate the fraction of triads, eg [PPP] is the fraction of PPP triads in all triads. therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (f-7)
is.
Also, k is a constant and I indicates spectral intensity, for example, I(Tββ) means the intensity of the peak at 28.7 ppm attributed to Tββ. By using the relational expressions (f-1) to (f-7) above, the fraction of each triad is obtained, and the ethylene content is obtained by the following expression (f-8).
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100 (f-8)
The ethylene content is converted from mol % to weight % using the following formula (f-9).
Ethylene content (% by weight) = (28 x X/100)/{28 x X/100 + 42 x (1-X/100)} x 100 (f-9)
Here, X is the ethylene content in mol%.

The propylene-ethylene block copolymer (F) in the present embodiment contains additives, fillers, other resin components, etc. containing the hindered amine light stabilizer and/or ultraviolet absorber, as long as the effects of the present invention are not impaired. may be included. That is, it may be a resin composition (polypropylene-based resin composition) of a propylene-ethylene block copolymer (F), an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the resin composition.

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

The resin composition can be prepared by melt-kneading the propylene-ethylene block copolymer (F) with additives, fillers, other resin components, etc., or by mixing the propylene-ethylene block copolymer (F) with additives, fillers, etc. A method of dry blending other resin components into the melt-kneaded product, and a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin at a high concentration in addition to the propylene-ethylene block copolymer (F) and other resin components. It can be produced by a dry blending method or the like.

[7. Seal layer (I) containing polyolefin adhesive resin (G)]
As one form of the decorative film in the present invention, the seal layer (I) includes a seal layer (I) containing a polyolefin adhesive resin (G), and the polyolefin adhesive resin (G) meets the following requirement (g1) and (g2).
(g1) A polyolefin resin having a polar functional group containing at least one heteroatom.
(g2) Melt flow rate (230° C., 2.16 kg load) (MFR(G)) is 100 g/10 minutes or less.

The seal layer (I) in this embodiment is a layer that comes into contact with the resin molded body (substrate) during three-dimensional decorative thermoforming. By laminating the seal layer (I) on the layer (II), sufficient adhesive strength is exhibited even if the film is heated for a short time during three-dimensional decorative thermoforming. Thus, it becomes possible to suppress deterioration in weather resistance, and furthermore, it is possible to firmly adhere to a substrate made of a polar resin material.

Melt flow rate (MFR (G)): (g2)
The melt flow rate (230° C., 2.16 kg load) (MFR (G)) of the polyolefin adhesive resin (G) in this embodiment must be 100 g/10 min or less, preferably 50 g/10 min. Below, more preferably 20 g/10 minutes or less. By adjusting the MFR (G) of the polyolefin adhesive resin (G) to the above value or less, the layer (II) containing the resin composition (B') containing the polypropylene resin (B) is formed by extrusion molding. It becomes possible to laminate a sealing layer (I) containing a polyolefin adhesive resin (G).
Although the lower limit of MFR (G) of the polyolefin adhesive resin (G) is not particularly limited, it is preferably 0.1 g/10 minutes or more, more preferably 0.3 g/10 minutes or more. By setting the MFR (G) of the polyolefin adhesive resin (G) to the above value or more, in coextrusion molding of the resin composition (B') containing the polypropylene resin (B) and the polyolefin adhesive resin (G) In addition, it is possible to suppress the occurrence of problems such as the occurrence of interface roughness at the lamination interface and the polyolefin adhesive resin (G) not being laminated to the end of the film.

A polar functional group containing a heteroatom: (g1)
The polyolefin adhesive resin (G) in the present embodiment contains at least one heteroatom from the viewpoint of improving adhesion with the layer (II) containing the resin composition (B′) containing the polypropylene resin (B). It is a polyolefin resin having polar functional groups containing

Polar functional groups having at least one heteroatom include epoxy groups, carbonyl groups, ester groups, ether groups, hydroxy groups, carboxy groups or metal salts thereof, alkoxy groups, aryloxy groups, acyl groups, acyloxy groups, acid Examples include an anhydride group, amino group, imide group, amide group, nitrile group, thiol group, sulfo group, isocyanate group, and halogen group. Among them, the polyolefin adhesive resin (G) is selected from the group consisting of epoxy groups, hydroxy groups, carboxy groups, acid anhydride groups, amino groups, imide groups, amide groups, nitrile groups, thiol groups, isocyanate groups, and halogen groups. More preferably, it is a polyolefin resin having at least one selected functional group.

Specific examples of polyolefins having such polar functional groups include acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene and acrylic acid-modified polypropylene; ethylene/vinyl chloride copolymer, ethylene/vinylidene chloride copolymer; Copolymer, ethylene/acrylonitrile copolymer, ethylene/methacrylonitrile copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylamide copolymer, ethylene/methacrylamide copolymer, ethylene/acrylic acid copolymer, ethylene /methacrylic acid copolymer, ethylene/maleic acid copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/isopropyl acrylate copolymer, ethylene/butyl acrylate copolymer , ethylene/isobutyl acrylate copolymer, ethylene/2-ethylhexyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/isopropyl methacrylate copolymer, ethylene/ Butyl methacrylate copolymer, ethylene/isobutyl methacrylate copolymer, ethylene/2-ethylhexyl methacrylate copolymer, ethylene/maleic anhydride copolymer, ethylene/ethyl acrylate/maleic anhydride copolymer, ethylene /metal acrylate copolymer, ethylene/metal methacrylate copolymer, ethylene/vinyl acetate copolymer or saponified product thereof, ethylene/vinyl propionate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene Ethylene or α-olefin/vinyl monomer copolymer such as / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer; chlorinated polyolefin such as chlorinated polypropylene chlorinated polyethylene etc.
Moreover, these resins may be used alone, or two or more of them may be mixed. Further, if necessary, other resins or rubbers, tackifiers, various additives including the hindered amine light stabilizer and/or ultraviolet absorber, fillers, and the like may be mixed.

Among the polyolefin resins having a polar functional group, from the viewpoint of adhesion with the layer (II), commercially available products such as "ADMER" manufactured by Mitsui Chemicals, "MODIC" manufactured by Mitsubishi Chemical, and "MODIC" manufactured by Sanyo Kasei "Umex" and the like can be preferably used.

Examples of the other resins or rubbers include polyα-olefins such as polypentene-1 and polymethylpentene-1, ethylene or α-olefin/α-olefin copolymers such as propylene/butene-1 copolymer, Ethylene or α-olefin/α-olefin/diene monomer copolymers such as ethylene/propylene/5-ethylidene-2-norbornene copolymers, polydiene copolymers such as polybutadiene and polyisoprene, styrene/butadiene random copolymers Polymers, vinyl monomer/diene monomer random copolymers such as styrene/isoprene random copolymers, vinyl monomers such as styrene/butadiene/styrene block copolymers and styrene/isoprene/styrene block copolymers Hydrogenated (vinyl monomer/diene monomer random copolymer), hydrogenation (styrene/butadiene/styrene block copolymer), hydrogenation (styrene/isoprene/styrene block copolymer) (vinyl monomer/diene monomer /vinyl monomer block copolymer), acrylonitrile/butadiene/styrene graft copolymer, methyl methacrylate/butadiene/styrene graft copolymer, etc. Vinyl monomer/diene monomer/vinyl monomer graft copolymer Polymers, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, vinyl polymers such as polystyrene, vinyl chloride/acrylonitrile copolymers, vinyl chloride /vinyl acetate copolymer, acrylonitrile/styrene copolymer, methyl methacrylate/styrene copolymer, and other vinyl copolymers.

Examples of the tackifier include rosin-based resins (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resins, terpene resins ( Polymers such as α-pinene, β-pinene, and limonene), aromatic hydrocarbon-modified terpene resins, petroleum resins (aliphatic, alicyclic, aromatic, etc.), coumarone/indene resins, styrene resins, Examples include phenol resins (alkylphenol, phenol xylene formaldehyde, rosin-modified phenol resin, etc.), xylene resins, and the like, and these can be used alone or in combination of two or more. Among these, from the viewpoint of thermal stability, rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferable, and the polyolefin adhesive resin (G) of the present invention Rosin-based resins and terpene phenolic resins are particularly preferred because they are compatible with polar resins and can contribute to adhesion to polar resins.

Examples of the additives include stabilizers such as antioxidants, metal deactivators, phosphorus-based processing stabilizers, ultraviolet absorbers, ultraviolet stabilizers, metal soaps and antacid adsorbents, cross-linking agents, chain transfer agents, Lubricants, plasticizers, fillers, reinforcing agents, pigments, dyes, flame retardants, antistatic agents, fluorescent whitening agents, etc., may be added as long as the effects of the present invention are not impaired.

As additives and fillers, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

<Decorative film>
The decorative film in the present invention contains layer (II) and sealing layer (I). That is, the decorative film may be a two-layer film consisting of the layer (II) and the sealing layer (I), or a multi-layer film of three or more layers consisting of the layer (II) and the sealing layer (I) and other layers. There may be. The decorative film of the present invention can have various structures other than the layer (II) and the sealing layer (I). The seal layer (I) is adhered along the resin molding (substrate). The surface of the decorative film of the present invention may be textured, embossed, printed, sandblasted, scratched, or the like.

Three-dimensional decorative thermoforming has a high degree of freedom in the shape of the object to be decorated. Various textures can be expressed by applying textures to the surface. For example, in the case of imparting texture such as embossing to a resin molding, three-dimensional decorative thermoforming may be performed using an embossed decorative film. For this reason, there are problems when molding with a molded body mold that imparts embossing, that is, a molded body mold is required for each embossing pattern, and it is very difficult and expensive to apply complicated embossing to a curved surface mold. It is possible to solve the problem of being , and to obtain a decorative molded article to which various patterns of embossing are easily applied. Further, a decorative film having a higher gloss can be obtained by mirror-finishing the decorative film by surface-transferring a mirror-like cooling roll.

In addition to the seal layer (I) and layer (II), the multilayer film includes a substrate layer, a surface layer, a surface decorative layer (III), a printed layer, a light shielding layer, a colored layer, a barrier layer, and a layer provided between these layers. Can include tie layer layers and the like. The layer (II) containing the resin composition (B') may be any layer among the layers constituting the multilayer film, excluding the seal layer.

When the decorative film is a two-layer film consisting of the layer (II) and the seal layer (I), the layer (II) constitutes the surface layer opposite to the surface to be adhered to the resin molding, and the seal layer (I) constitutes the surface to be adhered to the resin molding. In this case, layer (II) preferably contains a hindered amine light stabilizer and/or an ultraviolet absorber.

Even a multilayer film having a more complicated layer structure similarly includes layer (II) and sealing layer (I).

Further, as another preferred embodiment of the multilayer film having more than two layers including the layer (II) and the seal layer (I), the layers other than the layer (II) and the seal layer (I) are preferably layers made of a thermoplastic resin. and more preferably a layer made of a polypropylene-based resin. The layers other than the layer (II) and the seal layer (I) have the MFR (230° C., 2.16 kg load) is not particularly limited. Each layer is preferably a layer containing no thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication of the layer structure can be suppressed, and recyclability is further improved.

FIGS. 1B(a) to 1B(c) show an embodiment of a decorative film comprising a layer (II) containing a resin composition (B′) containing a polypropylene resin (B) and a sealing layer (I). FIG. 1A(a) to FIG. 1A(c) are explanatory views schematically illustrating cross sections, and FIG. 1A(a) to FIG. 1A(c) are explanatory views schematically illustrating cross sections of embodiments of the decorative film adhered to a resin molded body. be. An embodiment of the decorative film will be described with reference to FIGS. 1A(a) to 1A(c). In FIGS. 1A(a) to 1A(c), the arrangement of the sealing layer (I) and the layer (II) will be specified and explained for ease of understanding. It should not be construed as being limited.
In the drawings, reference numeral 1 is a decorative film, reference numeral 2 is a layer (II), reference numeral 3 is a sealing layer (I), reference numeral 4 is a surface decoration layer (III), reference numeral 5 is a resin molding, and reference numeral 6 is a decorative molding. Show body. FIG. 1A(a) shows an example in which the decorative film 1 is made of a two-layer film, a seal layer (I) 3 is attached to the resin molding 5, and a polypropylene-based resin ( A layer (II) 2 containing a resin composition (B') containing B) is laminated. The decorative film 1 of FIG. 1A(b) is composed of a seal layer (I) 3, a layer (II) 2 and a surface layer. ) 3, the layer (II) 2 and the surface layer are laminated in this order. The decorative film 1 of FIG. 1A(c) is composed of a sealing layer (I) 3, a layer (II) 2, and a surface decorative layer (III) 4 containing a polypropylene-based resin. ) 3 is attached, and the layer (II) 2 and the surface decoration layer (III) 4 are laminated in this order on the sealing layer (I) 3 .

In addition, in FIGS. 1B(a) to 1B(c), in order to facilitate understanding, the arrangement of the seal layer (I) 3 and the layer (II) 2 will be specified and explained, but the layer structure of the decorative film should not be construed as being limited to these examples. Reference numeral 1 in the drawing indicates the decorative film, reference numeral 2 indicates the layer (II), reference numeral 3 indicates the sealing layer (I), and reference numeral 4 indicates the surface decoration layer (III). FIG. 1B(a) shows an example in which the decorative film 1 is made of a two-layer film, and a layer containing a resin composition (B′) containing a polypropylene resin (B) on a seal layer (I) 3 II) 2 is laminated. The decorative film 1 in FIG. 1B(b) consists of a sealing layer (I) 3, a layer (II) 2 and a surface layer, and the layer (II) 2 and the surface layer are laminated in this order on the sealing layer (I) 3. do. The decorative film 1 in FIG. 1B(c) is composed of a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4, and a layer (II) 2 and a layer (II) 2 are formed on the sealing layer (I) 3. The surface decorative layer (III) 4 is laminated in this order.

As a preferred aspect of the multilayer film, the layers other than the seal layer (I) and the layer (II) are preferably layers made of a thermoplastic resin, and more preferably made of a polypropylene resin other than the polypropylene resin (B). It is a layer. Each layer is preferably a layer containing no thermosetting resin. Recyclability is improved by using a thermoplastic resin. Furthermore, by using a polypropylene-based resin other than the polypropylene-based resin (B), complication of the layer structure can be suppressed, and recyclability is further improved.

As another preferred embodiment of the decorative film, a surface decorative layer (III ). The surface decorative layer resin is preferably a thermoplastic resin, more preferably a polypropylene resin (H) having an MFR (230° C., 2.16 kg load) exceeding 2.0 g/10 min. That is, by further providing the surface decorative layer (III) containing the polypropylene resin (H) on the surface layer of the decorative film, the gloss and grain transferability can be improved without greatly deteriorating the thermoformability. can be done. Further, by using the polypropylene-based resin (H), complication of layer structure and deterioration of recyclability can be suppressed. In addition, by using the polypropylene-based resin (H) for the surface decorative layer (III) of the decorative film, excellent solvent resistance and the like can be obtained. In addition, by using a polypropylene-based resin (H) for the surface decoration layer, the transferability of the surface during the production of the decorative film and during thermoforming is improved, and if a mirror surface roll is used during thermoforming, a highly glossy finish can be obtained. It can be used as a decorative film.

The polypropylene-based resin (H) in this embodiment includes various types of propylene-based resins such as propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene). Polymers, or combinations thereof can be selected. The polypropylene-based resin (H) preferably contains 50 mol % or more of polymerized units derived from propylene monomers. The polypropylene-based resin (H) preferably does not contain polymerized units derived from a polar group-containing monomer. The polypropylene-based resin (H) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance, and the like. Propylene-α-olefin copolymers are preferred from the viewpoint of gloss and transparency (color development). In this aspect, the polypropylene resin (H) constituting the surface decorative layer (III) may be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

The polypropylene-based resin (H) in this aspect preferably has a strain hardening degree of less than 1.1, more preferably 1.0 or less. By setting the degree of strain hardening of the polypropylene-based resin (H) to less than 1.1, the appearance of the decorated molded article can be improved. The strain hardening degree of the polypropylene-based resin (H) shall be determined by the method described above.

The polypropylene resin (H) preferably has an MFR (H) (230°C, 2.16 kg load) exceeding 2.0 g/10 minutes, more preferably 5.0 g/10 minutes or more, and still more preferably 9.0 g. / 10 minutes or more. By setting the MFR of the polypropylene-based resin (H) within the above range, effects such as easy improvement of the glossiness of the decorative film and easy improvement of texture transferability can be obtained, and the desired surface of the molded product can be obtained. It is possible to obtain a decorative molded article having a good appearance in terms of shape (glossy, non-glossy, embossed, etc.).

Although there is no particular upper limit for the MFR of the polypropylene resin (H), it is preferably 100 g/10 minutes or less, more preferably 50 g/10 minutes or less. By setting the MFR within the above range, good oil resistance, solvent resistance, scratch resistance, etc. can be exhibited.

The polypropylene resin (H) may contain additives including the hindered amine light stabilizer and/or ultraviolet absorber, fillers, other resin components, and the like. That is, it may be a resin composition (polypropylene-based resin composition) of a polypropylene-based resin (H), an additive, a filler, other resin components, and the like. The total amount of additives, fillers, other resin components, etc. is preferably 50% by weight or less with respect to the polypropylene resin composition.

As additives, fillers, and other resin components, the above [1. Seal layer (I) containing polypropylene-based resin (A)] can be used.

A resin composition containing a polypropylene-based resin (H) can be prepared by melt-kneading the polypropylene-based resin (H) with additives, fillers, other resin components, etc. A method of dry-blending other resin components into the melt-kneaded product, a method of dry-blending a masterbatch in which additives, fillers, etc. are dispersed in a carrier resin in addition to the polypropylene resin (H) and other resin components at a high concentration. etc. can be manufactured.

When the surface decorative layer (III) is a polypropylene-based resin composition containing a polypropylene-based resin (H), the polypropylene-based resin composition comprises the polypropylene-based resin (A) constituting the seal layer (I). It may be the same as or different from the polypropylene-based resin composition to be used. When both polypropylene-based resin compositions are the same, the seal layer (I) and the surface decorative layer (III) can be formed using a single extruder using a feed block or the like. have advantages.

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 even more preferably about 80 μm or more. By setting the thickness of the decorative film to such a value or more, the effect of imparting designability is improved, the stability during molding is also improved, and it becomes possible to obtain a better decorated molded product. On the other hand, the thickness of the decorative film is preferably about 2 mm or less, more preferably about 1.2 mm or less, still more preferably about 0.8 mm or less. By reducing the thickness of the decorative film to such a value or less, the time required for heating during thermoforming is shortened, thereby improving productivity and facilitating trimming of unnecessary portions.

In the decorative film of the present invention, the ratio of the thickness of the layer (II) to the total thickness of the decorative film is preferably 30 to 99%, and the ratio of the thickness of the seal layer (I) is preferably 1 to 99%. 70%. If the ratio of the thickness of the layer (II) to the entire decorative film is within the above range, it is possible to avoid insufficient thermoformability of the decorative film. Further, when the ratio of the thickness of the seal layer (I) to the entire decorative film is within the above range, the adhesiveness to the resin molding (substrate) is good, and the weather resistant agent can be decorated before volatilization. Molding can be completed.

In addition, in a multilayer film in which a surface decorative layer (III) containing a polypropylene resin (H) is provided on the outermost surface of the decorative film, the ratio of the thickness of the surface decorative layer (III) in the decorative film is preferably 30% or less of the thickness of the entire decorative film.

<Manufacturing of decorative film>
The decorative film of the present invention is produced by co-extrusion molding of various seal layers (I) and a layer (II) containing a resin composition (B') containing a polypropylene resin (B). And a method of co-extrusion molding of layer (II) and another layer, a heat lamination method of applying heat and pressure to laminate another layer on one side of one of the pre-extruded layers, adhesion Examples include a dry lamination method and a wet lamination method in which lamination is performed via an agent, and an extrusion lamination method and a sand lamination method in which a polypropylene-based resin is melt-extruded onto one surface of one layer that has been extruded in advance.

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

Methods for cooling the molten decorative film extruded from the die include a method of bringing the molten decorative film into contact with one cooling roll via air discharged from an air knife unit or an air chamber unit, A method of pressing and cooling with a plurality of cooling rolls can be used.

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

Furthermore, the surface of the decorative film of the present invention may have a textured shape. Such a decorative film is produced by a method in which a melted resin extruded from a die is directly pressed between a roll having an uneven shape and a smooth roll to transfer the uneven shape. It can be produced by a surface transfer method or the like in which a heated roll and a smooth (cooling) roll are brought into pressure contact with each other. Examples of the embossed shape include pear-skin tone, animal skin tone, hairline tone, carbon tone, and the like.

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

<Decorative molding>
As a molded article to be decorated (to be decorated) in the present invention, it is preferable to use various resin molded articles (hereinafter sometimes referred to as "substrate") made of a polypropylene resin or a polypropylene resin composition. can. The molding method of the resin molding is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

Since the polypropylene resin is non-polar, it is a difficult-to-adhere polymer, but the decorative film in the present invention is a resin composition (B' ) containing the layer (II), the decorating object made of polypropylene resin and the decorating film are attached to each other to exhibit extremely high adhesive strength, and the decorating molding can be performed before the weathering agent volatilizes. can be completed.

As the base resin of the polypropylene-based resin and polypropylene-based resin composition of the molded article to be decorated, propylene homopolymer (homopolypropylene), propylene-α-olefin copolymer, or propylene block copolymer, etc. Various types based on various known propylene monomers can be selected. In addition, it may contain a filler such as talc for imparting rigidity and an elastomer or the like for imparting impact resistance, as long as the effects of the present invention are not impaired. In addition, it may contain additive components and other resin components in the same manner as the polypropylene-based resin composition that can constitute the decorative film described above.

In addition, as the molded body to be decorated (decorative object) in the present invention, various molded bodies made of polar resin materials can be used. In that case, polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic Various molded bodies made of polar resin materials selected from resins, polyvinyl alcohol resins, polycarbonate resins, ABS resins, urethane resins, melamine resins, polyphenylene ether resins, and composite materials thereof can be preferably used. In addition, additives such as reinforcing agents such as inorganic fillers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, and lubricants may be added to these resins. More than one type may be used together. The molding method is not particularly limited, and examples thereof include injection molding, blow molding, press molding, extrusion molding, and the like.

The above-mentioned polar resin materials are usually not heat-bonded because non-polar polypropylene-based resins are difficult-to-adhere resins. On the other hand, in the decorative film of the present invention, the sealing layer (I) contains the polyolefin adhesive resin (G), so that the decorative film can be thermally bonded to the object to be decorated, and the adhesive strength is high. can be demonstrated. As the polyolefin adhesive resin (G), modified polyolefin resins grafted with α,β-unsaturated carboxylic acids are preferably exemplified.

The decorative molded article obtained by attaching the decorative film of the present invention to various molded articles made of polypropylene resin, especially various molded articles formed in a three-dimensional shape, has greatly reduced VOCs contained in coatings and adhesives. Therefore, it can be suitably used as automobile members, home electric appliances, vehicles (railways, etc.), building materials, daily necessities, and the like.

[Manufacturing of decorative molding]
The method for manufacturing a decorated molded article of the present invention includes the steps of preparing the above-described decorative film, preparing a resin molded article, and setting the resin molded article and the decorative film in a chamber box capable of being decompressed. , the step of reducing the pressure in the chamber box, the step of heat-softening the decorative film, the step of pressing the heat-softened decorative film against the resin molding, and returning the pressure-reduced pressure in the chamber box to atmospheric pressure, or It is characterized by including a step of pressurizing.

According to the method for producing the decorated molded article of the present invention, air is not entrained between the decorative film and the resin molded article, and it is possible to obtain a beautifully decorated molded article with good texture reproducibility such as embossing. can. The decorative molded article obtained in this manner does not contain a thermosetting resin layer because the constituent material of the decorative film is a polypropylene-based resin and does not need to contain a thermosetting resin layer. Low deterioration in performance and high recyclability.

In three-dimensional decorative thermoforming, the object to be decorated and the decorative film are set in a chamber box that can be depressurized. It has a basic process of pressing the decorative film and returning the inside of the chamber box to the atmospheric pressure or applying pressure to attach the decorative film to the surface of the object to be decorated. paste. As a result, it is possible to obtain a clean decorative molded article free from air pockets. In the manufacturing method of the present invention, any known technique can be used as long as the device and conditions are suitable for three-dimensional decorative thermoforming.

That is, the chamber box may contain all of the object to be decorated, the decorative film, the mechanism for pressing it, the device for heating the decorative film, etc., or the decorative film A plurality of divided objects may be used.

Also, the mechanism for pressing the decorative film against the decorative object may be of any type, such as a mechanism that moves the decorative object, a mechanism that moves the decorative film, or a mechanism that moves both.
More specifically, representative molding methods are exemplified below.

A method of adhering a decorative film to an object to be decorated using a three-dimensional decorating thermoforming machine will be exemplified below with reference to the drawings.

As shown in FIG. 2, the three-dimensional decorating thermoforming machine of this embodiment comprises upper and lower chamber boxes 11 and 12, and the decorating film 1 is thermoformed in the two chamber boxes 11 and 12. I'm trying A vacuum circuit (not shown) and an air circuit (not shown) are connected to the upper and lower chamber boxes 11 and 12, respectively.

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

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

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

As shown in FIG. 4, after lowering the upper chamber box 11 and joining the upper and lower chamber boxes 11 and 12 to close the inside of the chamber boxes 11 and 12, the insides of the chamber boxes 11 and 12 are vacuum-sucked. Then, the decorative film 1 is heated by the heater 15 .

After the decorative film 1 is heated and softened, as shown in FIG. 5, the table 14 in the lower chamber box 12 is raised while the upper and lower chamber boxes 11 and 12 are kept in a vacuum state. The decorative film 1 is pressed against the resin molded body 5 to cover the resin molded body 5 . Furthermore, as shown in FIG. 6, by opening the upper chamber box 11 to atmospheric pressure or supplying compressed air from a compressed air tank, the decorative film 1 is brought into close contact with the resin molding 5 with a greater force.

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

[Molding condition]
The pressure in the chamber boxes 11 and 12 may be reduced as long as air pockets are not generated, and the pressure in the chamber boxes is preferably 10 kPa or less, more preferably 3 kPa or less, and still more preferably 1 kPa or less.

In addition, in the two chamber boxes 11 and 12 divided into upper and lower parts by the decorative film 1, the internal pressure of the chamber box on the side to which the resin molded body 5 and the decorative film 1 are attached should be within the above range. By changing the pressure of the upper and lower chamber boxes 11 and 12, the drawdown of the decorative film 1 can be suppressed.

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

However, since the decorative film of the present invention includes the layer (II) containing the resin composition (B') containing the specific polypropylene resin (B), it is not only difficult to draw down, but also the film due to pressure fluctuations Resistant to deformation.

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

In the present invention, in order to adhere the polypropylene-based decorative film 1 to the resin molded body 5 made of polypropylene-based resin, the surface of the resin molded body 5 and the decorative film 1 to be decorated must be sufficiently softened or melted. is required.

Therefore, the heater temperature must be higher than the melting temperature of the polypropylene resin forming the resin molding 5 and the polypropylene resin forming the decorative film 1 . The heater temperature is preferably 160° C. or higher, more preferably 180° C. or higher, and most preferably 200° C. or higher.

The higher the heater temperature, the shorter the time required for heating. If the temperature of the heater becomes too high, not only the moldability deteriorates but also the resin thermally deteriorates. It is below.

Although the appropriate heating time varies depending on the heater temperature, it is preferable that the polypropylene-based decorative film is heated and heated for a period of time longer than the time until the polypropylene-based decorative film starts to stretch back, which is called springback, although it varies depending on the heater temperature.
In some embodiments, it is preferred that the heating is performed for up to 2 seconds or more after the end of unrolling.

In other words, the decorative film heated by the heater thermally expands when heated from a solid state, and once sagged as the crystals melt, and once the crystals melt, the molecules relax and temporarily spring back. After that, the decorative film exhibits the behavior of sagging under its own weight, but after springback, the crystals of the decorative film are completely melted and the molecules are sufficiently relaxed, so sufficient adhesive strength is obtained.
Furthermore, the decorative film containing the sealing layer (I) of the present invention surprisingly can be strongly adhered to the substrate even if it is decoratively thermoformed before the end of stretching, so that the thermoforming can be performed. The time can be shortened, and molding can be completed before the weathering agent contained in the decorative film volatilizes. In addition, there is a great effect in suppressing grain return.

On the other hand, if the heating time is too long, the decorative film may sag under its own weight or be deformed due to the pressure difference between the upper and lower chamber boxes. .

In the case of decorating a molded article having a complicated shape having irregularities or in the case of achieving higher adhesive strength, it is preferable to supply compressed air when adhering the decorative film to the substrate. The pressure in the upper chamber box when the compressed air is introduced is preferably 150 kPa or higher, more preferably 200 kPa or higher, and still more preferably 250 kPa or higher. Although there is no particular upper limit, the pressure is preferably 450 kPa or less, more preferably 400 kPa or less, since there is a risk of damaging the equipment if the pressure is too high.

EXAMPLES Hereinafter, the present invention will be described in more detail as examples, but the present invention is not limited to these examples.

1. Measurement method of various physical properties (i) Melt flow rate (MFR)
Measured according to ISO 1133:1997 Conditions M at 230° C. and a load of 2.16 kg. The unit is g/10 minutes.

(ii) strain hardening degree λ
The method for obtaining the strain hardening degree λ was performed by the method described above. At this time, η ^* (0.01) used as the shear viscosity value and ηe (3.5) used as the elongational viscosity value were measured by the following methods. In addition, the sample used for the measurement at this time was formed into a flat plate with a thickness of 0.7 mm and 2 mm by pressing for 1 hour at a temperature of 180 ° C. and a pressure of 10 MPa. was used for extensional viscosity measurements and 2 mm samples for dynamic frequency sweep experiments.

(ii-1) shear viscosity η ^* (0.01)
Dynamic frequency sweep experiments were performed using a Rheometric Scientific ARES. Parallel discs with a diameter of 25 mm were used for the measurement geometry. The measurement was performed in the measurement mode Dynamic Frequency Sweep Test using the device control software TA Orchestrator. The sample used was a 2 mm-thick press-formed body produced by the above method. The measurement temperature was 180°C. The angular frequency ω was measured at 5 points per digit at equal intervals on a logarithmic scale between 0.01 and 100 rad/s.
The complex viscosity η ^* (0.01) [unit: Pa·s] at ω=0.01 rad/s is employed as an index indicating the viscosity of the sample at a low shear rate. The complex viscosity η ^* is calculated by η ^* =G ^* /ω from the complex elastic modulus G ^* [unit: Pa] and ω.

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

(iii) melting peak temperature (melting point)
Using a differential scanning calorimeter (DSC), once the temperature was raised to 200° C. and held for 10 minutes, the temperature was lowered to 40° C. at a cooling rate of 10° C./min, and again at a heating 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.

(iv) Measurement of branching index g' at an absolute molecular weight Mabs of 1,000,000 According to the method described above, measurement was performed using GPC equipped with a light scattering meter and a viscometer as detectors, and the branching index was determined based on the analysis method described above. g' was obtained.

(v) Detection of long-chain branched structure using ¹³ C-NMR Measurement using ¹³ C-NMR was performed according to the method described above to determine the presence or absence of long-chain branched structure.

(vi) GPC measurement GPC measurement was performed using the following apparatus and conditions, and Mw/Mn was calculated.
・Apparatus: GPC manufactured by Waters (ALC/GPC 150C)
・ Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
・Column: Showa Denko AD806M/S (3 columns)
・ Mobile phase solvent: ortho-dichlorobenzene (ODCB)
・Measurement temperature: 140°C
・Flow rate: 1.0 ml/min
・Injection volume: 0.2 ml
- Sample preparation: The sample was prepared as a 1 mg/mL solution using ODCB (containing 0.5 mg/mL BHT) and dissolved at 140°C for about 1 hour.

Conversion from the retention volume obtained by GPC measurement to the molecular weight was carried out using a previously prepared standard polystyrene (PS) calibration curve. The standard polystyrene used is the following brand manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve was prepared by injecting 0.2 mL of a solution of 0.5 mg/mL each in ODCB (containing 0.5 mg/mL BHT). A cubic equation obtained by approximation by the method of least squares was used for the calibration curve.
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

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

(viii) Tensile Modulus The tensile modulus of the thermoplastic elastomer (D) was measured according to ASTM D638 by ASTM-IV Injection Specimen at 23° C. and a tensile speed of 50 mm/min.

(ix-1) ethylene content [E (C)]
The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) was obtained from the integrated intensity obtained by ¹³ C-NMR measurement based on the method described above. Sample preparation and measurement conditions are as follows.
200 mg of the sample ethylene-α-olefin random copolymer (C) was mixed with 2.4 ml of o-dichlorobenzene/deuterated brominated benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and chemical shift It was placed in an NMR sample tube with an inner diameter of 10 mm and dissolved together with hexamethyldisiloxane as a reference substance.
¹³ C-NMR measurement was performed using an AV400 type NMR apparatus manufactured by Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe.
The ¹³ C-NMR measurement conditions were a sample temperature of 120° C., a pulse angle of 90°, a pulse interval of 20 seconds, and an accumulation count of 512 times, and the broadband decoupling method was used.

(ix-2) 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 of was measured using the ¹³ C-NMR ethylene content measurement method described above.

(x) isothermal crystallization time:
The isothermal crystallization time was measured by the method described above 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 polypropylene resin (A) and the thermoplastic resin (E) are biaxially Melt-kneading was performed using an extruder to obtain pellets of the polypropylene resin (A) and the resin composition (X5), and the isothermal crystallization time was measured using the pellets. KZW-15 manufactured by Technovel Co., Ltd. was used for the twin-screw extruder, the screw rotation speed was 400 RPM, and the kneading temperature was set to 80 ° C., 120 ° C. and 200 ° C. from the bottom of the hopper (the same temperature until the die exit). .

2. Evaluation of physical properties of decorated molded product (1) Evaluation of thermoformability The drawdown state of the decorative film during three-dimensional decorative thermoforming and the decorative film of the decorative molded product with the decorative film attached to the substrate The adhered state was visually observed and evaluated according to the criteria shown below.
○: During the three-dimensional decorative thermoforming, the decorative film did not draw down and the base and the decorative film were in contact with each other over the entire contact surface at the same time. ing.
x: Contact unevenness occurred over the entire surface of the substrate due to a large drawdown of the decorative film during three-dimensional decorative thermoforming.

(2) Adhesive strength between the resin molded body (substrate) and the decorative film "Craft Adhesive Tape No. 712N" manufactured by Nitoms Co., Ltd. is cut into a width of 75 mm and a length of 120 mm, and 75 mm from the end of the resin molded body (substrate). It was affixed to a resin molding (substrate) in the range of ×120 mm and subjected to masking treatment (the substrate surface exposed portion was 45 mm wide and 120 mm long). The resin molding (substrate) was placed in a three-dimensional decorative thermoforming apparatus NGF-0406-SW so that the masking surface of the resin molded body (substrate) was in contact with the decorative film, and three-dimensional decorative thermoforming was performed.

The decorative film surface of the obtained decorative molding was cut with a cutter in a direction perpendicular to the longitudinal direction of the adhesive tape with a width of 10 mm to the surface of the substrate to prepare a test piece. In the obtained test piece, the adhesive surface between the substrate and the decorative film had a width of 10 mm and a length of 45 mm. Attach the test piece to the tensile tester so that the base part and the decorative film part of the test piece are 180 °, measure the 180 ° peel strength of the adhesive surface at a tensile speed of 200 mm / min, and measure the maximum strength at the time of peeling or breaking (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) Weather resistance After holding the flat plate sample after three-dimensional decorative thermoforming at 23 ° C. 50% RH for 48 hours, cut a test piece of 30 mm in length and 70 mm in width from the flat plate, Toyo Seiki Co., Ltd. Atlas tester Ci65AW 504 MJ of xenon arc lamp light was applied to the decorative film side of the decorative molding under the conditions of a black panel temperature of 89° C., a humidity of 50%, and an irradiance of 100 W/m 2 . The irradiation time is as follows.
Irradiation time (1). When the decorative film contains only the hindered amine light stabilizer: 400 hr
Irradiation time (2). When the decorative film contains only UV absorber: 200hr
Irradiation time (3). When the decorative film contains both the hindered amine light stabilizer and the UV absorber: 600 hr
After irradiation, the surface of the test piece was observed and evaluated under a microscope at a magnification of 20 times. In addition, the evaluation criteria are as follows.
◯: No change is observed on the irradiated surface, or staining is slightly observed.
x: Fine cracks are observed on the irradiated surface.

(4) Recyclability Evaluation The obtained decorative molded article was pulverized, and a recycled molded article was produced by injection molding in the same manner as in the production of the resin molded article (substrate). evaluated according to the standard.
◯: Excellent appearance without poor dispersion such as fish eyes.
x: A fish eye occurs in the ejected piece, and the appearance is poor.

3. Production of resin molding (substrate) 3-1. Polypropylene resin used for resin molding The following polypropylene-based resins were used.
(Z-1): Propylene homopolymer (MFR = 40 g/10 min, Tm = 165°C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) MA04H"
(Z-2): Propylene ethylene block copolymer (MFR = 30 g/10 min, Tm = 164°C), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) NBC03HR"
(Z-3): 60% by weight of polypropylene resin (Z-2), 20% by weight of EBR (Tafmer (registered trademark) A0550S manufactured by Mitsui Chemicals, Inc.) with MFR = 1.0, inorganic filler (Nippon Talc Talc P-6 manufactured by Co., Ltd., average particle size 4.0 μm) is blended at 20 wt% polypropylene resin composition

3-2. Production of Resin Molded Article (Substrate) Using polypropylene resins (Z-1) to (Z-3), injection molded articles were obtained by the following method.
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 200°C
Mold temperature: 40°C
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate Condition adjustment: Maintained 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)
[1: Decorative film containing sealing layer (I) made of polypropylene-based resin (A) having MFR (A) exceeding 2.0 g/10 min]
1-1. Materials Used Polypropylene Resins The following polypropylene resins were used.
(A-1): Propylene homopolymer having no long chain branch (MFR = 10 g/10 min, Tm = 161°C, strain hardening degree λ = 1.0, tensile modulus = 1600 MPa), Japan Polypropylene Corporation (trade name) "Novatec (registered trademark) FA3KM" manufactured by Sanyo Co., Ltd., branching index g' = 1.0 at an absolute molecular weight Mabs of 1,000,000. It was confirmed by ¹³ C-NMR measurement that it did not have a long-chain branched structure.
(A-2): Propylene-α-olefin random copolymer having no long chain branch (MFR = 5.0 g/10 min, Tm = 127°C, tensile modulus = 650 MPa), manufactured by Japan Polypropylene Corporation, Trade name "Novatec (registered trademark) FX4G".
(A-3): Propylene-α-olefin random copolymer having no long chain branch (MFR = 7.0 g/10 min, Tm = 146°C, Mw/Mn = 4.0, tensile modulus = 1200 MPa) , Japan Polypropylene Co., Ltd., trade name "Novatec (registered trademark) FW3GT".
(A-1-1): Polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (A-1) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin770"). Product (MFR = 10 g / 10 minutes, Tm = 161 ° C.)

(B-1): A propylene homopolymer having long chain branches produced by a macromer copolymerization method, manufactured by Japan Polypropylene Corporation, trade name "WAYMAX (registered trademark) MFX8", MFR = 1.0 g/10 min. , Mw/Mn = 5.3, strain hardening degree λ = 9.7, Tm = 154°C, branching index g' = 0.89 at absolute molecular weight Mabs of 1,000,000, long-chain branched structure determined by ¹³ C-NMR measurement It was confirmed to have
(B-2): A propylene homopolymer having long chain branches produced by a macromer copolymerization method, manufactured by Japan Polypropylene Corporation, trade name "WAYMAX (registered trademark) MFX3", MFR = 8.8 g/10 min. , strain hardening degree λ=7.8, Tm=154° C., branching index g′=0.85 at absolute molecular weight ^Mabs of 1,000,000.
(B-1-1): A polypropylene resin composition obtained by blending 100 parts by weight of a polypropylene resin (B-1) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin770"). Product (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-1-2): Polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (B-1) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Chimassorb 944"). Product (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-1-3): Polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (B-1) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by ADEKA Co., Ltd., trade name "LA57"). Product (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-1-4): A polypropylene resin composition obtained by blending 0.2 parts by weight of a hindered amine light stabilizer (manufactured by ADEKA Co., Ltd., trade name "LA52") with 100 parts by weight of polypropylene resin (B-1). Product (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-1-5): A polypropylene-based resin composition obtained by blending 100 parts by weight of polypropylene-based resin (B-1) with 0.2 parts by weight of an ultraviolet absorber (manufactured by ADEKA Co., Ltd., trade name "ADEKA STAB 1413"). (MFR=1.0 g/10 min, Tm=154° C.)
(B-1-6): 100 parts by weight of polypropylene resin (B-1), 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin770"), and further an ultraviolet absorber ( Made by ADEKA Co., Ltd., trade name "ADEKA STAB 1413") blended with 0.2 parts by weight of a polypropylene resin composition (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-1-7): Polypropylene-based resin obtained by blending 100 parts by weight of polypropylene-based resin (B-1) with 0.2 parts by weight of an ultraviolet absorber (manufactured by ADEKA Co., Ltd., trade name "ADEKA STAB LA-31G"). Composition (MFR = 1.0 g/10 min, Tm = 154°C)
(B-1-8): 100 parts by weight of polypropylene resin (B-1), 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Chimassorb 944"), and further an ultraviolet absorber ( ADEKA Co., Ltd., trade name "ADEKA STAB LA-31G") blended polypropylene resin composition (MFR = 1.0 g / 10 minutes, Tm = 154 ° C.)
(B-2-1): A polypropylene resin composition obtained by blending 100 parts by weight of a polypropylene resin (B-2) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Tinuvin770"). Product (MFR = 8.8 g / 10 minutes, Tm = 154 ° C.)
(B-2-2): Polypropylene resin composition obtained by blending 100 parts by weight of polypropylene resin (B-2) with 0.2 parts by weight of a hindered amine light stabilizer (manufactured by BASF Corporation, trade name "Chimassorb 944"). Product (MFR = 8.8 g / 10 minutes, Tm = 154 ° C.)

Example 1-1
・Production of decorative film 2 types 2 with a lip opening of 0.8 mm and a die width of 400 mm, which are connected to a seal layer extruder-1 with a diameter of 30 mm (diameter) and an extruder-2 with a diameter of 40 mm (diameter) A layer T die was used. The polypropylene resin (A-1) was put into the seal layer extruder-1, and the polypropylene resin (B-1-1) was put into the extruder-2. Melt extrusion was carried out under the conditions of a discharge rate of 4 kg/h and a discharge rate of Extruder-2 of 12 kg/h.

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

• Three-dimensional decorative thermoforming As the resin molded body (substrate) 5, an injection molded body made of the polypropylene-based resin (Z-1) obtained above was used.
"NGF-0406-SW" manufactured by Fuse Vacuum Co., Ltd. was used as a three-dimensional decoration thermoforming apparatus. As shown in FIGS. 2 to 7, the decorative film 1 is cut into a width of 250 mm and a length of 350 mm so that the seal layer (I) faces the substrate and the longitudinal direction is the MD direction of the film. It was set on a film fixing jig 13 having a size of 210 mm×300 mm. The resin molded body (substrate) 5 was placed on a sample installation table with a height of 20 mm, which was installed on a table 14 located below the film fixing jig 13, and placed on a sample installation table manufactured by Nichiban Co., Ltd. “Nice Tac NW-K15. ” pasted through. The film fixing jig 13 and the table 14 were installed in the chamber boxes 11 and 12, and the chambers were closed to make the insides of the chamber boxes 11 and 12 airtight. The chamber box is vertically divided through the decorative film 1. - 特許庁The upper and lower chamber boxes are evacuated and the pressure is reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa. was heated. Vacuum suction was continued even during heating, and finally the pressure was reduced to 0.1 kPa. 10 seconds after the decorative film 1 is heated and temporarily slackened and then stretched back, the table 14 installed in the lower chamber box 12 is moved upward, and the resin molded body ( The substrate) 5 was pressed against the decorative film 1, and immediately after that, compressed air was fed into the upper chamber box 11 so that the pressure in the upper chamber box 11 was 270 kPa, and the resin molding (substrate) 5 and the decorative film 1 were brought into close contact with each other. Thus, a three-dimensional decorated thermoformed product 6 was obtained in which the decorative film 1 was adhered to the top and side surfaces of the resin molded body (substrate) 5 . Table 2 shows the evaluation results. The evaluation of weather resistance was performed under the condition of irradiation time (1).

Example 1-2
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Example 1-3
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Examples 1-4
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Examples 1-5
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 1-1, except that the condition of time (2) was used. Table 2 shows the evaluation results.

Examples 1-6
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 1-1. Table 2 shows the evaluation results.

Examples 1-7
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, and molding and evaluation were performed in the same manner as in Example 1-1. Table 2 shows the evaluation results.

Examples 1-8
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Examples 1-9
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 1-1. Table 2 shows the evaluation results.

Examples 1-10
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, and molding and evaluation were performed in the same manner as in Example 1-1. Table 2 shows the evaluation results.

Examples 1-11
Same as Example 1-1, except that the polypropylene resin (A-1) of the sealing layer (I) was changed to the polypropylene resin (A-2) in the production of the decorative film of Example 1-1. was molded and evaluated. Table 2 shows the evaluation results.

Examples 1-12
Same as Example 1-1, except that the polypropylene resin (A-1) of the sealing layer (I) was changed to the polypropylene resin (A-3) in the production of the decorative film of Example 1-1. was molded and evaluated. Table 2 shows the evaluation results.

Examples 1-13
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. Polypropylene resin (A-1) in seal layer extruder -1, polypropylene resin (B-1-1) in extruder -2, polypropylene resin (A -1-1) were charged respectively, the resin temperature was 240 ° C., the discharge rate of extruder-1 for seal layer was 4 kg / h, the discharge rate of extruder-2 was 8 kg / h, and the extruder for surface decoration layer - 3 was melt-extruded under the conditions of a discharge amount of 4 kg/h.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed in the same manner as in Example 1-1 and evaluated. Table 2 shows the evaluation results.

Examples 1-14
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to a polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 1-1, except that the condition of time (3) was used. Table 2 shows the evaluation results.

Examples 1-15
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 body made of polypropylene resin (Z-2). Table 2 shows the evaluation results.

Examples 1-16
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 body made of polypropylene resin (Z-3). Table 2 shows the evaluation results.

Examples 1-17
In the production of the decorative film of Example 1-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to a polypropylene-based resin (B-1-7), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 1-1, except that the condition of time (2) was used. Table 2 shows the evaluation results.

Examples 1-18
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Examples 1-19
In the production of the decorative film of Example 1-13, Example 1- Molding and evaluation were performed in the same manner as in No. 13. Table 2 shows the evaluation results.

Example 1-20
In the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1-8), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 1-1, except that the condition of time (3) was used. Table 2 shows the evaluation results.

Comparative Example 1-1
Example 1-1, except that the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 1-1. Molding and evaluation were performed in the same manner. Table 2 shows the evaluation results.

Comparative Example 1-2
In the production of the decorative film of Example 1-1, Example 1- Molding and evaluation were performed in the same manner as in 1. Table 2 shows the evaluation results.

Comparative Example 1-3
Same as Example 1-1, except that the polypropylene resin (A-1) of the seal layer (I) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 1-1. was molded and evaluated. Table 2 shows the evaluation results.

Comparative Example 1-4
In the production of the decorative film of Example 1-1, the polypropylene-based resin (A-1) of the sealing layer (I) was changed to polypropylene-based resin (B-1), and the springback occurred in the 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. Table 2 shows the evaluation results.

Comparative Example 1-5
In the production of the decorative film of Example 1-1, the polypropylene resin (B-1-1) of layer (II) was changed to polypropylene resin (B-1-5), and the seal layer (I) Polypropylene resin (A-1) was changed to polypropylene resin (B-1), molding was performed 40 seconds after the springback phenomenon ended in three-dimensional decorative thermoforming, and irradiation was performed to evaluate weather resistance. Molding and evaluation were performed in the same manner as in Example 1-1, except that the condition of time (2) was used. Table 2 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 1-1 to 1-20 each contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) Regarding the polypropylene resin (A) in the layer (II), the resin composition (a1) has a melt flow rate (MFR (A)) exceeding 2.0 g/10 min and contains the polypropylene resin (B) in the layer (II) ( Regarding B′), (b1) the melt flow rate (MFR (B′)) is 40 g/10 min or less and (b2) the degree of strain hardening is 1.1 or more, so there is no contact unevenness and thermoforming is possible. The adhesiveness was excellent and the adhesiveness was good. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 1-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 1-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. The decorative films of Comparative Examples 1-3, in which the MFR of the polypropylene-based resin used for the seal layer (I) was 2.0 g/10 minutes or less, were inferior in adhesive strength, and weather resistance was not evaluated. Comparative Example 1-4, in which the same decorative film as in Comparative Example 1-3 was used and molding was performed 40 seconds after the end of the springback phenomenon, was achieved by increasing the heating time of three-dimensional decorative molding. Although the properties were exhibited, the added hindered amine light stabilizer volatilized, and the weather resistance was inferior to that of Example 1-1. The MFR (A) of the polypropylene resin used for the seal layer (I) is 2.0 g/10 minutes or less, and the layer (II) is blended with an ultraviolet absorber, and after 40 seconds from the end of the springback phenomenon In Comparative Example 1-5 in which molding was performed, the adhesiveness was exhibited by prolonging the heating time of the three-dimensional decorative molding, but the added ultraviolet absorber volatilized, compared with Example 1-5. As a result, it became inferior in weather resistance.

(Test example 2)
[2: Decorative film containing seal layer (I) made of polypropylene resin (A) that satisfies requirements (a2) to (a4)]
2-1. Materials Used Polypropylene Resins In addition to the polypropylene resins used in "1-1. Materials Used", the following polypropylene resins were used.
(A-4): Propylene-α-olefin copolymer with a metallocene catalyst (MFR = 7.0 g/10 minutes, Tm = 125°C, Mw/Mn = 2.5), manufactured by Japan Polypropylene Corporation, commercial product Name "Wintec (registered trademark) WFX4M"
(A-5): Propylene-α-olefin copolymer with a metallocene catalyst (MFR = 25 g/10 min, Tm = 125°C, Mw/Mn = 2.4), manufactured by Japan Polypropylene Corporation, trade name " Wintech (registered trademark) WSX03”
(A-6): Propylene-α-olefin copolymer with a metallocene catalyst (MFR = 7.0 g/10 minutes, Tm = 135°C, Mw/Mn = 2.3), manufactured by Japan Polypropylene Corporation, commercial product Name "Wintech (registered trademark) WFW4M"
(A-7): Propylene-α-olefin copolymer with metallocene catalyst (MFR = 3.5 g/10 min, Tm = 143°C, Mw/Mn = 2.8), manufactured by Japan Polypropylene Corporation, commercial product Name "Wintec (registered trademark) WFW5T"

Example 2-1
In the production of the decorative film of Example 1-1, the polypropylene-based resin (A-1) of the seal layer (I) was changed to polypropylene-based resin (A-4), and the springback occurred in the three-dimensional decorative thermoforming. Molding and evaluation were performed in the same manner as in Example 1-1, except that molding was performed 5 seconds after the phenomenon was completed. Table 3 shows the evaluation results.

Example 2-2
In the production of the decorative film of Example 2-1, Example 2- Molding and evaluation were performed in the same manner as in 1. Table 3 shows the evaluation results.

Example 2-3
In the production of the decorative film of Example 2-1, Example 2- Molding and evaluation were performed in the same manner as in 1. Table 3 shows the evaluation results.

Example 2-4
In the production of the decorative film of Example 2-1, Example 2- Molding and evaluation were performed in the same manner as in 1. Table 3 shows the evaluation results.

Example 2-5
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 2-1, except that the condition of time (2) was used. Table 3 shows the evaluation results.

Example 2-6
In the production of the decorative film of Example 2-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended at a weight ratio of 70:30 (Tm(B′)=161° C.), molding and evaluation were carried out in the same manner as in Example 2-1. Table 3 shows the evaluation results.

Examples 2-7
In the production of the decorative film of Example 2-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90 (Tm(B′)=161° C.), but molding and evaluation were performed in the same manner as in Example 2-1. Table 3 shows the evaluation results.

Example 2-8
In the production of the decorative film of Example 2-1, Example 2- Molding and evaluation were performed in the same manner as in 1. Table 3 shows the evaluation results.

Example 2-9
In the production of the decorative film of Example 2-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended at a weight ratio of 70:30 (Tm(B′)=161° C.), molding and evaluation were carried out in the same manner as in Example 2-1. Table 3 shows the evaluation results.

Example 2-10
In the production of the decorative film of Example 2-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90 (Tm(B′)=161° C.), but molding and evaluation were performed in the same manner as in Example 2-1. Table 3 shows the evaluation results.

Example 2-11
In the production of the decorative film of Example 2-1, except that the polypropylene resin (A-4) of the seal layer (I) was changed to the polypropylene resin (A-5), the same as in Example 2-1. Molding and evaluation were performed in the same manner. Table 3 shows the evaluation results.

Example 2-12
In the production of the decorative film of Example 2-1, except that the polypropylene resin (A-4) of the sealing layer (I) was changed to the polypropylene resin (A-6), the same as in Example 2-1. Molding and evaluation were performed in the same manner. Table 3 shows the evaluation results.

Example 2-13
In the production of the decorative film of Example 2-1, the polypropylene resin (A-4) of the seal layer (I) was changed to the polypropylene resin (A-7), as in Example 2-1. Molding and evaluation were performed in the same manner. Table 3 shows the evaluation results.

Example 2-14
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. Polypropylene resin (A-4) in seal layer extruder -1, polypropylene resin (B-1-1) in extruder -2, polypropylene resin (A -1-1) were charged respectively, the resin temperature was 240 ° C., the discharge rate of extruder-1 for seal layer was 4 kg / h, the discharge rate of extruder-2 was 8 kg / h, and the extruder for surface decoration layer - 3 was melt-extruded under the conditions of a discharge amount of 4 kg/h.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed in the same manner as in Example 2-1 and evaluated. Table 3 shows the evaluation results.

Example 2-15
In the production of the decorative film of Example 2-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 2-1, except that the condition of time (3) was used. Table 3 shows the evaluation results.

Example 2-16
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 body made of polypropylene resin (Z-2). Table 3 shows the evaluation results.

Example 2-17
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 body made of polypropylene resin (Z-3). Table 3 shows the evaluation results.

Comparative Example 2-1
Example 2-1 except that the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 2-1. Molding and evaluation were performed in the same manner. Table 3 shows the evaluation results.

Comparative example 2-2
In the production of the decorative film of Example 2-1, Example 2- Molding and evaluation were performed in the same manner as in 1. Table 3 shows the evaluation results.

Comparative example 2-3
Same as Example 2-1, except that the polypropylene resin (A-4) of the sealing layer (I) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 2-1. was molded and evaluated. Table 3 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 2-1 to 2-17 contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) The polypropylene-based resin (A) in (a1) has a melt flow rate (MFR (A)) exceeding 2.0 g/10 min, (a2) is a metallocene-catalyzed propylene-based polymer, and (a3) has a melting peak Temperature (Tm (A)) is less than 150 ° C., (a4) Mw / Mn (A) is 1.5 to 3.5, and layer (II) contains polypropylene resin (B) Regarding the resin composition (B'), (b1) a melt flow rate (MFR (B')) of 40 g/10 min or less, (b2) a strain hardening degree of 1.1 or more, and (b3) a melting peak Since the temperature (Tm(B')) was higher than Tm(A), there was no contact unevenness, excellent thermoformability, and good adhesion. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 2-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 2-2, in which the strain hardening degree of the polypropylene-based resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. Comparative Example 2-3, in which a polypropylene-based resin (B-1) having a MFR of 2.0 g/10 min or less and a high Mw/Mn of 5.3 was used for the sealing layer (I), was inferior in adhesive strength. Therefore, the weather resistance was not evaluated.

(Test example 3)
[3: Decorative film containing sealing layer (I) containing polypropylene resin (A) and ethylene-α-olefin random copolymer (C)]
3-1. Materials Used Polypropylene Resins The polypropylene resins used in the above "1-1. Materials used" and "2-1. Materials used" were used.

Ethylene-α-olefin random copolymer (C)
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 Chemicals, Inc. Product name: Toughmer A4085S
(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 Chemicals, Inc. Product name: Toughmer 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% by weight): manufactured by DuPont Dow, Product name “Engage EG8003”
(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 Chemicals, Inc. Product name: Toughmer P0280

Example 3-1
In the production of the decorative film of Example 1-1, the polypropylene-based resin (A-1) of the sealing layer (I) was mixed with the polypropylene-based resin (A-3) and the ethylene-α-olefin random copolymer (C- 1) and 1) are blended so that the weight ratio is 85:15, and molding is performed immediately after the springback phenomenon ends in three-dimensional decorative thermoforming (that is, the heating time after springback is 0 seconds). Molding and evaluation were carried out in the same manner as in Example 1-1 except for the above. Table 4 shows the evaluation results.

Example 3-2
In the production of the decorative film of Example 3-1, Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-3
In the production of the decorative film of Example 3-1, Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-4
In the production of the decorative film of Example 3-1, Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-5
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 3-1, except that the condition of time (2) was used. Table 4 shows the evaluation results.

Examples 3-6
In the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Examples 3-7
In the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-8
In the production of the decorative film of Example 3-1, Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-9
In the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Examples 3-10
In the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

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 sealing layer (I) was replaced with the ethylene-α-olefin random copolymer (C-2 ), molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-12
In the production of the decorative film of Example 3-1, the ethylene-α-olefin random copolymer (C-1) used for the sealing layer (I) was replaced with the ethylene-α-olefin random copolymer (C-3 ), molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-13
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-4 ), molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-14
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 ), molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-15
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-6 ), molding and evaluation were performed in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-16
In the production of the decorative film of Example 3-1, the compounding ratio of the resin of the sealing layer (I) was polypropylene resin (A-3): ethylene-α-olefin random copolymer (C-1) = 70: Molding and evaluation were carried out in the same manner as in Example 3-1, except that 30 was used. Table 4 shows the evaluation results.

Example 3-17
In the production of the decorative film of Example 3-1, the compounding ratio of the resin for the seal layer (I) was polypropylene resin (A-3): 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. Table 4 shows the evaluation results.

Example 3-18
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. Also, a three-kind three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. A blend of the polypropylene resin (A-3) and the ethylene-α-olefin random copolymer (C-1) in a seal layer extruder-1 at a weight ratio of 85:15 was passed through the extruder. The polypropylene resin (B-1-1) was put into -2, and the polypropylene resin (A-1-1) was put into the surface decoration layer extruder -3, and the resin temperature was 240°C. Melt extrusion was carried out under the conditions of a discharge rate of 4 kg/h from Extruder-1, a discharge rate of 8 kg/h from Extruder-2, and a discharge rate of 4 kg/h from Extruder-3 for the surface decorative layer.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed and evaluated in the same manner as in Example 3-1. Table 4 shows the evaluation results.

Example 3-19
In the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 3-1, except that the condition of time (3) was used. Table 4 shows the evaluation results.

Example 3-20
In the production of the decorative film of Example 3-1, except that the polypropylene resin (A-3) used for the seal layer (I) was changed to the polypropylene resin (A-1), Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-21
In the production of the decorative film of Example 3-1, except that the polypropylene resin (A-3) used in the seal layer (I) was changed to the polypropylene resin (A-2), Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Example 3-22
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 body made of polypropylene resin (Z-2). Table 4 shows the evaluation results.

Example 3-23
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 body made of polypropylene resin (Z-3). Table 4 shows the evaluation results.

Comparative Example 3-1
Example 3-1 except that in the production of the decorative film of Example 3-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to the polypropylene-based resin (B-1). Molding and evaluation were performed in the same manner. Table 4 shows the evaluation results.

Comparative Example 3-2
In the production of the decorative film of Example 3-1, Example 3- Molding and evaluation were performed in the same manner as in 1. Table 4 shows the evaluation results.

Comparative Example 3-3
Molding and evaluation were performed in the same manner as in Example 3-1, except that the resin of the sealing layer (I) was changed to the polypropylene-based resin (B-1) in the production of the decorative film of Example 3-1. . Table 4 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 3-1 to 3-23 each contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) contains a resin composition (X3) in which the weight ratio of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95, and the polypropylene resin (A) , (a1) a melt flow rate (MFR (A)) exceeding 2.0 g/10 min, and an ethylene-α-olefin random copolymer (C) having (c1) an ethylene content [E (C)] of 65 % by weight or more, (c2) a density of 0.850 to 0.950 g/cm ³ , (c3) a melt flow rate (MFR(C)) of 0.1 to 100 g/10 min, and Regarding the resin composition (B') containing the polypropylene resin (B) in the layer (II), (b1) the melt flow rate (MFR (B')) is 40 g/10 minutes or less, and (b2) strain hardening Since the degree was 1.1 or more, there was no contact unevenness, the thermoformability was excellent, and the adhesiveness was good. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 3-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 3-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. A comparative example in which the seal layer (I) does not contain the ethylene-α-olefin random copolymer (C) and the MFR of the polypropylene-based resin used in the seal layer (I) is 2.0 g/10 minutes or less. 3-3 was inferior in adhesive strength, and weather resistance was not evaluated.

(Test example 4)
[4: Decorative film containing seal layer (I) containing polypropylene resin (A) and thermoplastic elastomer (D)]
4-1. Materials Used Polypropylene Resin The polypropylene resins used in the above "1-1. Materials Used" and "2-1. Materials Used" were used.

Thermoplastic elastomer (D)
The following thermoplastic elastomers were used.
(D-1): Propylene-butene random copolymer containing propylene as a main component (MFR = 7.0 g/10 min, Tm = 75°C, density = 0.885 g/cm ³ , tensile modulus = 290 MPa, propylene content = 69% by weight, butene content = 31% by weight, ethylene content [E] = 0% by weight): Mitsui Chemicals, Inc., trade name "Tafmer XM7070"
(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% by weight) : Made by Mitsui Chemicals, Inc., trade name “Tafmer BL4000”
(D-3): Propylene-ethylene-butene random copolymer containing propylene as the main component (MFR = 6.0 g/10 min, Tm = 160°C, density = 0.868 g/cm ³ , tensile modulus = 50 MPa , propylene content = 84% by weight, ethylene content [E] = 9% by weight, butene content = 7% by weight): Mitsui Chemicals, Inc., trade name "Tafmer PN2060"
(D-4): Propylene-ethylene random copolymer containing propylene as the main component (MFR = 8.0 g/10 min, Tm = 61°C, density = 0.871 g/cm ³ , tensile modulus = 45 MPa, propylene content = 89% by weight, ethylene content [E] = 11% by weight): Exxon Mobil Chemical Company, trade name "VISTAMAXX3000"

Example 4-1
In the production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (A-1) of the sealing layer (I) to the polypropylene resin (A-3) and the thermoplastic elastomer (D-1) Molded in the same manner as in Example 1-1 except that the mixture was blended so that the ratio was 85:15, and molding was performed 5 seconds after the springback phenomenon ended in the three-dimensional decorative thermoforming. , made an evaluation. Table 5 shows the evaluation results.

Example 4-2
In the production of the decorative film of Example 4-1, Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-3
In the production of the decorative film of Example 4-1, Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-4
In the production of the decorative film of Example 4-1, Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-5
In the production of the decorative film of Example 4-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 4-1, except that the condition of time (2) was used. Table 5 shows the evaluation results.

Example 4-6
In the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Examples 4-7
In the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Examples 4-8
In the production of the decorative film of Example 4-1, Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-9
In the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Examples 4-10
In the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Examples 4-11
In the production of the decorative film of Example 4-1, except that the thermoplastic elastomer (D-1) used in the seal layer (I) was changed to the thermoplastic elastomer (D-2), Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-12
In the production of the decorative film of Example 4-1, except that the thermoplastic elastomer (D-1) used in the seal layer (I) was changed to the thermoplastic elastomer (D-3), Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Examples 4-13
In the production of the decorative film of Example 4-1, except that the thermoplastic elastomer (D-1) used in the seal layer (I) was changed to the thermoplastic elastomer (D-4), Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-14
Except that in the production of the decorative film of Example 4-1, the compounding ratio of the resin of the sealing layer (I) was set to polypropylene resin (A-3):thermoplastic elastomer (D-1)=70:30. , was molded and evaluated in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Example 4-15
Except that in the production of the decorative film of Example 4-1, the compounding ratio of the resin of the seal layer (I) was set to polypropylene resin (A-3):thermoplastic elastomer (D-1)=30:70. , was molded and evaluated in the same manner as in Example 4-1. Table 5 shows the evaluation results.

Example 4-16
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. A blend of a polypropylene resin (A-3) and a thermoplastic elastomer (D-1) at a weight ratio of 85:15 is fed to the seal layer extruder-1, and a polypropylene resin is fed to the extruder-2. (B-1-1) and the polypropylene resin (A-1-1) were put into the extruder-3 for the surface decorative layer, and the resin temperature was 240 ° C., and the discharge rate of the extruder-1 for the sealing layer was adjusted. Melt extrusion was carried out under the conditions of 4 kg/h, an extruder-2 discharge rate of 8 kg/h, and a surface decorative layer extruder-3 discharge rate of 4 kg/h.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed in the same manner as in Example 4-1 and evaluated. Table 5 shows the evaluation results.

Example 4-17
In the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 4-1, except that the condition of time (3) was used. Table 5 shows the evaluation results.

Example 4-18
In the production of the decorative film of Example 4-1, except that the polypropylene resin (A-3) used in the seal layer (I) was changed to the polypropylene resin (A-1), Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-19
In the production of the decorative film of Example 4-1, except that the polypropylene resin (A-3) used in the sealing layer (I) was changed to the polypropylene resin (A-2), Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Example 4-20
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 body made of polypropylene resin (Z-2). Table 5 shows the evaluation results.

Example 4-21
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 body made of polypropylene resin (Z-3). Table 5 shows the evaluation results.

Comparative Example 4-1
Example 4-1 except that in the production of the decorative film of Example 4-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to the polypropylene-based resin (B-1). Molding and evaluation were performed in the same manner. Table 5 shows the evaluation results.

Comparative Example 4-2
In the production of the decorative film of Example 4-1, Example 4- Molding and evaluation were performed in the same manner as in 1. Table 5 shows the evaluation results.

Comparative Example 4-3
Molding and evaluation were performed in the same manner as in Example 4-1, except that the resin of the sealing layer (I) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 4-1. . Table 5 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 4-1 to 4-21 contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) contains a resin composition (X4) in which the weight ratio of the polypropylene resin (A) and the thermoplastic elastomer (D) is 97:3 to 5:95, and for the polypropylene resin (A), (a1) melt flow for a thermoplastic elastomer (D) having a rate (MFR(A)) of more than 2.0 g/10 min, (d1) containing at least one of propylene and butene as a main component, and (d2) having a density of 0.850 (d3) Melt flow rate (MFR (D)) is 0.1 to 100 g/ ¹⁰ min, (d4) Tensile modulus is smaller than polypropylene resin (A) And, regarding the resin composition (B') containing the polypropylene resin (B) in the layer (II), (b1) the melt flow rate (MFR (B')) is 40 g/10 minutes or less, and (b2 ) Since the degree of strain hardening was 1.1 or more, there was no contact unevenness, the thermoformability was excellent, and the adhesiveness was good. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 4-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 4-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. Comparative Example 4-3, in which the sealing layer (I) did not contain the thermoplastic elastomer (D) and the MFR of the polypropylene-based resin used in the sealing layer (I) was 2.0 g/10 minutes or less, showed adhesion It was inferior in strength and weatherability was not evaluated.

(Test Example 5)
[5: Decorative film containing seal layer (I) containing polypropylene resin (A) and thermoplastic resin (E)]
5-1. Materials Used Polypropylene Resin As the polypropylene resin for the seal layer (I), the following polypropylene resin was used.
(A-1): Propylene homopolymer (MFR = 10 g/10 min, Tm = 161°C, crystallization initiation temperature = 123°C, isothermal crystallization time (t) = 613 seconds (measured at 133°C)), Japan Polypro Co., Ltd., trade name “Novatec (registered trademark) FA3KM”
(A-3): Propylene-α-olefin copolymer (MFR = 7.0 g/10 min, Tm = 146°C, crystallization initiation temperature = 111°C, isothermal crystallization time (t) = 263 seconds (121°C )), manufactured by Japan Polypropylene Co., Ltd., trade name “Novatec (registered trademark) FW3GT”
(A-4): Propylene-α-olefin copolymer (MFR = 7.0 g/10 min, Tm = 125°C, crystallization initiation temperature = 97°C, isothermal crystallization time (t) = 570 seconds (107°C )), manufactured by Japan Polypropylene Co., Ltd., trade name “Wintech (registered trademark) WFX4M”
(A-8): Propylene block copolymer (MFR = 6.0 g/10 min, Tm = 135°C, crystallization initiation temperature = 99°C, isothermal crystallization time (t) = 478 seconds (measured at 109°C) ), manufactured by Japan Polypropylene Co., Ltd., trade name “Wellnex (registered trademark) RFG4VA”

For the layer (II) and the surface decorative layer (III), the polypropylene resin used in the above "1-1. Materials used" and "2-1. Materials used" was used.

Thermoplastic resin (E)
The following thermoplastic resins were used.
(E-1): Hydrogenated styrene 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 "Kraton G1645"
(E-3): Alicyclic hydrocarbon resin: manufactured by Arakawa Chemical Co., Ltd., trade name "Arcon P125"

Example 5-1
In the 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-3) and the thermoplastic resin (E-1) was changed to a blend so that the ratio was 50:50, and molding was performed immediately after the springback phenomenon ended in three-dimensional decorative thermoforming (that is, the heating time after springback was 0 seconds). Molding and evaluation were performed in the same manner as in Example 1-1. Table 6 shows the evaluation results.

Example 5-2
In the production of the decorative film of Example 5-1, Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Example 5-3
In the production of the decorative film of Example 5-1, Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Example 5-4
In the production of the decorative film of Example 5-1, Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Example 5-5
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 5-1, except that the condition of time (2) was used. Table 6 shows the evaluation results.

Example 5-6
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, and molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-7
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-8
In the production of the decorative film of Example 5-1, Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Examples 5-9
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, and molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-10
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-11
In the production of the decorative film of Example 5-1, except that the thermoplastic resin (E-1) used for the seal layer (I) was changed to the thermoplastic resin (E-2), Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Examples 5-12
In the production of the decorative film of Example 5-1, the thermoplastic resin (E-1) used for the seal layer (I) was changed to a thermoplastic resin (E-3), and a polypropylene resin (A-3 ) and the thermoplastic resin (E-3) were evaluated in the same manner as in Example 5-1, except that the blending ratio was 85:15. Table 6 shows the evaluation results.

Examples 5-13
Except that in the production of the decorative film of Example 5-1, the compounding ratio of the resin of the sealing layer (I) was set to polypropylene resin (A-3): thermoplastic resin (E-1) = 70:30. , molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-14
Except that in the production of the decorative film of Example 5-1, the compounding ratio of the resin of the seal layer (I) was set to polypropylene resin (A-3): thermoplastic resin (E-1) = 30:70. , molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-15
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. A blend of the polypropylene resin (A-3) and the thermoplastic resin (E-1) in a seal layer extruder-1 at a weight ratio of 50:50, and a polypropylene resin in the extruder-2 (B-1-1) and the polypropylene resin (A-1-1) were put into the extruder-3 for the surface decorative layer, and the resin temperature was 240 ° C., and the discharge rate of the extruder-1 for the sealing layer was adjusted. Melt extrusion was carried out under the conditions of 4 kg/h, an extruder-2 discharge rate of 8 kg/h, and a surface decorative layer extruder-3 discharge rate of 4 kg/h.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed and evaluated in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Examples 5-16
In the production of the decorative film of Example 5-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 5-1, except that the condition of time (3) was used. Table 6 shows the evaluation results.

Examples 5-17
In the production of the decorative film of Example 5-1, except that the polypropylene resin (A-3) used in the seal layer (I) was changed to the polypropylene resin (A-1), Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Examples 5-18
In the production of the decorative film of Example 5-1, except that the polypropylene resin (A-3) used in the seal layer (I) was changed to the polypropylene resin (A-4), Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Examples 5-19
In the production of the decorative film of Example 5-1, the polypropylene resin (A-3) used for the sealing layer (I) was changed to polypropylene resin (A-8), and polypropylene resin (A-8 ) and the thermoplastic resin (E-1) was set to 70:30, molding and evaluation were performed in the same manner as in Example 5-1. Table 6 shows the evaluation results.

Example 5-20
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 body made of polypropylene resin (Z-2). Table 6 shows the evaluation results.

Example 5-21
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 body made of polypropylene resin (Z-3). Table 6 shows the evaluation results.

Comparative Example 5-1
In the production of the decorative film of Example 5-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1), as in Example 5-1. Molding and evaluation were performed in the same manner. Table 6 shows the evaluation results.

Comparative Example 5-2
In the production of the decorative film of Example 5-1, Example 5- Molding and evaluation were performed in the same manner as in 1. Table 6 shows the evaluation results.

Comparative Example 5-3
Molding and evaluation were performed in the same manner as in Example 5-1, except that the resin of the sealing layer (I) was changed to the polypropylene resin (B-1) in the production of the decorative film of Example 5-1. . Table 6 shows the evaluation results.

The decorated moldings obtained from the decorated films of Examples 5-1 to 5-21 contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) contains a resin composition (X5) in which the weight ratio of polypropylene resin (A) and thermoplastic resin (E) is 97:3 to 5:95, and for polypropylene resin (A), (a1) melt flow a rate (MFR(A)) exceeding 2.0 g/10 min, and for the thermoplastic resin (E), (e1) containing at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group; (x1) The isothermal crystallization time (t (X5)) (seconds) of the resin composition (X5) is 1.5 times the isothermal crystallization time (t (A)) (seconds) of the polypropylene resin (A). above, and for the resin composition (B') containing the polypropylene resin (B) in the layer (II), (b1) the melt flow rate (MFR (B')) is 40 g/10 minutes or less (b2) Since the degree of strain hardening was 1.1 or more, there was no contact unevenness, excellent thermoformability, and good adhesion. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 5-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 5-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. Comparative Example 5-3, in which the sealing layer (I) does not contain the thermoplastic resin (E) and the MFR of the polypropylene-based resin used in the sealing layer (I) is 2.0 g/10 min or less, has adhesion It was inferior in strength and weatherability was not evaluated.

(Test example 6)
[6: Decorative film containing seal layer (I) made of propylene-ethylene block copolymer (F)]
6-1. Materials Used Polypropylene Resins In addition to the polypropylene resins used in “1-1. Materials Used” above, the following resins were used.

・Production of propylene-ethylene block copolymer (F) As the propylene-ethylene block copolymer (F) used for the sealing layer (I) of the decorative film, the propylene-ethylene block copolymer obtained in the following production example was used. Combinations (F-1) to (F-4) were used. Polymerization conditions and polymerization results are shown in Table 7-1, and polymer analysis results are shown in Table 7-2.

[Production Example F-1: Production of propylene-ethylene block copolymer (F-1)]
Analysis of catalyst composition Ti content: A sample was accurately weighed, hydrolyzed, and then measured using a colorimetric method. For the prepolymerized sample, the content was calculated using the weight excluding the prepolymerized polymer.
Silicon compound content: Samples were accurately weighed and digested with methanol. The silicon compound concentration in the resulting methanol solution was determined by comparison with a standard sample using gas chromatography. The silicon compound content in the sample was calculated from the silicon compound concentration in methanol and the weight of the sample. For the prepolymerized sample, the content was calculated using the weight excluding the prepolymerized polymer.

Preparation of prepolymerized catalyst (1) Preparation of solid catalyst A 10-liter autoclave equipped with a stirring device was sufficiently purged with nitrogen, and 2 liters of purified toluene was introduced. At room temperature, 200 g of magnesium diethoxide [Mg(OEt) ₂ ] was added, 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 were introduced. After that, the temperature was raised to 110° C. and the reaction was carried out for 3 hours. The reaction product was thoroughly washed with purified toluene. Next, refined toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, 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. Next, refined toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl ₄ was added at room temperature, 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, purified n-heptane was used to replace toluene with n-heptane to obtain a slurry of solid components. A portion of this slurry was sampled and dried. An analysis revealed that the Ti content of the solid component was 2.7% by weight.

Next, an autoclave with a capacity of 20 L equipped with a stirring device was sufficiently purged with nitrogen, and 100 g of the solid component slurry was introduced as a solid component. Purified n-heptane was introduced to adjust the solid component concentration to 25 g/L. 50 ml of silicon tetrachloride (SiCl ₄ ) was added and reacted 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 4L. 30 ml of dimethyldivinylsilane, 30 ml of diisopropyldimethoxysilane [i-Pr ₂ Si(OMe) ₂ ], and 80 g of Et ₃ Al diluted with triethylaluminum (Et ₃ Al) in n-heptane were added thereto. for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A part of the resulting solid catalyst slurry was sampled, dried and analyzed. The solid catalyst contained 1.2% by weight of Ti and 8.9% by weight of i-Pr ₂ Si(OMe) ₂ .

(2) Prepolymerization Using the solid catalyst obtained above, prepolymerization was performed according to the following procedure. Refined n-heptane was introduced into the above slurry to adjust the solid catalyst concentration to 20 g/L. After cooling the slurry to 10° C., 10 g of Et ₃ Al diluted in n-heptane was added as Et ₃ Al and 280 g of propylene was fed over 4 hours. After the supply of propylene was finished, the reaction was continued for an additional 30 minutes. Then, the gas phase was sufficiently purged with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The resulting slurry was extracted from the autoclave and dried in a vacuum to obtain a prepolymerized catalyst. This prepolymerized catalyst contained 2.5 grams of polypropylene per gram of solid catalyst. Analysis revealed that the portion of the prepolymerized catalyst excluding polypropylene contained 1.0% by weight of Ti and 8.3% by weight of i-Pr ₂ Si(OMe) ₂ .
Using this prepolymerization catalyst, a propylene-ethylene block copolymer (F) was produced according to the following procedure.

(3) Production of propylene-ethylene block copolymer (F) Propylene-ethylene block copolymer (F) was produced using a two-tank continuous polymerization facility in which two fluidized bed polymerization tanks having an internal volume of 2 m ³ were connected in series. was manufactured. The conditions for producing the propylene-ethylene block copolymer (F-1) are as described in 7A-1 of Table 7-1. The propylene, ethylene, hydrogen and nitrogen used were purified using a common 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 obtained from the cooling water temperature of the heat exchanger used for temperature control of the polymerization tank.

First Polymerization Step: Production of Component (F1) Consisting of Propylene Homopolymer Propylene was homopolymerized using the first polymerization tank. The polymerization temperature was 65° C., the total pressure was 3.0 MPaG (gauge pressure, hereinafter the same), 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 fed continuously at a rate of 5.0 g/hour. The prepolymerized catalyst obtained above was continuously supplied to the polymerization tank so that the production amount of the component (F1) in the first polymerization tank was 20.0 kg/hour. The produced component (F1) was continuously extracted 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 the propylene-ethylene random copolymer was continued.

Second Polymerization Step: Production of Propylene-Ethylene Random Copolymer Component (F2) Random copolymerization of propylene and ethylene was carried out using the second polymerization tank. 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 supplied 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 supplying ethanol as 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 extracted and adjusted so that the powder hold amount was constant at 40 kg. The propylene-ethylene block copolymer (F) extracted from the second polymerization tank was further transferred to a dryer and thoroughly dried.

A portion of the produced propylene-ethylene block copolymer (F) was analyzed and found to have an MFR (F) of 7.0 g/10 min and an ethylene content E (F) of 9.5% by weight. The weight ratio W(F1) of the component (F1) and the weight ratio W(F2) of the component (F2) were obtained from the production amount in the first polymerization step and the production amount in the second polymerization step, and each was 75% by weight. , 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 the 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. In the above formula, the above formula for E (F) is rearranged for E (F2). It is what was done.)
The ethylene content E (F2) was 38.0% by weight.

[Production Examples F-2 and F-3: Production of propylene-ethylene block copolymers (F-2) and (F-3)]
A propylene-ethylene block copolymer ( F-2) and (F-3) were produced.

[Production Example F-4: Production of propylene-ethylene block copolymer (F-4)]
(Preparation of prepolymerization catalyst)
(1) Chemical treatment of silicate 3.75 liters of distilled water and then 2.5 kg of concentrated sulfuric acid (96%) were slowly added to a 10 liter separable glass flask equipped with a stirring blade. At 50° C., 1 kg of montmorillonite (Benclay SL manufactured by Mizusawa Chemical; average particle size=25 μm, particle size distribution=10 to 60 μm) was dispersed, heated to 90° C., and maintained at that temperature for 6.5 hours. After cooling to 50° C., the slurry was filtered under reduced pressure to collect a cake. The cake was reslurried by adding 7 liters of distilled water and filtered. This washing operation was carried out until the pH of the washing liquid (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 using a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotation speed with scraping blade: 2 rpm
Tilt angle: 20/520
Feed rate of silicate: 2.5 g/min Gas flow rate: Nitrogen 96 l/h Countercurrent drying temperature: 200°C (powder temperature)

(3) Preparation of catalyst An autoclave having an internal volume of 16 liters equipped with a stirring and temperature control device was sufficiently purged with nitrogen. Here, 200 g of dry silicate was introduced, 1,160 ml of mixed heptane, and 840 ml of triethylaluminum heptane solution (0.60 M) were further added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry of 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, 2,180 mg (0.3 mM) of (r)-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4H-azulenyl}]zirconium and 870 ml of heptane were added. , 33.1 ml of a heptane solution (0.71 M) of triisobutylaluminum was added and reacted at room temperature for 1 hour. The mixture was added to the silicate slurry and stirred for 1 hour. was prepared to

(4) Prepolymerization/Washing Subsequently, the temperature inside 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 feed was stopped and maintained for an additional 2 hours.
After the prepolymerization was completed, the residual monomer was purged, the stirring was stopped, and the mixture was allowed to stand still for about 10 minutes, after which 2,400 ml of the supernatant was decanted. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M) and 5600 ml of mixed heptane were added, stirred at 40° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. Furthermore, this operation was repeated 3 times. When the final supernatant was analyzed for components, the concentration of the organoaluminum component was 1.23 mmol/liter, and the concentration of zirconium (Zr) was 8.6 × 10 ^-6 g/L. The abundance of was 0.016%. Subsequently, after adding 170 ml of a heptane solution of triisobutylaluminum (0.71 M), drying was performed under reduced pressure at 45°C. A prepolymerized catalyst containing 2.0 g of polypropylene per g of catalyst was obtained.

(5) Production of propylene-ethylene block copolymer (F) First polymerization step: Production of component (F1) consisting of propylene-ethylene random copolymer Horizontal reactor having stirring blades (L/D = 6, contents 100 liters) was sufficiently dried, and the inside was sufficiently 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 the prepolymerized catalyst prepared in the upstream part of the reactor (as a solid catalyst amount excluding the prepolymerized powder) and triisobutylaluminum were added. It was fed continuously at 15.0 mmol/hour. The temperature of the reactor is maintained at 65°C and the pressure at 2.00 MPaG, and the monomer mixed gas is continuously reacted so that the gas phase in the reactor has an ethylene/propylene molar ratio of 0.058 and a hydrogen concentration of 150 ppm. Gas phase polymerization was carried out by circulating in the vessel. The polymer powder produced by the reaction was continuously withdrawn from the downstream portion of the reactor so that the amount of powder bed in the reactor was constant. At this time, the amount of polymer withdrawn when the steady state was reached was 10.0 kg/hour.
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) composed of propylene-ethylene random copolymer Propylene extracted from the first polymerization step was placed in a horizontal reactor (L/D = 6, internal volume: 100 liters) having a stirring blade. Ethylene copolymer was fed continuously. While stirring at a rotation speed of 25 rpm, the temperature of the reactor was kept at 70 ° C., the pressure was kept at 1.88 MPaG, and the ethylene / propylene molar ratio in the gas phase part in the reactor was 0.450, and the hydrogen concentration was 300 ppm. Gas phase polymerization was performed by continuously circulating the monomer mixed gas in the reactor. The polymer powder produced by the reaction was continuously withdrawn from the downstream portion of the reactor so that the amount of powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer withdrawn was 18.0 kg/hour, and the amount of polymerization reaction in the second polymerization step was controlled.
The propylene-ethylene block copolymer (F-4) thus obtained was analyzed and found to have an MFR of 7.0 g/10 min and an ethylene content of 6.3% by 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))
Tetrakis[methylene-3-(3′,5′-di-t-butyl- 0.05 parts by weight of 4-hydroxyphenyl)propionate]methane, 0.10 parts by weight of tris(2,4-di-t-butylphenyl)phosphite, and 0.05 parts by weight of calcium stearate were mixed in a tumbler and mixed uniformly. The resulting mixture was melt-kneaded at 230° C. using a twin-screw extruder with a diameter of 35 mm to obtain pellets of propylene-ethylene block copolymers (F-1) to (F-4).

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) was changed to a propylene-ethylene block copolymer (F-1), and three-dimensional decorative heat was applied. Molding and evaluation were performed in the same manner as in Example 1-1, except that the molding was performed immediately after the springback phenomenon ended in molding (that is, the heating time after springback was 0 seconds). Table 8 shows the evaluation results.

Example 6-2
In the production of the decorative film of Example 6-1, Example 6- Molding and evaluation were performed in the same manner as in 1. Table 8 shows the evaluation results.

Example 6-3
In the production of the decorative film of Example 6-1, Example 6- Molding and evaluation were performed in the same manner as in 1. Table 8 shows the evaluation results.

Example 6-4
In the production of the decorative film of Example 6-1, Example 6- Molding and evaluation were performed in the same manner as in 1. Table 8 shows the evaluation results.

Example 6-5
In the production of the decorative film of Example 6-1, the polypropylene resin (B-1-1) of the layer (II) was changed to the polypropylene resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 6-1, except that the condition of time (2) was used. Table 8 shows the evaluation results.

Example 6-6
In the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-7
In the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-8
In the production of the decorative film of Example 6-1, Example 6- Molding and evaluation were performed in the same manner as in 1. Table 8 shows the evaluation results.

Examples 6-9
In the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-10
In the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-11
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the sealing layer (I) was changed to propylene-ethylene block copolymer (F-2). Except for this, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-12
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the sealing layer (I) was changed to propylene-ethylene block copolymer (F-3). Except for this, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-13
In the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) used for the sealing layer (I) was changed to propylene-ethylene block copolymer (F-4). Except for this, molding and evaluation were performed in the same manner as in Example 6-1. Table 8 shows the evaluation results.

Examples 6-14
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. Propylene-ethylene block copolymer (F-1) for seal layer extruder-1, polypropylene resin (B-1-1) for extruder-2, and polypropylene for surface decoration layer extruder-3 The system resin (A-1-1) is charged respectively, the resin temperature is 240 ° C., the discharge rate of extruder -1 for seal layer is 4 kg / h, the discharge rate of extruder -2 is 8 kg / h, surface decoration layer Melt extrusion was carried out under the conditions of a discharge rate of 4 kg/h from extruder-3.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed in the same manner as in Example 6-1 and evaluated. Table 8 shows the evaluation results.

Examples 6-15
In the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 6-1, except that the condition of time (3) was used. Table 8 shows the evaluation results.

Examples 6-16
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 body made of polypropylene resin (Z-2). Table 8 shows the evaluation results.

Examples 6-17
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 body made of polypropylene resin (Z-3). Table 8 shows the evaluation results.

Comparative Example 6-1
Example 6-1 except that in the production of the decorative film of Example 6-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to the polypropylene-based resin (B-1). Molding and evaluation were performed in the same manner. Table 8 shows the evaluation results.

Comparative Example 6-2
In the production of the decorative film of Example 6-1, Example 6- Molding and evaluation were performed in the same manner as in 1. Table 8 shows the evaluation results.

Comparative Example 6-3
Example 6 except that in the production of the decorative film of Example 6-1, the propylene-ethylene block copolymer (F-1) of the sealing layer (I) was changed to the polypropylene resin (B-1). Molding and evaluation were performed in the same manner as in -1. Table 8 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 6-1 to 6-17 contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and were polypropylene resin (A ) is a propylene-ethylene block copolymer (F), and the propylene-ethylene block copolymer (F) has (a1) a melt flow rate (MFR (A)) exceeding 2.0 g/10 minutes, ( f1) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, and the component (F2) consisting of a propylene-ethylene random copolymer having a higher ethylene content than the component (F1) 3 to 95% by weight, (f2) a melting peak temperature (Tm (F)) of 110 to 170 ° C., and a resin composition (B) containing a polypropylene resin (B) in the layer (II) '), (b1) the melt flow rate (MFR (B')) is 40 g/10 min or less, and (b2) the strain hardening degree is 1.1 or more, so there is no contact unevenness and excellent thermoformability , the adhesion was good. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 6-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 6-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. Comparative Example 6-3 in which no propylene-ethylene block copolymer (F) was used in the seal layer (I) and the MFR of the polypropylene resin used in the seal layer (I) was 2.0 g/10 min or less , was inferior in adhesive strength, and weather resistance was not evaluated.

(Test Example 7)
[7: Decorative film containing seal layer (I) made of olefin adhesive resin (G)]
7-1. Materials Used In addition to the polypropylene-based resins used in "1-1. Materials Used" above, the following resins were used.

Polyolefin adhesive resin (G)
(G-1): Maleic anhydride-modified polyolefin (MFR = 7.0 g/10 min), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F534A"
(G-2): Maleic anhydride-modified polyolefin (MFR = 1.6 g/10 min), manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP (registered trademark) F532"

7-2. Preparation of resin molded body (substrate) (1) Polar resin used for resin molded body (substrate) The following polar resins were used.
(Z-4): PMMA (polymethyl methacrylate) resin, manufactured by Mitsubishi Rayon Co., Ltd., "Acrypet MD"
(Z-5): ABS (acrylonitrile-butadiene-styrene copolymer) resin, manufactured by Techno Polymer Co., Ltd., "ABS130"
(Z-6): PC (polycarbonate) resin, manufactured by Mitsubishi Engineering-Plastics Co., Ltd., "Novarex 7022A"

(2) Production of Resin Mold (Substrate) The polar resins (Z-4) to (Z-6) were dried at 80° C. for 2 hours using a box oven. The dried resin was injection-molded by the following method to obtain an injection-molded article.
(i) PMMA resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 230°C
Mold temperature: 40°C
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate Condition adjustment: Maintained for 5 days in a constant temperature and humidity room with a temperature of 23 ° C and a humidity of 50% RH

(ii) ABS resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 210°C
Mold temperature: 40°C
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate Condition adjustment: Maintained for 5 days in a constant temperature and humidity room with a temperature of 23 ° C and a humidity of 50% RH

(iii) PC resin molding conditions:
Injection molding machine: "IS100GN" manufactured by Toshiba Machine Co., Ltd., mold clamping pressure: 100 tons Cylinder temperature: 290°C
Mold temperature: 80°C
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate Condition adjustment: Maintained for 5 days in a constant temperature and humidity room with a temperature of 23 ° C and a humidity of 50% RH

Example 7-1
・Production of decorative film 2 types 2 with a lip opening of 0.8 mm and a die width of 400 mm, which are connected to a seal layer extruder-1 with a diameter of 30 mm (diameter) and an extruder-2 with a diameter of 40 mm (diameter) A layer T die was used. The polyolefin adhesive resin (G-1) was put into the seal layer extruder-1, and the polypropylene resin (B-1-1) was put into the extruder-2. Melt extrusion was carried out under the conditions of a discharge rate of 8 kg/h for extruder-1 and a discharge rate of 8 kg/h for extruder-2.

The melt-extruded film is cooled and solidified on a cooling roll rotating at 80 ° C. and 3 m / min so that the seal layer (I) is in contact with the layer (II) with a thickness of 100 μm and the seal layer with a thickness of 100 μm ( A two-layer unstretched film with I) laminated was obtained.

Three-dimensional decorative thermoforming In the three-dimensional decorative thermoforming of Example 1-1, the substrate was changed to an injection molded body made of PMMA resin (Z-4), and immediately after the springback phenomenon ended (that is, the springback Molding and evaluation were carried out in the same manner as in Example 1-1, except that the decorative molding was performed after the heating time was 0 second). Table 9 shows the evaluation results.

Example 7-2
In the production of the decorative film of Example 7-1, Example 7- Molding and evaluation were performed in the same manner as in 1. Table 9 shows the evaluation results.

Example 7-3
In the production of the decorative film of Example 7-1, Example 7- Molding and evaluation were performed in the same manner as in 1. Table 9 shows the evaluation results.

Example 7-4
In the production of the decorative film of Example 7-1, Example 7- Molding and evaluation were performed in the same manner as in 1. Table 9 shows the evaluation results.

Example 7-5
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to the polypropylene-based resin (B-1-5), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 7-1, except that the condition of time (2) was used. Table 9 shows the evaluation results.

Example 7-6
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, and molding and evaluation were performed in the same manner as in Example 7-1. Table 9 shows the evaluation results.

Example 7-7
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-1-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 7-1. Table 9 shows the evaluation results.

Examples 7-8
In the production of the decorative film of Example 7-1, Example 7- Molding and evaluation were performed in the same manner as in 1. Table 9 shows the evaluation results.

Examples 7-9
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 70:30, and molding and evaluation were performed in the same manner as in Example 7-1. Table 9 shows the evaluation results.

Examples 7-10
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was combined with the polypropylene-based resin (B-2-1) and the polypropylene-based resin (A-1-1 ) was blended so that the weight ratio was 10:90, molding and evaluation were performed in the same manner as in Example 7-1. Table 9 shows the evaluation results.

Examples 7-11
In the production of the decorative film of Example 7-1, except that the polyolefin adhesive resin (G-1) used for the seal layer (I) was changed to the polyolefin adhesive resin (G-2) Molding and evaluation were performed in the same manner as in 7-1. Table 9 shows the evaluation results.

Examples 7-12
・Production of decorative film A seal layer extruder-1 with a diameter of 30 mm, an extruder-2 with a diameter of 40 mm, and a surface decoration layer extruder-3 with a diameter of 30 mm are connected. A three-kind, three-layer T die with a lip opening of 0.8 mm and a die width of 400 mm was used. Polyolefin adhesive resin (G-1) for seal layer extruder-1, polypropylene resin (B-1-1) for extruder-2, polypropylene resin (B-1-1) for surface decoration layer extruder-3 A-1-1) was charged respectively, the resin temperature was 240 ° C., the discharge rate of extruder-1 for seal layer was 8 kg / h, the discharge rate of extruder-2 was 8 kg / h, and the extruder for surface decoration layer Melt extrusion was carried out under the conditions of -3 discharge rate and 4 kg/h.

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

Using the unstretched film obtained in the production of the above-described decorated film, three-dimensional decorative thermoforming was performed and evaluated in the same manner as in Example 7-1. Table 9 shows the evaluation results.

Examples 7-13
In the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of layer (II) was changed to polypropylene-based resin (B-1-6), and the weather resistance was evaluated by irradiation. Molding and evaluation were performed in the same manner as in Example 7-1, except that the condition of time (3) was used. Table 9 shows the evaluation results.

Examples 7-14
In the three-dimensional decorative thermoforming of Example 7-1, molding and evaluation were performed in the same manner as in Example 7-1, except that the substrate was changed to an injection molded body made of ABS resin (Z-5). Table 9 shows the evaluation results.

Examples 7-15
In the three-dimensional decorative thermoforming of Example 7-1, molding and evaluation were performed in the same manner as in Example 7-1, except that the substrate was changed to an injection molded body made of PC resin (Z-6). Table 9 shows the evaluation results.

Comparative Example 7-1
Example 7-1 except that in the production of the decorative film of Example 7-1, the polypropylene-based resin (B-1-1) of the layer (II) was changed to the polypropylene-based resin (B-1). Molding and evaluation were performed in the same manner. Table 9 shows the evaluation results.

Comparative Example 7-2
In the production of the decorative film of Example 7-1, Example 7- Molding and evaluation were performed in the same manner as in 1. Table 9 shows the evaluation results.

Comparative Example 7-3
In the production of the decorative film of Example 7-1, the procedure was the same as in Example 7-1, except that the polyolefin adhesive resin (G-1) of the sealing layer (I) was changed to the polypropylene resin (B-1). Molding and evaluation were performed in the same manner. Table 9 shows the evaluation results.

The decorated molded articles obtained from the decorated films of Examples 7-1 to 7-15 contained a hindered amine light stabilizer and/or an ultraviolet absorber in any layer, and the seal layer (I) Regarding the polyolefin adhesive resin (G) in the above, (g1) a polyolefin resin having a polar functional group containing at least one heteroatom, and (g2) a melt flow rate (MFR (G)) of 100 g/10 minutes or less. and the resin composition (B′) containing the polypropylene resin (B) in the layer (II) has (b1) a melt flow rate (MFR (B′)) of 40 g/10 minutes or less, (b2) Since the degree of strain hardening was 1.1 or more, there was no contact unevenness, the thermoformability was excellent, and the adhesiveness to the resin molding made of a polar resin was good. In addition, since the decorative thermoforming was performed for a short period of time, volatilization of the hindered amine light stabilizer and/or the ultraviolet absorber could be reduced, and high weather resistance was maintained even after thermoforming. . Furthermore, the molded article obtained was excellent in recyclability.

On the other hand, the decorative film of Comparative Example 7-1, in which none of the layers contained a hindered amine light stabilizer and/or an ultraviolet absorber, had poor weather resistance. In Comparative Example 7-2, in which the strain hardening degree of the polypropylene resin used for layer (II) is less than 1.1, the decorative film draws down during three-dimensional decorative thermoforming, resulting in poor thermoformability. was inferior. The obtained decorative molded article was inferior in appearance, and the adhesive strength and weather resistance were not evaluated. Comparative Example 7-3, in which the polyolefin adhesive resin (G) was not used in the seal layer (I) and the MFR of the polypropylene resin used in the seal layer (I) was 2.0 g/10 min or less, had adhesive strength weatherability was not evaluated.

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

1 decorative film 2 layer (II)
3 sealing layer (I)
4 Surface decoration layer (III)
5 Resin molding (decorative object, substrate)
6 decorative molding 11 upper chamber box 12 lower chamber box 13 jig 14 table 15 heater

Claims (25)

A decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber for adhering to a resin molded body by thermoforming, the decorative film being a seal containing a polypropylene resin (A) Layer (II) containing a layer (I) and a resin composition (B') containing a polypropylene resin (B),
A decorative film in which the polypropylene-based resin (A) satisfies the following requirement (a1), and the resin composition (B') satisfies the following requirements (b1) and (b2).
(a1) Melt flow rate (230° C., 2.16 kg load) (MFR(A)) exceeds 2.0 g/10 min.
(b1) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 40 g/10 minutes or less.
(b2) The strain hardening degree λ is 1.1 or more. The decorative film according to claim 1, wherein the polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the resin composition (B') further satisfies the following requirement (b3). .
(a2) Metallocene-catalyzed 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.
(b3) The melting peak temperature (Tm(B')) and Tm(A) satisfy the relational expression (b-3).
Tm(B')>Tm(A) Formula (b-3) The seal layer (I) contains a resin composition (X3) in which the weight ratio of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95,
3. The decorative film according to claim 1, wherein the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3).
(c1) Ethylene content [E(C)] is 65% by weight or more.
(c2) 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 minutes. The seal layer (I) contains a resin composition (X4) in which the weight ratio of the polypropylene resin (A) and the thermoplastic elastomer (D) is 97:3 to 5:95,
3. The decorative film according to claim 1, wherein the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d4).
(d1) A thermoplastic elastomer containing at least one of propylene and butene as a main component.
(d2) 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 minutes.
(d4) The tensile elastic modulus is smaller than the tensile elastic modulus of the polypropylene-based resin (A). The seal layer (I) contains a resin composition (X5) in which the weight ratio of the polypropylene resin (A) and the thermoplastic resin (E) is 97:3 to 5:95,
The decorative film according to claim 1 or 2, wherein the thermoplastic resin (E) satisfies the following requirement (e1), and the resin composition (X5) satisfies the following requirement (x1).
(e1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group;
(x1) The isothermal crystallization time (t(X5)) (seconds) obtained by a differential scanning calorimeter (DSC) satisfies the following formula (x-1).
t(X5)≧1.5×t(A) Expression (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 initiation temperature of the polypropylene resin (A), and t ( X5) is the isothermal crystallization time (seconds) of the resin composition (X5) measured at a temperature 10°C higher than the crystallization initiation temperature of the polypropylene resin (A).) The decoration according to any one of claims 1 and 3 to 5, wherein the polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following requirements (f1) and (f2). the film.
(f1) 5 to 97% by weight of the component (F1) consisting of a propylene homopolymer or a propylene-ethylene random copolymer, and a component (F1) consisting of a propylene-ethylene random copolymer having a higher ethylene content than the component (F1) F2) is contained in an amount of 3 to 95% by weight.
(f2) Melting peak temperature (Tm(F)) is 110 to 170°C. A decorative film containing a hindered amine light stabilizer and/or an ultraviolet absorber for adhering to a resin molding by thermoforming, the decorative film containing a polyolefin adhesive resin (G) A layer (II) containing a seal layer (I) and a resin composition (B') containing a polypropylene resin (B),
A decorative film in which the polyolefin adhesive resin (G) satisfies the following requirements (g1) and (g2), and the resin composition (B') satisfies the following requirements (b1) and (b2).
(g1) A polyolefin resin having a polar functional group containing at least one heteroatom.
(g2) Melt flow rate (230° C., 2.16 kg load) (MFR(G)) is 100 g/10 minutes or less.
(b1) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 40 g/10 minutes or less.
(b2) The strain hardening degree λ is 1.1 or more. The decorative film according to any one of claims 1 to 7, wherein the resin composition (B') satisfies the following requirements (b1') and (b2').
(b1′) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 20 g/10 minutes or less.
(b2′) The strain hardening degree λ is 1.8 or more. The decorative film according to any one of claims 1 to 7, wherein the resin composition (B') satisfies the following requirements (b1'') and (b2'').
(b1″) Melt flow rate (230° C., 2.16 kg load) (MFR(B′)) is 12 g/10 minutes or less.
(b2'') The strain hardening degree λ is 2.3 or more. The decorative film according to any one of claims 1 to 9, wherein the polypropylene resin (B) is a polypropylene resin (BL) having a long-chain branched structure. 11. The decorative film according to claim 10, wherein the polypropylene-based resin (BL) is a low-gel polypropylene-based resin produced by a method other than a cross-linking method. The decorative film according to any one of claims 1 to 5 and 8 to 11, wherein the polypropylene resin (A) is a propylene/α-olefin copolymer. The decorative film according to any one of claims 1 to 5 and 8 to 12, wherein the Tm(A) is 140°C or less. 4. The decorative film according to claim 3, wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4).
(c4) Melting peak temperature (Tm(C)) is 30 to 130°C. 15. The decorative film according to claim 3, wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c5).
(c5) A random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The thermoplastic elastomer (D) is a propylene-ethylene copolymer with an ethylene content of less than 50% by weight, a butene-ethylene copolymer with an ethylene content of less than 50% by weight, and an ethylene content of less than 50% by weight. 5. The decorative film according to claim 4, which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer. The decorative film according to claim 4 or 16, wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(d5) The melting peak temperature (Tm(D)) is 30-170°C. The decorative film according to claim 5, wherein the thermoplastic resin (E) is a styrene elastomer. The decorative film according to claim 5, wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin. 7. The decorative film according to claim 6, wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f3).
(f3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight. 21. The decorative film according to claim 6, wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f4).
(f4) The ethylene content of component (F1) is in the range of 0 to 6% by weight. 22. The decorative film according to claim 6, 20 or 21, wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f5).
(f5) The ethylene content of component (F2) is in the range of 5 to 90% by weight. preparing the decorative film according to any one of claims 1 to 22;
preparing a resin molded body;
setting the resin molding and the decorative film in a chamber box that can be evacuated;
depressurizing the inside of the chamber box;
a step of heating and softening the decorative film;
A method for producing a decorated molded product, comprising: pressing the decorative film softened by heating against the resin molded product; 24. The method for manufacturing a decorative molded article according to claim 23, wherein the resin molded article is made of a propylene-based resin composition. The decorative film is the decorative film according to any one of claims 7 to 11,
The resin molding is at least selected from polyester resins, polyamide resins, polyimide resins, polystyrene resins, acrylic resins, polyvinyl alcohol resins, polycarbonate resins, ABS resins, urethane resins, melamine resins, polyphenylene ether resins, and composite materials thereof. 24. The method of manufacturing a decorated molding according to claim 23, comprising a polar resin material containing one.

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