JP2019137057A - Decorative film and manufacturing method of decorative molded body using the same - Google Patents

Abstract

To provide a decorative film excellent in heat moldability without irregular contact, good in surface glossiness and adhesive force, of which reduction of the surface glossiness and change of appearance of a surface before and after heat molding is suppressed, excellent in recycling property, and capable of being used for three-dimensional decorative heat molding, and a manufacturing method of a decorative molded body using the same.SOLUTION: There is provided a decorative film containing a nucleation agent for adhesion on a resin molded body by heat molding, in which the decorative film contains a seal layer (I) containing a polypropylene resin (A) and a layer (II) containing a resin composition (B') containing a polypropylene resin (B), the polypropylene resin (A) satisfies a following requirement (a1), the resin composition (B') satisfies following requirements (b1) and (b2). (a1) melt flow rate (230°C, 2.16 kg load) (MFR(A)) is over 2.0 g/10 min. (b1) melt flow rate (230°C, 2.16 kg load) (MFR(B')) is 40 g/10 min. or less. (b2) strain cure extent λ is 1.1 or more.SELECTED DRAWING: None

Description

  The present invention relates to a decorative film for sticking by thermoforming on a resin molded body and a method for producing a decorative molded body using the decorative film. Specifically, the decorative film for sticking by thermoforming on the resin molded body, which can suppress wrinkles and film breakage of the film during thermoforming, and can exhibit sufficient adhesive strength to the resin molded body, and The present invention relates to a method for producing a decorative molded body using the decorative film. Furthermore, there is no contact unevenness, thermoformability is excellent, surface gloss and adhesive strength are good, surface gloss deterioration is suppressed before and after thermoforming, and recyclability is excellent, and it is used for three-dimensional decorative thermoforming. The present invention relates to a decorative film and a method for producing a decorative molded body using the decorative film.

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

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

  Decorative molding by vacuum pressure forming and vacuum molding has a greater degree of freedom than other decorative moldings typified by insert molding, and the end face of the decorative film is rolled up to the back side of the decorative object. Therefore, it can be thermoformed at a relatively low temperature and low pressure, so that the surface of the decorative molded body has a texture such as a wrinkle by applying a wrinkle to the surface of the decorative film. 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 body are adhered, the decorative film may be broken or wrinkled, or the decorative film and the molded body are bonded. There was a problem that sufficient strength could not be obtained. In addition, the use of adhesives, tackifiers, etc. has been proposed as a layer for improving the adhesive strength, but it is expensive, the layer structure becomes extremely complicated, and the solvent resistance and heat resistance are insufficient. Have problems such as.

  For such problems, a decorative film including an adhesive layer containing a polypropylene resin is applied to a base body (molded body) made of a polypropylene resin, so that the decorative film and the molded body are heat-sealed. (For example, see Patent Documents 2 and 3). In the inventions disclosed in Patent Documents 2 and 3, a polypropylene resin is used as the adhesive layer of the decorative film. However, the surface layer on the adhesive layer, and the acrylic layer on the bonding layer and the bulk layer are substantially further provided. It is necessary to provide a layer of resin, polyurethane resin, polycarbonate or the like. In this way, by combining different raw materials, thermoformability such as draw-down property is expressed, and it is possible to ensure thermoformability in a decorative film made of polypropylene resin that does not contain these different raw materials. Can not. For this reason, holes, wrinkles and air are likely to be entrained on the surface of the molded product on which the decorative film is adhered, and furthermore, a decorative molded body having an excellent appearance cannot be obtained due to film breakage. In addition, when a polyurethane resin is included as a different raw material, the polyurethane resin, which is a thermosetting resin, does not melt when heated, so that it is easy to maintain the form of the film and greatly enhances thermoformability, but has a problem that recyclability is extremely low. there were.

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

  In automobile parts, home appliance parts and building material parts, polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic resin, polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, polyphenylene ether resin, etc. A resin molded body made of a polar resin material is often used. Since these polar resin materials are inferior in water resistance and chemical resistance, it is expected to improve water resistance and chemical resistance by attaching a decorative film.

Japanese Unexamined Patent Publication No. 2002-67137 Japanese Unexamined Patent Publication No. 2013-14027 Japanese Unexamined Patent Publication No. 2014-124940

  Polyolefin resins such as polypropylene resins have excellent water resistance and chemical resistance, and various decorative films made of polyolefin resins have been proposed. Here, since the polyolefin-based resin is a crystalline resin, it is known that a coarse spherulite structure is formed, and transparency and surface gloss deteriorate. On the other hand, by adding a nucleating agent, it has been studied to reduce the spherulite size and to impart transparency and surface gloss to the decorative film. However, by including such a nucleating agent, a highly glossy decorative film can be obtained, but there are problems such as a dull surface after three-dimensional decorative molding.

  In other words, the conventional technology is easy to recycle, can achieve both excellent adhesiveness and appearance, and is made of a polypropylene resin that has low gloss reduction and small change in surface appearance even after decorative molding. Film has not yet been achieved. In view of the above problems, the problem of the present invention is that there is no contact unevenness and excellent thermoformability, the surface gloss and adhesive force are good, the decrease in surface gloss and the change in surface appearance before and after thermoforming, And it is providing the manufacturing method of the decorative film which can be used for the three-dimensional decorative thermoforming which is excellent in recyclability, and the decorative molded object using the same.

In three-dimensional decorative thermoforming, in order to stick a solid decorative film to a solid resin molded body, it is necessary that the surface of the molded body and the film are sufficiently softened or melted. Therefore, it is important to add a heat amount necessary for softening or melting the surface of the molded body and the film, or to use a molded body and a film that are easily softened or melted. On the other hand, if the film is heated too much, the viscosity of the film decreases, and the film breaks or rampages due to the pushing up of the molded body in the three-dimensional decorative thermoforming process or the inflow of air when the vacuum chamber is returned to atmospheric pressure. Doing so leads to poor appearance. As a result of paying attention to the mechanism that causes the appearance defect, the present inventors have found that a decorative film including a layer made of a specific polypropylene resin can solve the above-described problem.
Furthermore, it was found that the nucleating agent added to the resin in order to impart gloss was remarkably volatilized in the decorative molding conditions, that is, the process of heating the decorative film under vacuum. By including a sealing layer having good adhesiveness, the present inventors can perform decorative molding at a low temperature in a short time, and by completing the decorative molding before the nucleating agent volatilizes, It has been found that the reduction can be suppressed, and the present invention has been completed.

  That is, the present invention includes the following.

(1) A decorative film containing a nucleating agent for adhering to a resin molded body by thermoforming, the decorative film comprising a sealing layer (I) containing a polypropylene resin (A) and A layer (II) containing a resin composition (B ′) containing a polypropylene resin (B),
The polypropylene resin (A) satisfies the following requirement (a1), and the resin composition (B ′) is a decorative film that satisfies the following requirements (b1) and (b2).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 2.0 g / 10 minutes.
(B1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 40 g / 10 min or less.
(B2) The strain hardening degree λ is 1.1 or more.

(2) The decoration according to (1), wherein the nucleating agent is selected from an aromatic carboxylic acid metal salt, an aromatic phosphate metal salt, a sorbitol derivative, a nonitol derivative, an amide compound, or a rosin metal salt. the film.

(3) The polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the resin composition (B ′) further satisfies the following requirement (b3): (1) or (2 ) Decorative film.
(A2) A metallocene catalyst-based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B3) The melting peak temperature (Tm (B ′)) and Tm (A) satisfy the relational expression (b-3).
Tm (B ′)> Tm (A) (formula (b-3))

(4) 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 said ethylene-alpha-olefin random copolymer (C) is a decorating film as described in any one of (1)-(3) which satisfy | fills the following requirements (c1)-(c3).
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min.

(5) The seal layer (I) includes 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 said thermoplastic elastomer (D) is a decorating film as described in any one of (1)-(3) which satisfy | fills the following requirements (d1)-(d4).
(D1) A thermoplastic elastomer mainly composed of at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile elastic modulus is smaller than the tensile elastic modulus of the polypropylene resin (A).

(6) The seal layer (I) includes 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 any one of (1) to (3), 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 thermal scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) (formula (x−1))
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t ( 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).

(7) The polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following requirements (f1) and (f2): (1), (2) and (4) to (6) ). The decorative film according to any one of
(F1) Component (F1) composed of propylene homopolymer or propylene-ethylene random copolymer, 5 to 97% by weight, component composed of propylene-ethylene random copolymer having a higher ethylene content than component (F1) ( F2) is contained in an amount of 3 to 95% by weight.
(F2) Melting peak temperature (Tm (F)) is 110-170 degreeC.

(8) A decorative film containing a nucleating agent for adhering onto a resin molded body by thermoforming, the decorative film comprising a polyolefin adhesive resin (G) and a sealing layer (I) And a layer (II) containing a resin composition (B ′) containing a polypropylene resin (B),
The polyolefin adhesive resin (G) satisfies the following requirements (g1) and (g2), and the resin composition (B ′) is a decorative film that 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 min or less.
(B1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 40 g / 10 min or less.
(B2) The strain hardening degree λ is 1.1 or more.

(9) The decorative film according to any one of (1) to (8), wherein the resin composition (B ′) satisfies the following requirements (b1 ′) and (b2 ′).
(B1 ′) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 20 g / 10 min or less.
(B2 ′) The strain hardening degree λ is 1.8 or more.

(10) The decorative film according to any one of (1) to (8), 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 min or less.
(B2 ″) The strain hardening degree λ is 2.3 or more.

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

(12) The decorative film according to (11), wherein the polypropylene-based resin (B-L) is a polypropylene-based resin with less gel manufactured by a method other than the crosslinking method.

(13) The layer (II) has a surface decorating layer (III) containing a surface decorating layer resin on the side opposite to the sticking surface side to the resin molded body, (1) to (12 ) The decorative film according to any one of the above.

(14) The decorative film according to (13), wherein the surface decoration layer resin is made of a polypropylene resin (H), and the polypropylene resin (H) has a strain hardening degree λ of less than 1.1. .

(15) The decorative film according to any one of (1) to (6) and (9) to (14), wherein the polypropylene resin (A) is a propylene / α-olefin copolymer.

(16) The decorative film according to any one of (1) to (6) and (9) to (15), wherein the Tm (A) is 140 ° C. or lower.

(17) The decorative film according to (4), wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4).
(C4) The melting peak temperature (Tm (C)) is 30 to 130 ° C.

(18) The decorative film according to (4) or (17), 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.

(19) The thermoplastic elastomer (D) comprises a propylene-ethylene copolymer having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of 50% by weight. The decorative film according to (5), which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer that is less than.

(20) The decorative film according to (5) or (19), wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(D5) The melting peak temperature (Tm (D)) is 30 to 170 ° C.

(21) The decorative film according to (6), wherein the thermoplastic resin (E) is a styrene-based elastomer.

(22) The decorative film according to (6), wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin.

(23) The decorative film according to (7), 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.

(24) The decorative film according to (7) or (23), wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f4).
(F4) The ethylene content of the component (F1) is in the range of 0 to 6% by weight.

(25) The decorative film according to (7), (23) or (24), wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f5).
(F5) The ethylene content of the component (F2) is in the range of 5 to 90% by weight.

(26) In the step of preparing the decorative film according to any one of (1) to (25), the step of preparing a resin molded body, the pressure-reducible chamber box, the resin molded body and the decoration A step of setting a film, a step of depressurizing the interior of the chamber box, a step of heat-softening the decorative film, a step of pressing the heat-softened decorative film on the resin molding, and the interior of the decompressed chamber box A method for producing a decorative molded body comprising a step of returning to atmospheric pressure or pressurizing.

(27) The method for producing a decorative molded body according to (26), wherein the resin molded body is made of a propylene-based resin composition.

(28) The decorative film is the decorative film according to any one of (8) to (14), and the resin molded body includes a polyester resin, a polyamide resin, a polyimide resin, a polystyrene resin, and an acrylic resin. , A decorative molded body according to (26), comprising a polar resin material comprising at least one selected from polyvinyl alcohol resin, polycarbonate resin, ABS resin, urethane resin, melamine resin, polyphenylene ether resin, and composite materials thereof. Manufacturing method.

  According to the present invention, there is no contact unevenness, thermoformability is excellent, surface gloss and adhesive strength are good, surface gloss reduction and surface appearance change are suppressed before and after thermoforming, and recyclability is excellent. A decorative film that can be used for three-dimensional decorative thermoforming and a method for producing a decorative molded body using the decorative film can be provided.

1A (a) to 1A (c) are schematic cross-sectional views illustrating embodiments of a decorative molded body in which the decorative film of the present invention is attached to a resin molded body, and each is a layer of the decorative film. This is an example in which the configuration is different. Drawing 1B (a)-Drawing 1B (c) are figures showing an example of layer composition of a decoration 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 body of the present invention. FIG. 3 is a schematic cross-sectional view illustrating a state in which a resin molded body and a 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 depressurized. FIG. 5 is a schematic cross-sectional view for explaining a state in which the decorative film is pressed against the resin molded body in the apparatus of FIG. FIG. 6 is a schematic cross-sectional view illustrating 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 a state in which an edge of an unnecessary decorative film is trimmed in the obtained decorative molded body.

In this specification, the decorative film refers to a film for decorating a molded body. Decorative molding refers to molding in which a decorative film and a molded body are attached. Three-dimensional decorative thermoforming is a process of adhering a decorative film and a molded body, and has a step of applying a decorative film at the same time as thermoforming along the adhesive surface of the molded body, In order for this process to suppress air from being caught between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum), the heated decorative film is adhered to the molded body, and pressure is applied. It refers to molding, which is a step of bringing in close contact by release (pressurization). In addition, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
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 nucleating agent for adhering to a resin molded body by thermoforming, and the decorative film contains a polypropylene resin (A). A layer (II) containing a resin composition (B ′) comprising a layer (I) and a polypropylene resin (B), wherein the polypropylene 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 minutes.
(B1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 40 g / 10 min 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 without including a thermosetting resin layer, it is possible to obtain a decorative molded body having excellent thermoformability at the time of three-dimensional decorative thermoforming and having a good product appearance.
Furthermore, the decorative film contains a nucleating agent and includes a sealing layer (adhesive layer) (I) containing a polypropylene resin having a specific melt flow rate (MFR), so that heating can be performed for a short time. Since it can be attached to the resin molded body (base) in time, it is possible to complete the decorative molding before the added nucleating agent volatilizes, suppress the reduction in gloss, and obtain a high gloss decorative molded body Is possible.
Depending on the configuration of the sealing layer (I), a decorative film can be attached to a substrate having polarity, and a decorative molded body manufactured from a substrate made of a decorative film and a polar resin material is particularly water resistant. Excellent chemical resistance.

  According to the method for producing a decorative molded body of the present invention, there is no hole or wrinkle on the surface, no air entrainment between the decorative film and the resin molded body, and beautiful decorative molding in which a decrease in gloss is suppressed. You can get a body. Furthermore, in the decorative molded body obtained in this manner, the constituent materials of the decorative film are the polypropylene resin (A) and the polypropylene resin (B), and do not include or include the thermosetting resin layer. Since there is no need to reduce the appearance and performance during recycling, the suitability for recycling is high.

<Nucleating agent>
In the present specification, the nucleating agent is an additive blended with a polyolefin resin or the like, and the crystallization of the resin can be promoted by blending with the polyolefin resin or the like. Therefore, it is possible to increase the crystallization speed of the polyolefin-based resin and increase the crystallization temperature and the melting temperature. In addition, the addition of the nucleating agent rapidly generates fine crystals, so that the surface smoothness, gloss, transparency, etc. of the film can be improved.
The nucleating agent is likely to volatilize under decorative molding conditions, that is, under the molding conditions of heating under vacuum, but by including the sealing layer (I) that exhibits good adhesion, before the nucleating agent volatilizes. Thus, the molding can be completed and the reduction in gloss can be suppressed.

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

  As commercial products, “ADEKA STAB NA-11”, “ADEKA STAB NA-21” and “ADEKA STAB NA-25” manufactured by Adeka Co., Ltd. “NJESTER TF-1”, “PC-1” manufactured by Shin Nippon Rika Co., Ltd. And “Gerall MD”, “IRGACLEAR XT386” manufactured by BASF Japan Ltd., “Mirad NX8000J” and “Mirad 3988” manufactured by Milliken & Company.

  A nucleating agent can be used individually or in combination of 2 or more types as appropriate.

  The addition amount of the nucleating agent is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50 parts by weight with respect to 100 parts by weight of the resin constituting the layer containing the nucleating agent. Part. When the addition amount is in the above range, a decorative film and a decorative molded body having good gloss, transparency and surface smoothness can be obtained.

  The nucleating agent may be included in the entire layer of the decorative film, but may be included only in the surface layer of the decorative film that is the surface of the decorative molded body. For example, in the case of a two-layer decorative film composed of a sealing layer (I) and a layer (II), the layer (II) preferably contains a nucleating agent. Furthermore, when surface decoration layer (III) which is arbitrary layers is laminated | stacked on layer (II), it is preferable that the surface decoration layer (III) contains the nucleating agent.

<Layer (II)>
The layer (II) contained in the decorative film in the present invention contains a resin composition (B ′) containing a polypropylene resin (B), and the resin composition (B ′) is a requirement (b1) described later. Specific melt flow rate (MFR (B ′)) satisfying the above and a strain hardening degree in elongational viscosity measurement satisfying the requirement (b2) described later.

By providing the layer (II), it is possible to suppress the occurrence of poor appearance due to the film breaking or rampage during (three-dimensional decoration) thermoforming. Thereby, since the thermoformability of a decorating film is improved, it is not necessary to contain the thermosetting resin layer excellent in 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 a very simple configuration of layering of the layer (II) and the sealing layer (I). With such a configuration, it is possible to produce 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 of only the polypropylene resin (B), or can be composed of a plurality of polypropylene resins including the polypropylene resin (B). Any of a composition of blends of polypropylene resins can be used.

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

  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 the requirement (b1 ′), and more preferably satisfies the requirement (b1 ″). By setting the MFR (B ′) of the resin composition (B ′) to the following value or less, a decorative molded body having a good appearance can be obtained.
(B1) MFR (B ′) is 40 g / 10 min or less.
(B1 ′) MFR (B ′) is 20 g / 10 min or less.
(B1 ″) MFR (B ′) is 12 g / 10 min or less.

  Although there is no restriction | limiting in particular about the minimum of MFR (B ') of a resin composition (B'), Preferably it is 0.1 g / 10min or more, More preferably, it is 0.3 g / 10min or more. By setting MFR (B ′) to be equal to or higher than the above value, the moldability at the time of producing a decorative film is improved, and it is possible to suppress the appearance of defects such as shark skin or rough interface on the film surface.

  In this specification, the measurement of each MFR of a polypropylene resin and a resin composition was performed in accordance with 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 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 the requirement (b2 ″). Meet. By setting the degree of strain hardening of the resin composition (B ′) to a value within the following range, a decorative molded body having good moldability during decorative thermoforming and a good appearance can be obtained.
(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 there is no restriction | limiting in particular about the upper limit of the strain hardening degree of a resin composition (B '), Preferably it is 50 or less, More preferably, it is 20 or less. By setting the strain hardening degree to a value within the above range, the appearance of the decorative film can be improved.

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

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

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

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

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

  As a method for introducing a long-chain branched structure into a polypropylene resin, a method of irradiating polypropylene having no long-chain branched structure with high-energy ionizing radiation (Japanese Patent Application Laid-Open No. 62-121704), or a long-chain branched structure. A method of reacting an organic peroxide with polypropylene having no structure (Japanese Patent Publication No. 2001-524565) or 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), but the strain of the polypropylene resin is produced even when any method is used. The degree of cure can be greatly improved.

  The polypropylene resin (B-L) having a long chain branched structure is not particularly limited as long as it has a long chain branched structure, but is a polypropylene resin produced by a method other than the crosslinking method. And those obtained by a method using a macromer copolymerization method having a comb chain structure and forming a long chain branched structure upon polymerization are preferred. Examples of such a method include, for example, Japanese National Publication No. 2001-525460, Japanese Unexamined Patent Publication No. 10-338717, Japanese Special Publication 2002-523575, Japanese Unexamined Patent Publication No. 2009-57542. Examples thereof include methods disclosed in Japanese Patent Laid-Open No. 2005-0537353 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 gel and can obtain a long-chain branched polypropylene resin.

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

The branching index g ′ is known as a direct index regarding the long chain branching structure. There is a detailed description in “Development in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983). The definition of the branching index g ′ is as follows.
Branch index g ′ = [η] br / [η] lin
[Η] br: Intrinsic viscosity of polymer (br) having a long-chain branched structure [η] lin: Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br) As is clear from the above definition, branching index g ′ is When a value smaller than 1 is taken, it is determined that a long chain branching structure exists, and the value of the branching index g ′ decreases as the long chain branching structure increases.

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

{analysis method}
When calculating the absolute molecular weight (Mabs) obtained from the multi-angle laser light scattering detector (MALLS), the root mean square radius of inertia (Rg), and the intrinsic viscosity ([η]) obtained from the Viscometer, data processing attached to MALLS Calculation is performed using the software ASTRA (version 4.73.04) with reference to the following document.
References:
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

In the decorative film of the present invention, when the polypropylene-based resin (B) contains a gel, the film appearance deteriorates. Therefore, it is preferable to use a resin composition (B ′) containing no gel. In particular, a polypropylene resin (BL) having the above-mentioned long-chain branched structure, which is a polypropylene resin having a low gel produced by a method other than the crosslinking method, is preferably terminated with a metallocene catalyst having a specific structure. It is more preferable to produce a macromonomer having an unsaturated bond and to produce a long chain branched structure by copolymerizing it with propylene.
In particular, those having a branching index g ′ satisfying 0.3 or more and less than 1.0 when the absolute molecular weight Mabs is 1,000,000 described below are preferable, more preferably 0.55 or more and 0.98 or less, and still more preferably 0.8. It is 75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less.
In the present invention, “the gel is low” means that the branching index g ′ of the polypropylene resin having an absolute molecular weight Mabs of 1,000,000 is within the above range. When the branching index g ′ is in this range, a highly crosslinked component is not formed, and no gel is formed or very little, so that a polypropylene resin (B-L) having a long-chain branched structure is particularly preferable. When the layer (II) containing contains the surface of the product, the appearance is not deteriorated.

{ ¹³ C-NMR}
As described above, ¹³ C-NMR can distinguish between a short-chain branched structure and a long-chain branched structure. Macromol. Chem. Phys. 2003, vol. 204 and 1738 have detailed explanations, the outline of which is as follows.

The polypropylene resin having a long chain branched structure has a specific branched structure as shown in the following structural formula (1). In Structural Formula (1), C _a , C _b and C _c represent methylene carbon adjacent to the branched carbon, C _br represents the methine carbon at the root of the branched chain, and P ¹ , P ² and P ³ represent Represents a propylene-based polymer residue.

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

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

The ¹³ C-NMR spectrum of a polypropylene-based resin having a long-chain branched structure is characterized in that three methylene carbons adjacent to the branched methine carbon C _br are observed in three non-equivalent diastereotopics. It is.

Such a branched chain assigned by ¹³ C-NMR represents a propylene polymer residue having 5 or more carbon atoms branched from the main chain of the polypropylene resin, and a branch having 4 or less carbon atoms is a branched carbon. 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.
In addition, about the measuring method of ¹³ C-NMR in this invention, it is as follows.

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

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

  The polypropylene resin (B-L) having such a long-chain branched structure is contained in an amount sufficient for imparting strain-hardening properties to the resin composition (B ′) containing the polypropylene resin (B). It only has to be done. The polypropylene resin (B-L) having a long-chain branched structure is contained in 100% by weight of the resin composition (B ′), preferably 1 to 100% by weight, and more preferably 5% by weight or more.

  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, or combinations thereof can be selected. The polypropylene resin preferably contains 50 mol% or more of polymer units derived from a propylene monomer.

  The polypropylene resin (B) in the present invention preferably has higher crystallinity from the viewpoints of heat resistance, scratch resistance and solvent resistance. The melting point (DSC melting peak temperature) of the polypropylene resin (B) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 140 to 170 ° C., still 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 a low crystalline component is included, scratch resistance and solvent resistance are lowered. Therefore, the polypropylene resin (B) is an ethylene-α-olefin having an ethylene content of 50 to 70% by weight. It is preferable not to contain a copolymer.

Moreover, it is preferable that the melting peak temperature (Tm (B ′)) in the DSC measurement of the polypropylene resin (B) is higher than the melting peak temperature (Tm (A)) in the DSC measurement of the polypropylene resin (A). 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) Expression (b-3)
Within the above range, the thermoformability is good.

  The resin composition (B ′) containing the polypropylene resin (B) may contain an additive containing the nucleating agent, a filler, a colorant, other resin components, and the like. At this time, the total amount of additives, fillers, colorants, other resin components, and the like may be 50% by weight or less based on the resin composition (B ′) containing the polypropylene resin (B) including them. preferable.

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

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

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

  Examples of the nucleating agent include the above-described nucleating agents.

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

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

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

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

  A resin composition (B ′) containing a polypropylene resin (B) is a method of melt-kneading a polypropylene resin and an additive, a filler, other resin components, etc., and melt-kneading a polypropylene resin, an additive, a filler, and the like. It can be manufactured by a method of dry blending other resin components to a thing, a method of dry blending a master batch in which additives, fillers, etc. are dispersed in a carrier resin in a high concentration in addition to a polypropylene resin and other resin components it can.

<Sealing layer (I)>
[1. Sealing layer (I) containing polypropylene resin (A)]
The decorative film of the present invention includes a seal layer (I) containing a polypropylene resin (A) that satisfies the following requirement (a1).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 2.0 g / 10 minutes.
Adhesion sufficient to include a sealing layer (I) containing a polypropylene resin (A) on the surface to be bonded to the resin molded body (substrate), even when the film heating time during three-dimensional decorative thermoforming is short Since the strength is developed, it is possible to complete the molding before the nucleating agent volatilizes and suppress the decrease in surface gloss.

  The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) of the polypropylene resin (A) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g / 10 minutes or more. More preferably, it is 4.0 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (A), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

  The polypropylene resin (A) is a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), various types of propylene polymers such as a propylene block copolymer (block polypropylene), Or a combination thereof can be selected. The polypropylene resin (A) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (A) preferably does not contain a polymer unit 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 resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties, and the propylene-α-olefin copolymer usually has a lower melting point than the propylene homopolymer. In addition, since the crystallization temperature is also lowered, the adhesiveness is good even in short-time heating in the three-dimensional decorative molding.

  The polypropylene resin (A) may contain an additive containing the nucleating agent, a filler, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) of a polypropylene resin and additives, fillers, other resin components, and the like. The total amount of additives, fillers, and other resin components is preferably 50% by weight or less based on the polypropylene resin composition.

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

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

  Examples of the nucleating agent include the above-described nucleating agents.

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

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

  Examples of other resin components include polyolefins such as polyethylene resins and ethylene 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 an additive, a filler, other resin components, and the like, a melt-kneaded polypropylene-based resin, an additive, a filler, etc. It can be produced by a method of dry blending a resin component, a method of dry blending a master batch in which additives, fillers and the like are dispersed in a carrier resin in a high concentration in addition to a polypropylene resin and other resin components.

[2. Sealing layer (I) containing polypropylene resin (A)]
As one aspect of the decorative film of the present invention, the polypropylene resin (A) satisfies the following requirements (a2) to (a4) in addition to the requirement (a1), and includes the polypropylene resin (B). It is preferable that the composition (B ′) further satisfies the following requirement (b3).
(A2) A metallocene catalyst-based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B3) Tm (B ′) satisfies the following relational expression (b-3) with respect to Tm (A).
Tm (B ′)> Tm (A) Expression (b-3)

  The seal layer (I) containing the polypropylene-based resin (A) in this embodiment is a layer that comes into contact with the resin molded body (base) during three-dimensional decorative thermoforming. The polypropylene resin (A) is preferably a resin that is easily melted and relaxed. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short. Therefore, the molding is completed before the nucleating agent volatilizes, It is possible to suppress the decrease.

Melt flow rate (MFR (A)): (a1)
The melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) of the polypropylene resin (A) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g / 10 minutes or more. More preferably, it is 4.0 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (A), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

Molecular weight distribution (Mw / Mn (A)): (a4)
The 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, there are few components with a relatively long relaxation time, it is easy to relax sufficiently, surface roughness hardly occurs at the time of film forming, and it is preferable because of excellent surface appearance.
Mn and Mw are described in “Basics of Polymer Chemistry” (edited by the Society of Polymer Science, Tokyo Kagaku Dojin, 1978), etc., and are values respectively calculated from molecular weight distribution curves 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, still more preferably 140 ° C. or less, particularly Preferably it is 130 degrees C or less. When it is in the above range, sufficient adhesive strength can be exhibited. If Tm (A) is too low, the heat resistance may be reduced and problems may occur in the use of the molded article. Therefore, the temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher.

Further, the melting peak temperature (Tm (B ′)) in the DSC measurement of the resin composition (B ′) containing the polypropylene resin (B) needs to be higher than Tm (A), and Tm (B ′) It is preferable that> Tm (A) (requirement (b3)). Within the above range, the thermoformability is good.
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., and further preferably 150 to 168 ° C. The polypropylene resin (B) is preferably a propylene homopolymer or a propylene-α-olefin copolymer having such a melting point. In addition, since the scratch resistance and the solvent resistance are lowered when a low crystalline component is contained even if the melting point is high, the resin composition (B ′) has an ethylene content of 50 to 70% by weight of ethylene-α-. It is preferable not to contain an olefin copolymer.

Resin composition: (a2)
The polypropylene resin (A) is preferably a so-called metallocene catalyst-based propylene 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 resin (A) in this embodiment is a propylene-based polymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The polypropylene resin (A) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (A) preferably does not contain a polymer unit derived from a polar group-containing monomer.

The polypropylene resin (A) is preferably a propylene-α-olefin copolymer from the viewpoint of sealing properties, and the propylene-α-olefin copolymer usually has a lower melting point than the propylene homopolymer. Since the crystallization temperature is also low, sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short, so the molding is completed before the nucleating agent volatilizes, and the surface gloss Can be suppressed.
As the α-olefin, one or a combination of two or more selected from ethylene and an α-olefin having 3 to 8 carbon atoms can be used.

  The polypropylene resin (A) may contain an additive containing the nucleating agent, a filler, other resin components, and the like. That is, it may be a resin composition (polypropylene resin composition) of a polypropylene resin and additives, fillers, other resin components, and the like. The total amount of additives, fillers, and other resin components is preferably 50% by weight or less based on the polypropylene resin composition.

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

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

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

[3. Seal layer (I) containing resin composition (X3) in which weight ratio of polypropylene resin (A) and ethylene-α-olefin random copolymer (C) is 97: 3 to 5:95]
As an aspect of the decorative film of the present invention, the sealing layer (I) has a weight ratio of 97: 3 to 5:95 of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C). A certain resin composition (X3) is contained, the polypropylene resin (A) satisfies the following requirement (a1), and the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3). It is preferable.
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 2.0 g / 10 minutes.
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min.

  The seal layer (I) in this embodiment is a layer that is in contact with a resin molded body (base) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short. Therefore, the molding is completed before the nucleating agent volatilizes, It is possible to suppress the decrease.

{Polypropylene resin (A)}
The polypropylene resin (A) in this embodiment is a propylene-based polymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The polypropylene resin (A) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (A) preferably does not contain a polymer unit 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) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g / 10 minutes or more. More preferably, it is 4.0 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (A), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

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

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

{Ethylene-α-olefin random copolymer (C)}
The ethylene-α-olefin random copolymer (C) used in the seal layer (I) of the present embodiment has the following characteristics (c1) to (c3), preferably (c4) and / or (c5) ).
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min.
(C4) The 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 this embodiment is 65% by weight or more based on the total amount of the ethylene-α-olefin random copolymer (C). Is more preferable, 68% by weight or more, 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. The upper limit of the ethylene content [E (C)] is not particularly limited, but is preferably 95% by weight or less.

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

(Calculation method 1 (binary system))
First, a method for calculating the ethylene content [E (C)] in a binary copolymer composed of two kinds 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)] (wt%) = [ethylene content (mol%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + α-olefin content (mol%) × 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 ··· ( wherein c-2)
_{IX = I αα + (I αγ} + I αδ) / 2 ··· ( wherein c-3)
Here, the subscript symbol I on the right side represents carbon described in the following structural formulas (a) to (d). For example, αα represents a methylene carbon based on an α-olefin chain, and I _αα represents an integrated intensity of a signal of methylene carbon based on an _α -olefin chain.

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

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

(In the case of ethylene-propylene copolymer)
When the α-olefin is propylene, the following integrated intensity value is substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E (C)].
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 of the subscript I on the right side indicates the range of chemical shift. For example, I _39.0-36.2 indicates the integrated intensity of the ¹³ C signal detected between 39.0 ppm and 36.2 ppm.
The chemical shift sets the ¹³ C signal of hexamethyldisiloxane to 1.98 ppm, and the chemical shift of the signal due to the other ¹³ C is based on this. Similarly to the ethylene-propylene copolymer, the ethylene-1-butene copolymer, the ethylene-1-hexene copolymer, and the ethylene-1-octene copolymer will be described below.

(In the case of ethylene-1-butene copolymer)
When the α-olefin is 1-butene, the following integral intensity value is substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E (C)].
_I ββ = I _24.6-24.4
I γγ = I _30.9-30.7
I _βδ = I _27.8-26.8
I _γδ = I _30.5-30.2
I _δδ = I _30.2-28.0
I αα = I _39.3-38.1
I _αγ + I _αδ = I _34.5-33.8

(In the case of ethylene-1-hexene copolymer)
When the α-olefin is 1-hexene, the value of the following integrated intensity is substituted into (Formula c-2) and (Formula c-3) to determine the ethylene content [E (C)].
_I ββ = I _24.5-24.4
I γγ = I _31.0-30.8
I _βδ = I _27.5-27.0
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _40.0-39.0
I _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 overlapped with the methylene carbon of the hexyl branch based on 1-octene (5B6 and 6B6 in the following structural formulas).
I _βδ + I _5B6 = I _27.6-26.7
I _αγ + I _αδ + I _6B6 = I _35.0-34.0

Therefore, I _βδ corrected for the overlap of 5B6 and 6B6 and I _αγ + I _αδ are substituted, and the integral strength shown below is substituted into (Equation c-2) and (Equation c-3), and the ethylene content [E (C)] is obtained.
_I ββ = I _{24.7-24.2
I γγ + I γδ + I δδ} = I 32.0-28.0
_Iβδ = 2/3 × I _27.6-26.7
I αα = I _40.8-39.6
I _αγ + I _αδ = I _βδ + 2 × I _ββ

(Calculation method 2 (ternary system))
Next, a method for calculating the ethylene content [E (C)] in a ternary copolymer composed of three types of repeating units will be described.
For example, the ethylene content of the ethylene-propylene-butene ternary copolymer can be determined by the following (formula 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%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + propylene content (mol%) × propylene molecular weight + Butene content (mol%) × butene molecular weight] (formula c4-2)
Here, IE, IP, and IB are integral intensities for ethylene, propylene, and butene, respectively, and can be obtained from (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 ··· ( wherein c-5)
IP = 1/3 × [I _{CH3 (P)} + I _{CH (P)} + I _{αα (PP)} + 1/2 × (I _{αα ( PB)} + I _{αγ (P)} + I _{αδ (P)} )] (Formula c -6)
IB = 1/4 × [(I _{CH3 (B)} + I _{CH (B)} + I _2B2 + I _{αα (BB)} ) + 1/2 × (I _{αα ( PB)} + I _{αγ (B)} + I _{αδ (B)} )] (Formula 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.
Αα (PP) means a methylene carbon signal based on a propylene chain, similarly αα (BB) means a methylene carbon signal based on a butene chain, and αα (PB) means a methylene carbon based on a propylene-butene chain. Signal.

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

Βδ appears in the structural formula (d) having three or more ethylene chains, and the integrated intensity of βδ in the 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 the structural formula (c) and the structural formula (d) is obtained by (Formula c-10).
I _βδ = I _βδ (Structural Formula (c)) + I _βδ (Structural Formula (d)) = 2 × I _γγ + I _γδ (Formula c-10)
That is,
_{I γγ = (I βδ -I γδ} ) / 2 ··· ( wherein c-10 ')

Therefore, when (Expression c-10 ′) is substituted into (Expression c-5), IE can be replaced with (Expression 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 ··· ( wherein c-11)
Here, the βδ signal corrects the overlap of ethyl branches based on 1-butene, and becomes (Formula c-12).
_{I βδ = I αγ (P)} + I αδ (P) + I αγ (B) + I αδ (B) -2 × I ββ ··· ( wherein 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) ··· ( wherein c-13)
Substitute the following into (Formula c-13), (Formula c-6) and (Formula c-7) to determine the ethylene content.
I _ββ = I _25.2-23.8
I _γδ = I _30.4-30.2
I _δδ = I _30.2-29.8
I _{αγ (P)} + I _{αδ (P)} = I _39.5-37.3
I _{αγ (B)} + I _{αδ (B)} = I _34.6-33.9
I _{CH3 (P)} = I _22.6-19.0
I _{CH (P)} = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I _{αα (PP)} = I _48.0-45.0
I _{CH3 (B)} = I _11.4-10.0
I _{CH (B)} = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
I _{αα (BB)} = I _40.3-40.0
I _{αα (PB)} = I _44.2-42.0
I _2B2 = I _26.7-26.4

In addition, the following five references were referred to the assignment of each signal.
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 when the α-olefin of the ethylene-α-olefin random copolymer is a case other than the above, it is possible to assign each signal and determine the ethylene content [E (C)] in the same manner as described above.

Density: (c2)
The density of the ethylene -α- olefin random copolymer (C) is preferably 0.850~0.950g / cm ^3, more preferably 0.855~0.900g / cm ^3, more preferably 0 860 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 minutes, 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, still more preferably. Is 40-110 ° C. When it is in the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming.

Kind of ethylene-α-olefin random copolymer (C): (c5)
The ethylene-α-olefin random copolymer (C) is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene and the like. Of these, propylene, 1-butene, 1-hexene and 1-octene are particularly preferably used.

  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) uses a gas phase method, a solution method, a high pressure method using a catalyst such as a Ziegler catalyst, a Philips catalyst, or a metallocene catalyst as an olefin polymerization catalyst. It can be produced by copolymerizing ethylene and an α-olefin such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene by a process such as a slurry method.

Moreover, the ethylene-alpha-olefin random copolymer (C) used for the sealing layer (I) of this form can be used 1 type or in combination of 2 or more types in the range which does not impair the effect of this invention.
Commercially available products of such ethylene-α-olefin random copolymers (C) include Kernel Series manufactured by Nippon Polyethylene Co., Ltd., Tuffmer P Series, Tuffmer A Series manufactured by Mitsui Chemicals, Inc., Engage manufactured by DuPont Dow EG series etc. are mentioned.

{Resin composition (X3)}
The resin composition (X3) constituting the seal layer (I) contains the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) as main components, and the polypropylene resin (A) It may be a mixture or melt-kneaded product of ethylene-α-olefin random copolymer (C), and is a sequential polymer of polypropylene resin (A) and ethylene-α-olefin random copolymer (C). It may be.

  In the resin composition (X3) constituting the sealing layer (I), the weight ratio ((A) :( C)) of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is 97. : 3 to 5:95 is preferable, more preferably 95: 5 to 10:90, and still more preferably 93: 7 to 20:80. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the adhesion between the sealing layer (I) and the layer (II) is good. is there.

  The resin composition (X3) may contain additives including the nucleating agent, 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, and the like is preferably 50% by weight or less based on the resin composition (X3).

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

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

[4. Seal layer (I) containing resin composition (X4) in which weight ratio of polypropylene resin (A) to thermoplastic elastomer (D) is 97: 3 to 5:95]
As an aspect of the decorative film of the present invention, the sealing layer (I) is 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 polypropylene resin (A) satisfies the following requirement (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 mainly composed of at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile elastic modulus is smaller than that of the polypropylene resin (A).

  The seal layer (I) in this embodiment is a layer that is in contact with a resin molded body (base) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short. Therefore, the molding is completed before the nucleating agent volatilizes, It is possible to suppress the decrease.

{Polypropylene resin (A)}
The polypropylene resin (A) in this embodiment is a propylene-based polymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The polypropylene resin (A) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (A) preferably does not contain a polymer unit 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) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g / 10 minutes or more. More preferably, it is 4.0 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (A), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

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

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

{Thermoplastic elastomer (D)}
The thermoplastic elastomer (D) used in the seal layer (I) of this embodiment has the following characteristics (d1) to (d4), and preferably further has (d5) and / or (d6). .
(D1) A thermoplastic elastomer mainly composed of at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile elastic modulus is smaller than that of the polypropylene resin (A).
(D5) Melting peak temperature (Tm) (D) is 30-170 degreeC.
(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 mainly composed of propylene and / or butene. Here, “a thermoplastic elastomer mainly composed of propylene and / or butene” means (i) a thermoplastic elastomer mainly composed of propylene, (ii) a thermoplastic elastomer mainly composed of butene, and (iii) Included are thermoplastic elastomers whose main component is the sum of propylene and butene. In the present specification, the unit “wt%” means weight%.

Although there is no restriction | limiting in particular about content of propylene or butene in a thermoplastic elastomer (D), Preferably it is 30 weight% or more, More preferably, it is 40 weight% or more, More preferably, it is 50 weight% or more. For example, the thermoplastic elastomer (D) can contain more than 35% by weight of propylene or butene.
The thermoplastic elastomer (D) may contain both propylene and butene. In that case, the total component of propylene and butene becomes the main component of the thermoplastic elastomer (D), and the total content of propylene and butene is Preferably it is 30 weight% or more, More preferably, it is 40 weight% or more, More preferably, it is 50 weight% or more. When both propylene and butene are contained, for example, the thermoplastic elastomer (D) can contain more than 35% by weight of propylene and butene in total. 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)
Preferably the density of the thermoplastic elastomer (D) is 0.850~0.950g / cm ^3, more preferably 0.855~0.940g / cm ^3, more preferably 0.860～0.930G / cm ³ . Within the above range, sufficient adhesive strength is exhibited during three-dimensional decorative thermoforming, and film formability 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 minutes, more preferably 0.5 to 50 g / 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 elastic modulus of the thermoplastic elastomer (D) is preferably smaller than the tensile elastic 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. When it is in 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, and further preferably 40 to 165 ° C or more. It is. When it is in 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 characteristics (d1) to (d4), but the propylene-ethylene copolymer having an ethylene content of less than 50% by weight. A butene-ethylene copolymer having an ethylene content of less than 50% by weight, a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer having an ethylene content of less than 50% by weight. It is preferable.

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

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

(Calculation method 1 (binary system))
The ethylene content [E (D)] in a binary elastomer (such as a propylene-ethylene copolymer or a butene-ethylene copolymer) composed of two types of repeating units will be described. The ethylene content of the ethylene-α-olefin binary elastomer can be determined by (Formula 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%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + α-olefin content (mol%) × α− Molecular weight of olefin] (formula d1-2)

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

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

The integrated intensity used for (Formula d-2) and (Formula d-3) is described below.
If it is a propylene-ethylene copolymer, the following integrated intensity | strength is substituted into (Formula d-2) and (Formula d-3), and ethylene content [E (D)] is calculated | required.
I _ββ = I _25.0-24.2
I γγ = I _30.8-30.6
I _βδ = I _27.8-26.8
I _γδ = I _30.6-30.2
I _δδ = I _30.2-28.0
I αα = I _48.0-43.9
I _αγ + I _αδ = I _39.0-36.2

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

(Calculation method 2 (ternary system))
Next, the ethylene content [E (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 determined 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)] (wt%) = [ethylene content (mol%) × ethylene molecular weight] × 100 / [ethylene content (mol%) × ethylene molecular weight + propylene content (mol%) × propylene molecular weight + Butene content (mol%) × butene molecular weight] (formula d4-2)
Here, IE, IP, and IB are integral intensities for ethylene, propylene, and butene, respectively, and can be obtained by (Expression d-5), (Expression d-6), and (Expression 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 ··· ( wherein d-5)
IP = 1/3 × [I _{CH3 (P)} + I _{CH (P)} + I _{αα (PP)} + 1/2 × (I _{αα ( PB)} + I _{αγ (P)} + I _{αδ (P)} )] (formula d -6)
IB = 1/4 × [(I _{CH3 (B)} + I _{CH (B)} + I _2B2 + I _{αα (BB)} ) + 1/2 × (I _{αα ( PB)} + I _{αγ (B)} + I _{αδ (B)} )] (Formula 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.
Αα (PP) means a methylene carbon signal based on a propylene chain, similarly αα (BB) means a methylene carbon signal based on a butene chain, and αα (PB) means a methylene carbon based on a propylene-butene chain. Signal.

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

Βδ appears in the structural formula (d) having three or more ethylene chains, and the integrated strength of βδ in the structural formula (d) is equal to the integrated strength of γδ (formula d-9).
I _βδ (Structural Formula (d)) = I _γδ (Formula d-9)
Therefore, βδ based on the structural formula (c) and the structural formula (d) can be obtained by (Formula d-10).
I _βδ = I _βδ (Structural Formula (c)) + I _βδ (Structural Formula (d)) = 2 × I _γγ + I _γδ (Formula d-10)
That is,
_{I γγ = (I βδ -I γδ} ) / 2 ··· ( formula d-10 ')

Therefore, when (Expression d-10 ′) is substituted into (Expression d-5), IE can be replaced with (Expression 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 ··· ( wherein d-11)
Here, the βδ signal corrects the overlap of ethyl branches based on 1-butene, and becomes (formula d-12).
_{I βδ = I αγ (P)} + I αδ (P) + I αγ (B) + I αδ (B) -2 × I ββ ··· ( wherein 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) ··· ( wherein d-13)
Substitute the following into (Formula d-13), (Formula d-6) and (Formula d-7) to determine the ethylene content.
I _ββ = I _25.2-23.8
I _γδ = I _30.4-30.2
I _δδ = I _30.2-29.8
I _{αγ (P)} + I _{αδ (P)} = I _39.5-37.3
I _{αγ (B)} + I _{αδ (B)} = I _34.6-33.9
I _{CH3 (P)} = I _22.6-19.0
I _{CH (P)} = I _29.5-27.6 + I _31.2-30.4 + I _33.4-32.8
I _{αα (PP)} = I _48.0-45.0
I _{CH3 (B)} = I _11.4-10.0
I _{CH (B)} = I _35.5-34.7 + I _37.4-36.8 + I _39.7-39.6
I _{αα (BB)} = I _40.3-40.0
I _{αα (PB)} = I _44.2-42.0
I _2B2 = I _26.7-26.4

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

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

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

Moreover, the thermoplastic elastomer (D) used for the sealing layer (I) of this form can be used 1 type or in combination of 2 or more types in the range which does not impair the effect of this invention.
Examples of such thermoplastic elastomers (D) include commercially available products such as Tafmer XM series, Tafmer BL series, and Tafmer PN series manufactured by Mitsui Chemicals, Inc., and VISTAMAXX series manufactured by ExxonMobil Chemical.

{Resin composition (X4)}
The resin composition (X4) constituting the seal 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 material of the polypropylene resin (A) and the thermoplastic elastomer (D), or the polypropylene resin (A) and the thermoplastic elastomer (D). The sequential polymer may be used.

  In the resin composition (X4) constituting the seal layer (I), the weight ratio ((A) :( D)) of the polypropylene resin (A) and the thermoplastic elastomer (D) is 97: 3 to 5:95. It is preferable to be selected in the range of 95: 5 to 10:90, more preferably 93: 7 to 20:80. Within the above range, sufficient adhesive strength can be exhibited during three-dimensional decorative thermoforming, the heating time of the film can be shortened, and the adhesiveness between the sealing layer (I) and the layer (II) is good. Become.

  The resin composition (X4) may contain additives including the nucleating agent, 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 and the like is preferably 50% by weight or less based on the resin composition (X4).

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

  The production method of the resin composition (X4) is a method of melt-kneading the polypropylene resin (A), the thermoplastic elastomer (D), additives, fillers, other resin components, etc., the polypropylene resin (A). A method of dry blending the thermoplastic elastomer (D) into a melt-kneaded mixture of additives, fillers, fillers and other resin components, etc., and additives, fillers, etc. by adding the polypropylene resin (A) to the thermoplastic elastomer (D) It can be produced by a method of dry blending a master batch 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 an aspect of the decorative film of the present invention, the sealing layer (I) is 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 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 thermal scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) Expression (x−1)
(Wherein 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 is in contact with a resin molded body (base) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short. Therefore, the molding is completed before the nucleating agent volatilizes, It is possible to suppress the decrease.

{Polypropylene resin (A)}
The polypropylene resin (A) in this embodiment is a propylene-based polymer (homopolypropylene), a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), or any other type of propylene-based resin. Polymers or combinations thereof can be selected. The polypropylene resin (A) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (A) preferably does not contain a polymer unit 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) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g / 10 minutes or more. More preferably, it is 4.0 g / 10 min or more. Within the above range, relaxation during three-dimensional decorative thermoforming sufficiently proceeds and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (A), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

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

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

{Thermoplastic resin (E)}
The thermoplastic resin (E) used in the seal layer (I) of this embodiment is a component having a function of delaying crystallization of the polypropylene resin (A) by being contained in the polypropylene resin (A). By delaying the crystallization speed of the polypropylene resin (A), the resin of the seal layer (I) is crystallized before the sealing layer (I) and the substrate surface are heat-sealed during decorative molding. It is possible to prevent the adhesive force from being reduced by (solidifying). As a result, even if the heating time of the decorative film is short, a strong adhesive force is expressed. The effect of delaying the crystallization of the polypropylene resin (A) was evaluated by the isothermal crystallization time of the resin composition (X5) described later.

(E1) Resin composition The thermoplastic resin (E) in this embodiment preferably contains an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group. When the thermoplastic resin (E) has the above-mentioned characteristics, when mixed with the polypropylene resin (A), the effect of delaying the crystallization of the polypropylene resin (A) is exhibited, and the adhesion to the substrate is improved. To do.

Specifically, examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a substituent derivative thereof, a condensed cyclized product, and a crosslinked structure. In particular, it preferably contains a cyclopentyl group or a cyclohexyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a methylphenyl group, a biphenyl group, an indenyl group, a fluorenyl group, a substituent derivative thereof, a condensed cyclized product, and the like, and particularly a phenyl group, a biphenyl group, and an indenyl group. It is preferable. 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 elastomers include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), styrene-ethylene / butylene copolymer elastomer (SEB), and styrene. -Ethylene / propylene copolymer elastomer (SEP), Styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), Styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), Hydrogenated styrene / butadiene elastomer (HSBR) ), Styrene-ethylene / propylene-styrene copolymer elastomer (SEPS), styrene-ethylene / ethylene / propylene-styrene copolymer elastomer (SEEPS), styrene- Tajien butylene - styrene copolymer elastomer (SBBS) or the like can be exemplified, those hydrogenated can be particularly preferably used.
Examples of commercially available products include the Dynalon series manufactured by JSR Corporation, the Clayton G series manufactured by Kraton Polymer Japan Corporation, and the Tuftec series manufactured by Asahi Kasei Corporation.

  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 the main raw material. Resin, hydrogenated coumarone / indene resin, hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin, C5 / C9 copolymer petroleum resin, hydrogenated terpene resin, hydrogenated rosin resin, etc., and commercially available Products can be used, and specific examples include the Alcon series manufactured by Arakawa Chemical Co., Ltd.

{Resin composition (X5)}
The resin composition (X5) constituting the sealing layer (I) contains the polypropylene resin (A) and the thermoplastic resin (E) as main components, and the polypropylene resin (A) and the thermoplastic resin (E ) Or 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. It is preferable to be selected in the range of 95: 5 to 10:90, more preferably 93: 7 to 20:80. Here, a plurality of types of polypropylene resins (A) or thermoplastic resins (E) may be included. For example, when the thermoplastic resin (E1) and the thermoplastic resin (E2) are included, the thermoplastic resin The total of the resin (E1) and the thermoplastic resin (E2) is defined 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) obtained by a differential thermal scanning calorimeter (DSC) satisfying the following relational expression (x-1): The relational expression (x-2) is more preferable, and the relational expression (x-3) is more preferably satisfied.
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)
(Wherein 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, until the sealing layer (I) of the decorative film and the substrate surface are thermally fused during the decorative molding. Time can be earned, and high adhesive strength is developed.
Although there is no restriction | limiting in particular about the upper limit of isothermal crystallization time (t (X5)), If the relational expression of 30xt (A)> = t (X5) is satisfy | filled, the moldability of a film will be favorable.

(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 “Plastic transition temperature measurement method”.

  Specifically, 5 mg of a sample of polypropylene resin (A) is put in an aluminum holder and heated from 40 ° C. to 200 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere. After maintaining 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 the polypropylene resin (A) or the resin composition (X5) is put in an aluminum holder, heated from 40 ° C. to 200 ° C. at a rate of 10 ° C./min in 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. Maintain the temperature and measure the behavior of the sample crystallizing and generating heat. The time from when the temperature of the sample reaches the measurement temperature until the peak of exotherm is defined as the isothermal crystallization time. Here, since it is considered that the adhesive force is greatly reduced by slightly crystallizing the sealing layer (I) of the decorative film during the decorative molding, there are two or more exothermic peaks in the isothermal crystallization measurement. In this case, the time until the first exothermic peak is defined as the isothermal crystallization time.

  Depending on the type of the polypropylene resin (A), the isothermal crystallization time of the polypropylene resin (A) is extremely short (for example, 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 measurement is performed, the isothermal crystallization time of the resin composition (X5) must also be measured in accordance with the measurement temperature of the polypropylene resin (A).

  The resin composition (X5) may contain additives including the nucleating agent, 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 and the like is preferably 50% by weight or less based on the resin composition (X5).

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

  The method for producing the resin composition (X5) is a method in which a polypropylene resin (A), a thermoplastic resin (E), an additive, a filler, other resin components, and the like are melt-kneaded, and a polypropylene resin (A). A method of dry blending a thermoplastic resin (E) into a melt-kneaded mixture of additives, fillers, fillers and other resin components, etc., additives, fillers, etc. by adding a polypropylene resin (A) to a thermoplastic resin (E) It can be produced by a method of dry blending a master batch 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 seal layer (I) contains a propylene-ethylene block copolymer (F) as the polypropylene resin (A), and the propylene-ethylene block copolymer (F) is The following requirements (a1), (f1) and (f2) are preferably satisfied, and 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) Component (F1) composed of propylene homopolymer or propylene-ethylene random copolymer, 5 to 97% by weight, component composed of propylene-ethylene random copolymer having a higher ethylene content than component (F1) ( F2) is contained in an amount of 3 to 95% by weight.
(F2) Melting peak temperature (Tm (F)) is 110-170 degreeC.
(F3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15 to 85% by weight.
(F4) The ethylene content of the component (F1) is in the range of 0 to 6% by weight.
(F5) The ethylene content of the component (F2) is in the range of 5 to 90% by weight.

  The seal layer (I) in this embodiment is a layer that is in contact with a resin molded body (base) during three-dimensional decorative thermoforming. By providing the sealing layer (I), sufficient adhesive strength is exhibited even if the film heating time during three-dimensional decorative thermoforming is short. Therefore, the molding is completed before the nucleating agent volatilizes, It is possible to suppress the decrease.

{Propylene-ethylene block copolymer (F)}
The propylene-ethylene block copolymer (F) of this embodiment is a propylene-ethylene containing a component (F1) composed of a propylene homopolymer or a propylene-ethylene random copolymer and more ethylene than the component (F1). The component (F2) which consists of a random copolymer is contained. The adhesive force with the resin molded body (substrate) is improved by the component (F2) which is a rubber component in the propylene-ethylene block copolymer (F). In addition, the component (F2) has a high uniformity of the dispersion form with respect to propylene, and the adhesiveness is improved accordingly.
The propylene-ethylene block copolymer (F) is obtained by (co) polymerizing the component (F1) consisting of propylene homopolymer or propylene-ethylene random copolymer in the first polymerization step, and from the component (F1) in the second polymerization step. Can be obtained by sequentially copolymerizing a component (F2) comprising a propylene-ethylene random copolymer containing a large amount of ethylene.

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

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) needs to exceed 2.0 g / 10 minutes, preferably 3.0 g. / 10 min or more, more preferably 4.0 g / 10 min or more. When the MFR (F) is in the above range, the propylene-ethylene block copolymer (F) is sufficiently relaxed during three-dimensional decorative thermoforming, and sufficient adhesive strength can be exhibited. Although there is no restriction | limiting in the upper limit of MFR (F), It is preferable that it is 100 g / 10min or less. Within the above range, the adhesive strength is not deteriorated due to a decrease in physical properties.

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

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

Ethylene content in propylene-ethylene block copolymer (F) [E (F)]: (f3)
The ethylene content (hereinafter referred to as “E (F)”) in the propylene-ethylene block copolymer (F) in this embodiment is preferably 0.15 to 85% by weight. More preferably, it is 0.5 to 75 weight%, More preferably, it is 2 to 50 weight%. When E (F) is in the above range, sufficient adhesive strength can be exhibited, and the adhesiveness with the layer (II) of the decorative film is good and the film formability is also excellent.

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

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

{Production method of propylene-ethylene block copolymer (F)}
The propylene-ethylene block copolymer (F) used in this embodiment and the component (F1) comprising the propylene homopolymer or propylene-ethylene random copolymer constituting the propylene-ethylene random copolymer (F2) ) Can be preferably produced by the following raw materials and polymerization method. The manufacturing method of the propylene-ethylene block copolymer (F) used for this invention is demonstrated below.

(Raw materials used)
As a catalyst used in producing the propylene-ethylene block copolymer (F) used in the present embodiment, a magnesium-supported catalyst having magnesium, halogen, titanium, and an electron donor as catalyst components, and titanium trichloride as a catalyst A catalyst comprising a solid catalyst component and organoaluminum, or a metallocene catalyst can be used. A specific method for producing the catalyst is not particularly limited, and examples thereof include a Ziegler catalyst disclosed in Japanese Unexamined Patent Publication No. 2007-254671 and a metallocene catalyst disclosed in Japanese Unexamined Patent Publication No. 2010-105197. Can be illustrated.

  The raw material olefins to be polymerized are propylene and ethylene. If necessary, other olefins that do not impair the object of the present invention, such as 1-butene, 1-hexene, 1-octene, 4-methyl-1 -Penten etc. can also be used.

(Polymerization process)
The polymerization process performed in the presence of the catalyst includes a first polymerization process for producing the component (F1) and a second polymerization process for producing the component (F2).

-1st polymerization process The 1st polymerization process supplies a propylene homopolymer or a mixture of propylene / ethylene to the polymerization system which added the said catalyst, manufactures a propylene homopolymer or a propylene-ethylene random copolymer, In this step, the component (F1) is formed so as to be an amount corresponding to 5 to 97% by weight of the polymer amount.

  The MFR of the component (F1) (hereinafter referred to as “MFR (F1)”) can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR (F1) of the component (F1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is only necessary to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is extremely easy for those skilled in the art. Moreover, when a component (F1) is a propylene-ethylene random copolymer, it is easy to use the method of controlling the quantity of ethylene supplied to a polymerization tank as a means to control ethylene content. Specifically, if the quantity ratio of ethylene to propylene supplied to the polymerization tank (ethylene supply amount ÷ propylene supply amount) is increased, the ethylene content of the component (F1) is increased. The reverse is also true. Although the relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of component (F1) varies depending on the type of catalyst used, the component having the desired ethylene content 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, which is 3 to 95% by weight of the total polymer amount. In this step, the component (F2) is formed so as to have an amount corresponding to.

  The MFR of the 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 MFR control method of component (F1). As a means for controlling the ethylene content of the component (F2), it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank. The specific control method is the same as when 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 between the component (F1) and the component (F2) will be described. The weight ratio of the component (F1) and the component (F2) is controlled by the production amount in the first polymerization step for producing the component (F1) and the production amount in the second polymerization step for producing the component (F2). For example, in order to increase the amount of the component (F1) and reduce the amount of the component (F2), the production amount of the second polymerization step may be reduced while maintaining the production amount of the first polymerization step. The residence time in the polymerization process may be shortened or the polymerization temperature may be lowered. It can also be controlled by adding a polymerization inhibitor such as ethanol or oxygen or increasing the amount of addition when it is originally added. The reverse is also true.

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

  In an industrial production facility, the production amount is usually obtained 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 quantity ratio may be obtained by separating and identifying both using an analysis method such as TREF (temperature rising temperature elution fractionation method). A technique for evaluating the crystallinity distribution of polypropylene by TREF measurement is well known to those skilled in the art. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. Detailed measurement methods are shown in documents such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

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

This formula shows the material balance regarding ethylene content.
Therefore, if the weight ratio between the component (F1) and the component (F2) is determined, that is, if W (F1) and W (F2) are determined, E (F) is uniquely determined by E (F1) and E (F2). Determined. That is, E (F) can be controlled by controlling the weight ratio between the component (F1) and the component (F2), and the three factors E (F1) and E (F2).
For example, in order to increase E (F), E (F1) may be increased or E (F2) may be increased. If it is noted that E (F2) is higher than E (F1), it can be easily understood that W (F1) may be reduced and W (F2) may be increased. The reverse control method is the same.

  In addition, it is E (F) and E (F1) that can actually obtain the measured value directly, and E (F2) is calculated using the measured values of both. Therefore, if an operation for increasing E (F2), that is, an operation for increasing the amount of ethylene supplied to the second polymerization step is selected as a means when performing an operation for increasing E (F), the measured value is directly measured. It can be confirmed that E (F) is not E (F2), but it is obvious that the reason why E (F) increases is that E (F2) increases.

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

This equation is an empirical formula generally called the logarithm addition law of viscosity log _e [MFR (F)] = (W (F1) / 100) × log _e [MFR (F1)] + (W (F2) / 100) × log _e [MFR (F2)]
It is a modified version and is used daily in the industry.

  In order to define by this formula, the weight ratio of component (F1) to component (F2), MFR (F), MFR (F1) and MFR (F2) are not independent. Therefore, in order to control MFR (F), the weight ratio of component (F1) and component (F2), three factors of MFR (F1) and MFR (F2) may be controlled. For example, in order to increase MFR (F), MFR (F1) may be increased or MFR (F2) may be increased. In addition, when MFR (F2) is lower than MFR (F1), it can be easily understood that MFR (F) can be increased even if W (F1) is increased and W (F2) is decreased. . The reverse control method is the same.

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

  The polymerization process of the propylene-ethylene block copolymer can be carried out by either a batch method or a continuous method. At this time, a method of performing polymerization in an inert hydrocarbon solvent such as hexane or heptane, a method of using propylene as a solvent without substantially using an inert solvent, or a gas without using a liquid solvent. A method in which polymerization is performed in a monomer, and a method in which these are combined can be employed. Further, the first polymerization step and the second polymerization step may use the same polymerization tank or separate polymerization tanks.

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

  Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15, 1150 (1982) and the like, the concentration of these triads and the peak intensity of the spectrum are linked 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)

Here, the brackets [] indicate the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1 (f-7)
It is.
Further, k is a constant, I indicates the spectral intensity, and 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)
In addition, conversion from mol% of ethylene content to weight% is performed using the following formula | equation (f-9).
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1-X / 100)} × 100 (f-9)
Here, X is the ethylene content in mol%.

  The propylene-ethylene block copolymer (F) in this embodiment may contain additives including the nucleating agent, fillers, other resin components, and the like as long as the effects of the present invention are not impaired. That is, it may be a resin composition (polypropylene resin composition) of the propylene-ethylene block copolymer (F) and additives, fillers, other resin components, and the like. The total amount of additives, fillers, other resin components, and the like is preferably 50% by weight or less based on the resin composition.

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

  The resin composition comprises a method of melt-kneading a propylene-ethylene block copolymer (F) with additives, fillers, other resin components, etc., a propylene-ethylene block copolymer (F) with additives, fillers, etc. A method of dry blending other resin components into the melt-kneaded material, a master batch in which propylene-ethylene block copolymer (F) and other resin components are added in a high concentration to the carrier resin with additives, fillers, etc. 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) has the following requirements (g1): And (g2) is satisfied.
(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 min or less.

  The seal layer (I) in this embodiment is a layer that is in contact with a resin molded body (base) during three-dimensional decorative thermoforming. By laminating the sealing layer (I) on the layer (II), sufficient adhesive strength is exhibited even if the film heating time at the time of three-dimensional decorative thermoforming is short, so it is molded before the nucleating agent volatilizes. Thus, it is possible to suppress a decrease in surface gloss, and it is possible to firmly adhere to a base made of a resin material having polarity.

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 needs to be 100 g / 10 min or less, preferably 50 g / 10 min. Hereinafter, it is more preferably 20 g / 10 min or less. By setting the MFR (G) of the polyolefin adhesive resin (G) to be equal to or less than the above value, the layer (II) containing the resin composition (B ′) containing the polypropylene resin (B) is formed by extrusion molding. It becomes possible to laminate | stack the sealing layer (I) containing polyolefin adhesive resin (G).
Although there is no restriction | limiting in particular about the minimum of MFR (G) of polyolefin adhesive resin (G), Preferably it is 0.1 g / 10min or more, More preferably, it is 0.3 g / 10min or more. In coextrusion molding of the resin composition (B ′) containing the polypropylene resin (B) and the polyolefin adhesive resin (G) by setting the MFR (G) of the polyolefin adhesive resin (G) to the above value or more. Further, it is possible to suppress the occurrence of problems such as the occurrence of interface roughness at the lamination interface or the lamination of the polyolefin adhesive resin (G) up to the film end.

Polar functional group containing a hetero atom: (g1)
In the present embodiment, the polyolefin adhesive resin (G) contains at least one heteroatom from the viewpoint of improving adhesiveness with the layer (II) containing the resin composition (B ′) containing the polypropylene resin (B). It is a polyolefin resin having a polar functional group.

  Examples of the polar functional group having at least one hetero atom include an epoxy group, a carbonyl group, an ester group, an ether group, a hydroxy group, a carboxy group or a metal salt thereof, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, and an acid. An anhydride group, amino group, imide group, amide group, nitrile group, thiol group, sulfo group, isocyanate group, halogen group and the like can be mentioned. Among them, the polyolefin adhesive resin (G) is selected from the group consisting of epoxy group, hydroxy group, carboxy group, acid anhydride group, amino group, imide group, amide group, nitrile group, thiol group, isocyanate group, and halogen group. A polyolefin resin having at least one selected functional group is more preferable.

Specific examples of the polyolefin having such a polar functional group include: acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer Polymer, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer ,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 / acrylic acid Metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic acid Ethyl / glycidyl methacrylate co Coalescing, ethylene / ethylene or α- olefin / vinyl monomer copolymers such as vinyl acetate / glycidyl methacrylate copolymer; chlorinated polyolefins such as chlorinated polypropylene chlorinated polyethylene.
Moreover, these resin may be used independently and may be mixed with 2 or more types. Furthermore, you may mix other resin or rubber | gum, a tackifier, the various additives containing the said nucleating agent, a filler, etc. as needed.

  Among the polyolefin resins having polar functional groups, from the viewpoint of adhesiveness to the layer (II), as commercial products, Mitsui Chemicals' product name "Admer", Mitsubishi Chemical Corporation's product name "Modic", Sanyo Kasei Co., Ltd. “YUMEX” or the like can be preferably used.

  Examples of the other resin or rubber include poly α-olefins such as polypentene-1 and polymethylpentene-1, ethylene such as propylene / butene-1 copolymer, and α-olefin / α-olefin copolymers. Ethylene such as ethylene / propylene / 5-ethylidene-2-norbornene copolymer or α-olefin / α-olefin / diene monomer copolymer, polydiene copolymer such as polybutadiene and polyisoprene, styrene / butadiene random copolymer Polymer, vinyl monomer / diene monomer random copolymer such as styrene / isoprene random copolymer, vinyl monomer such as styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer / Diene monomer / Vinyl monomer block copolymer, Hydrogenated (Styrene / Butadiene random copolymer), Hydrogenation (styrene / isoprene random copolymer) and other hydrogenation (vinyl monomer / diene monomer random copolymer), hydrogenation (styrene / butadiene / styrene block copolymer) ), Hydrogenation (styrene / isoprene / styrene block copolymer), etc. (vinyl monomer / diene monomer / vinyl monomer block copolymer), acrylonitrile / butadiene / styrene graft copolymer, Vinyl methacrylate / diene monomer / vinyl monomer graft copolymer such as methyl methacrylate / butadiene / styrene graft copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, polyacrylic acid Vinyl polymers such as ethyl, polybutyl acrylate, polymethyl methacrylate, polystyrene, Vinyl / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer, Rael and vinyl copolymers such as methyl methacrylate / styrene copolymer.

  Examples of the tackifier include rosin resins (gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, rosin ester, etc.), terpene phenol resin, terpene resin ( 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, Phenol resins (alkyl phenol, phenol xylene formaldehyde, rosin-modified phenol resin, etc.), xylene resins and the like can be mentioned, 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. In particular, rosin-based resins and terpene phenol resins are preferable because they are compatible with each other and can contribute to adhesion to polar resins.

  Examples of the additives include antioxidants, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, metal soaps, stabilizers such as antacid adsorbents, or crosslinking agents, chain transfer agents, Examples thereof include a lubricant, a plasticizer, a filler, a reinforcing material, a pigment, a dye, a flame retardant, an antistatic agent, and a fluorescent brightening agent, and may be added within a range not impairing the effects of the present invention.

  As the additive and filler, the above-mentioned [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

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

  Three-dimensional decorative thermoforming has a high degree of freedom in the shape of the decoration target, and the end face of the decorative film is rolled up to the back side of the decoration target, so there is no seam, and the appearance of the decorative film is further improved. Various textures can be expressed by applying grain or the like to the surface. For example, when a texture such as embossing is applied to the resin molded body, three-dimensional decorative thermoforming may be performed using a decorative film provided with embossing. For this reason, it is very difficult and expensive to perform molding with a molded body mold that gives embossing, that is, a molded body mold is required for each embossing pattern, and that complicated embossing is applied to a curved surface mold. Thus, it is possible to obtain a decorative molded body to which various patterns of embossing can be easily applied. Moreover, if a mirror-like cooling roll is surface-transferred and the decorative film is mirror-finished, a decorative film with higher gloss can be obtained. Furthermore, in the decorative film which contains a nucleating agent in the surface layer which comprises a decorative film, a decorative film with high surface gloss can be obtained. Furthermore, in the decorative film of the present invention, the surface texture can be maintained even after decorative molding, and a decorative molded body having a good appearance can be obtained.

  In addition to the sealing layer (I) and the layer (II), the multilayer film is provided between the base material layer, the surface layer, the surface decoration layer (III), the printing layer, the light shielding layer, the coloring layer, the barrier layer, and these layers. Tie layer layers etc. that can be included. The layer (II) containing the resin composition (B ′) may be any layer other than the seal layer among the layers constituting the multilayer film.

  When the decorative film is a two-layer film composed of the layer (II) and the seal layer (I), the layer (II) constitutes a surface layer opposite to the sticking surface to the resin molded body, and the seal layer (I) will comprise the sticking surface to a resin molding. In this case, the layer (II) preferably contains a nucleating agent.

  Further, even a multilayer film having a complicated layer structure includes the layer (II) and the sealing layer (I).

  Moreover, as another preferred embodiment of the multilayer film having more than two layers including the layer (II) and the sealing layer (I), the layers other than the layer (II) and the sealing layer (I) are preferably layers made of a thermoplastic resin. More preferably, it is a layer made of a polypropylene resin. As long as the layers other than the layer (II) and the sealing layer (I) can be distinguished from the layer (II) and the sealing layer (I), the MFR (230 ° C., 2.16 kg) of the polypropylene resin constituting the layer. (Load) is not particularly limited. Each layer is preferably a layer that does not contain a thermosetting resin. By using a thermoplastic resin, recyclability is improved, and by using a polypropylene-based resin, complication of the layer structure can be suppressed, and the recyclability is further improved.

FIG. 1B (a) to FIG. 1B (c) show an embodiment of a decorative film including a layer (II) containing a resin composition (B ′) containing a polypropylene resin (B) and a sealing layer (I). BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which illustrates a cross section typically, and FIG. 1A (a)-FIG. 1A (c) are explanatory drawings which illustrate typically the cross section of embodiment of the said decoration film stuck on the resin molding. is there. An embodiment of a decorative film will be described with reference to FIGS. 1A (a) to 1A (c). In FIG. 1A (a) to FIG. 1A (c), for easy understanding, the arrangement of the sealing layer (I) and the layer (II) will be specified and described. It is not construed as limiting.
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 decorative molding. Showing the body. FIG. 1A (a) is an example in which the decorative film 1 is composed of a two-layer film. A seal layer (I) 3 is adhered to the resin molded body 5 and a polypropylene resin ( The layer (II) 2 containing the resin composition (B ′) containing B) is laminated. The decorative film 1 in FIG. 1A (b) is composed of a seal layer (I) 3, a layer (II) 2 and a surface layer. The seal layer (I) 3 is adhered to the resin molded body 5, and the seal layer (I ) The layer (II) 2 and the surface layer are laminated on the layer 3 in this order. The decorative film 1 in FIG. 1A (c) is composed of a seal layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4 containing a polypropylene resin, and the resin molded body 5 has a seal layer (I ) 3 is stuck, and the layer (II) 2 and the surface decoration layer (III) 4 are laminated in this order on the seal layer (I) 3.

  In addition, in FIGS. 1B (a) to 1B (c), the arrangement of the sealing layer (I) 3 and the layer (II) 2 is specified and described for easy understanding. Is not construed as being limited to these examples. Reference numeral 1 in the drawing denotes a decorative film, reference numeral 2 denotes a layer (II), reference numeral 3 denotes a sealing layer (I), and reference numeral 4 denotes a surface decorative layer (III). FIG. 1B (a) is an example in which the decorative film 1 is composed of a two-layer film, and a layer containing a resin composition (B ′) containing a polypropylene resin (B) on the sealing layer (I) 3 ( II) 2 are stacked. The decorative film 1 in FIG. 1B (b) is composed of a sealing layer (I) 3, a layer (II) 2 and a surface layer, and the layer (II) 2 and the surface layer are arranged in this order on the sealing layer (I) 3. Laminate. 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 the layer (II) 2 is formed on the sealing layer (I) 3. And the surface decoration layer (III) 4 is laminated | stacked in this order.

  As a preferred embodiment of the multilayer film, the layers other than the seal layer (I) and the layer (II) are preferably layers made of a thermoplastic resin, more preferably from a polypropylene resin other than the polypropylene resin (B). It is a layer. Each layer is preferably a layer that does not contain a thermosetting resin. Recyclability is improved by using a thermoplastic resin. Furthermore, by using a polypropylene resin other than the polypropylene resin (B), complication of the layer structure can be suppressed, and the recyclability is further improved.

  As another preferable aspect of the decorative film, a surface decorative layer (III) made of a surface decorative layer resin is provided on the outermost surface on the opposite surface side to the resin-molded surface, more preferably on the outermost surface. ). The surface decorating 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 providing a surface decoration layer (III) containing a polypropylene resin (H) on the surface layer of the decorative film, the gloss and texture transferability can be improved without greatly reducing the thermoformability. Can do. Further, by using the polypropylene resin (H), it is possible to suppress complication of the layer structure and a decrease in recyclability. In addition, by using the polypropylene resin (H) for the surface decoration layer (III) of the decorative film, the solvent resistance and the like can be improved. In addition, the use of polypropylene resin (H) for the surface decoration layer improves the transferability of the surface during the production of the decorative film and during thermoforming. It can be set as a decorative film. Furthermore, when the surface decoration layer contains the nucleating agent exemplified in the present specification, higher surface gloss is exhibited.

  The polypropylene resin (H) in this embodiment is a propylene homopolymer (homopolypropylene), various types of propylene resins such as a propylene-α-olefin copolymer (random polypropylene), a propylene block copolymer (block polypropylene), and the like. Polymers or combinations thereof can be selected. The polypropylene resin (H) preferably contains 50 mol% or more of polymer units derived from a propylene monomer. The polypropylene resin (H) preferably does not contain a polymer unit derived from a polar group-containing monomer. The polypropylene resin (H) is preferably homopolypropylene from the viewpoint of oil resistance, solvent resistance, scratch resistance, and the like. Further, from the viewpoint of gloss and transparency (coloring property), a propylene-α-olefin copolymer is preferable. In this embodiment, the polypropylene resin (H) constituting the surface decoration layer (III) may be the same as or different from the polypropylene resin (A) constituting the seal layer (I).

  The polypropylene resin (H) in this embodiment 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 resin (H) to less than 1.1, the appearance of the decorative molded body can be improved. The strain hardening degree of polypropylene resin (H) shall be calculated | required by the method mentioned above.

  The polypropylene resin (H) preferably has an MFR (H) (230 ° C., 2.16 kg load) of more than 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 resin (H) within the above range, effects such as easy improvement of the gloss of the decorative film and improvement of the texture transfer property can be obtained, and the required surface of the molded article A decorative molded body having a good appearance can be obtained with respect to the shape (gloss, non-gloss, grain, etc.).

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

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

  Examples of additives, fillers, and other resin components include those described in [1. What was illustrated by the sealing layer (I) containing a polypropylene resin (A)] can be used.

  The resin composition containing the polypropylene resin (H) includes a method of melt-kneading the polypropylene resin (H), an additive, a filler, other resin components, etc., a polypropylene resin (H), an additive, a filler, etc. A method of dry blending other resin components to a melt-kneaded product, a method of dry blending a master batch in which additives, fillers and the like are dispersed in a carrier resin in a high concentration in addition to the polypropylene resin (H) and other resin components Etc. can be manufactured.

  When the surface decoration layer (III) is a polypropylene resin composition containing a polypropylene resin (H), this polypropylene resin composition is composed of the polypropylene resin (A) constituting the seal layer (I). The same or different polypropylene resin composition may be used. When both polypropylene resin compositions are the same, the seal layer (I) and the surface decoration layer (III) can be formed by using a feed block or the like with one extruder. Have advantages.

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

  In the decorative film of the present invention, the ratio of the thickness of the layer (II) in 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 1. 70%. If the ratio of the thickness of the layer (II) to the whole decorative film is within the above range, it is possible to avoid insufficient thermoformability of the decorative film. If the ratio of the thickness of the sealing layer (I) to the whole decorative film is within the above range, the adhesion to the resin molded body (substrate) is good, and it is applied before the nucleating agent volatilizes. The decorative molding can be completed.

  Moreover, in the multilayer film which provided the surface decoration layer (III) containing a polypropylene resin (H) in the outermost surface of a decoration film, the ratio for which the thickness of the surface decoration layer (III) accounts in a decoration film Is preferably 30% or less with respect to the thickness of the entire decorative film.

<Manufacture of decorative film>
The decorative film of the present invention is a method of coextrusion of various seal layers (I) and a layer (II) containing a resin composition (B ′) containing a polypropylene resin (B), a seal layer (I) And a method of co-extrusion of layer (II) with another layer, a thermal lamination method in which the other layer is bonded to one surface of one layer that has been previously extruded by applying heat and pressure, and adhesion Examples thereof include a dry lamination method and a wet lamination method in which bonding is performed through an agent, and an extrusion lamination method and a sand lamination method in which a polypropylene resin is melt-extruded on one surface of one layer that has been previously extruded.

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

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

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

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

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

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

  Polypropylene resin is a non-polar polymer because it is nonpolar, but the decorative film in the present invention is a resin composition (B ′) containing various seal layers (I) and polypropylene resin (B). ) -Containing layer (II), the decorative object made of polypropylene resin and the decorative film are attached to provide a very high adhesive strength and decorate before the nucleating agent volatilizes. Molding can be completed.

  As a base resin of a polypropylene resin and a polypropylene resin composition of a molded object to be decorated, a propylene homopolymer (homopolypropylene), a propylene-α-olefin copolymer, a propylene block copolymer, etc. Various types using various known propylene monomers as main raw materials can be selected. Moreover, as long as the effects of the present invention are not impaired, a filler such as talc may be included for imparting rigidity, or an elastomer may be included for imparting impact resistance. Moreover, you may contain an additive component and another resin component similarly to the polypropylene resin composition which can comprise the decorating film mentioned above.

  Moreover, as a molded object (decoration object) decorated in this invention, the various molded object which consists of polar resin materials can also be used, In that case, polyester resin, polyamide resin, polyimide resin, polystyrene resin, acrylic Various molded articles 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, reinforcing agents such as inorganic fillers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants and the like may be added to these resins, and these additives may be used alone. More than one type may be used in combination. The molding method is not particularly limited, and examples thereof include injection molding, blow molding, press molding, and extrusion molding.

  Since the above-mentioned polar resin material is a non-polar polypropylene resin, which is hardly adhesive, it is usually not thermally bonded. On the other hand, the decorative film in the present invention allows the decorative object and the decorative film to be thermally bonded by the seal layer (I) containing the polyolefin adhesive resin (G), and has high adhesive strength. Can be demonstrated. A preferred example of the polyolefin adhesive resin (G) is a modified polyolefin resin grafted with α, β-unsaturated carboxylic acids.

  The decorative molded body in which the decorative film of the present invention is attached to various molded articles made of polypropylene resin, particularly various molded articles formed in a three-dimensional shape, greatly reduces the VOC contained in the coating and adhesive. Therefore, it can be suitably used as an automobile member, a home appliance, a vehicle (railway or the like), a building material, a daily necessities, or the like.

[Manufacture of decorative molded bodies]
The method for producing a decorative molded body according to the present invention includes a step of preparing the above-described decorative film, a step of preparing a resin molded body, and a step of setting the resin molded body and the decorative film in a depressurizable chamber box. , Depressurizing the interior of the chamber box, heating and softening the decorative film, pressing the softened decorative film on the resin molding, and returning the decompressed chamber box to atmospheric pressure or The method includes a step of applying pressure.

  In three-dimensional decorative thermoforming, a decorative object and a decorative film are set in a chamber box that can be depressurized, and the decorative film is heated and softened in a state where the pressure in the chamber box is reduced, and the softened decorative object is added to the decorative box. It has the basic process of pressing the decorative film and returning the inside of the chamber box to atmospheric pressure, or applying pressure to the surface of the decorative object, and decorating the film under reduced pressure. Paste. As a result, it is possible to obtain a beautiful decorative molded body free from air accumulation. In the production method of the present invention, any known technique can be used as long as the apparatus and conditions are suitable for three-dimensional decorative thermoforming.

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

In addition, the mechanism for pressing the decoration target and the decoration film may be any type such as one that moves the decoration target, one that moves the decoration film, and one that moves both.
More specifically, typical molding methods are exemplified below.

  Hereinafter, a method for sticking a decorative film to a decoration object using a three-dimensional decorative thermoforming machine will be exemplarily described with reference to the drawings.

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

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

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

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

  As shown in FIG. 4, the upper chamber box 11 is lowered, the upper and lower chamber boxes 11 and 12 are joined, and the chamber boxes 11 and 12 are closed, and then the chamber boxes 11 and 12 are in a vacuum suction state. 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 in a vacuum suction state. The decorative film 1 is pressed against the resin molded body 5 to cover the resin molded body 5. Further, as shown in FIG. 6, the decorative film 1 is brought into close contact with the resin molded body 5 with a larger force by opening the upper chamber box 11 under atmospheric pressure or supplying compressed air from a pressurized air tank.

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

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

  Moreover, in the two chamber boxes 11 and 12 divided | segmented up and down by the decorating film 1, the chamber box internal pressure by which the resin molded object 5 and the decorating film 1 are affixed should just be in the said range, The draw-down of the decorative film 1 can also be suppressed by changing the pressure of the upper and lower chamber boxes 11 and 12.

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

  However, since the decorative film 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 a film caused by pressure fluctuations. Resistant to deformation.

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

  In the present invention, in order to attach the polypropylene decorative film 1 to the resin molded body 5 made of polypropylene resin, the surface of the resin molded body 5 to be decorated and the decorative film 1 are sufficiently softened or melted. is necessary.

  Therefore, the heater temperature needs to be higher than the melting temperature of the polypropylene resin constituting the resin molded body 5 and the polypropylene resin constituting the decorative film 1. The heater temperature is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, and most preferably 200 ° C. or higher.

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

Although an appropriate heating time varies depending on the heater temperature, it is preferable that the polypropylene-based decorative film is heated and heated for a period of time before the start of rebound called springback or for a time longer than that.
In a certain aspect, it is preferable to heat for 2 hours after the end of the rebounding or for a time longer than that.

In other words, the decorative film heated by the heater expands by heating from the solid state and sags once with the melting of the crystal. However, after the springback, the decorative film has completely melted crystals and sufficient relaxation of the molecules, so that sufficient adhesive strength can be obtained.
Furthermore, since the decorative film containing the sealing layer (I) of the present invention can be strongly bonded to the substrate even if it is subjected to decorative thermoforming before the end of rebounding, The time can be shortened and the molding can be completed before the nucleating agent contained in the decorative film volatilizes. In addition, it has a great effect on suppressing the wrinkle return.

  On the other hand, if the heating time is too long, the decorative film hangs down due to its own weight or deforms due to the pressure difference between the upper and lower chamber boxes, and therefore it is preferable that the heating time is less than 30 seconds after the end of the springback. .

  In the case of decorating a complex shaped article having irregularities or achieving higher adhesion, it is preferable to supply compressed air when the decorative film is brought into close contact with the substrate. The pressure in the upper chamber box when compressed air is introduced is preferably 150 kPa or more, more preferably 200 kPa or more, and further preferably 250 kPa or more. The upper limit is not particularly limited, but if the pressure is too high, the device may be damaged, so 450 kPa or less is preferable, and 400 kPa or less is more preferable.

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

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

(Ii) Degree of strain hardening λ
The method of obtaining the strain hardening degree λ was performed by the method described above. At this time, η ^* (0.01) used as the shear viscosity value and ηe (3.5) used as the extension viscosity value were measured by the following methods. Moreover, the sample used for the measurement at this time was formed into a 0.7 mm thick and 2 mm flat plate by pressing for 1 hour under conditions of a temperature of 180 ° C. and a pressure of 10 MPa. Was used for the extensional viscosity measurement, and a 2 mm sample was used for the dynamic frequency sweep experiment.

(Ii-1) Shear viscosity η ^* (0.01)
A dynamic frequency sweep experiment was conducted using ARES manufactured by Rheometric Scientific. A parallel disk having a diameter of 25 mm was used for the measurement geometry. Using the apparatus control software TA Orchestrator, measurement was performed in the measurement mode Dynamic Frequency Sweep Test. As a sample, a press-molded body having a thickness of 2 mm produced by the above method was used. The measurement temperature was 180 ° C. The angular frequency ω was measured at 5 points per digit so as to be equally spaced on a logarithmic scale between 0.01 and 100 rad / s.
The complex viscosity η ^* (0.01) [unit: Pa · s] at ω = 0.01 rad / s is adopted as an index indicating the viscosity of the sample at a low shear rate. The complex viscosity η ^* is calculated as η ^* = G ^* / ω from the complex elastic modulus G ^* [unit: Pa] and ω.

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

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

(Iv) Measurement of the branching index g ′ when the absolute molecular weight Mabs is 1,000,000 According to the method described above, measurement is performed using GPC equipped with a light scatterometer and a viscometer in the detector, and the branching index is determined based on the analysis method described above. g ′ was determined.

(V) Detection of long-chain branched structure using ¹³ C-NMR According to the method described above, measurement using ¹³ C-NMR was performed to determine the presence or absence of a long-chain branched structure.

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

Conversion from the retention capacity obtained by the GPC measurement to the molecular weight was performed using a calibration curve of standard polystyrene (PS) prepared in advance. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve was created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximation by the least square method was used.
In addition, the following numerical value was 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 density of the ethylene-α-olefin random copolymer (C) and the thermoplastic elastomer (D) was measured in accordance with the density gradient tube method of JIS K7112 (1999).

(Viii) Tensile elastic modulus The tensile elastic modulus of the thermoplastic elastomer (D) was measured according to ASTM D638 at ASTM-IV injection specimen, 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 determined 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 o-dichlorobenzene / deuterated benzene bromide (C ₆ D ₅ Br) = 4/1 (volume ratio) 2.4 ml and chemical shift. The sample was dissolved together with hexamethyldisiloxane as a reference substance in an NMR sample tube having an inner diameter of 10 mmφ.
¹³ C-NMR measurement was performed using an AV400 NMR apparatus manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
^{The 13} C-NMR measurement conditions were as follows: the sample temperature was 120 ° C., the pulse angle was 90 °, the pulse interval was 20 seconds, and the number of integrations was 512 times.

(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 above-described method for measuring ethylene content by ¹³ C-NMR.

(X) Isothermal crystallization time:
The isothermal crystallization time was measured by the above-described method using a differential scanning calorimeter (DSC).
When measuring the isothermal crystallization time of the polypropylene resin (A) and the resin composition (X5), the polypropylene resin (A), the polypropylene resin (A), and the thermoplastic resin (E) are biaxial. Melt-kneading was carried out using an extruder to obtain pellets of polypropylene resin (A) and resin composition (X5), and the isothermal crystallization time was measured using the pellets. For the twin screw extruder, KZW-15 manufactured by Technobel was used, the screw rotation speed was set to 400 RPM, and the kneading temperatures were set to 80 ° C., 120 ° C. and 200 ° C. (hereinafter, the same temperature until the die outlet) from the bottom of the hopper. .

2. Evaluation of physical properties of decorative molded body (1) Evaluation of thermoformability Drawdown state of the decorative film during three-dimensional decorative thermoforming, and the decorative film of the decorative molded body with the decorative film attached to the substrate The sticking state was visually observed and evaluated according to the criteria shown below.
○: At the time of three-dimensional decorative thermoforming, the decorative film did not draw down, and the contact between the substrate and the decorative film was made simultaneously on the entire contact surface, so contact unevenness did not occur and it was evenly attached ing.
X: During the three-dimensional decorative thermoforming, the decorative film was greatly drawn down, so contact unevenness occurred on the entire surface of the substrate.

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

  The decorative film surface of the obtained decorative molded body was cut to a substrate surface with a width of 10 mm using a cutter in a direction perpendicular to the longitudinal direction of the adhesive tape to prepare a test piece. In the obtained test piece, the bonding surface between the base and the decorative film is 10 mm wide × 45 mm long. Attach to the tensile tester so that the base part of the test piece and the decorative film part are 180 °, measure the 180 ° peel strength of the adhesive surface at a tensile speed of 200 mm / min, and take the maximum strength at the time of peeling or breaking (N / 10 mm) was measured 5 times, and the average strength was defined as the adhesive strength. The test was performed at 23 ° C. and 50% RH.

(3) Gloss (Gloss)
The gloss (gross) near the center of the decorative molded body on which the decorative film was attached was measured at an incident angle of 60 ° using a GLOSS meter Gloss Meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. The measuring method was based on JIS-Z-8741. Moreover, the surface gloss of the decorative film before decorative molding was measured in advance by the same method, and the amount of change in surface gloss was evaluated by calculating the difference in gloss between the two.

(4) Recyclability evaluation The obtained decorative molded body was pulverized, and a recycled molded body was produced by injection molding in the same manner as in the production of a resin molded body (substrate). Evaluated by criteria.
○: There is no dispersion failure such as fish eyes, and the appearance is excellent.
X: Fish eyes are generated in the injection piece, and the appearance is poor.

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

3-2. Production of Resin Molded Body (Substrate) Using polypropylene resins (Z-1) to (Z-3), an injection molded body was 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 ℃
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate condition adjustment: hold for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 50% RH

(Test Example 1)
[1: A decorative film including a sealing layer (I) made of a polypropylene resin (A) having an MFR (A) of more than 2.0 g / 10 minutes]
1-1. Materials Used Polypropylene Resin The following polypropylene resin was 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 elastic modulus = 1600 MPa), Nippon Polypro Co., Ltd. Product name “Novatech (registered trademark) FA3KM”, branching index g ′ = 1.0 when the absolute molecular weight Mabs is 1 million. It was confirmed by measurement of ¹³ C-NMR that there was no 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 elastic modulus = 650 MPa), manufactured by Nippon Polypro Co., Ltd. Product name “Novatech (registered trademark) FX4G”.
(A-3): Propylene-α-olefin random copolymer having no long chain branching (MFR = 7.0 g / 10 min, Tm = 146 ° C., Mw / Mn = 4.0, tensile elastic modulus = 1200 MPa) Product name “NOVATEC (registered trademark) FW3GT” manufactured by Nippon Polypro Co., Ltd.

(A-1-1): Polypropylene based on 100 parts by weight of a polypropylene resin (A-1) blended with 0.4 parts by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Ltd.) Resin composition (MFR = 10 g / 10 min, Tm = 164 ° C.)
(A-1-2): Polypropylene resin obtained by blending 0.4 parts by weight of a nucleating agent (trade name “Gelall MD”, manufactured by Shin Nippon Rika Co., Ltd.) with 100 parts by weight of a polypropylene resin (A-1) Resin composition (MFR = 10 g / 10 min, Tm = 164 ° C.)
(A-1-3): Polypropylene system obtained by blending 100 parts by weight of a polypropylene resin (A-1) with 0.2 parts by weight of a nucleating agent (manufactured by Adeka, trade name “Adeka Stub NA-11”). Resin composition (MFR = 10 g / 10 min, Tm = 163 ° C.)
(A-1-4): Polypropylene system in which 0.2 part by weight of a nucleating agent (trade name “Adeka Stub NA-21” manufactured by Adeka Co., Ltd.) is blended with 100 parts by weight of a polypropylene resin (A-1). Resin composition (MFR = 10 g / 10 min, Tm = 163 ° C.)
(A-1-5): A polypropylene resin obtained by blending 100 parts by weight of a polypropylene resin (A-1) with 0.2 parts by weight of a nucleating agent (trade name “IRGACLEAR XT386” manufactured by BASF Japan Ltd.). Composition (MFR = 10 g / 10 min, Tm = 163 ° C.)

(B-1): Propylene homopolymer having a long chain branch produced by a macromer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX (registered trademark) MFX8”, MFR = 1.0 g / 10 min Strain hardening degree λ = 9.7, Tm = 154 ° C., branching index g ′ = 0.89 when absolute molecular weight Mabs is 1 million, and confirmed to have long chain branched structure by measurement of ¹³ C-NMR.
(B-2): Propylene homopolymer having a long chain branch produced by a macromer copolymerization method, manufactured by Nippon Polypro Co., Ltd., trade name “WAYMAX (registered trademark) MFX3”, MFR = 8.8 g / 10 min Strain hardening degree λ = 7.8, Tm = 154 ° C., branching index g ′ = 0.85 when absolute molecular weight Mabs is 1,000,000, and confirmed to have long chain branched structure by ¹³ C-NMR measurement.
(B-1-1): Polypropylene system obtained by blending 100 parts by weight of a polypropylene resin (B-1) with 0.4 part by weight of a nucleating agent (trade name “Millad NX8000J” manufactured by Milliken Japan Co., Ltd.) Resin composition (MFR = 1.0 g / 10 min, Tm = 156 ° C.)
(B-1-2): Polypropylene resin composition (MFR = 96 wt%) blended with 4 wt% of black pigment MB (EPP-K-120601 manufactured by Polycol Kogyo Co., Ltd.). (1.0 g / 10 min, strain hardening degree λ = 9.3, Tm = 154 ° C.)
(B-1-3): Polypropylene based on 100 parts by weight of polypropylene resin (B-1) blended with 0.2 parts by weight of a nucleating agent (trade name “ADK STAB NA-11” manufactured by Adeka Co., Ltd.) Resin composition (MFR = 1.0 g / 10 min, Tm = 156 ° C.)

Example 1-1
-Manufacture of decoration film Extruder-1 for sealing layer with a diameter of 30 mm (diameter), Extruder-2 with a diameter of 40 mm (diameter), and Extruder-3 for surface decoration layer with a diameter of 30 mm (diameter) are connected. In addition, a three-layer three-layer T die having a lip opening of 0.8 mm and a die width of 400 mm was used. Polypropylene resin (A-1) is used for the extruder 1 for the seal layer, polypropylene resin (B-1) is used for the extruder-2, and polypropylene resin (A-1) is used for the extruder 3 for the surface decoration layer. -1), the resin temperature is 240 ° C., the discharge rate of the seal layer extruder-1 is 4 kg / h, the discharge rate of the extruder-2 is 8 kg / h, and the surface decoration layer extruder-3 is Melt extrusion was performed at a discharge rate of 4 kg / h.

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

-Three-dimensional decoration thermoforming As the resin molding (base | substrate) 5, the injection molding which consists of the polypropylene resin (Z-1) obtained by the above was used.
As a three-dimensional decorative thermoforming apparatus, “NGF-0406-SW” manufactured by Fuse Vacuum Co., Ltd. was used. As shown in FIGS. 2 to 7, the decorative film 1 is cut out with a width of 250 mm × a length of 350 mm so that the seal layer (I) faces the base and the longitudinal direction is the MD direction of the film. It set to the jig 13 for film fixing whose size is 210 mm x 300 mm. The resin molded body (base body) 5 is placed on a table 14 positioned below the film fixing jig 13 and placed on a sample mounting table having a height of 20 mm, “Nystack NW-K15” manufactured by Nichiban Co., Ltd. ”Pasted through. The film fixing jig 13 and the table 14 were installed in the chamber boxes 11 and 12, the chamber was closed, and the chamber boxes 11 and 12 were sealed. The chamber box is divided up and down via the decorative film 1. The upper and lower chamber boxes are vacuum-sucked, and the far-infrared heater 15 installed on the upper chamber box 11 is started at an output of 80% in a state where the pressure is reduced from atmospheric pressure (101.3 kPa) to 1.0 kPa. Was heated. Vacuum suction was continued during heating, and the pressure was finally reduced to 0.1 kPa. The decorative film 1 is heated to sag temporarily, and then 10 seconds after the end of the springback phenomenon, the table 14 installed in the lower chamber box 12 is moved upward to form a resin molded body ( The substrate 5 was pressed against the decorative film 1, and immediately after that, compressed air was fed so that the pressure in the upper chamber box 11 was 270 kPa, thereby bringing the resin molded body (substrate) 5 and the decorative film 1 into close contact. In this way, a three-dimensional decorative thermoformed product 6 in which the decorative film 1 was adhered to the upper surface and the side surface of the resin molded body (substrate) 5 was obtained. The evaluation results are shown in Table 2.

Example 1-2
In the production of the decorative film of Example 1-1, Example 1 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 1-3
In the production of the decorative film of Example 1-1, Example 1 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 1-4
In the production of the decorative film of Example 1-1, Example 1 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 1-5
In the production of the decorative film of Example 1-1, Example 1 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 1-6
In the production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-7
In the production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-8
In the production of the decorative film of Example 1-1, the same procedure as in Example 1-1 was performed except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2). Molding and evaluation were performed. The evaluation results are shown in Table 2.

Example 1-9
In the production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-10
In the production of the decorative film of Example 1-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-11
In the production of the decorative film of Example 1-1, the procedure was the same as Example 1-1 except that the polypropylene resin (A-1) of the seal layer (I) was changed to the polypropylene resin (A-2). Were molded and evaluated. The evaluation results are shown in Table 2.

Example 1-12
In manufacture of the decorative film of Example 1-1, it is the same as that of Example 1-1 except having changed the polypropylene resin (A-1) of the sealing layer (I) to the polypropylene resin (A-3). Were molded and evaluated. The evaluation results are shown in Table 2.

Example 1-13
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . The polypropylene resin (A-1) and the polypropylene resin (B-1-1) are charged in the seal layer extruder-1 and the extruder-2, respectively, and the resin temperature is 240 ° C. and the seal layer extruder-1 is used. The extrusion was performed under the conditions of a discharge rate of 4 kg / h and a discharge rate of the extruder-2 of 12 kg / h.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decoration thermoforming similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-14
In the production of the decorative film of Example 1-1, Example 1-1 was used except that the polypropylene resin (B-1) of the layer (II) was changed to a polypropylene resin (B-1-2). Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 2.

Example 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 base body was changed to an injection-molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 2.

Example 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 base body was changed to an injection-molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 2.

Example 1-17
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-3), and the polypropylene resin (A) of the layer (II). Except having changed B-1) into the polypropylene resin (B-2), it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 2.

Example 1-18
In production of the decorative film of Example 1-13, Example 1-13 was performed except that the polypropylene resin (B-1-1) of the layer (II) was changed to a polypropylene resin (B-1-3). Molding and evaluation were performed in the same manner as described above. The evaluation results are shown in Table 2.

Comparative Example 1-1
In the production of the decorative film of Example 1-1, Example 1-1 was used except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1). Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 2.

Comparative Example 1-2
In the production of the decorative film of Example 1-1, the procedure was the 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). Were molded and evaluated. The evaluation results are shown in Table 2.

Comparative Example 1-3
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the seal layer (I) is changed to the polypropylene resin (B-1), and the spring back 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 50 seconds after the phenomenon was completed. The evaluation results are shown in Table 2.

Comparative Example 1-4
In production of the decorative film of Example 1-1, the same procedure as in Example 1-1 was performed except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1). Molding and evaluation were performed. The evaluation results are shown in Table 2.

  The decorative molded body obtained from the decorative film of Examples 1-1 to 1-18 contains a nucleating agent in any layer, and the polypropylene resin (A) in the seal layer (I). (A1) About a resin composition (B ′) having a melt flow rate (MFR (A)) exceeding 2.0 g / 10 min and containing a polypropylene resin (B) in the layer (II), (b1) Melt flow rate (MFR (B ′)) is 40 g / 10 min or less, and (b2) strain hardening degree is 1.1 or more, so there is no contact unevenness, excellent thermoformability, surface gloss and adhesion The force was good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 1-14 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 1-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface is further dull after the decorative molding, and the surface gloss is significantly reduced. . The decorative film of Comparative Example 1-2 in which the MFR of the polypropylene resin used for the seal layer (I) was 2.0 g / 10 min or less was inferior in adhesive strength. Comparative Example 1-3, which uses the same decorative film as Comparative Example 1-2 and was molded 50 seconds after the end of the springback phenomenon, has an adhesive property by increasing the heating time for three-dimensional decorative molding. However, the nucleating agent added to the surface decorating layer (III) was volatilized and the surface gloss was significantly reduced. In Comparative Example 1-4 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

(Test Example 2)
[2: Decorative film including sealing layer (I) made of polypropylene resin (A) satisfying 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 metallocene catalyst (MFR = 7.0 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.5), manufactured by Nippon Polypro Co., Ltd. Name "Wintech (registered trademark) WFX4M"
(A-5): Propylene-α-olefin copolymer with metallocene catalyst (MFR = 25 g / 10 min, Tm = 125 ° C., Mw / Mn = 2.4), manufactured by Nippon Polypro Co., Ltd., trade name “ Wintech (registered trademark) WSX03 "
(A-6): Propylene-α-olefin copolymer with metallocene catalyst (MFR = 7.0 g / 10 min, Tm = 135 ° C., Mw / Mn = 2.3), manufactured by Nippon Polypro Co., Ltd. Name "Wintech (registered trademark) WFW4M"
(A-7): Propylene-α-olefin copolymer by metallocene catalyst (MFR = 3.5 g / 10 min, Tm = 143 ° C., Mw / Mn = 2.8), manufactured by Nippon Polypro Co., Ltd. Name "Wintech (registered trademark) WFW5T"

Example 2-1
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the seal layer (I) is changed to the polypropylene resin (A-4), and the spring back 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. The evaluation results are shown in Table 3.

Example 2-2
In the production of the decorative film of Example 2-1, Example 2 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 3.

Example 2-3
In the production of the decorative film of Example 2-1, Example 2 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 3.

Example 2-4
In the production of the decorative film of Example 2-1, Example 2 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 3.

Example 2-5
In production of the decorative film of Example 2-1, Example 2 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 3.

Example 2-6
In the production of the decorative film of Example 2-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30 (Tm (B ') = 161 degreeC), it shape | molded and evaluated similarly to Example 2-1. The evaluation results are shown in Table 3.

Example 2-7
In the production of the decorative film of Example 2-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 10:90 (Tm (B ') = 161 degreeC), it shape | molded and evaluated similarly to Example 2-1. The evaluation results are shown in Table 3.

Example 2-8
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2) in the same manner as in Example 2-1. Molding and evaluation were performed. The evaluation results are shown in Table 3.

Example 2-9
In the production of the decorative film of Example 2-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30 (Tm (B ') = 161 degreeC), it shape | molded and evaluated similarly to Example 2-1. The evaluation results are shown in Table 3.

Example 2-10
In the production of the decorative film of Example 2-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 10:90 (Tm (B ') = 161 degreeC), it shape | molded and evaluated similarly to Example 2-1. The evaluation results are shown in Table 3.

Example 2-11
In 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), Example 2-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 3.

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), Example 2-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 3.

Example 2-13
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-7), Example 2-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 3.

Example 2-14
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . The polypropylene resin (A-4) and the polypropylene resin (B-1-1) are fed into the seal layer extruder-1 and the extruder-2, respectively. The extrusion was performed under the conditions of a discharge rate of 4 kg / h and a discharge rate of the extruder-2 of 12 kg / h.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decorative thermoforming similarly to Example 2-1. The evaluation results are shown in Table 3.

Example 2-15
In the production of the decorative film of Example 2-1, except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-1-2), Example 2-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 3.

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 base body was changed to an injection molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 3.

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 base was changed to an injection-molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 3.

Comparative Example 2-1
In the production of the decorative film of Example 2-1, except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1), Example 2-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 3.

Comparative Example 2-2
In the production of the decorative film of Example 2-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1) in the same manner as in Example 2-1. Molding and evaluation were performed. The evaluation results are shown in Table 3.

  The decorative molded body obtained from the decorative film of Examples 2-1 to 2-17 contains a nucleating agent in any layer, and the polypropylene resin (A) in the seal layer (I). (A1) Melt flow rate (MFR (A)) exceeds 2.0 g / 10 min, (a2) is a metallocene catalyst-based propylene polymer, and (a3) melting peak temperature (Tm (A)) is Resin composition (B ′) having a temperature of less than 150 ° C., (a4) Mw / Mn (A) of 1.5 to 3.5, and containing polypropylene resin (B) in layer (II) (B1) Melt flow rate (MFR (B ′)) is 40 g / 10 min or less, (b2) Strain hardening is 1.1 or more, (b3) Melting peak temperature (Tm (B ′)) Is higher than Tm (A), so there is no contact unevenness and excellent thermoformability. Sawa and adhesion were good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 2-15 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 2-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface becomes dull after the decorative molding, and the surface gloss is significantly reduced. . In Comparative Example 2-2 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

(Test Example 3)
[3: Decorative film including a sealing layer (I) including a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C)]
3-1. Materials Used Polypropylene Resin 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 = 0.85 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 wt%): Mitsui Chemicals, Inc. Product name "Toughmer A4050S"
(C-3): ethylene-octene random copolymer (MFR = 2.0 g / 10 min, Tm = 77 ° C., density = 0.85 g / cm ³ , ethylene content = 85 wt%): manufactured by DuPont Dow, Product name “Engage EG8003”
(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 wt%): 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 wt%): Mitsui Chemicals, Inc. Product name "Toughmer P0280"

Example 3-1.
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the seal layer (I) was replaced with the polypropylene resin (A-3) and the ethylene-α-olefin random copolymer (C- 1) and blended so that the weight ratio is 85:15, and molding is performed immediately after the end of the springback phenomenon (that is, the heating time after the springback is 0 second) in the three-dimensional decorative thermoforming. Except having performed, it shape | molded and evaluated similarly to Example 1-1. The evaluation results are shown in Table 4.

Example 3-2
In production of the decorative film of Example 3-1, Example 3 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 4.

Example 3-3
In the production of the decorative film of Example 3-1, Example 3 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 4.

Example 3-4
In the production of the decorative film of Example 3-1, Example 3 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 4.

Example 3-5
In production of the decorative film of Example 3-1, Example 3 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 4.

Example 3-6
In the production of the decorative film of Example 3-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) was changed between the polypropylene resin (B-1) and the polypropylene resin (A-1). Except having changed to what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-7
In the production of the decorative film of Example 3-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) was changed between the polypropylene resin (B-1) and the polypropylene resin (A-1). Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-8
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2) in the same manner as in Example 3-1. Molding and evaluation were performed. The evaluation results are shown in Table 4.

Example 3-9
In the production of the decorative film of Example 3-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed to what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-10
In the production of the decorative film of Example 3-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

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

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 seal layer (I) was replaced with the ethylene-α-olefin random copolymer (C-3). Except for the change to), molding and evaluation were performed in the same manner as in Example 3-1. The evaluation results are shown in Table 4.

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). Except for the change to), molding and evaluation were performed in the same manner as in Example 3-1. The evaluation results are shown in Table 4.

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). Except for the change to), molding and evaluation were performed in the same manner as in Example 3-1. The evaluation results are shown in Table 4.

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). Except for the change to), molding and evaluation were performed in the same manner as in Example 3-1. The evaluation results are shown in Table 4.

Example 3-16
In production of the decorative film of Example 3-1, the compounding ratio of the resin of the seal layer (I) was changed to polypropylene resin (A-3): ethylene-α-olefin random copolymer (C-1) = 70: Except having set it as 30, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-17
In production of the decorative film of Example 3-1, the compounding ratio of the resin of the seal layer (I) was changed to polypropylene resin (A-3): ethylene-α-olefin random copolymer (C-1) = 30: Except having set to 70, it shape | molded and evaluated similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-18
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . Extruder obtained by blending polypropylene resin (A-3) and ethylene-α-olefin random copolymer (C-1) so as to have a weight ratio of 85:15 to seal layer extruder-1 -2 is charged with polypropylene resin (B-1-1), the resin temperature is 240 ° C., the discharge amount of the seal layer extruder-1 is 4 kg / h, and the discharge amount of the extruder-2 is 12 kg / h. Melt extrusion was performed under the conditions.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decorative thermoforming similarly to Example 3-1. The evaluation results are shown in Table 4.

Example 3-19
In the production of the decorative film of Example 3-1, except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-1-2), Example 3-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 4.

Example 3-20
In production of the decorative film of Example 3-1, Example 3 was changed 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 Example 1. The evaluation results are shown in Table 4.

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

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 base was changed to an injection molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 4.

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 base was changed to an injection-molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 4.

Comparative Example 3-1
In the production of the decorative film of Example 3-1, except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1), Example 3-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 4.

Comparative Example 3-2
In the production of the decorative film of Example 3-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1) in the same manner as in Example 3-1. Molding and evaluation were performed. The evaluation results are shown in Table 4.

The decorative molded body obtained from the decorative film of Examples 3-1 to 3-23 contains a nucleating agent in any layer, and the sealing layer (I) is made of polypropylene resin (A). Including the resin composition (X3) having a weight ratio of 97: 3 to 5:95 with the ethylene-α-olefin random copolymer (C), and for the polypropylene resin (A), (a1) Melt flow rate ( MFR (A)) exceeds 2.0 g / 10 min, and for the ethylene-α-olefin random copolymer (C), (c1) ethylene content [E (C)] is 65% by weight or more, (c2 ) The density is 0.850-0.950 g / cm ³ , (c3) the melt flow rate (MFR (C)) is 0.1-100 g / 10 min, and the polypropylene system in layer (II) Resin composition (B ′) containing resin (B) (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. The gloss and adhesion were good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 3-19 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 3-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface is further dull after the decorative molding, and the surface gloss is significantly reduced. . In Comparative Example 3-2 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

(Test Example 4)
[4: Decorative film containing a sealing layer (I) containing a polypropylene resin (A) and a 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 the main component (MFR = 7.0 g / 10 min, Tm = 75 ° C., density = 0.85 g / cm ³ , tensile modulus = 290 MPa, propylene Content = 69 wt%, butene content = 31 wt%, ethylene content [E] = 0 wt%): manufactured by Mitsui Chemicals, Inc., trade name “Tuffmer XM7070”
(D-2): Butene homopolymer (MFR = 5.0 g / 10 min, Tm = 125 ° C., density = 0.915 g / cm ³ , tensile elastic modulus = 430 MPa, ethylene content [E] = 0 wt%) : Mitsui Chemicals, trade name "Toughmer BL4000"
(D-3): Propylene-ethylene-butene random copolymer mainly composed of propylene (MFR = 6.0 g / 10 min, Tm = 160 ° C., density = 0.868 g / cm ³ , tensile modulus = 50 MPa , Propylene content = 84 wt%, ethylene content [E] = 9 wt%, butene content = 7 wt%): manufactured by Mitsui Chemicals, Inc., trade name “Toughmer 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 wt%, ethylene content [E] = 11 wt%): ExxonMobil Chemical Co., Ltd., trade name “VISTAMAX3000”

Example 4-1
In the production of the decorative film of Example 1-1, the polypropylene resin (A-1) of the sealing layer (I), the weight ratio of the polypropylene resin (A-3) and the thermoplastic elastomer (D-1). In the same manner as in Example 1-1 except that the blend was changed to 85:15 and the molding was performed 5 seconds after the completion of the springback phenomenon in the three-dimensional decorative thermoforming. And evaluated. The evaluation results are shown in Table 5.

Example 4-2
In the production of the decorative film of Example 4-1, Example 4 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 5.

Example 4-3
In the production of the decorative film of Example 4-1, Example 4 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 5.

Example 4-4
In the production of the decorative film of Example 4-1, Example 4 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 5.

Example 4-5
In the production of the decorative film of Example 4-1, Example 4 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 5.

Example 4-6
In the production of the decorative film of Example 4-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed to what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 4-1. The evaluation results are shown in Table 5.

Example 4-7
In the production of the decorative film of Example 4-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 4-1. The evaluation results are shown in Table 5.

Example 4-8
In the production of the decorative film of Example 4-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2), as in Example 4-1. Molding and evaluation were performed. The evaluation results are shown in Table 5.

Example 4-9
In the production of the decorative film of Example 4-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed to what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 4-1. The evaluation results are shown in Table 5.

Example 4-10
In the production of the decorative film of Example 4-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might be set to 10:90, it shape | molded and evaluated similarly to Example 4-1. The evaluation results are shown in Table 5.

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

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

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

Example 4-14
In manufacture of the decorative film of Example 4-1, except that the compounding ratio of the resin of the sealing layer (I) was set to polypropylene resin (A-3): thermoplastic elastomer (D-1) = 70: 30. The molding and the evaluation were performed in the same manner as in Example 4-1. The evaluation results are shown in Table 5.

Example 4-15
In manufacture of the decorative film of Example 4-1, except that the compounding ratio of the resin of the seal layer (I) was polypropylene resin (A-3): thermoplastic elastomer (D-1) = 30: 70. The molding and the evaluation were performed in the same manner as in Example 4-1. The evaluation results are shown in Table 5.

Example 4-16
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . A blend of a polypropylene resin (A-3) and a thermoplastic elastomer (D-1) so as to have a weight ratio of 85:15 is added to the extruder 2 for the seal layer, and a polypropylene resin is added to the extruder-2. (B-1-1) was added, and melt extrusion was performed under the conditions of a resin temperature of 240 ° C., a discharge rate of the seal layer extruder-1 of 4 kg / h, and a discharge rate of the extruder-2 of 12 kg / h. It was.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decoration thermoforming similarly to Example 4-1. The evaluation results are shown in Table 5.

Example 4-17
In production of the decorative film of Example 4-1, except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-1-2), Example 4-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 5.

Example 4-18
In production of the decorative film of Example 4-1, Example 4 was changed 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 Example 1. The evaluation results are shown in Table 5.

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

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 base body was changed to an injection molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 5.

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 base body was changed to an injection molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 5.

Comparative Example 4-1
In production of the decorative film of Example 4-1, except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1), Example 4-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 5.

Comparative Example 4-2
In production of the decorative film of Example 4-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1), and was the same as in Example 4-1. Molding and evaluation were performed. The evaluation results are shown in Table 5.

The decorative molded body obtained from the decorative film of Examples 4-1 to 4-21 contains a nucleating agent in any layer, and the sealing layer (I) is made of polypropylene resin (A). Including the resin composition (X4) having a weight ratio of 97: 3 to 5:95 with the thermoplastic elastomer (D), the polypropylene resin (A) has (a1) a melt flow rate (MFR (A)) More than 2.0 g / 10 minutes, with regard to the thermoplastic elastomer (D), (d1) the main component is at least one of propylene and butene, and (d2) the density is 0.850 to 0.950 g / cm ³ Yes, (d3) Melt flow rate (MFR (D)) is 0.1 to 100 g / 10 min, (d4) Tensile elastic modulus is smaller than polypropylene resin (A), and in layer (II) Polypropylene resin For the resin composition (B ′) containing (B), (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. There was no contact unevenness, thermoformability was excellent, and surface gloss and adhesion were good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 4-17 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 4-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface becomes dull after the decorative molding, and the surface gloss is significantly reduced. . In Comparative Example 4-2 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

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

  About layer (II) and surface decoration layer (III), the polypropylene resin used by the said "1-1. Used material" and "2-1. Used material" 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 elastomer (SEBS): manufactured by Kraton Polymer Japan, trade name “Clayton 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 polypropylene resin (A-1) of the sealing layer (I), the weight ratio of the polypropylene resin (A-3) and the thermoplastic resin (E-1). Except that the molding is performed immediately after the end of the springback phenomenon (that is, the heating time after the springback is 0 second) in the three-dimensional decorative thermoforming. Molding and evaluation were performed in the same manner as in Example 1-1. The evaluation results are shown in Table 6.

Example 5-2
In production of the decorative film of Example 5-1, Example 5 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 6.

Example 5-3
In the production of the decorative film of Example 5-1, Example 5 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 6.

Example 5-4
In production of the decorative film of Example 5-1, Example 5 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 6.

Example 5-5
In the production of the decorative film of Example 5-1, Example 5 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 6.

Example 5-6
In the production of the decorative film of Example 5-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 5-1. The evaluation results are shown in Table 6.

Example 5-7
In the production of the decorative film of Example 5-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed to what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 5-1. The evaluation results are shown in Table 6.

Example 5-8
In the production of the decorative film of Example 5-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2) in the same manner as in Example 5-1. Molding and evaluation were performed. The evaluation results are shown in Table 6.

Example 5-9
In the production of the decorative film of Example 5-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 5-1. The evaluation results are shown in Table 6.

Example 5-10
In the production of the decorative film of Example 5-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed to what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 5-1. The evaluation results are shown in Table 6.

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

Example 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) was used. ) 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. The evaluation results are shown in Table 6.

Example 5-13
In manufacture of the decorative film of Example 5-1, except that the compounding ratio of the resin of the seal layer (I) was polypropylene resin (A-3): thermoplastic resin (E-1) = 70: 30. Then, molding and evaluation were performed in the same manner as in Example 5-1. The evaluation results are shown in Table 6.

Example 5-14
In manufacture of the decorative film of Example 5-1, except that the compounding ratio of the resin of the seal layer (I) was polypropylene resin (A-3): thermoplastic resin (E-1) = 30: 70. Then, molding and evaluation were performed in the same manner as in Example 5-1. The evaluation results are shown in Table 6.

Example 5-15
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . A blend of polypropylene resin (A-3) and thermoplastic resin (E-1) so as to have a weight ratio of 50:50 to the extruder for sealing layer-1 and polypropylene resin to the extruder-2. (B-1-1) was added, and melt extrusion was performed under the conditions of a resin temperature of 240 ° C., a discharge rate of the seal layer extruder-1 of 4 kg / h, and a discharge rate of the extruder-2 of 12 kg / h. It was.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decoration thermoforming similarly to Example 5-1. The evaluation results are shown in Table 6.

Example 5-16
In production of the decorative film of Example 5-1, except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-1-2), Example 5-1 and Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 6.

Example 5-17
In production of the decorative film of Example 5-1, Example 5 was changed 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 Example 1. The evaluation results are shown in Table 6.

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

Example 5-19
In the production of the decorative film of Example 5-1, the polypropylene resin (A-3) used for the seal layer (I) was changed to the polypropylene resin (A-8), and the polypropylene resin (A-8) was changed. ) And the thermoplastic resin (E-1) were molded and evaluated in the same manner as in Example 5-1, except that the blending ratio was 70:30. The evaluation results are shown in Table 6.

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 base body was changed to an injection molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 6.

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 base was changed to an injection-molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 6.

Comparative Example 5-1
In the production of the decorative film of Example 5-1, Example 5-1, except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1). Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 6.

Comparative Example 5-2
In production of the decorative film of Example 5-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1), and was the same as in Example 5-1. Molding and evaluation were performed. The evaluation results are shown in Table 6.

  The decorative molded body obtained from the decorative film of Examples 5-1 to 5-21 contains a nucleating agent in any layer, and the sealing layer (I) is composed of the polypropylene resin (A). Including the resin composition (X5) having a weight ratio of 97: 3 to 5:95 with the thermoplastic resin (E), and for the polypropylene resin (A), (a1) the melt flow rate (MFR (A)) is More than 2.0 g / 10 min, and for the thermoplastic resin (E), it contains at least one of (e1) alicyclic hydrocarbon group and aromatic hydrocarbon group, and (x1) resin composition (X5 ) Is more than 1.5 times the isothermal crystallization time (t (A)) (second) of the polypropylene resin (A), and the layer ( II) About the resin composition (B ′) containing the polypropylene resin (B) in (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, excellent thermoformability, surface gloss and adhesive strength. It was good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 5-16 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 5-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface is further dull after the decorative molding, and the surface gloss is significantly reduced. . In Comparative Example 5-2 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

(Test Example 6)
[6: Decorative film including 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”, the following resins were used.

-Manufacture of propylene-ethylene block copolymer (F) As propylene-ethylene block copolymer (F) used for the sealing layer (I) of a decorative film, the propylene-ethylene block copolymer obtained by the following manufacture examples Combined (F-1) to (F-4) were used. The polymerization conditions and polymerization results are shown in Table 7-1, and the results of polymer analysis 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 and hydrolyzed, and then measured using a colorimetric method. About the sample after preliminary polymerization, content was calculated using the weight remove | excluding the preliminary polymerization polymer.
Silicon compound content: The sample was accurately weighed and decomposed with methanol. The silicon compound concentration in the obtained methanol solution was determined by comparison with a standard sample using gas chromatography. The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in methanol and the weight of the sample. About the sample after preliminary polymerization, content was calculated using the weight remove | excluding the preliminary polymerization polymer.

-Preparation of prepolymerization catalyst (1) Preparation of solid catalyst A 10 L autoclave equipped with a stirrer was sufficiently substituted with nitrogen, and 2 L of purified toluene was introduced. At room temperature, 200 g of magnesium diethoxide [Mg (OEt) ₂ ] was added thereto, and 1 L of titanium tetrachloride (TiCl ₄ ) was slowly added thereto. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. and the reaction was carried out for 3 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Further, using purified n-heptane, toluene was replaced with n-heptane to obtain a solid component slurry. A portion of this slurry was sampled and dried. As a result of analysis, the Ti content of the solid component was 2.7% by weight.

Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the 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 4 L. 30 ml of dimethyldivinylsilane, 30 ml of diisopropyldimethoxysilane [i-Pr ₂ Si (OMe) ₂ ], and 80 g of an n-heptane diluted solution of triethylaluminum (Et ₃ Al) as Et ₃ Al were added thereto at 40 ° C. The reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A portion of the resulting solid catalyst slurry was sampled and dried for analysis. The solid catalyst contained 1.2% by weight of Ti and 8.9% by weight of i-Pr ₂ Si (OMe) ₂ .

(2) Prepolymerization Prepolymerization was performed by the following procedure using the solid catalyst obtained above. Purified n-heptane was introduced into the slurry, and the solid catalyst concentration was adjusted to 20 g / L. After cooling the slurry to 10 ° C., and 10g added n- heptane dilution of _Et 3 Al as _Et 3 Al, were added over 4 hours propylene 280 g. After the supply of propylene was completed, the reaction was continued for another 30 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum dried to obtain a prepolymerized catalyst. This prepolymerized catalyst contained 2.5 g of polypropylene per gram of solid catalyst. As a result of analysis, the portion of the prepolymerization catalyst excluding polypropylene contained 1.0% by weight of Ti and 8.3% by weight of i-Pr ₂ Si (OMe) ₂ .
Using this prepolymerized 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) using a two-tank continuous polymerization facility in which two fluidized bed polymerization tanks with an internal volume of 2 m ³ are connected in series. Was manufactured. The production conditions of the propylene-ethylene block copolymer (F-1) are as described in 7A-1 of Table 7-1. Propylene, ethylene, hydrogen, and nitrogen used were purified using a general purification catalyst. The production amount of the component (F1) in the first polymerization tank and the production amount of the component (F2) in the second polymerization tank were determined from the value of the cooling water temperature of the heat exchanger used for temperature control of the polymerization tank.

1st polymerization process: Manufacture of the component (F1) which consists of a propylene homopolymer Propylene homopolymerization was performed using the 1st polymerization tank. The polymerization temperature was 65 ° C., the total pressure was 3.0 MPaG (gauge pressure, the same applies hereinafter), and the powder hold amount was 40 kg. Propylene, hydrogen, and nitrogen were continuously supplied to the polymerization tank, and the concentrations of propylene and hydrogen were adjusted to 70.83 mol% and 0.92 mol%, respectively. As a cocatalyst, Et ₃ Al was continuously supplied 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) extracted from the first polymerization tank was continuously supplied to the second polymerization tank, and the production of the component (F2) composed of a propylene-ethylene random copolymer was continuously performed.

Second polymerization step: Production of propylene-ethylene random copolymer component (F2) Random copolymerization of propylene and ethylene was performed using a 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 drier and sufficiently dried.

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

From the W (F1), W (F2), and E (F) thus obtained, the ethylene content E (F2) of the propylene-ethylene random copolymer component (F2) was calculated. The following formula was used for the calculation.
E (F2) = {E (F) −E (F1) × W (F1) / 100} ÷ (W (F2) / 100)
(Here, since component (F1) is a propylene homopolymer, E (F1) is 0% by weight. In addition, the above formula is re-arranged for E (F2) from what is described for E (F) above. (It has been 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-1) was produced in the same manner as in the production example of the propylene-ethylene block copolymer (F-1) except that the conditions described in 7A-2 and 7A-3 in Table 7-1 were used. 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 To a glass separable flask equipped with a 10 liter stirring blade, 3.75 liters of distilled water and then 2.5 kg of concentrated sulfuric acid (96%) were slowly added. At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 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 recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(2) Drying of silicate The silicate which was previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50mm Heating zone 550mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(3) Preparation of catalyst An autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently substituted with nitrogen. To this, 200 g of dry silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M) was added to the silicate slurry prepared above, and the mixture was reacted at 25 ° C. for 1 hour. In parallel, 187 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(4) Preliminary polymerization / washing Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M) and 5600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / liter and the zirconium (Zr) concentration was 8.6 × 10 ⁻⁶ g / L. The abundance of was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, followed by drying under reduced pressure at 45 ° C. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 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 (L / D = 6, content with stirring blades) 100 liters of product) was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. While stirring at a rotation speed of 30 rpm in the presence of a polypropylene powder bed, 0.444 g / hour of prepolymerized catalyst (as the amount of solid catalyst excluding the prepolymerized powder) prepared in the upstream part of the reactor, It was continuously fed at 15.0 mmol / hour. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.00 MPaG, the ethylene / propylene molar ratio in the gas phase in the reactor is 0.058, and the hydrogen concentration is 150 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of polymer extracted when the steady state was reached was 10.0 kg / hour.
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the ethylene content was 1.7% by weight.

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

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

(Pelination of propylene-ethylene block copolymer (F))
Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-) is added to 100 parts by weight of each of the propylene-ethylene block copolymers (F) obtained in Production Examples F-1 to F-4. 4-hydroxyphenyl) propionate] 0.05 parts by weight of 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 to be uniform. The resulting mixture was melt kneaded at 230 ° C. with a 35 mm diameter twin screw extruder to obtain propylene-ethylene block copolymers (F-1) to (F-4) pellets.

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

Example 6-2
In production of the decorative film of Example 6-1, Example 6 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 8.

Example 6-3
In production of the decorative film of Example 6-1, Example 6 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 8.

Example 6-4
In the production of the decorative film of Example 6-1, Example 6 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 8.

Example 6-5
In production of the decorative film of Example 6-1, Example 6 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. The evaluation results are shown in Table 8.

Example 6-6
In the production of the decorative film of Example 6-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) is changed between the polypropylene resin (B-1) and the polypropylene resin (A-1). Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 6-1. The evaluation results are shown in Table 8.

Example 6-7
In the production of the decorative film of Example 6-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) is changed between the polypropylene resin (B-1) and the polypropylene resin (A-1). Except having changed into what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 6-1. The evaluation results are shown in Table 8.

Example 6-8
In production of the decorative film of Example 6-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2), and was the same as in Example 6-1. Molding and evaluation were performed. The evaluation results are shown in Table 8.

Example 6-9
In the production of the decorative film of Example 6-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 6-1. The evaluation results are shown in Table 8.

Example 6-10
In the production of the decorative film of Example 6-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 6-1. The evaluation results are shown in Table 8.

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

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

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

Example 6-14
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . The propylene-ethylene block copolymer (F-1) is charged into the seal layer extruder-1 and the polypropylene resin (B-1-1) is charged into the extruder-2, and the resin temperature is 240 ° C. for the seal layer. Melt extrusion was performed under the conditions of a discharge rate of the extruder-1 of 4 kg / h and a discharge rate of the extruder-2 of 12 kg / h.

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

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decoration thermoforming similarly to Example 6-1. The evaluation results are shown in Table 8.

Example 6-15
In production of the decorative film of Example 6-1, Example 6-1 except that the polypropylene resin (B-1) of the layer (II) was changed to a polypropylene resin (B-1-2). Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 8.

Example 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 base body was changed to an injection molded body made of polypropylene resin (Z-2). The evaluation results are shown in Table 8.

Example 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 base body was changed to an injection-molded body made of polypropylene resin (Z-3). The evaluation results are shown in Table 8.

Comparative Example 6-1
In the production of the decorative film of Example 6-1, Example 6-1 except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1). Molding and evaluation were performed in the same manner. The evaluation results are shown in Table 8.

Comparative Example 6-2
In production of the decorative film of Example 6-1, the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1), and was the same as in Example 6-1. Molding and evaluation were performed. The evaluation results are shown in Table 8.

  The decorative molded body obtained from the decorative film of Examples 6-1 to 6-17 contains a nucleating agent in any layer, and the polypropylene resin (A) is propylene-ethylene block copolymer. (A1) Melt flow rate (MFR (A)) exceeds 2.0 g / 10 min, and (f1) propylene homopolymer or propylene for the propylene-ethylene block copolymer (F). -The component (F1) made of an ethylene random copolymer is contained in an amount of 5 to 97% by weight, and the component (F2) made of a propylene-ethylene random copolymer having an ethylene content higher than that of the component (F1) is contained in an amount of 3 to 95% by weight. (F2) For the resin composition (B ′) having a melting peak temperature (Tm (F)) of 110 to 170 ° C. and containing the 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, excellent thermoformability, surface gloss and adhesive strength. It was good. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 6-15 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 6-1 in which none of the layers contains a nucleating agent has a low surface gloss of the decorative film, and the surface becomes dull after the decorative molding, and the surface gloss is significantly reduced. . In Comparative Example 6-2, in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

(Test Example 7)
[7: Decorative film including seal layer (I) made of olefin adhesive resin (G)]
7-1. Materials used The following resins were used in addition to the polypropylene-based resins used in “1-1.

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 minutes), manufactured by Mitsubishi Chemical Corporation, trade name “Modic AP (registered trademark) F532”

7-2. Production 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 Technopolymer Co., Ltd., “ABS130”
(Z-6): PC (polycarbonate) resin, manufactured by Mitsubishi Engineering Plastics Co., Ltd., “NOVAREX 7022A”

(2) Production of resin molded body (substrate) Polar resins (Z-4) to (Z-6) were dried at 80 ° C. for 2 hours using a box oven. The resin after drying was injection molded by the following method to obtain an injection molded body.
(I) PMMA resin molding conditions:
Injection molding machine: “IS100GN” manufactured by Toshiba Machine Co., Ltd. Clamping pressure: 100 tons Cylinder temperature: 230 ° C
Mold temperature: 40 ℃
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate condition adjustment: hold for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 50% RH

(Ii) ABS resin molding conditions:
Injection molding machine: “IS100GN” manufactured by Toshiba Machine Co., Ltd. Clamping pressure: 100 tons Cylinder temperature: 210 ° C
Mold temperature: 40 ℃
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate condition adjustment: hold for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 50% RH

(Iii) PC resin molding conditions:
Injection molding machine: “IS100GN” manufactured by Toshiba Machine Co., Ltd. Clamping pressure: 100 tons Cylinder temperature: 290 ° C
Mold temperature: 80 ℃
Injection mold: Width x height x thickness = 120 mm x 120 mm x 3 mm flat plate condition adjustment: hold for 5 days in a constant temperature and humidity chamber at a temperature of 23 ° C and a humidity of 50% RH

Example 7-1
-Manufacture of decoration film Extruder-1 for sealing layer with a diameter of 30 mm (diameter), Extruder-2 with a diameter of 40 mm (diameter), and Extruder-3 for surface decoration layer with a diameter of 30 mm (diameter) are connected. In addition, a three-layer three-layer T die having a lip opening of 0.8 mm and a die width of 400 mm was used. Polyolefin adhesive resin (G-1) is used for the extruder 1 for the sealing layer, polypropylene resin (B-1) is used for the extruder-2, and polypropylene resin (A-) is used for the extruder 3 for the surface decoration layer. 1-1), respectively, the resin temperature is 240 ° C., the discharge rate of the seal layer extruder-1 is 8 kg / h, the discharge rate of the extruder-2 is 8 kg / h, and the surface decoration layer extruder-3. The melt extrusion was carried out at a discharge rate of 4 kg / h.

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

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

Example 7-2
In the production of the decorative film of Example 7-1, Example 7 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-2). Molding and evaluation were performed in the same manner as in Example-1. Table 9 shows the evaluation results.

Example 7-3
In the production of the decorative film of Example 7-1, Example 7 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-3). Molding and evaluation were performed in the same manner as in Example-1. Table 9 shows the evaluation results.

Example 7-4
In the production of the decorative film of Example 7-1, Example 7 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to a polypropylene resin (A-1-4). Molding and evaluation were performed in the same manner as in Example-1. Table 9 shows the evaluation results.

Example 7-5
In the production of the decorative film of Example 7-1, Example 7 was performed except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-1-5). Molding and evaluation were performed in the same manner as in Example-1. Table 9 shows the evaluation results.

Example 7-6
In the production of the decorative film of Example 7-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 7-1. Table 9 shows the evaluation results.

Example 7-7
In the production of the decorative film of Example 7-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-1) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 7-1. Table 9 shows the evaluation results.

Example 7-8
In the production of the decorative film of Example 7-1, except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-2), the same as in Example 7-1. Molding and evaluation were performed. Table 9 shows the evaluation results.

Example 7-9
In the production of the decorative film of Example 7-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 70:30, it shape | molded and evaluated similarly to Example 7-1. Table 9 shows the evaluation results.

Example 7-10
In the production of the decorative film of Example 7-1, the weight ratio of the polypropylene resin (B-1) of the layer (II) between the polypropylene resin (B-2) and the polypropylene resin (A-1) is as follows. Except having changed into what was blended so that it might become 10:90, it shape | molded and evaluated similarly to Example 7-1. Table 9 shows the evaluation results.

Example 7-11
Except having changed the polyolefin adhesive resin (G-1) used for sealing layer (I) into the polyolefin adhesive resin (G-2) in manufacture of the decorative film of Example 7-1, Example Molding and evaluation were performed in the same manner as in 7-1. Table 9 shows the evaluation results.

Examples 7-12
A two-layer two-layer T die having a lip opening of 0.8 mm and a die width of 400 mm, to which a seal layer extruder 1 having a diameter of 30 mm (diameter) and an extruder 2 having a diameter of 40 mm (diameter) were connected, was used. . Polyolefin adhesive resin (G-1) is charged into Extruder-1 for seal layer, and Polypropylene resin (B-1-1) is input into Extruder-2. The melt extrusion was carried out under the condition that the discharge amount of 1 was 8 kg / h and the discharge amount of the extruder-2 was 12 kg / h.

  The melt-extruded film was cooled and solidified so that the sealing layer (I) was in contact with a cooling roll rotating at 80 ° C. and 3 m / min, and the sealing layer (I) having a thickness of 100 μm and a layer having a thickness of 150 μm ( A two-layer unstretched film on which II) was laminated was obtained.

  Using the unstretched film obtained by said decorative film manufacture, it evaluated by performing three-dimensional decoration thermoforming similarly to Example 7-1. Table 9 shows the evaluation results.

Example 7-13
In the production of the decorative film of Example 7-1, Example 7-1 was used except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (B-1-2). Molding and evaluation were performed in the same manner. 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 base body 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 base body was changed to an injection molded body made of PC resin (Z-6). Table 9 shows the evaluation results.

Comparative Example 7-1
In the production of the decorative film of Example 7-1, Example 7-1 was used except that the polypropylene resin (A-1-1) of the surface decoration layer was changed to the polypropylene resin (A-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, the same procedure as in Example 7-1 was performed except that the polypropylene resin (B-1) of the layer (II) was changed to the polypropylene resin (A-1). Molding and evaluation were performed. Table 9 shows the evaluation results.

  The decorative molded body obtained from the decorative films of Examples 7-1 to 7-15 contains a nucleating agent in any layer, and the polyolefin adhesive resin (G in the sealing layer (I) ) Is a polyolefin resin having a polar functional group containing at least one heteroatom, (g2) the melt flow rate (MFR (G)) is 100 g / 10 min or less, and the layer (II (B1) Melt flow rate (MFR (B ′)) is 40 g / 10 min or less, and (b2) strain hardening degree is 1. Since it was 1 or more, there was no contact unevenness, excellent thermoformability, surface gloss, and good adhesion to a resin molded body made of a polar resin. Moreover, since it was decorating thermoforming for a short time, volatilization of the nucleating agent could be reduced, and high surface gloss was maintained even after thermoforming. Furthermore, the obtained molded product was excellent in recyclability. The decorative molded body obtained from the decorative film of Example 7-13 was excellent in appearance and design because the layer (II) was colored black.

  On the other hand, the decorative film of Comparative Example 7-1 in which none of the layers contained a nucleating agent had a low surface gloss of the decorative film, and the surface became dull after the decorative molding, and the surface gloss was significantly reduced. . In Comparative Example 7-2 in which the degree of strain hardening of the polypropylene resin used for the layer (II) is less than 1.1, the decorative film is drawn down during the three-dimensional decorative thermoforming, and the thermoformability is improved. It was inferior. The obtained decorative molded body was inferior in appearance, and evaluation of adhesive strength and surface gloss was not performed.

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

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

Claims (28)

A decorative film containing a nucleating agent for adhering to a resin molded body by thermoforming, the decorative film comprising a sealing layer (I) containing a polypropylene resin (A) and a polypropylene resin A layer (II) containing a resin composition (B ′) containing (B),
The polypropylene resin (A) satisfies the following requirement (a1), and the resin composition (B ′) is a decorative film that satisfies the following requirements (b1) and (b2).
(A1) Melt flow rate (230 ° C., 2.16 kg load) (MFR (A)) exceeds 2.0 g / 10 minutes.
(B1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 40 g / 10 min or less.
(B2) The strain hardening degree λ is 1.1 or more.   The decorative film according to claim 1, wherein the nucleating agent is selected from an aromatic carboxylic acid metal salt, an aromatic phosphate metal salt, a sorbitol derivative, a nonitol derivative, an amide compound, or a metal salt of rosin. The additive according to claim 1 or 2, wherein the polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the resin composition (B ') further satisfies the following requirement (b3). Decorative film.
(A2) A metallocene catalyst-based propylene polymer.
(A3) The melting peak temperature (Tm (A)) is less than 150 ° C.
(A4) The molecular weight distribution (Mw / Mn (A)) obtained by GPC measurement is 1.5 to 3.5.
(B3) The melting peak temperature (Tm (B ′)) and Tm (A) satisfy the relational expression (b-3).
Tm (B ′)> Tm (A) (formula (b-3)) The sealing layer (I) includes 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,
The decorative film according to any one of claims 1 to 3, wherein the ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3).
(C1) The ethylene content [E (C)] is 65% by weight or more.
(C2) The density is 0.850 to 0.950 g / cm ³ .
(C3) Melt flow rate (230 ° C., 2.16 kg load) (MFR (C)) is 0.1 to 100 g / 10 min. The sealing layer (I) includes 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 any one of claims 1 to 3, wherein the thermoplastic elastomer (D) satisfies the following requirements (d1) to (d4).
(D1) A thermoplastic elastomer mainly composed of at least one of propylene and butene.
(D2) The density is 0.850 to 0.950 g / cm ³ .
(D3) The melt flow rate (230 ° C., 2.16 kg load) (MFR (D)) is 0.1 to 100 g / 10 min.
(D4) The tensile elastic modulus is smaller than the tensile elastic modulus of the polypropylene resin (A). The sealing layer (I) includes 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 any one of claims 1 to 3, wherein the thermoplastic resin (E) satisfies the following requirement (e1) and the resin composition (X5) satisfies the following requirement (x1).
(E1) 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 thermal scanning calorimeter (DSC) satisfies the following formula (x-1).
t (X5) ≧ 1.5 × t (A) (formula (x−1))
(In the formula, t (A) represents the isothermal crystallization time (seconds) of the polypropylene resin (A) measured at a temperature 10 ° C. higher than the crystallization start temperature of the polypropylene resin (A), and t ( 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 polypropylene resin (A) is a propylene-ethylene block copolymer (F) satisfying the following requirements (f1) and (f2), according to any one of claims 1, 2, and 4-6. Decorative film.
(F1) Component (F1) composed of propylene homopolymer or propylene-ethylene random copolymer, 5 to 97% by weight, component composed of propylene-ethylene random copolymer having a higher ethylene content than component (F1) ( F2) is contained in an amount of 3 to 95% by weight.
(F2) Melting peak temperature (Tm (F)) is 110-170 degreeC. A decorative film containing a nucleating agent for adhering to a resin molded body by thermoforming, the decorative film comprising a sealing layer (I) containing a polyolefin adhesive resin (G) and a polypropylene-based film A layer (II) containing a resin composition (B ′) containing a resin (B),
The polyolefin adhesive resin (G) satisfies the following requirements (g1) and (g2), and the resin composition (B ′) is a decorative film that 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 min or less.
(B1) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 40 g / 10 min or less.
(B2) The strain hardening degree λ is 1.1 or more. The decorative film according to any one of claims 1 to 8, wherein the resin composition (B ') satisfies the following requirements (b1') and (b2 ').
(B1 ′) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 20 g / 10 min or less.
(B2 ′) The strain hardening degree λ is 1.8 or more. The decorative film according to any one of claims 1 to 8, wherein the resin composition (B ') satisfies the following requirements (b1'') and (b2'').
(B1 ″) The melt flow rate (230 ° C., 2.16 kg load) (MFR (B ′)) is 12 g / 10 min or less.
(B2 ″) The strain hardening degree λ is 2.3 or more.   The decorative film according to any one of claims 1 to 10, wherein the polypropylene resin (B) is a polypropylene resin (B-L) having a long-chain branched structure.   The decorative film according to claim 11, wherein the polypropylene resin (B-L) is a polypropylene resin having a low gel produced by a method other than the crosslinking method.   The layer (II) has a surface decorating layer (III) containing a surface decorating layer resin on the side opposite to the sticking surface side to the resin molded body. The decorative film according to item.   The decorative film according to claim 13, wherein the surface decoration layer resin is made of a polypropylene resin (H), and the polypropylene resin (H) has a strain hardening degree λ of less than 1.1.   The said polypropylene resin (A) is a decorating film of any one of Claims 1-6 and 9-14 which are a propylene * alpha-olefin copolymer.   Said Tm (A) is a decorating film of any one of Claims 1-6 and 9-15 which are 140 degrees C or less. The decorative film according to claim 4, wherein the ethylene-α-olefin random copolymer (C) further satisfies the following requirement (c4).
(C4) The melting peak temperature (Tm (C)) is 30 to 130 ° C. The decorative film according to claim 4 or 17, 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 having an ethylene content of less than 50% by weight, a butene-ethylene copolymer having an ethylene content of less than 50% by weight, and an ethylene content of less than 50% by weight. The decorative film according to claim 5, which is a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer. The decorative film according to claim 5 or 19, wherein the thermoplastic elastomer (D) further satisfies the following requirement (d5).
(D5) The melting peak temperature (Tm (D)) is 30 to 170 ° C.   The decorative film according to claim 6, wherein the thermoplastic resin (E) is a styrene-based elastomer.   The decorative film according to claim 6, wherein the thermoplastic resin (E) is an alicyclic hydrocarbon resin. The decorative film according to claim 7, 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. The decorative film according to claim 7 or 23, wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f4).
(F4) The ethylene content of the component (F1) is in the range of 0 to 6% by weight. The decorative film according to claim 7, 23 or 24, wherein the propylene-ethylene block copolymer (F) further satisfies the following requirement (f5).
(F5) The ethylene content of the component (F2) is in the range of 5 to 90% by weight. A step of preparing the decorative film according to any one of claims 1 to 25,
Preparing a resin molded body;
Setting the resin molded body and the decorative film in a chamber box capable of decompression;
Reducing the pressure in the chamber box;
Heating and softening the decorative film;
A method for producing a decorative molded body, comprising: pressing the decorative film heated and softened against the resin molded body; and returning or pressurizing the reduced pressure inside the chamber box.   The method for producing a decorative molded body according to claim 26, wherein the resin molded body is made of a propylene-based resin composition. The said decorating film is a decorating film of any one of Claims 8-14,
The resin molding is at least selected from 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 composite materials thereof. The manufacturing method of the decorative molded body of Claim 26 containing the polar resin material containing one.