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

Abstract

The present invention relates to a method for manufacturing a decorative film and a decorative molded body using the same. The decorative film is used to be attached to a resin molded body by thermoforming, and contains at least one additive selected from a nucleating agent, a hindered amine light stabilizer, and an ultraviolet absorber. The decorative film comprises: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), and the surface layer of the decorative film contains the additive.

Description

[0001] This application is a divisional application of the application filed on November 19, 2018, with application number 201880075603.x and invention title "Decorative Film and Method for Manufacturing Decorative Molded Article Using the Thereof". Technical Field

[0002] This invention relates to a decorative film for thermoforming and bonding onto a resin molded body, and a method for manufacturing a decorative molded body using the decorative film. More specifically, it relates to a decorative film for thermoforming and bonding onto a resin molded body, and a method for manufacturing a decorative molded body using the decorative film, wherein the decorative film exhibits excellent transparency, scratch resistance, and appearance, and provides excellent surface gloss and / or weather resistance before and after thermoforming, and suppresses changes in surface appearance. Background Technology

[0003] In recent years, due to VOC (volatile organic compound) reduction requirements and other factors, the demand for decorative technologies to replace coatings has increased, leading to the development of various decorative technologies.

[0004] Among them, a technique was proposed that applies a decorative film, which replaces the coating, to a molded body by vacuum forming or vacuum forming, thereby forming a decorative molded article that integrates the decorative film and the molded body (see, for example, Patent Document 1), which has received particular attention in recent years.

[0005] Compared with other decorative molding methods such as insert molding, decorative molding using vacuum compression molding and vacuum forming offers greater freedom in shape. The end face of the decorative film is rolled into the back of the decorative object, thus eliminating seams and resulting in an excellent appearance. Furthermore, it can be thermoformed at lower temperatures and pressures, thus offering advantages such as excellent reproducibility of textures such as embossing applied to the surface of the decorative film.

[0006] On the other hand, for decorative films with a glossy finish, issues such as a dull surface after decorative molding have been reported. Furthermore, hindered amine light stabilizers and UV absorbers are sometimes added to impart weather resistance to decorative films. However, such decorative films containing hindered amine light stabilizers and UV absorbers exhibit significantly compromised weather resistance after decorative molding.

[0007] Furthermore, it was proposed to apply a decorative film containing an adhesive layer of polypropylene resin to a matrix (molded body) containing polypropylene resin, and to thermally fuse the decorative film and the molded body (see, for example, Patent Documents 2 and 3).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2002-67137

[0011] Patent Document 2: Japanese Patent Application Publication No. 2013-14027

[0012] Patent Document 3: Japanese Patent Application Publication No. 2014-124940 Summary of the Invention

[0013] The problem the invention aims to solve

[0014] In existing technologies, it has not yet been achieved that decorative films can suppress the reduction of gloss and / or weather resistance, as well as changes in surface appearance, even after decorative molding via vacuum compression forming and vacuum forming. The objective of this invention is to provide a decorative film that suppresses the reduction of gloss and / or weather resistance, as well as changes in surface appearance, which can be used for three-dimensional decorative thermoforming, and a method for manufacturing a decorative molded body using the same.

[0015] Solution for solving the problem

[0016] To address the aforementioned issues, the inventors conducted repeated and in-depth research, and the results clarified that during the decorative molding process, specifically the heating of the decorative film under vacuum, additives such as nucleating agents, hindered amine light stabilizers, and ultraviolet absorbers added to the resin to impart gloss and / or weather resistance significantly volatilize. On the other hand, it was discovered that for decorative films containing specific additives, even with heating under vacuum, the additives do not readily volatilize, and even after decorative molding, the reduction in gloss and / or weather resistance, as well as changes in surface appearance, can be suppressed.

[0017] That is, the present invention includes the following.

[0018] [1] A decorative film for thermoforming and attaching to a three-dimensional resin molded body, the decorative film comprising: at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers that meets the following necessary conditions.

[0019] Necessary condition: For a glass plate that has undergone the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40.

[0020] <Atomization Test> Place 1g (±0.01g) of additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0021] [2]The decorative film according to [1] comprises a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B),

[0022] The aforementioned polypropylene resin (A) satisfies the following necessary condition (a1), and the aforementioned polypropylene resin (B) satisfies the following necessary condition (b1).

[0023] (a1) The melt flow rate (at 230°C, 2.16 kg load) (MFR(A)) exceeds 0.5 g / 10 minutes.

[0024] (b1) The melt flow rate (at 230°C, 2.16 kg load) (MFR(B)) and MFR(A) satisfy the relational expression (b-1).

[0025] MFR(B) < MFR(A) ··· Formula (b-1)

[0026] [3]The decorative film according to [1] comprises a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a resin composition (B'), and the resin composition (B') contains a polypropylene resin (B),

[0027] The aforementioned polypropylene resin (A) satisfies the following necessary condition (a'1), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2), preferably satisfies the following necessary conditions (b'1') and (b'2'), and more preferably satisfies the following necessary conditions (b'1") and (b'2").

[0028] (a'1) The melt flow rate (at 230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 minutes.

[0029] (b'1) The melt flow rate (at 230°C, 2.16 kg load) (MFR(B')) is 40 g / 10 minutes or less.

[0030] (b'2) The strain hardening degree λ is 1.1 or more.

[0031] (b'1') The melt flow rate (at 230°C, 2.16 kg load) (MFR(B')) is 20 g / 10 minutes or less.

[0032] (b'2') The strain hardening degree λ is 1.8 or more.

[0033] (b'1") The melt flow rate (at 230°C, 2.16 kg load) (MFR(B')) is 12 g / 10 minutes or less.

[0034] (b'2") The strain hardening degree λ is 2.3 or more.

[0035] [4] The decorative film according to [1] comprises: a sealing layer (I) containing a polyolefin adhesive resin (G) and a layer (II) containing a resin composition (B'), said resin composition (B') comprising a polypropylene resin (B).

[0036] The aforementioned polyolefin adhesive resin (G) satisfies the following necessary conditions (g'1) and (g'2), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2), preferably satisfies the following necessary conditions (b'1') and (b'2'), and more preferably satisfies the following necessary conditions (b'1”) and (b'2”).

[0037] (g'1) is a polyolefin resin having a polar functional group containing at least one heteroatom.

[0038] (g'2) Melt flow rate (230℃, 2.16kg load) (MFR(G)) is less than 100g / 10min.

[0039] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0040] (b'2) The strain hardening degree λ is 1.1 or higher.

[0041] (b'1') Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 20 g / 10 min.

[0042] (b'2') The strain hardening degree λ is 1.8 or higher.

[0043] (b'1") The melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 12 g / 10 min.

[0044] (b'2") The strain hardening degree λ is 2.3 or higher.

[0045] [5] The decorative film according to any one of [1] to [4] is characterized in that the layer containing the aforementioned additives comprises a polyolefin resin composition, preferably a polypropylene resin composition.

[0046] [6] The decorative film according to any one of [1] to [5] is characterized in that the aforementioned additive is a nucleating agent, the aforementioned nucleating agent is an organometallic compound, preferably a compound represented by the following general formula (1).

[0047]

[0048] (where R is in the formula)1 ~R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 9 branched carbon atoms, R 5 This represents a hydrogen atom or a methyl group, where m represents 1 or 2. When m is 1, M... 1 M represents a hydrogen atom or an alkali metal atom, where m is 2. 1 This indicates a Group 2 element, Al(OH) or Zn.

[0049] [7] The decorative film according to any one of [1] to [5] is characterized in that the aforementioned additive is a nucleating agent, and the aforementioned nucleating agent is an amide compound.

[0050] [8] The decorative film according to any one of [1] to [5], wherein the aforementioned additive is a hindered amine light stabilizer and / or an ultraviolet absorber, and the molecular weight of the aforementioned additive is 490 g / mol or more.

[0051] [9] The decorative film according to any one of [3] to [8], wherein the aforementioned polypropylene resin (B) is a polypropylene resin (BL) having a long branched structure.

[0052]

[10] According to the decorative film of [9], wherein the aforementioned polypropylene resin (BL) is a polypropylene resin with less gel produced by a method other than crosslinking.

[0053]

[11] The decorative film according to any one of [1] to

[10] , wherein the aforementioned decorative film is a multilayer film and the outermost layer of the aforementioned decorative film opposite to the bonding surface facing the resin molded body contains the aforementioned additive.

[0054]

[12] The decorative film according to any one of [2] to

[11] , wherein a surface decorative layer (III) is provided on the side of the aforementioned layer (II) opposite to the side of the surface to which it is attached to the aforementioned resin molded body, the surface decorative layer (III) comprising: a surface decorative layer resin containing the aforementioned additives.

[0055]

[13] The decorative film according to

[12] , wherein the aforementioned surface decorative layer (III) comprises a polypropylene resin (H) that satisfies the following necessary condition (h1).

[0056] (h1) The melt flow rate (230℃, 2.16kg load) (MFR(H)) and MFR(B) satisfy the relationship (h-1).

[0057] MFR(H)>MFR(B)···Equation (h-1)

[0058]

[14] According to the decorative film of

[12] , wherein the aforementioned surface decorative layer resin comprises a polypropylene resin (H) and the strain hardening degree λ of the aforementioned polypropylene resin (H) is less than 1.1.

[0059]

[15] A method for manufacturing a decorative molded body includes the following steps: preparing a decorative film as described in any one of [1] to

[14] ; preparing a resin molded body; placing the resin molded body and the decorative film in a depressurized chamber; depressurizing the chamber; heating and softening the decorative film; pressing the decorative film onto the resin molded body; and restoring or pressurizing the depressurized chamber to atmospheric pressure.

[0060]

[16] The method for manufacturing a decorative molded body according to

[15] , wherein the aforementioned resin molded body comprises a polypropylene resin composition.

[0061]

[17] The method for manufacturing a decorative molded article according to

[15] , wherein the aforementioned decorative film is any one of [4] to

[14] ,

[0062] The aforementioned resin molded body comprises a polar resin material, which includes at least one 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.

[0063]

[18] A polypropylene resin composition for decorative film, the decorative film being thermoformed and attached to a resin molded body of a three-dimensional shape, the polypropylene resin composition containing, relative to 100 parts by weight of polypropylene resin, at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, satisfying the following necessary conditions.

[0064] Necessary condition: For a glass plate that has undergone the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40.

[0065] <Atomization Test> Place 1g (±0.01g) of additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0066]

[19] Application of polypropylene resin composition in decorative film, the decorative film being thermoformed and attached to a three-dimensional resin molded body, wherein the polypropylene resin composition contains 0.001 to 1.00 parts by weight of at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, relative to 100 parts by weight of polypropylene resin, which meets the following necessary conditions.

[0067] Necessary condition: For a glass plate that has undergone the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40.

[0068] <Atomization Test> Place 1g (±0.01g) of additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0069]

[20] A decorative molded body having a decorative film attached as described in any one of [1] to

[14] .

[0070] Furthermore, the invention of the first aspect of the present invention includes the following.

[0071] [1] A decorative film, characterized in that it is used to be thermoformed and attached to a resin molded body of a three-dimensional shape, the decorative film comprising a layer containing a nucleating agent that satisfies the following necessary conditions.

[0072] Necessary condition: For a glass plate that has undergone the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40.

[0073] <Atomization Test> Place 1g (±0.01g) of nucleating agent into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0074] [2] The decorative film according to [1] is characterized in that the aforementioned nucleating agent is an organometallic compound.

[0075] [3] The decorative film according to [1] or [2] is characterized in that the aforementioned nucleating agent is a compound represented by the following general formula (1).

[0076]

[0077] (where R is in the formula) 1 ~R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 9 branched carbon atoms, R 5This represents a hydrogen atom or a methyl group, where m represents 1 or 2. When m is 1, M... 1 M represents a hydrogen atom or an alkali metal atom, where m is 2. 1 This indicates a Group 2 element, Al(OH) or Zn.

[0078] [4] The decorative film according to [1] is characterized in that the aforementioned nucleating agent is an amide compound.

[0079] [5] The decorative film according to any one of [1] to [4] is characterized in that the aforementioned layer containing the nucleating agent comprises a polyolefin resin composition.

[0080] [6] The decorative film according to any one of [1] to [5] is characterized in that the aforementioned polyolefin resin composition is a polypropylene resin composition.

[0081] [7] A method for manufacturing a decorative molded body, characterized in that it includes the following steps: a step of preparing a decorative film as described in any one of [1] to [6]; a step of preparing a resin molded body; a step of placing the aforementioned resin molded body and the aforementioned decorative film in a chamber capable of depressurization; a step of depressurizing the aforementioned chamber; a step of heating and softening the aforementioned decorative film; a step of pressing the aforementioned decorative film onto the aforementioned resin molded body; and a step of restoring or pressurizing the aforementioned depressurized chamber to atmospheric pressure.

[0082] [8] The method for manufacturing a decorative molded body according to [7] is characterized in that the aforementioned resin molded body comprises a polypropylene resin composition.

[0083] The second aspect of the invention includes the following.

[0084] [1] A decorative film for thermoforming and attaching to a resin molded body of a three-dimensional shape, the decorative film comprising a hindered amine light stabilizer and / or a UV absorber that satisfies the following necessary conditions.

[0085] Necessary condition: For a glass plate that has undergone the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40.

[0086] <Atomization Test> Place 1g (±0.01g) of hindered amine light stabilizer or ultraviolet absorber into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0087] [2] The decorative film according to [1], wherein the molecular weight of the aforementioned hindered amine light stabilizer and / or ultraviolet absorber is 490 g / mol or more.

[0088] [3] The decorative film according to [1] or [2], wherein the aforementioned decorative film includes: at least one layer containing the aforementioned hindered amine light stabilizer and / or ultraviolet absorber, and the aforementioned layer contains 50% by weight or more of a polyolefin resin.

[0089] [4] The decorative film according to any one of [1] to [3], wherein the aforementioned polyolefin resin is a polypropylene resin.

[0090] [5] The decorative film according to any one of [1] to [4], wherein the outermost layer of the aforementioned decorative film opposite to the bonding surface facing the resin molded body contains the aforementioned hindered amine light stabilizer and / or ultraviolet absorber.

[0091] [6] A method for manufacturing a decorative molded body, which includes the following steps: a step of preparing the decorative film according to any one of [1] to [5]; a step of preparing a resin molded body; a step of setting the aforementioned resin molded body and the aforementioned decorative film in a chamber capable of decompression; a step of decompressing the interior of the aforementioned chamber; a step of heating and softening the aforementioned decorative film; a step of pressing the aforementioned decorative film against the aforementioned resin molded body; and a step of restoring or pressurizing the interior of the aforementioned decompressed chamber to atmospheric pressure.

[0092] [7] The method for manufacturing a decorative molded body according to [6], wherein the aforementioned resin molded body contains a polypropylene resin composition.

[0093] The invention of the third aspect of the present invention includes the following.

[0094] [1] A decorative film for thermoforming and bonding to a resin molded body, the decorative film contains a nucleating agent, and the decorative film includes: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), the aforementioned polypropylene resin (A) satisfies the following necessary condition (a1), and the aforementioned polypropylene resin (B) satisfies the following necessary condition (b1).

[0095] (a1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(A)) exceeds 0.5 g / 10 minutes.

[0096] (b1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(B)) and MFR(A) satisfy the relational expression (b-1).

[0097] MFR(B) < MFR(A) ··· Formula (b-1)

[0098] [2] According to the decorative film of [1], the aforementioned nucleating agent is selected from aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, nonitol derivatives, amide compounds, and metal salts of rosin.

[0099] [3] According to the decorative film described in [1] or [2], the aforementioned polypropylene resin (A) further satisfies the following necessary conditions (a2) to (a4), and the aforementioned polypropylene resin (B) further satisfies the following necessary condition (b2).

[0100] (a2) is a metallocene catalyst-based propylene polymer.

[0101] (a3) The melting peak temperature (Tm(A)) is below 150℃.

[0102] (a4) The molecular weight distribution (Mw / Mn(A)) measured by GPC is 1.5 to 3.5.

[0103] (b2) The melting peak temperature (Tm(B)) and Tm(A) satisfy the relationship (b-2).

[0104] Tm(B)>Tm(A)···Equation (b-2)

[0105] [4] According to the decorative film of [1] or [2], the aforementioned polypropylene resin (A) further satisfies the following necessary condition (a5), and the aforementioned polypropylene resin (B) further satisfies the following necessary condition (b3).

[0106] (a5) Crystallization temperature (Tc(A)) is below 100℃.

[0107] (b3) The crystallization temperature (Tc(B)) and Tc(A) satisfy the relationship (b-3).

[0108] Tc(B)>Tc(A)···Equation (b-3)

[0109] [5] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX3) of a weight ratio of polypropylene resin (A) to ethylene-α-olefin random copolymer (C) of 97:3 to 5:95, wherein the aforementioned ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c1) to (c3).

[0110] (c1) Ethylene content [E(C)] is 65% by weight or more.

[0111] (c2) Density is 0.850~0.950 g / cm³ 3 .

[0112] (c3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[0113] [6] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX4) of a polypropylene resin (A) and a thermoplastic elastomer (D) in a weight ratio of 97:3 to 5:95, wherein the aforementioned thermoplastic elastomer (D) satisfies the following necessary conditions (d1) to (d4).

[0114] (d1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[0115] (d2) Density is 0.850~0.950 g / cm³ 3 .

[0116] (d3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[0117] (d4) has a smaller tensile modulus than polypropylene resin (A).

[0118] [7] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX5) of a polypropylene resin (A) and a thermoplastic resin (E) in a weight ratio of 97:3 to 5:95, wherein the aforementioned thermoplastic resin (E) satisfies the following necessary condition (e1), and the aforementioned resin composition (XX5) satisfies the following necessary condition (xx1).

[0119] (e1) Contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0120] (xx1) The isothermal crystallization time (t(XX5)) (seconds) of the resin composition (XX5) determined by differential scanning calorimetry (DSC) satisfies the following formula (x-1).

[0121] t(XX5)≥1.5×t(A)···Equation (x-1)

[0122] (In the formula, t(A) represents the isothermal crystallization time (in seconds) of polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A), and t(XX5) represents the isothermal crystallization time (in seconds) of resin composition (XX5) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A).)

[0123] [8] The decorative film according to [1] or [2], wherein the aforementioned polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following necessary conditions (f1) and (f2).

[0124] (f1) The melting peak temperature (Tm(F)) is 110~170℃.

[0125] (f2) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[0126] [9] The decorative film according to [3] or [4], wherein the aforementioned polypropylene resin (A) is a propylene-α-olefin copolymer.

[0127]

[10] The decorative film according to [3], wherein the aforementioned Tm(A) is below 140°C.

[0128]

[11] According to the decorative film of [5], the aforementioned ethylene-α-olefin random copolymer (C) further satisfies at least one of the following necessary conditions (c4) and (c5).

[0129] (c4) The melting peak temperature (Tm(C)) is 30 to 130℃.

[0130] (c5) is a random copolymer of ethylene and α-olefins with 3 to 20 carbon atoms.

[0131]

[12] According to the decorative film of [6], wherein the aforementioned thermoplastic elastomer (D) is at least one copolymer selected from the group consisting of propylene-ethylene copolymer with less than 50 wt% ethylene content, butene-ethylene copolymer with less than 50 wt% ethylene content, propylene-ethylene-butene copolymer with less than 50 wt% ethylene content, propylene-butene copolymer, and butene homopolymer.

[0132]

[13] The decorative film according to [6] or

[12] , wherein the aforementioned thermoplastic elastomer (D) further satisfies the following necessary condition (d5).

[0133] (d5) The melting peak temperature (Tm(D)) is 30–170℃.

[0134]

[14] The decorative film according to [7], wherein the aforementioned thermoplastic resin (E) is a styrene-based elastomer.

[0135]

[15] The decorative film according to [7], wherein the aforementioned thermoplastic resin (E) is an alicyclic hydrocarbon resin.

[0136]

[16] According to the decorative film of [8], the aforementioned propylene-ethylene block copolymer (F) further satisfies at least one of the following necessary conditions (f3) to (f5).

[0137] (f3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15–85% by weight.

[0138] (f4) The ethylene content of the aforementioned component (F1) is in the range of 0 to 6% by weight.

[0139] (f5) The ethylene content of the aforementioned component (F2) is in the range of 5 to 90% by weight.

[0140]

[17] The decorative film according to any one of [1] to

[16] , wherein a surface decorative layer (III) is provided on the side of the aforementioned layer (II) opposite to the side of the surface to which it is attached to the aforementioned resin molded body, the surface decorative layer (III) comprising: a surface decorative layer resin containing a nucleating agent.

[0141]

[18] The decorative film according to

[17] , wherein the aforementioned surface decorative layer (III) comprises a polypropylene resin (H) that satisfies the following necessary condition (h1).

[0142] (h1) The melt flow rate (230℃, 2.16kg load) (MFR(H)) and MFR(B) satisfy the relationship (h-1).

[0143] MFR(H)>MFR(B)···Equation (h-1)

[0144]

[19] A method for manufacturing a decorative molded body includes the following steps: preparing a decorative film as described in any one of [1] to

[18] ; preparing a resin molded body; placing the resin molded body and the decorative film in a depressurized chamber; depressurizing the chamber; heating and softening the decorative film; pressing the decorative film onto the resin molded body; and restoring or pressurizing the depressurized chamber to atmospheric pressure.

[0145]

[20] The method for manufacturing a decorative molded body according to

[19] , wherein the aforementioned resin molded body comprises an acrylic resin composition.

[0146] The fourth aspect of the invention includes the following.

[0147] [1] A decorative film for thermoforming attachment to a resin molded body, the decorative film containing a hindered amine light stabilizer and / or an ultraviolet absorber, the decorative film comprising: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), the aforementioned polypropylene resin (A) satisfying the following necessary condition (a1), and the aforementioned polypropylene resin (B) satisfying the following necessary condition (b1).

[0148] (a1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(A)) exceeds 0.5 g / 10 minutes.

[0149] (b1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(B)) and MFR(A) satisfy the relational expression (b-1).

[0150] MFR(B) < MFR(A) ··· formula (b-1)

[0151] [2] The decorative film according to [1], wherein the aforementioned polypropylene resin (A) further satisfies the following necessary conditions (a2) to (a4), and the aforementioned polypropylene resin (B) further satisfies the following necessary condition (b2).

[0152] (a2) It is a metallocene catalyst-based propylene polymer.

[0153] (a3) The melting peak temperature (Tm(A)) is lower than 150 °C.

[0154] (a4) The molecular weight distribution (Mw / Mn(A)) measured by GPC is 1.5 to 3.5.

[0155] (b2) The melting peak temperature (Tm(B)) and Tm(A) satisfy the relational expression (b-2).

[0156] Tm(B) > Tm(A) ··· formula (b-2)

[0157] [3] The decorative film according to [1], wherein the aforementioned polypropylene resin (A) further satisfies the following necessary condition (a5), and the aforementioned polypropylene resin (B) further satisfies the following necessary condition (b3).

[0158] (a5) The crystallization temperature (Tc(A)) is lower than 100 °C.

[0159] (b3) The crystallization temperature (Tc(B)) and Tc(A) satisfy the relational expression (b-3).

[0160] Tc(B) > Tc(A) ··· formula (b-3)

[0161] [4] According to the decorative film of [1], the aforementioned sealing layer (I) comprises: a resin composition (XX3) of polypropylene resin (A) and ethylene-α-olefin random copolymer (C) in a weight ratio of 97:3 to 5:95, wherein the aforementioned ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c1) to (c3).

[0162] (c1) Ethylene content [E(C)] is 65% by weight or more.

[0163] (c2) Density is 0.850~0.950 g / cm³ 3 .

[0164] (c3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[0165] [5] According to the decorative film of [1], the aforementioned sealing layer (I) comprises: a resin composition (XX4) of polypropylene resin (A) and thermoplastic elastomer (D) in a weight ratio of 97:3 to 5:95, wherein the aforementioned thermoplastic elastomer (D) satisfies the following necessary conditions (d1) to (d4).

[0166] (d1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[0167] (d2) Density is 0.850~0.950 g / cm³ 3 .

[0168] (d3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[0169] (d4) has a smaller tensile modulus than polypropylene resin (A).

[0170] [6] According to the decorative film of [1], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX5) of a polypropylene resin (A) and a thermoplastic resin (E) in a weight ratio of 97:3 to 5:95, wherein the aforementioned thermoplastic resin (E) satisfies the following necessary condition (e1), and the aforementioned resin composition (XX5) satisfies the following necessary condition (xx1).

[0171] (e1) Contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0172] (xx1) The isothermal crystallization time (t(XX5)) (seconds) of the resin composition (XX5) determined by differential scanning calorimetry (DSC) satisfies the following formula (x-1).

[0173] t(XX5)≥1.5×t(A)···Equation (x-1)

[0174] In the formula, t(A) represents the isothermal crystallization time (in seconds) of polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A), and t(XX5) represents the isothermal crystallization time (in seconds) of resin composition (XX5) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A).

[0175] [7] According to the decorative film of [1], wherein the aforementioned polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following necessary conditions (f1) and (f2).

[0176] (f1) The melting peak temperature (Tm(F)) is 110~170℃.

[0177] (f2) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[0178] [8] The decorative film according to [2] or [3], wherein the aforementioned polypropylene resin (A) is a propylene-α-olefin copolymer.

[0179] [9] The decorative film according to [2], wherein the aforementioned Tm(A) is below 140°C.

[0180]

[10] According to the decorative film of [4], the aforementioned ethylene-α-olefin random copolymer (C) further satisfies at least one of the following necessary conditions (c4) and (c5).

[0181] (c4) The melting peak temperature (Tm(C)) is 30 to 130℃.

[0182] (c5) is a random copolymer of ethylene and α-olefins with 3 to 20 carbon atoms.

[0183]

[11] According to the decorative film of [5], wherein the aforementioned thermoplastic elastomer (D) is at least one copolymer selected from the group consisting of propylene-ethylene copolymer with less than 50 wt% ethylene content, butene-ethylene copolymer with less than 50 wt% ethylene content, propylene-ethylene-butene copolymer with less than 50 wt% ethylene content, propylene-butene copolymer, and butene homopolymer.

[0184]

[12] The decorative film according to [5] or

[11] , wherein the aforementioned thermoplastic elastomer (D) further satisfies the following necessary condition (d5).

[0185] (d5) The melting peak temperature (Tm(D)) is 30–170℃.

[0186]

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

[0187]

[14] The decorative film according to [6], wherein the aforementioned thermoplastic resin (E) is an alicyclic hydrocarbon resin.

[0188]

[15] According to the decorative film of [7], the aforementioned propylene-ethylene block copolymer (F) further satisfies at least one of the following necessary conditions (f3) to (f5).

[0189] (f3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15–85% by weight.

[0190] (f4) The ethylene content of the aforementioned component (F1) is in the range of 0 to 6% by weight.

[0191] (f5) The ethylene content of the aforementioned component (F2) is in the range of 5 to 90% by weight.

[0192]

[16] A method for manufacturing a decorative molded body includes the following steps: preparing a decorative film as described in any one of [1] to

[15] ; preparing a resin molded body; placing the resin molded body and the decorative film in a depressurized chamber; depressurizing the chamber; heating and softening the decorative film; pressing the decorative film onto the resin molded body; and restoring or pressurizing the depressurized chamber to atmospheric pressure.

[0193]

[17] The method for manufacturing a decorative molded article according to

[16] , wherein the aforementioned resin molded article comprises an acrylic resin composition.

[0194] The fifth aspect of the invention includes the following.

[0195] [1] A decorative film for thermoforming and bonding to a resin molded body, comprising a nucleating agent, the decorative film comprising: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a resin composition (B'), the resin composition (B') comprising a polypropylene resin (B),

[0196] The aforementioned polypropylene resin (A) satisfies the following necessary condition (a'1), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2).

[0197] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[0198] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0199] (b'2) The strain hardening degree λ is 1.1 or higher.

[0200] [2] According to the decorative film of [1], the aforementioned nucleating agent is selected from aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, nonitol derivatives, amide compounds or metal salts of rosin.

[0201] [3] According to the decorative film of [1] or [2], the aforementioned polypropylene resin (A) further satisfies the following necessary conditions (a'2) to (a'4), and the aforementioned resin composition (B') further satisfies the following necessary condition (b'3).

[0202] (a'2) is a metallocene catalyst-based propylene polymer.

[0203] (a'3) Melting peak temperature (Tm(A)) is below 150℃.

[0204] (a'4) The molecular weight distribution (Mw / Mn(A)) measured by GPC was 1.5 to 3.5.

[0205] (b'3) The melting peak temperature (Tm(B')) and Tm(A) satisfy the relationship (b-3).

[0206] Tm(B')>Tm(A)···Equation (b-3)

[0207] [4] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'3) of polypropylene resin (A) and ethylene-α-olefin random copolymer (C) in a weight ratio of 97:3 to 5:95.

[0208] The aforementioned ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c'1) to (c'3).

[0209] (c'1) Ethylene content [E(C)] is 65% by weight or more.

[0210] (c'2) Density is 0.850~0.950 g / cm³ 3 .

[0211] (c'3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[0212] [5] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'4) of polypropylene resin (A) and thermoplastic elastomer (D) in a weight ratio of 97:3 to 5:95.

[0213] The aforementioned thermoplastic elastomer (D) satisfies the following necessary conditions (d'1) to (d'4).

[0214] (d'1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[0215] (d'2) Density is 0.850~0.950 g / cm³ 3 .

[0216] (d'3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[0217] (d'4) has a smaller tensile modulus than that of polypropylene resin (A).

[0218] [6] The decorative film according to [1] or [2], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'5) of polypropylene resin (A) and thermoplastic resin (E) in a weight ratio of 97:3 to 5:95.

[0219] The aforementioned thermoplastic resin (E) satisfies the following necessary condition (e'1), and the aforementioned resin composition (XX'5) satisfies the following necessary condition (xx'1).

[0220] (e'1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0221] (xx'1) The isothermal crystallization time (t(XX'5)) (seconds) obtained by differential scanning calorimetry (DSC) satisfies the following formula (x'-1).

[0222] t(XX'5)≥1.5×t(A)···Formula (x'-1)

[0223] (In the formula, t(A) represents the isothermal crystallization time (in seconds) of the aforementioned polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of the aforementioned polypropylene resin (A), and t(XX'5) represents the isothermal crystallization time (in seconds) of the aforementioned resin composition (XX'5) measured at a temperature 10°C higher than the initial crystallization temperature of the aforementioned polypropylene resin (A).)

[0224] [7] The decorative film according to [1] or [2], wherein the aforementioned polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following necessary conditions (f'1) and (f'2).

[0225] (f'1) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[0226] (f'2) The melting peak temperature (Tm(F)) is 110~170℃.

[0227] [8] A decorative film for thermoforming and bonding to a resin molded body, comprising a nucleating agent, the decorative film comprising: a sealing layer (I) containing a polyolefin adhesive resin (G) and a layer (II) containing a resin composition (B') comprising a polypropylene resin (B).

[0228] The aforementioned polyolefin adhesive resin (G) satisfies the following necessary conditions (g'1) and (g'2), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2).

[0229] (g'1) is a polyolefin resin having a polar functional group containing at least one heteroatom.

[0230] (g'2) Melt flow rate (230℃, 2.16kg load) (MFR(G)) is less than 100g / 10min.

[0231] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0232] (b'2) The strain hardening degree λ is 1.1 or higher.

[0233] [9] The decorative film according to any one of [1] to [8], wherein the aforementioned resin composition (B') satisfies the following necessary conditions (b'1') and (b'2').

[0234] (b'1') Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 20 g / 10 min.

[0235] (b'2') The strain hardening degree λ is 1.8 or higher.

[0236]

[10] The decorative film according to any one of [1] to [8], wherein the aforementioned resin composition (B') satisfies the following necessary conditions (b'1”) and (b'2”).

[0237] (b'1") The melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 12 g / 10 min.

[0238] (b'2") The strain hardening degree λ is 2.3 or higher.

[0239]

[11] The decorative film according to any one of [1] to

[10] , wherein the aforementioned polypropylene resin (B) is a polypropylene resin (BL) having a long branched structure.

[0240]

[12] The decorative film according to

[11] , wherein the aforementioned polypropylene resin (BL) is a polypropylene resin with less gel produced by a method other than crosslinking.

[0241]

[13] The decorative film according to any one of [1] to

[12] , wherein a surface decorative layer (III) comprising a surface decorative layer resin is provided on the side of the aforementioned layer (II) opposite to the side of the surface to which the aforementioned resin molded body is attached.

[0242]

[14] According to the decorative film of

[13] , wherein the aforementioned surface decorative layer resin comprises a polypropylene resin (H) and the strain hardening degree λ of the aforementioned polypropylene resin (H) is less than 1.1.

[0243]

[15] According to the decorative film of [3], the aforementioned polypropylene resin (A) is a propylene-α-olefin copolymer.

[0244]

[16] The decorative film according to [3] or

[15] , wherein the aforementioned Tm(A) is below 140°C.

[0245]

[17] According to the decorative film of [4], the aforementioned ethylene-α-olefin random copolymer (C) further satisfies the following necessary condition (c'4).

[0246] (c'4) The melting peak temperature (Tm(C)) is 30 to 130℃.

[0247]

[18] The decorative film according to [4] or

[17] , wherein the aforementioned ethylene-α-olefin random copolymer (C) further satisfies the following necessary condition (c'5).

[0248] (c'5) is a random copolymer of ethylene and α-olefins with 3 to 20 carbon atoms.

[0249]

[19] According to the decorative film of [5], wherein the aforementioned thermoplastic elastomer (D) is: a propylene-ethylene copolymer with an ethylene content of less than 50% by weight, a butene-ethylene copolymer with an ethylene content of less than 50% by weight, a propylene-ethylene-butene copolymer with an ethylene content of less than 50% by weight, a propylene-butene copolymer, or a butene homopolymer.

[0250]

[20] The decorative film according to [5] or

[19] , wherein the aforementioned thermoplastic elastomer (D) further satisfies the following necessary condition (d'5).

[0251] (d'5) The melting peak temperature (Tm(D)) is 30–170℃.

[0252]

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

[0253]

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

[0254]

[23] According to the decorative film of [7], the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'3).

[0255] (f'3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15–85% by weight.

[0256]

[24] The decorative film according to [7] or

[23] , wherein the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'4).

[0257] (f'4) The ethylene content of the aforementioned component (F1) is in the range of 0 to 6% by weight.

[0258]

[25] The decorative film according to [7],

[23] or

[24] , wherein the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'5).

[0259] (f'5) The ethylene content of the aforementioned component (F2) is in the range of 5 to 90% by weight.

[0260]

[26] A method for manufacturing a decorative molded body includes the following steps: preparing a decorative film as described in any one of [1] to

[25] ; preparing a resin molded body; placing the resin molded body and the decorative film in a chamber capable of depressurization; depressurizing the chamber; heating and softening the decorative film; pressing the heated and softened decorative film onto the resin molded body; and restoring or pressurizing the depressurized chamber to atmospheric pressure.

[0261]

[27] The method for manufacturing a decorative molded article according to

[26] , wherein the aforementioned resin molded article comprises an acrylic resin composition.

[0262]

[28] The method for manufacturing a decorative molded body according to

[26] , wherein the aforementioned decorative film is any one of [8] to

[14] , and the aforementioned resin molded body comprises a polar resin material, wherein the polar resin material comprises at least one 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.

[0263] The sixth aspect of the invention includes the following.

[0264] [1] A decorative film for thermoforming and bonding to a resin molded body, comprising a hindered amine light stabilizer and / or an ultraviolet absorber, the decorative film comprising: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a resin composition (B') comprising a polypropylene resin (B).

[0265] The aforementioned polypropylene resin (A) satisfies the following necessary condition (a'1), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2).

[0266] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[0267] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0268] (b'2) The strain hardening degree λ is 1.1 or higher.

[0269] [2] According to the decorative film of [1], the aforementioned polypropylene resin (A) further satisfies the following necessary conditions (a'2) to (a'4), and the aforementioned resin composition (B') further satisfies the following necessary condition (b'3).

[0270] (a'2) is a metallocene catalyst-based propylene polymer.

[0271] (a'3) Melting peak temperature (Tm(A)) is below 150℃.

[0272] (a'4) The molecular weight distribution (Mw / Mn(A)) measured by GPC was 1.5 to 3.5.

[0273] (b'3) The melting peak temperature (Tm(B')) and Tm(A) satisfy the relationship (b-3).

[0274] Tm(B')>Tm(A)···Equation (b-3)

[0275] [3] According to the decorative film of [1], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'3) of polypropylene resin (A) and ethylene-α-olefin random copolymer (C) in a weight ratio of 97:3 to 5:95.

[0276] The aforementioned ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c'1) to (c'3).

[0277] (c'1) Ethylene content [E(C)] is 65% by weight or more.

[0278] (c'2) Density is 0.850~0.950 g / cm³ 3 .

[0279] (c'3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[0280] [4] According to the decorative film of [1], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'4) of polypropylene resin (A) and thermoplastic elastomer (D) in a weight ratio of 97:3 to 5:95.

[0281] The aforementioned thermoplastic elastomer (D) satisfies the following necessary conditions (d'1) to (d'4).

[0282] (d'1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[0283] (d'2) Density is 0.850~0.950 g / cm³ 3 .

[0284] (d'3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[0285] (d'4) has a smaller tensile modulus than that of polypropylene resin (A).

[0286] [5] According to the decorative film of [1], wherein the aforementioned sealing layer (I) comprises: a resin composition (XX'5) of polypropylene resin (A) and thermoplastic resin (E) in a weight ratio of 97:3 to 5:95.

[0287] The aforementioned thermoplastic resin (E) satisfies the following necessary condition (e'1), and the aforementioned resin composition (XX'5) satisfies the following necessary condition (xx'1).

[0288] (e'1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0289] (xx'1) The isothermal crystallization time (t(XX'5)) (seconds) obtained by differential scanning calorimetry (DSC) satisfies the following formula (x'-1).

[0290] t(XX'5)≥1.5×t(A)···Formula (x'-1)

[0291] (In the formula, t(A) represents the isothermal crystallization time (in seconds) of the aforementioned polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of the aforementioned polypropylene resin (A), and t(XX'5) represents the isothermal crystallization time (in seconds) of the aforementioned resin composition (XX'5) measured at a temperature 10°C higher than the initial crystallization temperature of the aforementioned polypropylene resin (A).)

[0292] [6] According to the decorative film of [1], wherein the aforementioned polypropylene resin (A) is a propylene-ethylene block copolymer (F) that satisfies the following necessary conditions (f'1) and (f'2).

[0293] (f'1) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[0294] (f'2) The melting peak temperature (Tm(F)) is 110~170℃.

[0295] [7] A decorative film for thermoforming and bonding to a resin molded body, comprising a hindered amine light stabilizer and / or an ultraviolet absorber, the decorative film comprising: a sealing layer (I) containing a polyolefin adhesive resin (G) and a layer (II) containing a resin composition (B') comprising a polypropylene resin (B).

[0296] The aforementioned polyolefin adhesive resin (G) satisfies the following necessary conditions (g'1) and (g'2), and the aforementioned resin composition (B') satisfies the following necessary conditions (b'1) and (b'2).

[0297] (g'1) is a polyolefin resin having a polar functional group containing at least one heteroatom.

[0298] (g'2) Melt flow rate (230℃, 2.16kg load) (MFR(G)) is less than 100g / 10min.

[0299] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0300] (b'2) The strain hardening degree λ is 1.1 or higher.

[0301] [8] The decorative film according to any one of [1] to [7], wherein the aforementioned resin composition (B') satisfies the following necessary conditions (b'1') and (b'2').

[0302] (b'1') Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 20 g / 10 min.

[0303] (b'2') The strain hardening degree λ is 1.8 or higher.

[0304] [9] The decorative film according to any one of [1] to [7], wherein the aforementioned resin composition (B') satisfies the following necessary conditions (b'1”) and (b'2”).

[0305] (b'1") The melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 12 g / 10 min.

[0306] (b'2") The strain hardening degree λ is 2.3 or higher.

[0307]

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

[0308]

[11] The decorative film according to

[10] , wherein the aforementioned polypropylene resin (BL) is a polypropylene resin with less gel produced by a method other than crosslinking.

[0309]

[12] According to the decorative film of [2], wherein the aforementioned polypropylene resin (A) is a propylene-α-olefin copolymer.

[0310]

[13] The decorative film according to [2] or

[12] , wherein the aforementioned Tm(A) is below 140°C.

[0311]

[14] According to the decorative film of [3], the aforementioned ethylene-α-olefin random copolymer (C) further satisfies the following necessary condition (c'4).

[0312] (c'4) The melting peak temperature (Tm(C)) is 30 to 130℃.

[0313]

[15] The decorative film according to [3] or

[14] , wherein the aforementioned ethylene-α-olefin random copolymer (C) further satisfies the following necessary condition (c'5).

[0314] (c'5) is a random copolymer of ethylene and α-olefins with 3 to 20 carbon atoms.

[0315]

[16] According to the decorative film of [4], wherein the aforementioned thermoplastic elastomer (D) is: a propylene-ethylene copolymer with an ethylene content of less than 50% by weight, a butene-ethylene copolymer with an ethylene content of less than 50% by weight, a propylene-ethylene-butene copolymer with an ethylene content of less than 50% by weight, a propylene-butene copolymer, or a butene homopolymer.

[0316]

[17] The decorative film according to [4] or

[16] , wherein the aforementioned thermoplastic elastomer (D) further satisfies the following necessary condition (d'5).

[0317] (d'5) The melting peak temperature (Tm(D)) is 30–170℃.

[0318]

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

[0319]

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

[0320]

[20] According to the decorative film of [6], the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'3).

[0321] (f'3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15–85% by weight.

[0322]

[21] The decorative film according to [6] or

[20] wherein the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'4).

[0323] (f'4) The ethylene content of the aforementioned component (F1) is in the range of 0 to 6% by weight.

[0324]

[22] The decorative film according to [6],

[20] or

[21] , wherein the aforementioned propylene-ethylene block copolymer (F) further satisfies the following necessary condition (f'5).

[0325] (f'5) The ethylene content of the aforementioned component (F2) is in the range of 5 to 90% by weight.

[0326]

[23] A method for manufacturing a decorative molded body includes the following steps: preparing a decorative film as described in any one of [1] to

[22] ; preparing a resin molded body; placing the resin molded body and the decorative film in a chamber capable of depressurization; depressurizing the chamber; heating and softening the decorative film; pressing the heated and softened decorative film onto the resin molded body; and restoring or pressurizing the depressurized chamber to atmospheric pressure.

[0327]

[24] The method for manufacturing a decorative molded article according to

[23] , wherein the aforementioned resin molded article comprises an acrylic resin composition.

[0328]

[25] According to the method for manufacturing a decorative molded body according to

[23] , wherein the aforementioned decorative film is any one of [7] to

[11] , and the aforementioned resin molded body comprises a polar resin material, wherein the polar resin material comprises at least one 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.

[0329] The effects of the invention

[0330] According to the decorative film of the present invention, it is possible to provide a decorative film that can be used for three-dimensional decorative thermoforming, which suppresses the reduction of gloss and / or weather resistance and changes in surface appearance after decorative molding, and a method for manufacturing a decorative molded article using the same. Furthermore, a decorative molded article with a good appearance formed using the decorative film can be obtained.

[0331] According to the method for manufacturing decorative molded articles of the present invention, no air is entangled between the decorative film and the resin molded article, and a beautiful decorative molded article with good reproducibility of textures such as embossing can be obtained. Attached Figure Description

[0332] Figure 1 A diagram illustrating an example of the layer composition of the decorative film of the present invention.

[0333] Figure 2 A cross-sectional schematic diagram illustrating the general structure of the apparatus used in the method for manufacturing the decorative molded body of the present invention.

[0334] Figure 3 In order to be in Figure 2 A cross-sectional schematic diagram illustrating the configuration of the device, which includes a resin molded body and a decorative film.

[0335] Figure 4 To explain Figure 2 A cross-sectional schematic diagram illustrating the heating and depressurization processes within the device.

[0336] Figure 5 In order to be in Figure 2 A cross-sectional schematic diagram illustrating the process of pressing a decorative film onto a resin molded body within the device.

[0337] Figure 6 To the general Figure 2 A cross-sectional schematic diagram illustrating the process of restoring or pressurizing the device to atmospheric pressure.

[0338] Figure 7 A cross-sectional schematic diagram illustrating the case where the edges of the decorative film that is not needed in the obtained decorative molded body are trimmed.

[0339] Figure 8 A diagram illustrating an example of the layered structure of the resulting decorative molded body. Detailed Implementation

[0340] The present invention will now be described in detail. It should be noted that the contents of Japanese Patent Applications 2017-222516, 2017-247629, 2017-249129, 2018-19640, 2018-21093 and 2018-33633, which form the basis of the priority claim of this application, are incorporated herein by reference in their entirety.

[0341] In this specification, decorative film refers to a film used to decorate a molded body. Decorative forming refers to the forming process of attaching a decorative film to a molded body. Three-dimensional decorative thermoforming, which is a forming process of attaching a decorative film to a molded body, refers to the following forming process: The decorative film is thermoformed along the bonding surface of the molded body while being attached; this process is as follows: To prevent air from being entangled between the decorative film and the molded body, thermoforming is performed under reduced pressure (vacuum); the heated decorative film is attached to the molded body; and pressure is released (pressurized) to seal it. Furthermore, the "~" indicating a numerical range is used to mean that the values ​​before and after it are both lower and upper limits.

[0342] In addition, the determination of the MFR of polypropylene resins and polypropylene resin compositions in this specification is carried out according to ISO 1133:1997 Conditions M, at 230°C and under a load of 2.16 kg. The unit is g / 10 minutes.

[0343] In addition, the Mn and Mw values ​​for polypropylene resins are recorded in "Fundamentals of Polymer Chemistry" (edited by the Polymer Society, Tokyo Chemical Association, 1978), etc., and are values ​​calculated based on molecular weight distribution curves based on GPC.

[0344] Additionally, in this specification, the unit "wt%" refers to weight%.

[0345] The following describes in detail the methods for implementing the present invention.

[0346] {First and Second Embodiments of the Invention}

[0347] The decorative film of the present invention is characterized in that it is used to be thermoformed and attached to a three-dimensional resin molded body, and comprises: a layer containing at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, wherein the additive satisfies the following necessary conditions.

[0348] Necessary condition: For a glass plate subjected to the following fogging test according to ISO 6452, the change in fog value measured according to JIS-K7136 is less than 40. The change in fog value after the fogging test is calculated using the following formula.

[0349] Change in haze value after fogging test = Haze value of glass plate after fogging test - Haze value of glass plate before fogging test

[0350] <Atomization Test> Place 1g (±0.01g) of additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0351] The decorative film of the present invention comprises: a layer containing at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers.

[0352] For the additives in this invention, the change in haze value of the glass plate after the following haze test according to ISO 6452, measured according to JIS-K7136, must be 40 or less, preferably 35 or less, more preferably 25 or less, and even more preferably 10 or less.

[0353] <Atomization Test> Place 1g (±0.01g) of additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150°C for 1 hour to cause fogging (atomization) of the glass plate.

[0354] Conventional fogging tests are conducted using resin composition samples containing the desired additives. However, this method cannot accurately determine the volatility of the additives in the decorative film of this invention. Specifically, it cannot determine whether the additives exhibit exudation phenomena different from those of conventional additives. By conducting fogging tests through direct heating of the additives, the volatility of the additives in the decorative film of this invention can be determined.

[0355] If the haze value of the glass plate after the haze test is within the aforementioned range, the additives are less likely to volatilize during decorative molding. Therefore, decorative molded articles with good transparency and surface smoothness, excellent gloss and / or weather resistance, and suppressed surface appearance changes can be obtained. Furthermore, it can suppress the transfer of additives to the surface (adhesive surface) of the decorative film and suppress the reduction of adhesion to the decorated object. Moreover, it can also prevent the interior of the thermoforming machine from being contaminated by additives.

[0356] [Nucleating agent]

[0357] In this specification, the nucleating agent is an additive that is blended into polyolefin resins, etc., and by blending it into polyolefin resins, it can promote the crystallization of the resin. Therefore, it can accelerate the crystallization rate of polyolefin resins, increase the crystallization temperature, and increase the melting temperature. In addition, by adding the nucleating agent, fine crystals are rapidly generated, thereby improving the surface smoothness, gloss, and transparency of the film.

[0358] The nucleating agent in this invention is not particularly limited as long as it meets the aforementioned conditions. Examples include organometallic compounds such as aromatic carboxylic acid metal salts and aromatic phosphate metal salts, sorbitol derivatives, nonitol derivatives, amide compounds, and metal salts of rosin. Among these, the aforementioned nucleating agent is preferably an organometallic compound or an amide compound.

[0359] [Organometallic compounds]

[0360] When the above-mentioned nucleating agent is an organometallic compound, it is more preferably a compound represented by the following general formula (1).

[0361]

[0362] (where R is in the formula) 1 ~R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 9 branched carbon atoms, R 5 This represents a hydrogen atom or a methyl group, where m represents 1 or 2. When m is 1, M... 1 M represents a hydrogen atom or an alkali metal atom, where m is 2. 1 This indicates a Group 2 element, Al(OH) or Zn.

[0363] As in the above general formula (1), R 1 R2 R 3 and R 4 The alkyl groups having 1 to 9 carbon atoms shown include, for example: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, isoheptyl, and tert-heptyl, with methyl, tert-butyl, and tert-heptyl being particularly preferred.

[0364] M in the above general formula (1) 1 The second group elements shown include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, magnesium and calcium have a significant nucleating effect on the nucleating agent components and are therefore preferred.

[0365] The above-mentioned organometallic compounds can be used alone or in combination of two or more.

[0366] Commercially available products include "ADK STAB NA-11", "ADK STAB NA-21", and "ADK STAB NA-25" manufactured by ADEKA Corporation.

[0367] [Amide compounds]

[0368] When the above-mentioned nucleating agent is an amide compound, there are no particular limitations as long as it is a compound containing at least one amide group. It is preferred to be a compound shown in general formula (2) or (3) below, and more preferably a compound shown in general formula (4) to (7).

[0369] General formula (2)

[0370] R 6 -(coNHR 7 ) a (2)

[0371] [In the formula, a represents an integer from 2 to 6. R] 6 Residues with an α-valence obtained by removing all carboxyl groups from linear or branched saturated or unsaturated aliphatic polycarboxylic acids with 6 to 18 carbon atoms; residues with an α-valence obtained by removing all carboxyl groups from alicyclic polycarboxylic acids with 9 to 18 carbon atoms; or residues with an α-valence obtained by removing all carboxyl groups from aromatic polycarboxylic acids with 9 to 18 carbon atoms. 2 to 6 R 7 "Same" or "different" respectively refer to: residues obtained by removing the amino group from linear or branched saturated or unsaturated aliphatic monoamines with 6 to 30 carbon atoms; residues obtained by removing the amino group from alicyclic monoamines with 6 to 30 carbon atoms; or residues obtained by removing the amino group from aromatic monoamines with 6 to 30 carbon atoms.

[0372] General formula (3)

[0373] R 8 -(NHCOR 9 ) b (3)

[0374] [In the formula, b represents an integer from 2 to 6. R] 8 Residues with a β-valent oxidation state are obtained by removing all amino groups from linear or branched saturated or unsaturated aliphatic polyamines with 2-30 carbon atoms; residues with a β-valent oxidation state are obtained by removing amino groups from alicyclic polyamines with 6-30 carbon atoms; or residues with a β-valent oxidation state are obtained by removing amino groups from aromatic polyamines with 6-30 carbon atoms. (2-6 R groups) 9 "Same" or "different" respectively refer to: residues obtained by removing a carboxyl group from a straight-chain or branched saturated or unsaturated aliphatic monocarboxylic acid with 3 to 18 carbon atoms; residues obtained by removing a carboxyl group from an alicyclic monocarboxylic acid with 9 to 18 carbon atoms; or residues obtained by removing a carboxyl group from an aromatic monocarboxylic acid with 9 to 18 carbon atoms.

[0375] General formula (4)

[0376]

[0377] [In the formula, there are 3 R's] 10 "Same" or "different" refers to: residues obtained by removing the amino group from aliphatic monoamines with 6 to 18 carbon atoms; residues obtained by removing the amino group from alicyclic monoamines with 6 to 18 carbon atoms; or residues obtained by removing the amino group from aromatic monoamines with 6 to 18 carbon atoms.

[0378] General formula (5)

[0379]

[0380] [In the formula, there are 4 R's] 11 "Same" or "different" refers to: residues obtained by removing the amino group from aliphatic monoamines with 6 to 18 carbon atoms; residues obtained by removing the amino group from alicyclic monoamines with 6 to 18 carbon atoms; or residues obtained by removing the amino group from aromatic monoamines with 6 to 18 carbon atoms.

[0381] General formula (6)

[0382]

[0383] [In the formula, there are 3 R's] 12 "Same" or "different" refers to: residues obtained by removing the amino group from aliphatic monoamines with 6 to 18 carbon atoms; residues obtained by removing the amino group from alicyclic monoamines with 6 to 18 carbon atoms; or residues obtained by removing the amino group from aromatic monoamines with 6 to 18 carbon atoms.

[0384] General formula (7)

[0385]

[0386] [In the formula, there are 2 R] 13 "Same" or "different" refers to: residues obtained by removing the amino group from aliphatic monoamines with 6-18 carbon atoms; residues obtained by removing the amino group from alicyclic monoamines with 6-30 carbon atoms; or residues obtained by removing the amino group from aromatic monoamines with 6-30 carbon atoms.

[0387] Specifically, examples of amide compounds represented by the above general formula (4) include: 1,2,3-propanetricarboxylic acid triphenylamine, 1,2,3-propanetricarboxylic acid tris(4-butylaniline), 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tris(2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-ethylcyclohexylamide), and 1,2,3-propanetricarboxylic acid tris(2-n-propylcyclohexylamide). ), 1,2,3-propanetricarboxylic acid tris(3-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-isobutylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-isobutylcyclohexylamide) ), 1,2,3-propanetricarboxylic acid tris(4-isobutylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(3-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-pentylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-hexylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-heptylcyclohexylamide) The following are examples of tricarboxylic acids: 1,2,3-propanetricarboxylic acid tris(4-n-octylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris[4-(2-ethylhexyl)cyclohexylamide], 1,2,3-propanetricarboxylic acid tris(4-n-nonylcyclohexylamide), 1,2,3-propanetricarboxylic acid tris(4-n-decylcyclohexylamide), 1,2,3-propanetricarboxylic acid [(cyclohexylamide) di(2-methylcyclohexylamide)], and 1,2,3-propanetricarboxylic acid [di(cyclohexylamide)(2-methylcyclohexylamide)]. Among these, 1,2,3-propanetricarboxylic acid tricyclohexylamide or 1,2,3-propanetricarboxylic acid tris(2-methylcyclohexylamide) is preferred, and 1,2,3-propanetricarboxylic acid tris(2-methylcyclohexylamide) is particularly preferred.

[0388] Specifically, examples of amide compounds represented by the above general formula (5) include: 1,2,3,4-butanetetracarboxylic acid tetraphenylamine, 1,2,3,4-butanetetracarboxylic acid tetra(4-butylaniline), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra(2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra(3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra(4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra(2-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra(3-ethylcyclohexylamide), 1,2 3,4-Butanetetracarboxylate tetracarboxylate (2-n-propylcyclohexylamide), 1,2,3,4-Butanetetracarboxylate tetra ... Tetracarboxylic acid tetracarboxylate (2-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate (3-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate (4-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate (2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate (3-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate (4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate (2-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate (3-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate (4-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate (4-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetracarboxylate tetracarboxylate ( 4-n-pentylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetra(4-n-hexylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetra(4-n-heptylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetra(4-n-octylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetra[4-(2-ethylhexyl)cyclohexylamide], 1,2,3,4-butanetetracarboxylate tetra(4-n-nonylcyclohexylamide), 1,2,3,4-butanetetracarboxylate tetra(4-n-decylcyclohexylamide), and 1,2,3,4-butanetetracarboxylate [di(cyclohexylamide)di(2-methylcyclohexylamide)], etc., among which 1,2,3,4-butanetetracarboxylate tetracyclohexylamide or 1,2,3,4-butanetetracarboxylate tetracyclohexylamide is preferred.4-Butanetetracarboxylic acid tetra(2-methylcyclohexylamide), particularly preferably 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide.

[0389] Specifically, examples of amide compounds represented by the above general formula (6) include triphenylamine 1,3,5-benzenetricarboxylic acid, tris(4-butylaniline) 1,3,5-benzenetricarboxylic acid, tricyclohexylamide 1,3,5-benzenetricarboxylic acid, tris(2-methylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, tris(3-methylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, tris(4-methylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, tris(2-ethylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, tris(3-ethylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, tris(4-ethylcyclohexylamide) 1,3,5-benzenetricarboxylic acid, and tris(2-n-propyl) Cyclohexylamide), tris(3-n-propylcyclohexylamide), tris(4-n-propylcyclohexylamide), tris(2-isopropylcyclohexylamide), tris(3-isopropylcyclohexylamide), tris(4-isopropylcyclohexylamide), tris(2-n-butylcyclohexylamide), tris(3-n-butylcyclohexylamide), tris(4-n-butylcyclohexylamide), tris(2-n-butylcyclohexylamide), tris(3-n-butylcyclohexylamide), tris(4-n-butylcyclohexylamide), tris(2-isobutylcyclohexylamide), tris(3-n-butylcyclohexylamide), tris(4-n-butylcyclohexylamide), tris(2-isobutylcyclohexylamide), tris(3-n-butylcyclohexylamide) (3-Isobutylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(4-isobutylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(2-sec-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(3-sec-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(4-sec-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(2-tert-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(3-tert-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(4-tert-butylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(4-n-pentylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris(4-n-hexylcyclohexylamide), 1,3,5 Tris(4-n-heptylcyclohexylamide), tris(4-n-octylcyclohexylamide), tris(4-(2-ethylhexyl)cyclohexylamide), tris(4-n-nonylcyclohexylamide), tris(4-n-decylcyclohexylamide), tris((cyclohexylamide)bis(2-methylcyclohexylamide)), tris(di(cyclohexylamide)(2-methylcyclohexylamide)), etc., among which, tris(4-n-heptylcyclohexylamide) or tris(2-methylcyclohexylamide) are particularly preferred.

[0390] As an amide compound represented by the above general formula (7), examples include 2,6-naphthodicarboxylic acid diphenylamine, 2,6-naphthodicarboxylic acid dicyclohexylamide, 2,6-naphthodicarboxylic acid di(2-methylcyclohexylamide), etc., with 2,6-naphthodicarboxylic acid dicyclohexylamide being particularly preferred.

[0391] As amide compounds represented by the above general formula (3), specific examples include 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 1,3,5-tris(cyclohexylcarbonylamino)benzene, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 1,3,5-tris(4-methylbenzoylamino)benzene, 1,3,5-tris(3,4-dimethylbenzoylamino)benzene, 1,3,5-tris(3,5-dimethylbenzoylamino)benzene, 1,3,5-tris(cyclopentanecarbonylamino)benzene, 1,3,5-tris(1-adamantanecarbonylamino)benzene, 1,3,5-tris(2-methylpropionylamino)benzene, 1,3,5-tris(3,3-dimethylbutyrylamino)benzene, 1,3,5 -Tris(2-ethylbutyrylamino)benzene, 1,3,5-tris(2,2-dimethylbutyrylamino)benzene, 1,3,5-tris(2-cyclohexyl-acetylamino)benzene, 1,3,5-tris(3-cyclohexyl-propionylamino)benzene, 1,3,5-tris(4-cyclohexyl-butyrylamino)benzene, 1,3,5-tris(5-cyclohexyl-pentanoylamino)benzene, 1-isobutyrylamino-3,5-bis(pentanoylamino)benzene, 2,2-dimethylbutyrylamino-3,5-bis(pentanoylamino)benzene, 3,3-dimethylbutyrylamino-3,5-bis(pentanoylamino)benzene, 1,3-bis(isobutyrylamino)-5-pentanoylaminobenzene, 1,3-bis(isobutyrylamino)-5-( 2,2-Dimethyl-butyryl)aminobenzene, 1,3-bis(isobutyrylamino)-5-(3,3-dimethyl-butyryl)aminobenzene, 1,3-bis(2,2-dimethylbutyrylamino)-5-pivaloylaminobenzene, 1,3-bis(2,2-dimethylbutyrylamino)-5-isobutyrylaminobenzene, 1,3-bis(2,2-dimethylbutyrylamino)-5-(3,3-dimethylbutyryl)-aminobenzene, 1,3-bis(3,3-dimethylbutyrylamino)-5-pivaloylaminobenzene, 1,3-bis(3,3-dimethylbutyrylamino)-5-isobutyryl-aminobenzene, 1,3-bis(3,3-dimethylbutyrylamino)-5-(2,2-dimethylbutyrylamino) Aminobenzene, 1,3,5-tris(3-(trimethylsilyl)propionylamino)benzene, N-tert-butyl-3,5-bis-(3-methylbutyrylamino)-benzamide, N-tert-butyl-3,5-bis-(pivaloylamino)-benzamide, N-tert-octyl-3,5-bis-(pivaloylamino)-benzamide, N-(1,1-dimethyl-propyl)-3,5-bis-(pivaloylamino)-benzamide, N-(tert-octyl)-3,5-bis-(isobutyrylamino)-benzamide, N-(tert-butyl)-3,5-bis-(pivaloylamino)-benzamide, N-(2,3-dimethyl-cyclohexyl)-3,5-bis-(pivaloylamino)-benzamide, N-tert-butyl-3,5-Bis-(cyclopentanecarbonylamino)-benzamide, N-(3-methylbutyl)-3,5-bis-(3-methylbutyrylamino)-benzamide, N-(3-methylbutyl)-3,5-bis-(pivaloylamino)-benzamide, N-(3-methylbutyl)-3,5-bis-(4-methylpentanoylamino)-benzamide, N-(3-methylbutyl)-3,5-bis-(cyclopentanecarbonylamino)-benzamide, N-(3-methylbutyl)-3,5 -bis-(cyclohexanecarbonylamino)-benzamide, N-cyclopentyl-3,5-bis-(3-methylbutyrylamino)-benzamide, N-cyclopentyl-3,5-bis-(petaloylamino)-benzamide, N-cyclopentyl-3,5-bis-(4-methylpentanoylamino)-benzamide, N-cyclopentyl-3,5-bis-(cyclopentanecarbonylamino)-benzamide, N-cyclopentyl-3,5-bis-(cyclohexanecarbonylamino)-benzamide, N-cyclohex ... -bis-(3-methylbutyrylamino)-benzamide, N-cyclohexyl-3,5-bis-(pivaloylamino)-benzamide, N-cyclohexyl-3,5-bis-(4-methylpentanoylamino)-benzamide, N-cyclohexyl-3,5-bis-(cyclopentanecarbonylamino)-benzamide, N-cyclohexyl-3,5-bis-(cyclohexanecarbonylamino)-benzamide, N-isopropyl-3,5-bis-(pivaloylamino)-benzamide, N-isopropyl-3,5- Bis-(isobutyrylamino)-benzamide, N-tert-butyl-3,5-bis-(2,2-dimethylbutyrylamino)-benzamide, N-tert-octyl-3,5-bis-(2,2-dimethylbutyrylamino)-benzamide, 1,6-bis(4-methylcyclohexylamide)hexane, 1,6-bis(4-butylcyclohexylamide)hexane, 1,6,11-tris(4-methylcyclohexylamide)undecane, 1,6,11-tris(4-butylcyclohexylamide)undecane, etc.

[0392] The aforementioned amide compounds can be used alone or in combination of two or more. Furthermore, the crystal morphology of the amide compounds of this invention is not particularly limited as long as the desired effects of this invention are achieved; any crystal morphology such as hexagonal, monoclinic, or cubic can be used.

[0393] As commercially available products, examples include New Japan Rika Co., Ltd.'s Enujestar TF-1 (registered trademark) and PC-1 (registered trademark), and BASF Japan Ltd.'s IRGACLEARXT386 (registered trademark).

[0394] Nucleating agents can be used alone or in combination of two or more.

[0395] The amount of the nucleating agent component is not particularly limited, but is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50 parts by weight, relative to 100 parts by weight of the resin constituting the layer containing the nucleating agent. When the amount added is within the above range, decorative films and decorative molded articles with good transparency and surface smoothness can be obtained.

[0396] [Hindered amine light stabilizers and ultraviolet absorbers]

[0397] For the hindered amine light stabilizers or ultraviolet absorbers (which are additives, but are sometimes specifically referred to as "weather resistant agents" in the following description to distinguish them from other additives) in this invention, there are no particular limitations as long as the aforementioned conditions are met. The molecular weight of the aforementioned hindered amine light stabilizers or ultraviolet absorbers is preferably 490 g / mol or more, more preferably 510 g / mol or more, and even more preferably 550 g / mol or more. By keeping the molecular weight within the aforementioned range, the hindered amine light stabilizers and / or ultraviolet absorbers are less prone to volatilization even under decorative molding conditions. There is no particular limitation on the upper limit of the molecular weight, but 10,000 g / mol or less is practically preferred.

[0398] Specific examples of hindered amine compounds used in this invention include, for instance, poly{[6-〔(1,1,3,3-tetramethylbutyl)amino〕-1,3,5-triazine-2,4-diyl]〔(2,2,6,6-tetramethyl-4-piperidinyl)imino〕hexamethylene〔(2,2,6,6-tetramethyl-4-piperidinyl)imino〕}, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis(2,2,6,6- Tetramethyl-4-piperidinyl)·di(tetrazyl)butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)·di(tetrazyl)butanetetracarboxylate, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaziro[5,5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaziro[5,5]decane Monoalkyl, 1,5,8,12-tetra[4,6-bis{N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamino}-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-triazine / N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine condensate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine / dibromoethane condensate, bis( 2,2,6,6-Tetramethyl-4-oxypiperidinyl) sebacate, tetra(2,2,6,6-tetramethyl-4-oxypiperidinyl)butane-1,2,3,4-tetracarboxylate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate, 3,9-bis(1,1-dimethyl-2-(tris(2,2,6,6-tetramethyl-N-oxypiperidinyl-4-oxocarbonyl)butylcarbonyloxy)ethyl)-2,4,8,10-tetraoxaziro[5,5]undecane, etc.Particularly preferred are poly{[6-〔(1,1,3,3-tetramethylbutyl)amino〕-1,3,5-triazine-2,4-diyl]〔(2,2,6,6-tetramethyl-4-piperidinyl)imino〕hexamethylene〔(2,2,6,6-tetramethyl-4-piperidinyl)imino〕}, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidinyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaziro[5,5]undecane, and tetra(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate.

[0399] Commercially available products include, for example: LA-68 (registered trademark) and LA-57 (registered trademark) manufactured by ADEKA Co., Ltd., and Chimassorb 944 (registered trademark) and Tinuvin 622 (registered trademark) manufactured by BASF Co., Ltd.

[0400] The amount of hindered amine light stabilizer added is preferably 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50 parts by weight, relative to 100 parts by weight of the resin constituting the layer containing the light stabilizer. When the amount added is within the above range, decorative films and decorative molded articles with good weather resistance can be obtained.

[0401] Specific examples of ultraviolet absorbers used in this invention include, for example, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0402] As commercially available products, examples include: LA-31G (registered trademark), LA-46 (registered trademark), and LA-F70 (registered trademark) manufactured by ADEKA Co., Ltd.

[0403] The amount of ultraviolet absorber added is preferably in the range of 0.001 to 1.00 parts by weight, more preferably 0.005 to 0.50 parts by weight, relative to 100 parts by weight of the resin constituting the layer containing the ultraviolet absorber. When the amount added is within the above range, decorative films and decorative molded articles with good weather resistance can be obtained.

[0404] Additionally, it may contain both hindered amine light stabilizers and ultraviolet absorbers. In this case, the combined amount of the two weathering agents is preferably 0.002 to 2.00 parts by weight, more preferably 0.01 to 1.00 parts by weight, relative to 100 parts by weight of the resin constituting the layer containing the weathering agent.

[0405] By maintaining a specific ratio of hindered amine light stabilizer and ultraviolet absorber within a certain range, a higher level of effectiveness can be achieved. For the mixing ratio of the two weather-resistant agents, a hindered amine light stabilizer / ultraviolet absorber ratio of 1 / 5 to 5 / 1 is preferred, and more preferably 1 / 4 to 4 / 1. By including both weather-resistant agents, decorative films and decorative molded articles with better weather resistance can be obtained due to the synergistic effect between them.

[0406] [Layer containing additives]

[0407] The decorative film of the present invention comprises a layer formed of a resin containing at least one additive selected from the above-mentioned nucleating agents, hindered amine light stabilizers, and ultraviolet absorbers. The decorative film may consist solely of the layer containing the additives, or it may be a multilayer structure containing other layers. By including the layer containing the additives, decorative films and decorative molded articles with good gloss variation and / or good weather resistance can be obtained.

[0408] Furthermore, when the additive is a nucleating agent, if the layer containing the nucleating agent is on the surface of the decorative film, a decorative film with good surface smoothness and high gloss can be obtained. Moreover, when the additive is a weather-resistant agent, since light-induced degradation occurs from the surface of the molded body, it is more preferable to include the aforementioned weather-resistant agent in the outermost layer of the decorative film opposite to the bonding surface facing the resin molded body.

[0409] The nucleating agent may be contained in all layers of the decorative film or only in the surface layer of the decorative film, which is the surface of the decorative molded body. For example, in the case of a two-layer decorative film formed of a sealing layer (I) and a layer (II), it is preferable that layer (II) contains a nucleating agent. Furthermore, in the case of a surface decorative layer (III) which is stacked on layer (II) as an arbitrary layer, it is preferable that the surface decorative layer (III) contains a nucleating agent.

[0410] Hindered amine light stabilizers and / or ultraviolet absorbers may be included in all layers of the decorative film or only in the surface layer of the decorative film, which serves as the surface of the decorative molded body. In particular, since light-induced degradation occurs from the surface of the molded body, it is more preferable to include weather-resistant agents in the surface layer of the decorative film. For example, in the case of a two-layer decorative film formed of a sealing layer (I) and a layer (II), it is preferable that layer (II) includes a hindered amine light stabilizer and / or ultraviolet absorber. Furthermore, in the case of a surface decorative layer (III) stacked on layer (II) as an arbitrary layer, it is preferable that surface decorative layer (III) includes a hindered amine light stabilizer and / or ultraviolet absorber.

[0411] [Polyolefin resins]

[0412] From the viewpoints of formability, recyclability, and solvent resistance, the resin constituting the additive-containing layer of the present invention preferably contains 50% by weight or more of a polyolefin resin. More preferably, the aforementioned layer contains 60% by weight or more of a polyolefin resin, and particularly preferably 70% by weight or more. In the present invention, a polyolefin resin refers to a resin containing 50 mol% or more of polymeric units derived from olefin monomers. Furthermore, in the present invention, modified polyolefin is a concept that includes polyolefin resins, referring to a resin containing polymeric units derived from olefin monomers and polymeric units derived from monomers other than those olefin monomers in any proportion.

[0413] Polyolefin resins are preferably homopolymers of α-olefins such as ethylene, propylene, and butene, as well as copolymers of ethylene, propylene, and other α-olefins. Specifically, they include high-density polyethylene, low-density polyethylene, ethylene-α-olefin copolymers, propylene homopolymers (homopolymers), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene). Monomer components other than olefin monomers constituting polyolefin resins include aromatic monomers such as styrene; monomers containing polar groups such as maleic anhydride and acrylic acid; and preferably, polyolefin resins do not contain polymerization units derived from monomers containing polar groups.

[0414] Among these, polypropylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene) are particularly preferred, and combinations thereof may also be selected. The polypropylene resin preferably contains at least 50 mol% of polymerization units derived from propylene monomers. For polypropylene resins, homopolymers are preferred from the viewpoints of oil resistance, solvent resistance, scratch resistance, and heat resistance. Furthermore, propylene-α-olefin copolymers are preferred from the viewpoints of gloss and transparency.

[0415] The polypropylene resin in this invention can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. Specifically, the polypropylene resin can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0416] Provided that the effects of the present invention are not impaired, the resin constituting the layer containing the additives may contain other additives, fillers, other resin components, etc., besides the nucleating agent and weathering agent described above. However, the total amount of other additives, fillers, other resin components, etc., is preferably 50% by weight or less relative to the resin composition.

[0417] As other additives, various known additives such as antioxidants, neutralizers, anti-blocking agents, lubricants, antistatic agents, and metal deactivators can be mixed in. Additionally, as other additives, nucleating agents or weathering agents other than the nucleating agents and weathering agents of this invention can be mixed in, but it is preferable not to mix in such nucleating agents or weathering agents.

[0418] Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and sulfur-based antioxidants. Examples of neutralizing agents include higher fatty acid salts such as calcium stearate and zinc stearate.

[0419] Examples of lubricants include higher fatty acid amides such as stearamide. Examples of antistatic agents include fatty acid partial esters such as glycerol fatty acid monoesters. Examples of metal deactivators include triazine derivatives, phosphonates, epoxy derivatives, triazole derivatives, acylhydrazides, and oxalamide derivatives.

[0420] As a filler, it can be formulated with various fillers, including inorganic and organic fillers. Examples of inorganic fillers include calcium carbonate, silica, hydrotalcite, zeolite, aluminum silicate, magnesium silicate, glass fiber, and carbon fiber. Examples of organic fillers include cross-linked rubber microparticles, thermosetting resin microparticles, and thermosetting resin hollow microparticles.

[0421] Examples of other resin components include styrene-based elastomers, modified polyolefin resins with less than 50 mol% of polymer units derived from olefin monomers, petroleum resins, and other thermoplastic resins.

[0422] In addition, coloring can be applied to impart aesthetic appeal, using various colorants such as inorganic pigments, organic pigments, and dyes. Furthermore, luminescent materials such as aluminum flakes, titanium dioxide flakes, and (synthetic) mica can be used.

[0423] When the decorative molded body of the present invention is formed into a colored molded body, the colorant is only used in the decorative film. Therefore, compared with the case where the entire resin molded body is colored, the use of expensive colorants can be suppressed. In addition, the changes in physical properties associated with the mixing of colorants can be suppressed.

[0424] In this invention, the resin composition containing the above-mentioned additives can be manufactured by the following methods: a method of melt-blending the resin, the aforementioned additives, other additives, fillers, other resin components, etc.; a method of dry-blending the aforementioned additives into a mixture formed by melt-blending the resin, other additives, fillers, other resin components, etc.; a method of dry-blending a masterbatch in which the aforementioned additives, other additives, fillers, other resin components, etc., are dispersed in a carrier resin at a high concentration into the resin, etc.

[0425] [Decorative film]

[0426] The decorative film of this invention comprises a layer containing at least one of the aforementioned additives. That is, the decorative film can be a single-layer film formed from the layer containing the additives, or it can be a multi-layer film composed of the layer containing the additives and other layers. Furthermore, the decorative film of this invention can be subjected to embossing, decals, printing, sandblasting, scratching, etc., on its surface.

[0427] For three-dimensional decorative thermoforming, the shape of the decorative object has a high degree of freedom. The end face of the decorative film is rolled into the back of the decorative object, thus eliminating seams and resulting in an excellent appearance. Furthermore, by applying embossing or other textures to the surface of the decorative film, various textures can be expressed. For example, when applying embossed or other textures to a resin mold, three-dimensional decorative thermoforming can be performed using an embossed decorative film. Therefore, it solves the problem of forming with an embossed mold, namely, that each embossed pattern requires a mold, and that applying complex embossing to a curved mold is very difficult and expensive, and it is possible to obtain decorative molds with embossed patterns that can be easily applied.

[0428] Furthermore, when the additive is a nucleating agent, a decorative film with higher gloss can be obtained when the decorative film is mirror-finished by surface transfer printing on a mirror-shaped cooling roller. Moreover, for the decorative film containing the nucleating agent of the present invention, a decorative molded body that maintains surface gloss and texture, has high surface gloss, and a good appearance can be obtained even after decorative molding.

[0429] As a preferred method for decorative films, in the case of single-layer films, it is preferable to include a resin with excellent thermoforming properties. For example, when the resin constituting the film is a polypropylene-based resin, it is preferable to (i) a resin composition (X) comprising a polypropylene-based resin having a long-branched structure, wherein the melt flow rate (MFR) of the resin composition (X) (temperature 230°C, load 2.16 kg) is 0.1 to 40 g / 10 min and the strain hardening degree λ is 1.1 or more, and / or (ii) a resin composition (Y) comprising a linear polypropylene-based resin, wherein the MFR of the resin composition (Y) is preferably 0.1 to 2.0 g / 10 min. By using resin compositions (X) and / or (Y), a decorative molded body with a good appearance can be obtained.

[0430] A resin composition (X) comprising a polypropylene-based resin having a long-branched structure.

[0431] A resin composition (X) comprising a polypropylene resin having a long branched structure will be described, wherein the polypropylene resin having a long branched structure is preferred as a resin with excellent thermoforming properties.

[0432] (X1) Melt Flow Rate (MFR(X))

[0433] For resin composition (X), if the viscosity is reduced too much, sufficient molding stability cannot be obtained. Therefore, resin composition (X) must have a certain viscosity. In this invention, the MFR (230°C, 2.16kg load) is specified as an indicator of this viscosity.

[0434] In this specification, the MFR (230°C, 2.16 kg load) of the resin composition (X) is defined as MFR(X). MFR(X) preferably satisfies the following necessary condition (x1), more preferably satisfies the necessary condition (x1'), and even more preferably satisfies the necessary condition (x1”). By setting the MFR(X) of the resin composition (X) to a value below the following, a decorative molded article with a good appearance can be obtained.

[0435] (x1)MFR(X) is less than 40g / 10 minutes.

[0436] (x1')MFR(X) is less than 20g / 10 minutes.

[0437] (x1”)MFR(X) is less than 12g / 10 minutes.

[0438] There is no particular limitation on the lower limit of the MFR(X) of the resin composition (X), but it is preferably 0.1 g / 10 min or more, and more preferably 0.3 g / 10 min or more. By setting the MFR(X) to the above value or above, the formability during the manufacture of the decorative film is improved, thereby suppressing the appearance defects on the film surface, which are called shark skin and have rough interfaces.

[0439] In this invention, the MFR of polypropylene resins and polypropylene resin compositions is determined according to ISO 1133:1997 Conditions M, under conditions of 230°C and a load of 2.16 kg. The unit is g / 10 minutes.

[0440] (X2) Strain hardening degree λ

[0441] The strain hardening degree λ of the resin composition (X) preferably satisfies the following necessary condition (x2), more preferably satisfies the necessary condition (x2'), and even more preferably satisfies the necessary condition (x2”). By setting the strain hardening degree λ of the resin composition (X) to a value within the following range, the formability during decorative thermoforming is good, and decorative molded articles with excellent appearance can be obtained.

[0442] (x2) The strain hardening degree λ is 1.1 or higher.

[0443] (x2') The strain hardening degree λ is 1.8 or higher.

[0444] (x2”) The strain hardening degree λ is 2.3 or higher.

[0445] There is no particular upper limit to the strain hardening degree λ of the resin composition (X), but it is preferably 50 or less, more preferably 20 or less. By setting the strain hardening degree λ to a value within the above range, the decorative film can achieve a good appearance.

[0446] The strain hardening degree λ of polypropylene resins and resin compositions (X) is determined based on the strain hardening property measured in tensile viscosity determination. The strain hardening property (nonlinearity) of tensile viscosity is described in "Lectures on Rheology," edited by the Japanese Society for Rheology, Polymer Industry Press, 1992, pp. 221-222. In this specification, the strain hardening property is determined based on that book. Figure 7-2 The strain hardening degree λ is calculated using the method illustrated in Figure 0, and is used as the value of the shear viscosity, employing η. * (0.01), as the value of tensile viscosity, is ηe(3.5), and the strain hardening degree λ is defined by the following equation (k-1).

[0447] λ=ηe(3.5) / {3×η * (0.01)} Equation (k-1)

[0448] In the above equation (k-1), η * (0.01) represents the complex viscosity [unit: Pa·s] determined by a dynamic frequency scanning experiment at a measurement temperature of 180℃ and an angular frequency of ω = 0.01 rad / s. The complex viscosity η * According to the complex modulus G * [Unit: Pa] and angular frequency ω, through η * =G * The value is calculated using / ω. Additionally, ηe(3.5) is determined by tensile viscosity measurement at a temperature of 180°C and a strain rate of 1.0 s⁻¹. -1 , Tensile viscosity at strain 3.5.

[0449] Typically, the data obtained through these viscoelastic measurements are a collection of discrete values ​​such as elastic modulus and viscosity at various frequencies or measurement time intervals. Therefore, when measurements are performed under different apparatus and conditions than those used in this invention, the complex viscosity η at an angular frequency ω = 0.01 rad / s may not always be available. * The data for tensile viscosity ηe(3.5) under strain 3.5 (0.01) allows for estimation of equivalent values ​​by using data before and after the strain and performing interpolation such as linear interpolation and spline interpolation. When performing interpolation, the stress and time scales are conventionally expressed using a logarithmic scale.

[0450] In this case, if the tensile viscosity does not exhibit strain hardening (nonlinearity), the strain hardening degree λ represents a value of about 1 (e.g., greater than 0.9 but less than 1.1) or smaller. The stronger the strain hardening (nonlinearity), the larger the value of the strain hardening degree λ becomes.

[0451] Typical crystalline polypropylene is a linear polymer and generally does not exhibit strain hardening properties. In contrast, the polypropylene resin suitably used in this invention is preferably a polypropylene resin (BL) with a long-branched structure, thereby enabling the resin composition (X) to exhibit good strain hardening properties.

[0452] The long branched structure in this invention refers to a branched structure based on a molecular chain formed by a carbon skeleton (main chain of the branch) having a carbon number of tens or more and a molecular weight of hundreds or more. This long branched structure is distinguished from the short branched structure formed by copolymerization with α-olefins such as 1-butene.

[0453] Methods for introducing long-branched structures into polypropylene resins include: irradiating polypropylene without long-branched structures with high-energy ionizing radiation (Japanese Patent Application Publication No. 62-121704); reacting polypropylene without long-branched structures with organic peroxides (Japanese Patent Application Publication No. 2001-524565); and manufacturing macromonomers with terminal unsaturated bonds and copolymerizing them with propylene (Japanese Patent Application Publication No. 2001-525460). Even when any method is used, the strain hardening degree λ of the polypropylene resin can be increased.

[0454] Polypropylene resins (BL) with long-branched structures are not particularly limited as long-branched structures are preferred, but those manufactured by methods other than crosslinking are preferred. Preferably, they are obtained by copolymerization of macromonomers that form long-branched structures during polymerization and have a comb-like chain structure. Examples of such methods include those disclosed in Japanese Patent Application Publication Nos. 2001-525460, 2002-523575, 2009-57542, 5027353, and 10-338717. In particular, the macromonomer copolymerization method in Japanese Patent Application Publication No. 2009-57542 does not produce gel and can yield polypropylene resins (BL) containing long branches, making it suitable for this invention.

[0455] For polypropylene with long branched structures, methods based on resin rheological properties, methods using the relationship between molecular weight and viscosity to calculate the branching index g', and methods using... 13The method is defined by C-NMR, etc. In this invention, it is defined as follows by the branching index g' and / or 13 C-NMR is used to define long-branched structures.

[0456] {branch index g'}

[0457] The branching index g' is known as a direct indicator of long branched structures. It is described in detail in "Developments in Polymer Characterization-4" (JV Dawkinsed. Applied Science Publishers, 1983), but the definition of the branching index g' is as follows.

[0458] Branching index g' = [η]br / [η]lin

[0459] [η]br: Intrinsic viscosity of polymers (br) with long branched chains.

[0460] [η]lin: The intrinsic viscosity of a linear polymer with the same molecular weight as polymer (br).

[0461] As clearly stated in the definition above, if the branching index g' takes a value less than 1, it is determined that there is a long branching structure. The more long branching structures there are, the smaller the value of the branching index g' becomes.

[0462] The branching index g' can be obtained as a function of the absolute molecular weight Mabs by using a GPC detector equipped with a light scattering meter and a viscometer. The method for determining the branching index g' in this invention is detailed in Japanese Patent Application Publication No. 2015-40213, as follows.

[0463] {Determination Method}

[0464] GPC: AllianceGPCV2000 (Made by Waters Corporation)

[0465] Detectors: Recorded in connection order

[0466] Multi-angle laser scattering detector (MALLS): DAWN-E (manufactured by Wyatt Technology)

[0467] Differential refractometer (RI): GPC accessory

[0468] Viscometer: GPC accessory

[0469] Mobile compatibilizer: 1,2,4-trichlorobenzene (added at a concentration of 0.5 mg / mL with Irganox 1076)

[0470] Mobile phase flow rate: 1 mL / min

[0471] Column: Connect two GMHHR-H(S)HT steel rods manufactured by Tosoh Corporation.

[0472] Sample injection temperature: 140℃

[0473] Column temperature: 140℃

[0474] Detector temperature: 140℃

[0475] Sample concentration: 1 mg / mL

[0476] Injection volume (sample loop capacity): 0.2175 mL

[0477] {Analysis Method}

[0478] When determining the absolute molecular weight (Mabs), mean square radius of gyration (Rg), and limiting viscosity ([η]) obtained from the multi-angle laser scattering detector (MALLS), the calculations were performed using the data processing software ASTRA (version 4.73.04) associated with MALLS, with reference to the following literature.

[0479] References:

[0480] 1. "Developments in Polymer Characterization-4" (JVDawkinsed.AppliedSciencePublishers,1983.Chapter1.)

[0481] 2. Polymer, 45, 6495-6505 (2004)

[0482] 3.Macromolecules,33,2424-2436(2000)

[0483] 4.Macromolecules,33,6945-6952(2000)

[0484] In the decorative film of the present invention, if the polypropylene resin or resin composition (X) having a long branched structure contains gel, the appearance of the film deteriorates. Therefore, it is preferable to use a polypropylene resin or resin composition (X) that does not contain gel. In particular, as the aforementioned polypropylene resin (BL) having a long branched structure, it is preferable to manufacture it by using a metallocene catalyst with a specific structure to produce a macromonomer with terminal unsaturated bonds, and copolymerizing it with propylene to form a long branched structure. In particular, it is preferable that the branching index g' when the absolute molecular weight Mabs is 1 million, as described below, is 0.3 or more and less than 1.0, more preferably 0.55 or more and less than 0.98, further preferably 0.75 or more and less than 0.96, and most preferably 0.78 or more and less than 0.95. In the present invention, "less gel" means that the branching index g' of the polypropylene resin with an absolute molecular weight Mabs of 1 million is within the above range. When the branching index g' is within this range, highly cross-linked components will not form, no gel will be formed, or very little gel will be formed. Therefore, especially in the case of the surface of a layered article containing polypropylene resin (BL), the appearance will not be deteriorated.

[0485] { 13 C-NMR}

[0486] 13 C-NMR can distinguish between short-branched and long-branched structures. This is explained in detail in Macromol.Chem.Phys.2003, vol.204, 1738, and is summarized below.

[0487] Polypropylene resins with long branched chains have a specific branched structure as shown in the following structural formula (1). In structural formula (1), C a C b and C c The C represents the methylene carbon adjacent to the branched carbon. br P represents the methylene carbon at the root of the branch chain. 1 P 2 and P 3 This indicates propylene polymer residues.

[0488] For propylene polymer residue P 1 P 2 and P 3 It may also contain C as described in structural formula (1). br Different branched carbons (C br ).

[0489]

[0490] Such a branched structure through 13Identification was performed using C-NMR analysis. The assignment of each peak can be referenced to the description in Macromolecules, Vol. 35, No. 10, 2002, pp. 3839-3842. Specifically, one methylene carbon (C10) was observed at each of the following three ppm values: 43.9–44.1 ppm, 44.5–44.7 ppm, and 44.7–44.9 ppm. a C b and C c Methylene carbon (C) was observed at 31.5–31.7 ppm. br The methylene carbon observed at 31.5–31.7 ppm above will sometimes be referred to simply as branched methylene carbon (C). br ).

[0491] Polypropylene resins with long branched chains 13 The spectral characteristics of C-NMR are: observation of carbon C of the branched methine chain. br The three closely spaced methylene carbons were diastereoisomerically and nonequivalently divided into three groups.

[0492] 13 In C-NMR, such branches represent propylene polymer residues with 5 or more carbon atoms branching from the main chain of polypropylene resins. They can be distinguished from branches with 4 or fewer carbon atoms by the different peak positions of the branched carbons. Therefore, in this invention, by confirming the peak of the methylene carbon in the branch, the presence or absence of long branched structures can be determined.

[0493] It should be noted that, regarding the present invention 13 The method for C-NMR determination is as follows.

[0494] { 13 C-NMR determination method}

[0495] 200 mg of sample, 2.4 ml of o-dichlorobenzene / deuterated brominated benzene (C6D5Br) = 4 / 1 (volume ratio), and hexamethyldisiloxane as the chemical shift reference were placed together in the inner diameter Dissolved in the NMR sample tube and subjected to NMR analysis. 13 C-NMR determination.

[0496] for 13 C-NMR measurements were performed using a device equipped with... The cryoprobe was used in an AV400M NMR instrument from Bruker BioSpin Co., Ltd.

[0497] The determination was carried out at a sample temperature of 120℃ using the complete proton decoupling method. Other conditions are as follows.

[0498] Pulse angle: 90°

[0499] Pulse interval: 4 seconds

[0500] Total number of times: 20,000

[0501] For chemical shifts, the peak of the methyl carbon in hexamethyldisiloxane was set at 1.98 ppm, with the chemical shifts of other carbon peaks based on this.

[0502] The amount of long-chain branches can be calculated using the peak around 44 ppm.

[0503] For polypropylene resins (BL) with long branched chains 13 According to the C-NMR spectrum, the amount of long-branched chains quantified based on the peak around 44 ppm is preferably 0.01 or more per 1000 total propylene atoms, more preferably 0.03 or more per 1000 total propylene atoms, and even more preferably 0.05 or more per 1000 total propylene atoms. If this value is too high, it will cause poor appearance such as gelling or fish-eyes. Therefore, it is preferably 1.00 or less per 1000 total propylene atoms, more preferably 0.50 or less per 1000 total propylene atoms, and even more preferably 0.30 or less per 1000 total propylene atoms.

[0504] For such a polypropylene resin (BL) with a long branched structure, the resin composition (X) only needs to contain an amount sufficient to impart strain hardening properties. Preferably, the polypropylene resin (BL) with a long branched structure contains 1 to 100% by weight, and more preferably 5% by weight or more, in 100% by weight of the resin composition (X).

[0505] For the polypropylene resin (BL) with a long branched structure in this invention, various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof, can be selected. Preferably, the polypropylene resin contains at least 50 mol% polymeric units derived from propylene monomers.

[0506] Resin composition (Y) comprising linear polypropylene resin.

[0507] A resin composition (Y) comprising a linear polypropylene resin is described, wherein the linear polypropylene resin is preferably a resin with excellent thermoforming properties.

[0508] The MFR (230°C, 2.16 kg load) of the resin composition (Y) containing a suitable linear polypropylene resin of the present invention is preferably 2.0 g / 10 min or less, more preferably 1.5 g / 10 min or less, and even more preferably 1.0 g / 10 min or less. By setting the MFR of the resin composition (Y) to the above-mentioned value or less, a decorative molded article with a good appearance can be obtained.

[0509] There is no particular limitation on the lower limit of the MFR of the resin composition (Y), but it is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. By setting the MFR to the above value or above, the formability during the manufacture of the decorative film is improved, and the appearance defects such as sharkskin-like roughness on the film surface can be suppressed.

[0510] As another preferred embodiment of the decorative film, in the case of a multilayer film, it may include: a surface layer, a surface decorative layer, a printing layer, a light-shielding layer, a coloring layer, a substrate layer, a sealing layer, a barrier layer, and a tie layer that can be disposed between these layers. The additive-containing layer of the present invention can be any layer constituting the multilayer film. Furthermore, multiple layers may contain the aforementioned additive, or all layers may contain the aforementioned additive. Wherein, if the additive is a weather-resistant agent, light-induced degradation occurs from the surface of the molded body; therefore, it is more preferable that the weather-resistant agent is contained in the outermost layer of the decorative film opposite to the bonding surface facing the resin molded body.

[0511] In multilayer films, layers other than the layers containing additives are preferably layers containing thermoplastic resins, and more preferably layers containing polypropylene-based resins. In the case of polypropylene-based resins, various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof, can be selected. Each layer is preferably a layer that does not contain thermosetting resins. By using thermoplastic resins, recyclability is improved. Furthermore, by using polypropylene-based resins, the complexity of the layer composition can be suppressed, and co-extrusionability and recyclability are further improved.

[0512] For example, in the case of a multilayer film consisting of two layers, the decorative film may consist of two layers: a surface layer that forms the surface of the decorative molded body and a substrate layer that is bonded to the molded body; or a substrate layer that forms the surface of the decorative molded body and a sealing layer that is bonded to the molded body. Furthermore, in the case of a multilayer film consisting of three layers, it may consist of three layers: a surface layer that forms the surface of the decorative molded body, a sealing layer that is bonded to the molded body, and a substrate layer inserted between the surface layer and the sealing layer. Furthermore, it may be a multilayer film with complex layers, wherein at least one layer constituting the multilayer film contains the aforementioned additive.

[0513] For decorative films, the outermost layer, opposite to the bonding surface facing the resin molded body, preferably contains at least one additive selected from nucleating agents, hindered amine light stabilizers, and ultraviolet absorbers. For example, when the decorative film consists of a surface layer and a substrate layer, the surface layer preferably contains the aforementioned additive; when the decorative film consists of a substrate layer and a sealing layer, the substrate layer preferably contains the aforementioned additive; and when the decorative film consists of three layers—a surface layer, a substrate layer, and a sealing layer—the surface layer preferably contains the aforementioned additive. Furthermore, when the film consists of three layers—a surface decorative layer, a substrate layer, and a sealing layer—the surface decorative layer preferably contains the aforementioned additive.

[0514] [Substrate Layer]

[0515] In this invention, the substrate layer refers to the thickest layer in the decorative film. When the decorative film is a single-layer film, its layer is the substrate layer. When the resin constituting the substrate layer of the decorative film of this invention is a polypropylene-based resin, similarly to the case of a single-layer film, it is preferable that the substrate layer comprises resin composition (X) and / or (Y). This results in good thermoformability, enabling the production of decorative molded articles with excellent appearance.

[0516] [Surface layer and surface decorative layer]

[0517] In this invention, the surface layer and the surface decorative layer refer to the outermost layer, which is different from the substrate layer, and constitutes the outermost layer opposite to the bonding surface facing the resin molded body. The surface layer and the surface decorative layer can be directly applied to the substrate layer, or they can be applied after inserting one or more other layers into the substrate layer. Here, the surface decorative layer refers to a surface layer containing nucleating agents, colorants, etc., to improve the transparency, surface gloss, appearance, etc. of the decorative film.

[0518] When the resin constituting the surface layer or surface decoration layer of the decorative film of the present invention is a polypropylene-based resin, the MFR (230°C, 2.16 kg load) is preferably more than 2.0 g / 10 min, more preferably 5.0 g / 10 min or more, and even more preferably 9.0 g / 10 min or more. By setting the MFR of the polypropylene-based resin within the above-mentioned range, effects such as improved surface smoothness, gloss, and embossing transferability of the decorative film can be obtained, resulting in a decorative molded body with a good appearance regarding the desired surface shape (gloss, non-gloss, embossed, etc.). Furthermore, the surface transferability during the manufacturing and thermoforming of the decorative film is improved, and when a mirror roller is used during thermoforming, a decorative film with higher gloss can be produced. There is no particular limitation on the upper limit of the MFR, but it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less. By setting the MFR within the above-mentioned range, good oil resistance, solvent resistance, and scratch resistance can be achieved.

[0519] [Sealing layer]

[0520] In this invention, the sealing layer refers to the outermost layer on the bonding side of the decorative film, which is different from the substrate layer and is used to improve the adhesion to the resin molded body. The resin constituting the sealing layer of the decorative film of this invention can be selected from common thermoplastic resins, such as polyethylene resins, polypropylene resins, ethylene elastomers and other polyolefins, modified polyolefins, styrene elastomers, petroleum resins, etc., and combinations thereof. As modified polyolefins, resins containing polymer units derived from monomers with polar groups such as maleic anhydride and polymer units derived from olefin monomers in any proportion can be listed. For example, when the sealing layer of this invention is a polypropylene resin, from the perspective of adhesion, the resin's MFR (230°C, 2.16 kg load) is preferably 0.1 g / 10 min or more, more preferably 0.4 g / 10 min or more, and even more preferably 2.0 g / 10 min or more. There is no particular limitation on the upper limit of the MFR, but it is preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less. By setting the MFR to the range of values ​​mentioned above, good adhesion can be achieved.

[0521] Figure 8 (a) to (c) are schematic cross-sectional explanatory views illustrating embodiments of decorative films attached to resin molded bodies. Figure 8 In (a) to (c), the configuration of the sealing layer (I) and the substrate layer (II) is described in a specific manner for ease of understanding, but the layer composition of the decorative film is not limited to these examples. In this specification, reference numeral 1 in the figures indicates the decorative film, reference numeral 2 indicates the substrate layer (II), reference numeral 3 indicates the sealing layer (I), reference numeral 4 indicates the surface decoration layer (III), and reference numeral 5 indicates the resin molded body. Figure 8 (a) is an example of a decorative film 1 comprising two films, with a sealing layer (I) 3 attached to a resin molded body 5 and a substrate layer (II) 2 stacked on the sealing layer (I) 3. Figure 8 The decorative film 1 of (b) includes a sealing layer (I) 3, a substrate layer (II) 2 and a surface layer. The sealing layer (I) 3 is attached to the surface of the resin molded body 5, and the substrate layer (II) 2 and the surface layer are stacked on the sealing layer (I) 3 in sequence. Figure 8 The decorative film 1 of (c) includes a sealing layer (I) 3, a substrate layer (II) 2 and a surface decorative layer (III) 4. The sealing layer (I) 3 is attached to the surface of the resin molded body 5, and the substrate layer (II) 2 and the surface decorative layer (III) 4 are sequentially stacked on the sealing layer (I) 3.

[0522] Each layer may contain other additives, fillers, colorants, and other resin components besides those mentioned above. The total amount of other additives, fillers, colorants, and other resin components is preferably 50% by weight or less relative to the resin composition. The aforementioned additives can be used as other additives.

[0523] The resin composition constituting each layer can be manufactured by the following methods: a method of melt-blending the resin with the aforementioned additives, other additives, fillers, colorants, and other resin components; a method of dry-blending other resin components into a mixture formed by melt-blending the resin, the aforementioned additives, other additives, fillers, colorants, etc.; and a method of dry-blending a masterbatch in which the aforementioned additives, other additives, fillers, colorants, etc., are dispersed in a high concentration in a carrier resin, based on the resin and other resin components.

[0524] {Third to Sixth Embodiments of the Invention}

[0525] In three-dimensional decorative thermoforming, in order to adhere a solid decorative film to a solid resin molded body, the surface of the molded body and the film must be sufficiently softened or melted. Therefore, it is important to apply the heat required to soften or melt the surface of the molded body and the film, or to use a molded body and film that are easy to soften or melt. On the other hand, if the film is overheated, the viscosity of the film decreases, and due to the protrusion of the molded body during the three-dimensional decorative thermoforming process or the inflow of air when restoring the vacuum chamber to atmospheric pressure, the film breaks and becomes rough, resulting in poor appearance. The inventors have studied the mechanism that causes the above-mentioned poor appearance and found that decorative films containing a layer of a specific polypropylene resin can solve the aforementioned problems.

[0526] For the decorative film of the third to sixth embodiments of the present invention, the aforementioned decorative film comprises: a layer containing at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, such that the decorative film further comprises a sealing layer with good adhesion, thereby enabling decorative forming at low temperature and in a short time, and allowing the decorative forming to be completed before the aforementioned additives evaporate, thereby further suppressing the reduction of surface gloss and / or weather resistance.

[0527] According to the third to sixth aspects of the present invention, it is possible to provide decorative films that can be used for three-dimensional decorative thermoforming, and a method for manufacturing decorative molded articles using the same, which have the following characteristics: no uneven contact, excellent thermoformability, good surface gloss and / or weather resistance, good adhesion, suppression of the reduction of surface gloss and / or weather resistance before and after thermoforming, and excellent recyclability.

[0528] According to the manufacturing method of the decorative molded body of the third to sixth aspects of the present invention, no air is involved between the decorative film and the resin molded body, and a decorative molded body with good reproducibility of textures such as embossing and a beautiful appearance can be obtained. For the decorative molded body obtained by such an operation, the constituent material of the decorative film is a polypropylene-based resin, and since it does not contain or may not contain a thermosetting resin layer, even if it is recycled, the reduction in appearance and performance is small and the recyclability is high.

[0529] Hereinafter, the description will be divided into the third and fourth aspects and the fifth and sixth aspects.

[0530] {{The third and fourth aspects of the present invention}}

[0531] The decorative film of the third and fourth aspects of the present invention is characterized in that the decorative film includes: a layer containing at least one additive selected from a nucleating agent, a hindered amine light stabilizer, and an ultraviolet absorber, and the decorative film includes: a sealing layer (I) containing a polypropylene-based resin (A) and a layer (II) containing a polypropylene-based resin (B), and the aforementioned polypropylene-based resin (A) satisfies the following necessary condition (a1), and the aforementioned polypropylene-based resin (B) satisfies the following necessary condition (b1).

[0532] (a1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(A)) exceeds 0.5 g / 10 minutes.

[0533] (b1) The melt flow rate (at 230 °C, 2.16 kg load) (MFR(B)) and MFR(A) satisfy the relational expression (b-1).

[0534] MFR(B) < MFR(A) ··· Formula (b-1)

[0535] In the first embodiment, it is preferable that the aforementioned polypropylene-based resin (A) further satisfies the following necessary conditions (a2) to (a4), and the aforementioned polypropylene-based resin (B) further satisfies the following necessary condition (b2).

[0536] (a2) It is a metallocene catalyst-based propylene polymer.

[0537] (a3) The melting peak temperature (Tm(A)) is lower than 150 °C.

[0538] (a4) The molecular weight distribution (Mw / Mn(A)) measured by GPC is 1.5 to 3.5.

[0539] (b2) The melting peak temperature (Tm(B)) and Tm(A) satisfy the relational expression (b-2).

[0540] Tm(B) > Tm(A) ··· Formula (b-2)

[0541] In the second embodiment, the aforementioned polypropylene resin (A) is preferably satisfied with the following necessary condition (a5), and the aforementioned polypropylene resin (B) is satisfied with the following necessary condition (b3).

[0542] (a5) Crystallization temperature (Tc(A)) is below 100℃.

[0543] (b3) The crystallization temperature (Tc(B)) and Tc(A) satisfy the relationship (b-3).

[0544] Tc(B)>Tc(A)···Equation (b-3)

[0545] In the third embodiment, the aforementioned sealing layer (I) preferably comprises a resin composition (XX3) of a weight ratio of polypropylene resin (A) to ethylene-α-olefin random copolymer (C) of 97:3 to 5:95, wherein the aforementioned ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c1) to (c3).

[0546] (c1) Ethylene content [E(C)] is 65% by weight or more.

[0547] (c2) Density is 0.850~0.950 g / cm³ 3 .

[0548] (c3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[0549] In the fourth embodiment, the aforementioned sealing layer (I) preferably comprises a resin composition (XX4) in which the weight ratio of polypropylene resin (A) to thermoplastic elastomer (D) is 97:3 to 5:95, and the aforementioned thermoplastic elastomer (D) satisfies the following necessary conditions (d1) to (d4).

[0550] (d1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[0551] (d2) Density is 0.850~0.950 g / cm³ 3 .

[0552] (d3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[0553] (d4) has a smaller tensile modulus than polypropylene resin (A).

[0554] In the fifth embodiment, the aforementioned sealing layer (I) preferably comprises a resin composition (XX5) in which the weight ratio of polypropylene resin (A) to thermoplastic resin (E) is 97:3 to 5:95, wherein the aforementioned thermoplastic resin (E) satisfies the following necessary condition (e1), and the aforementioned resin composition (XX5) satisfies the following necessary condition (xx1).

[0555] (e1) Contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0556] (xx1) The isothermal crystallization time (t(XX5)) (seconds) of the resin composition (XX5) determined by differential scanning calorimetry (DSC) satisfies the following formula (x-1).

[0557] t(XX5)≥1.5×t(A)···Equation (x-1)

[0558] In the formula, t(A) represents the isothermal crystallization time (in seconds) of polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A), and t(XX5) represents the isothermal crystallization time (in seconds) of resin composition (XX5) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A).

[0559] In the sixth embodiment, the aforementioned polypropylene resin (A) is preferably a propylene-ethylene block copolymer (F) that satisfies the following necessary conditions (f1) and (f2).

[0560] (f1) The melting peak temperature (Tm(F)) is 110~170℃.

[0561] (f2) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[0562] The decorative film in the third and fourth embodiments of the present invention includes a sealing layer (I) comprising a resin composition (XX) containing a polypropylene-based resin (A). The sealing layer (I) is a layer that contacts the resin molded body (matrix) during three-dimensional decorative thermoforming. By providing the sealing layer (I), good adhesion is exhibited even when the forming time of three-dimensional decorative thermoforming is shortened, thus enabling forming to be completed before the nucleating agent and / or weathering agent evaporates, thereby suppressing the reduction of surface gloss and / or weather resistance.

[0563] Hereinafter, the structure of the sealing layer (I) will be specifically described using the basic implementation method described above and the first to sixth implementation methods as examples.

[0564] <Basic Implementation Method of Sealing Layer (I)>

[0565] In the basic embodiments of the third and fourth aspects of the present invention, the sealing layer (I) contains a polypropylene resin (A). In the basic embodiments, the polypropylene resin (A) is preferably a resin that is easily relaxable. By providing such a sealing layer (I) containing a polypropylene resin (A), good adhesion is exhibited even when the molding time of the three-dimensional decorative thermoforming is shortened, thus making it easier to suppress the reduction of surface gloss and / or weather resistance by completing the molding before the nucleating agent and / or weather-resistant agent evaporates.

[0566] Polypropylene Resins (A)

[0567] 1. Melt flow rate (MFR(A)): (a1)

[0568] In the basic embodiment, the melt flow rate (MFR) of the polypropylene resin (A) (at 230°C and 2.16 kg load) is preferably greater than 0.5 g / 10 min, more preferably greater than 1 g / 10 min, and particularly preferably greater than 2 g / 10 min. Within the aforementioned range, relaxation during three-dimensional decorative thermoforming is sufficient, making it easier to achieve adequate bond strength. There is no upper limit to the MFR (A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of bond strength due to reduced physical properties will not occur.

[0569] 2. Resin Composition

[0570] The polypropylene resin (A) in the basic embodiment can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0571] In the basic embodiment, the polypropylene resin (A) can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0572] <First Implementation>

[0573] In the first embodiment, the sealing layer (I) comprises a resin composition (XX1) containing a polypropylene-based resin (A). In the first embodiment, the polypropylene-based resin (A) is preferably a resin that is easy to melt and relax. By providing a sealing layer (I) containing a resin composition (XX1) containing a polypropylene-based resin (A), good adhesion is exhibited even when the molding time of three-dimensional decorative thermoforming is shortened. Therefore, molding is completed before the nucleating agent and / or weather-resistant agent evaporates, making it easier to suppress the reduction of surface gloss and / or weather resistance.

[0574] Polypropylene Resins (A)

[0575] 1. Melt flow rate (MFR(A)): (a1)

[0576] In the first embodiment, the melt flow rate (MFR(A)) of the polypropylene resin (A) at 230°C and 2.16 kg load is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. Within the aforementioned range, relaxation during three-dimensional decorative thermoforming is sufficient, making it easier to achieve adequate adhesive strength. There is no upper limit to the MFR(A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of adhesive strength due to reduced physical properties will not occur.

[0577] 2. Molecular weight distribution (Mw / Mn(A)): (a4)

[0578] The Mw / Mn ratio of the polypropylene resin (A) is preferably 1.5 to 3.5, more preferably 2.0 to 3.0. Within the aforementioned range, there are fewer components with relatively long relaxation times, relaxation is easier to achieve, surface roughness is less likely to occur during film forming, and the surface appearance is excellent, thus making it preferable.

[0579] It should be noted that Mn and Mw are recorded in "Fundamentals of Polymer Chemistry" (edited by the Polymer Society, Tokyo Chemical Association, 1978), etc., and are values ​​calculated based on molecular weight distribution curves based on GPC.

[0580] 3. Melting peak temperature (Tm(A)): (a3)

[0581] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point" in this specification) (Tm(A)) of the polypropylene resin (A) is preferably below 150°C, more preferably below 145°C, even more preferably below 140°C, and particularly preferably below 130°C. Within the aforementioned range, sufficient adhesive strength can be achieved. If Tm(A) is excessively reduced, heat resistance may decrease, causing problems in the use of the molded article; therefore, it is preferably above 100°C, more preferably above 110°C.

[0582] 4. Resin composition: (a2)

[0583] The polypropylene resin (A) in the first embodiment is preferably a so-called metallocene catalyst-based propylene polymer polymerized using a metallocene catalyst. Because metallocene catalysts have a single active site, propylene polymers polymerized using metallocene catalysts have narrow molecular weight distributions and crystallinity distributions, and are easily melted and relaxed, thus enabling fusion with the matrix without applying a large amount of heat.

[0584] The polypropylene resin (A) in the first embodiment can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0585] From an adhesive point of view, propylene-α-olefin copolymers are preferred for polypropylene-based resins (A). For propylene-α-olefin copolymers, compared to propylene homopolymers, the crystallization temperature generally decreases with decreasing melting point, thus exhibiting good adhesiveness even with shortened molding time for three-dimensional decorative thermoforming. This allows molding to be completed before the nucleating agent and / or weather-resistant agent evaporates, suppressing the reduction in surface gloss and / or weather resistance.

[0586] As an α-olefin, one or more combinations of ethylene and α-olefins having 3 to 8 carbon atoms may be used.

[0587] <Second Implementation Method>

[0588] In the second embodiment, the sealing layer (I) comprises a resin composition (XX2) containing a polypropylene-based resin (A). In the second embodiment, the polypropylene-based resin (A) is preferably a resin with a late crystallization start. By providing a sealing layer (I) comprising a resin composition (XX2) containing a polypropylene-based resin (A), good adhesion is maintained even with a shortened molding time for three-dimensional decorative thermoforming. Therefore, molding is completed before the nucleating agent and / or weather-resistant agent evaporates, making it easier to suppress the reduction of surface gloss and / or weather resistance.

[0589] [Polypropylene Resin (A)]

[0590] 1. Melt flow rate (MFR(A)): (a1)

[0591] In the second embodiment, the melt flow rate (MFR(A)) of the polypropylene resin (A) at 230°C and 2.16 kg load is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. Within the aforementioned range, relaxation during three-dimensional decorative thermoforming is sufficient, making it easier to achieve adequate adhesive strength. There is no upper limit to the MFR(A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of adhesive strength due to reduced physical properties will not occur.

[0592] 2. Molecular weight distribution (Mw / Mn(A))

[0593] The Mw / Mn ratio of the polypropylene resin (A) is preferably 3.5 to 10, more preferably 3.7 to 7. Within the aforementioned range, surface roughness is less likely to occur during film forming, resulting in an excellent surface appearance, and is therefore preferred.

[0594] 3. Crystallization temperature (Tc(A)): (a5)

[0595] The crystallization temperature Tc(A) of the polypropylene resin (A) is preferably below 100°C, more preferably below 97°C, and even more preferably below 93°C. Within the aforementioned range, sufficient adhesive strength is achieved. If Tc(A) is excessively reduced, heat resistance may decrease, causing problems in the use of the molded article; therefore, Tc(A) is preferably 65°C or higher, more preferably 75°C or higher.

[0596] 4. Resin Composition

[0597] The polypropylene resin (A) in the second embodiment can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0598] In the second embodiment, the polypropylene resin (A) can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0599] From an adhesive point of view, propylene-α-olefin copolymers are preferred for polypropylene-based resins (A). Propylene-α-olefin copolymers generally exhibit lower crystallization temperatures compared to propylene homopolymers, and even with shorter molding times for three-dimensional decorative thermoforming, they readily demonstrate good adhesiveness. This allows molding to be completed before the nucleating agent and / or weather-resistant agent evaporates, making it easier to suppress the reduction in surface gloss and / or weather resistance.

[0600] As an α-olefin, one or more combinations of ethylene and α-olefins having 3 to 8 carbon atoms may be used.

[0601] <Third Implementation Method>

[0602] In the third embodiment, the sealing layer (I) comprises a resin composition (XX3) containing a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C). By providing such a sealing layer (I) containing the resin composition (XX3), sufficient adhesive strength can be easily achieved even with a shortened film heating time during three-dimensional decorative thermoforming.

[0603] Polypropylene Resins (A)

[0604] The polypropylene resin (A) in the third embodiment can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0605] 1. Melt flow rate (MFR(A)): (a1)

[0606] The melt flow rate (MFR) of the polypropylene resin (A) contained in the sealing layer (I) (at 230°C and 2.16 kg load) is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. Within the aforementioned range, sufficient relaxation occurs during the thermoforming of the three-dimensional decorative material, making it easier to achieve sufficient adhesive strength. There is no upper limit to the MFR (A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of adhesive strength due to reduced physical properties will not occur.

[0607] 2. Melting peak temperature (Tm(A))

[0608] The melting peak temperature (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, the formability during three-dimensional decorative thermoforming is good. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[0609] 3. Resin Composition

[0610] In the third embodiment, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0611] Ethylene-α-olefin random copolymer (C)

[0612] The ethylene-α-olefin random copolymer (C) used in the sealing layer (I) of the third embodiment has the following necessary conditions (c1) to (c3), and preferably has the necessary conditions (c4) to (c5).

[0613] 1. Ethylene content [E(C)]: (c1)

[0614] In the third embodiment, the ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) is preferably 65% ​​by weight or more, more preferably 68% by weight or more, and even more preferably 70% by weight or more, relative to the total amount of the ethylene-α-olefin random copolymer (C). Within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming, and the heating time of the film can be shortened. There is no particular upper limit to the ethylene content [E(C)], but it is preferably 95% by weight or less.

[0615] (Method for calculating ethylene content [E(C)])

[0616] The ethylene content [E(C)] of the ethylene-α-olefin random copolymer (C) can be determined by... 13 The integral intensity measured by C-NMR is used to determine the result.

[0617] (Calculate Method 1 (Binary System))

[0618] First, the method for calculating the ethylene content [E(C)] in a binary copolymer composed of two repeating units will be explained. In this case, the ethylene content of the ethylene-α-olefin binary copolymer can be determined by (Equation c1-1) and (Equation c1-2).

[0619] Ethylene content (mol%) = IE × 100 / (IE + IX) ... (Equation c1-1)

[0620] Ethylene content [E(C)] (wt%) = [Ethylene content (mol%) × molecular weight of ethylene] × 100 / [Ethylene content (mol%) × molecular weight of ethylene + α-olefin content (mol%) × molecular weight of α-olefin] ... (Equation c1-2)

[0621] Here, IE and IX are the integral intensities of ethylene and α-olefins, respectively, which can be obtained by the following (Equation c-2) and (Equation c-3).

[0622] IE = (I ββ +I γγ +I βδ +I γδ +I δδ ) / 2+(I αγ +I αδ ) / 4···(Formula c-2)

[0623] IX = I αα +(I αγ +I αδ ) / 2···(Formula c-3)

[0624] Here, the subscript of I on the right indicates the carbon described in the following structural formulas (a) to (d). For example, αα represents the methylene carbon based on the α-olefin chain, and I... αα This represents the integrated intensity of the signal based on the methylene carbon of the α-olefin chain.

[0625]

[0626]

[0627]

[0628]

[0629] In the structural formula (d), n represents an odd number greater than 1.

[0630] The integral strength used in (Formula c-2) and (Formula c-3) for each α-olefin of the ethylene-α-olefin binary copolymer is explained below.

[0631] In the case of ethylene-propylene copolymers

[0632] When the α-olefin is propylene, substitute the following integral intensity values ​​into (Equation c-2) and (Equation c-3) to calculate the ethylene content [E(C)].

[0633] I ββ =I 25.0-24.2

[0634] I γγ =I 30.8-30.6

[0635] I βδ =I 27.8-26.8

[0636] I γδ =I 30.6-30.2

[0637] I δδ =I30.2-28.0

[0638] I αα =I 48.0-43.9

[0639] I αγ +I αδ =I 39.0-36.2

[0640] Here, I represents the integral intensity, and the numerical value of the subscript of I on the right indicates the range of the chemical shift. For example, I 39.0-36.2 This indicates that it was detected between 39.0 ppm and 36.2 ppm. 13 The integral intensity of the C signal.

[0641] Regarding chemical shift, hexamethyldisiloxane... 13 The C signal was set to 1.98 ppm, and the others... 13 The chemical shift of the signal generated by C is based on it. Similarly, the same applies to ethylene-1-butene copolymers, ethylene-1-hexene copolymers, and ethylene-1-octene copolymers.

[0642] In the case of ethylene-1-butene copolymers

[0643] When the α-olefin is 1-butene, substitute the following integral intensity values ​​into (Equation c-2) and (Equation c-3) to obtain the ethylene content [E(C)].

[0644] I ββ =I 24.6-24.4

[0645] I γγ =I 30.9-30.7

[0646] I βδ =I 27.8-26.8

[0647] I γδ =I 30.5-30.2

[0648] I δδ =I 30.2-28.0

[0649] I αα =I 39.3-38.1

[0650] I αγ +I αδ =I 34.5-33.8

[0651] In the case of ethylene-1-hexene copolymers

[0652] When the α-olefin is 1-hexene, substitute the following integral intensity values ​​into (Equation c-2) and (Equation c-3) to obtain the ethylene content [E(C)].

[0653] I ββ =I 24.5-24.4

[0654] I γγ =I 31.0-30.8

[0655] I βδ =I 27.5-27.0

[0656] I γδ =I 30.6-30.2

[0657] I δδ =I 30.2-28.0

[0658] I αα =I 40.0-39.0

[0659] I αγ +I αδ =I 35.0-34.0

[0660] In the case of ethylene-1-octene copolymers

[0661] In the case of 1-octene as the α-olefin, the methylene carbon overlaps based on the hexyl branch of 1-octene at the βδ and αγ+αδ signals (5B6 and 6B6 of the following structural formulas).

[0662] I βδ +I 5B6 =I 27.6-26.7

[0663] I αγ +I αδ +I 6B6 =I 35.0-34.0

[0664]

[0665] Therefore, I, which corrects for the overlap of 5B6 and 6B6, was used instead. βδ , and I αγ +I αδ Substitute the integral intensities shown below into equations (c-2) and (c-3) to calculate the ethylene content [E(C)].

[0666] I ββ =I 24.7-24.2

[0667] Iγγ +I γδ +I δδ =I 32.0-28.0

[0668] I βδ =2 / 3×I 27.6-26.7

[0669] I αα =I 40.8-39.6

[0670] I αγ +I αδ =I βδ +2×I ββ

[0671] (Calculate Method 2 (Ternary System))

[0672] Next, the method for calculating the ethylene content [E(C)] in a ternary copolymer composed of three repeating units will be explained. For example, the ethylene content of an ethylene-propylene-butene ternary copolymer can be determined using the following formulas (c4-1) and (c4-2).

[0673] Ethylene content (mol%) = IE × 100 / (IE + IP + IB) ... (Equation c4-1)

[0674] Ethylene content [E(C)] (wt%) = [Ethylene content (mol%) × molecular weight of ethylene] × 100 / [Ethylene content (mol%) × molecular weight of ethylene + propylene content (mol%) × molecular weight of propylene + butene content (mol%) × molecular weight of butene] ... (Equation c4-2)

[0675] Here, IE, IP, and IB are the integral intensities of ethylene, propylene, and butene, respectively, which can be obtained by equations (c-5), (c-6), and (c-7).

[0676] IE = (I ββ +I γγ +I βδ +I γδ +I δδ ) / 2+(I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) ) / 4···(Formula c-5)

[0677] P = 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)

[0678] 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)

[0679] Here, the subscript (P) refers to a signal based on a methyl branch derived from propylene, and similarly (B) refers to a signal based on an ethyl branch derived from butene.

[0680] In addition, αα(PP) refers to the methylene carbon signal based on the propylene chain, similarly αα(BB) refers to the methylene carbon signal based on the butene chain, and αα(PB) refers to the methylene carbon signal based on the propylene-butene chain.

[0681] Here, the γγ signal is difficult to separate because it overlaps with the tail of the signal of the propylene methine carbon CH(PPE) at the center of the propylene-propylene-ethylene arrangement.

[0682] For the γγ signal, the ethylene chain appears in two structural formulas (c). For the integral intensity of γγ derived from ethylene and the integral intensity of βδ of structural formula (c), (Equation c-8) holds.

[0683] I βδ (Structural formula (c)) = 2 × I γγ ...(Equation c-8)

[0684] In addition, for βδ, the ethylene chain appears in more than three structural formulas (d), and the integral intensity of βδ for structural formula (d) is equal to the integral intensity of γδ, so (Equation c-9) holds.

[0685] I βδ (Structural formula (d)) = I γδ ...(Equation c-9)

[0686] Therefore, βδ based on structural formulas (c) and (d) is obtained through (equation c-10).

[0687] I βδ =I βδ (Structural formula (c)) + I βδ (Structural formula (d)) = 2 × I γγ +I γδ ...(Equation c-10) that is, I γγ =(I βδ -I γδ) / 2···(Formula c-10')

[0688] Therefore, when (Equation c-10') is substituted into (Equation c-5), IE can be replaced by (Equation c-11).

[0689] IE = (I ββ +I δδ ) / 2+(I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) +3×I βδ +I γδ ) / 4···(Formula c-11)

[0690] Here, for the βδ signal, the overlap of the ethyl branches based on 1-butene is corrected as shown in (Equation c-12).

[0691] I βδ =I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) -2×I ββ ...(Equation c-12)

[0692] According to (Equation c-11) and (Equation c-12), IE is (Equation c-13).

[0693] IE = I δδ / 2+I γδ / 4-I ββ +I αγ(P) +I αδ(P) +I αγ(B) +I αδ(B) ...(Equation c-13)

[0694] Substitute the following into equations (c-13), (c-6), and (c-7) to calculate the ethylene content.

[0695] I ββ =I 25.2-23.8

[0696] I γδ =I 30.4-30.2

[0697] I δδ =I 30.2-29.8

[0698] I αγ(P) +I αδ(P) =I 39.5-37.3

[0699] I αγ(B) +I αδ(B) =I34.6-33.9

[0700] I CH3(P) =I 22.6-19.0

[0701] I CH(P) =I 29.5-27.6 +I 31.2-30.4 +I 33.4-32.8

[0702] I αα(PP) =I 48.0-45.0

[0703] I CH3(B) =I 11.4-10.0

[0704] I CH(B) =I 35.5-34.7 +I 37.4-36.8 +I 39.7-39.6

[0705] I αα(BB) =I 40.3-40.0

[0706] I αα(PB) =I 44.2-42.0

[0707] I 2B2 =I 26.7-26.4

[0708] It should be noted that the attribution of each signal is based on the following five references.

[0709] Macromolecules,Vol.10,NO.4,1977、

[0710] Macromolecules,Vol.36,No.11,2003、

[0711] AnalyticalChemistry,Vol.76,No.19, 2004,

[0712] Macromolecules,2001,34,4757-4767、

[0713] Macromolecules, Vol. 25, No. 1, 1992.

[0714] For α-olefins in ethylene-α-olefin random copolymers, even in cases other than those described above, the assignment of each signal can be performed, and the ethylene content [E(C)] can be determined in the same manner as in the cases described above.

[0715] 2. Density: (c²)

[0716] The density of the ethylene-α-olefin random copolymer (C) is preferably 0.850–0.950 g / cm³. 3 More preferably, it is 0.855–0.900 g / cm³. 3 A further preferred value is 0.860–0.890 g / cm³. 3 If it falls within the aforementioned range, then sufficient adhesive strength will be achieved during three-dimensional decorative thermoforming, resulting in good film formability.

[0717] 3. Melt Flow Rate (MFR(C)): (c3)

[0718] The melt flow rate (MFR(C)) of the ethylene-α-olefin random copolymer (C) at 230°C and a load of 2.16 kg is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably 1 to 30 g / 10 min. Within the aforementioned range, good adhesion is maintained even with a shortened forming time for three-dimensional decorative thermoforming.

[0719] 4. Melting peak temperature (Tm(C)): (c4)

[0720] The melting temperature peak (DSC melting peak temperature) (Tm(C)) of the ethylene-α-olefin random copolymer (C) is preferably 30–130°C, more preferably 35–120°C, and even more preferably 40–110°C. If it is within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming.

[0721] 5. Types of ethylene-α-olefin random copolymers (C): (c5)

[0722] The ethylene-α-olefin random copolymer (C) is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Specifically, examples of the aforementioned α-olefin having 3 to 20 carbon atoms include: propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, propylene, 1-butene, 1-hexene, and 1-octene are particularly preferred.

[0723] Such ethylene-α-olefin random copolymers (C) are manufactured by copolymerizing the monomers in the presence of a catalyst. Specifically, for ethylene-α-olefin random copolymers (C), catalysts such as Ziegler catalysts, Philipp catalysts, and metallocene catalysts can be used as polymerization catalysts for olefins, and ethylene can be copolymerized with α-olefins such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene through processes such as gas-phase methods, solution methods, high-pressure methods, and slurry methods.

[0724] Furthermore, the ethylene-α-olefin random copolymer (C) used in the sealing layer (I) of the third embodiment may be one type or two or more types in combination without impairing the effect of the present invention.

[0725] Commercially available examples of such ethylene-α-olefin random copolymers include the Kernel series manufactured by Nippon Polyethylene Co., Ltd., the TAFMER P series and TAFMER A series manufactured by Mitsui Chemicals Co., Ltd., and the ENGAGE EG series manufactured by DuPontDow Co., Ltd.

[0726] Resin Composition (XX3)

[0727] In the third embodiment, the resin composition (XX3) constituting the sealing layer (I) includes polypropylene resin (A) and ethylene-α-olefin random copolymer (C) as main components. It can be a mixture or melt compound of polypropylene resin (A) and ethylene-α-olefin random copolymer (C), or a step-polymer of polypropylene resin (A) and ethylene-α-olefin random copolymer (C).

[0728] 1. Weight ratio of polypropylene resin (A) to ethylene-α-olefin random copolymer (C)

[0729] In the resin composition (XX3), the weight ratio ((A):(C)) of the polypropylene resin (A) and the ethylene-α-olefin random copolymer (C) is preferably selected in the range of 97:3 to 5:95, more preferably 95:5 to 10:90, and even more preferably 93:7 to 20:80. Within the aforementioned range, sufficient adhesive strength can be achieved 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.

[0730] <Fourth Implementation>

[0731] In the fourth embodiment, the sealing layer (I) comprises a resin composition (XX4) containing a polypropylene resin (A) and a thermoplastic elastomer (D) as main components. By providing such a sealing layer (I) containing the resin composition (XX4), good adhesion is achieved even with a shortened molding time for three-dimensional decorative thermoforming, thus making it easier to suppress the reduction of surface gloss and / or weather resistance by completing the molding before the nucleating agent and / or weather-resistant agent evaporates.

[0732] Polypropylene Resins (A)

[0733] 1. Melt flow rate (MFR(A)): (a1)

[0734] The melt flow rate (MFR) of the polypropylene resin (A) contained in the sealing layer (I) (at 230°C and 2.16 kg load) is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. Within the aforementioned range, sufficient relaxation occurs during the thermoforming of the three-dimensional decorative material, making it easier to achieve sufficient adhesive strength. There is no upper limit to the MFR (A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of adhesive strength due to reduced physical properties will not occur.

[0735] 2. Melting peak temperature (Tm(A))

[0736] The melting peak temperature (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, the formability during three-dimensional decorative thermoforming is good. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[0737] 3. Resin Composition

[0738] In the fourth embodiment, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0739] In the fourth embodiment, the polypropylene resin (A) can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0740] Thermoplastic Elastomers (D)

[0741] The thermoplastic elastomer (D) used in the sealing layer (I) of the fourth embodiment satisfies the following necessary conditions (d1) to (d4), and preferably further has the necessary condition (d5).

[0742] 1. Composition: (d1)

[0743] The thermoplastic elastomer (D) of the present invention is a thermoplastic elastomer with at least one of propylene and butene as its main component. Here, "thermoplastic elastomer with at least one of propylene and butene as its main component" includes: (i) a thermoplastic elastomer with propylene as its main component, (ii) a thermoplastic elastomer with butene as its main component, and (iii) a thermoplastic elastomer with a combination of propylene and butene as its main component.

[0744] There are no particular limitations on the content of propylene or butene in the thermoplastic elastomer (D), but it is preferably 30 wt% or more, more preferably 40 wt% or more, and even more preferably 50 wt% or more. For example, the thermoplastic elastomer (D) may contain more than 35 wt% propylene or butene.

[0745] Furthermore, the thermoplastic elastomer (D) may contain both propylene and butene. In this case, the combined composition of propylene and butene is the main component of the thermoplastic elastomer (D), and the total content of propylene and butene is preferably 30 wt% or more, more preferably 40 wt% or more, and even more preferably 50 wt% or more. When both propylene and butene are included, for example, the thermoplastic elastomer (D) may contain a total of more than 35 wt% of propylene and butene. Within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming, and the heating time of the film can be shortened.

[0746] 2. Density: (d2)

[0747] The density of the thermoplastic elastomer (D) is preferably 0.850–0.950 g / cm³. 3 More preferably, it is 0.855–0.940 g / cm³. 3 A further preferred value is 0.860–0.930 g / cm³. 3 If it falls within the aforementioned range, then sufficient adhesive strength is achieved during three-dimensional decorative thermoforming, resulting in good film formability.

[0748] 3. Melt flow rate (MFR(D)): (d3)

[0749] The melt flow rate (MFR) of the thermoplastic elastomer (D) at 230°C and 2.16 kg load is preferably 0.1–100 g / 10 min, more preferably 0.5–50 g / 10 min, and even more preferably 1.0–30 g / 10 min. Within the aforementioned range, good adhesion is maintained even with a shortened forming time for three-dimensional decorative thermoforming.

[0750] 4. Tensile modulus of elasticity: (d4)

[0751] The tensile modulus of elasticity of the thermoplastic elastomer (D) is preferably smaller than that of the polypropylene resin (A). More preferably, the tensile modulus of elasticity of the thermoplastic elastomer (D) is 500 MPa or less, and even more preferably 450 MPa or less. If it is within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming.

[0752] 5. Melting peak temperature (Tm(D)): (d5)

[0753] The melting peak temperature (Tm(D)) of the thermoplastic elastomer (D) is preferably 30–170°C, more preferably 35–168°C, and even more preferably 40–165°C or higher. If it is within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming.

[0754] The thermoplastic elastomer (D) of the present invention can be appropriately selected and used as long as it meets the above-mentioned necessary conditions (d1) to (d4), and is preferably a propylene-ethylene copolymer, a butene-ethylene copolymer, a propylene-ethylene-butene copolymer, a propylene-butene copolymer, or a butene homopolymer with an ethylene content of less than 50 wt%.

[0755] 6. Ethylene content [E(D)]

[0756] The ethylene content [E(D)] of the aforementioned propylene-ethylene copolymer, butene-ethylene copolymer, or propylene-ethylene-butene copolymer is more preferably 45 wt% or less, and even more preferably 40 wt% or less. If it is within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming.

[0757] (Method for calculating ethylene content [E(D)])

[0758] In the case of thermoplastic elastomer (D) containing ethylene, the ethylene content [E(D)] of the thermoplastic elastomer (D) can be determined by... 13 The integral intensity measured by C-NMR is used to determine the result.

[0759] The calculation method is the same as the "Calculation Method 1 (Binary System)" and "Calculation Method 2 (Ternary System)" mentioned in the calculation method of ethylene content [E(C)] of ethylene-α-olefin random copolymer (C) described in the third embodiment above.

[0760] Furthermore, the thermoplastic elastomer (D) may also be a copolymer of propylene and an α-olefin other than butene, provided that the effects of the present invention are not impaired. Specific examples of α-olefins include: ethylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, etc. These α-olefins may be used alone or in combination. Among these, 1-hexene and 1-octene are particularly preferred.

[0761] Thermoplastic elastomers (D) are manufactured by copolymerizing monomers in the presence of a catalyst. Specifically, catalysts such as Ziegler catalysts, Philipp catalysts, and metallocene catalysts can be used as polymerization catalysts for olefins, and propylene, 1-butene, and, depending on the case, α-olefins such as ethylene, 1-hexene, 4-methyl-1-pentene, and 1-octene can be copolymerized through processes such as gas-phase polymerization, solution polymerization, high-pressure polymerization, and slurry polymerization.

[0762] Furthermore, in the sealing layer (I) of the fourth embodiment, one type or two or more thermoplastic elastomers (D) may be selectively used, without impairing the effects of the present invention.

[0763] For such thermoplastic elastomers, commercially available products include the TAFMERXM series, TAFMER BL series, and TAFMER PN series manufactured by Mitsui Chemicals Co., Ltd., and the VISTAMAXX series manufactured by Exxon Mobil Chemical Company.

[0764] Resin Composition (XX4)

[0765] In the fourth embodiment, the resin composition (XX4) constituting the sealing layer (I) comprises a polypropylene resin (A) and a thermoplastic elastomer (D). The aforementioned resin composition (XX4) may be a mixture or melt compound of polypropylene resin (A) and thermoplastic elastomer (D), or it may be a step-polymer of polypropylene resin (A) and thermoplastic elastomer (D).

[0766] 1. Weight ratio of polypropylene resin (A) to thermoplastic elastomer (D)

[0767] In the resin composition (XX4), the weight ratio ((A):(D)) of the polypropylene resin (A) to the thermoplastic elastomer (D) is preferably 97:3 to 5:95, more preferably 95:5 to 10:90, and even more preferably 93:7 to 20:80. Within the aforementioned range, sufficient adhesive strength can be achieved 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) becomes better.

[0768] <Fifth Implementation>

[0769] In the fifth embodiment, the sealing layer (I) comprises a resin composition (XX5) containing a polypropylene resin (A) and a thermoplastic resin (E). By providing such a sealing layer (I) containing the resin composition (XX5), good adhesion is achieved even with a shortened molding time for three-dimensional decorative thermoforming, thus making it easier to suppress the reduction of surface gloss and / or weather resistance by completing the molding before the nucleating agent and / or weather-resistant agent evaporates.

[0770] Polypropylene Resins (A)

[0771] In the fifth embodiment, the polypropylene resin (A) can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains 50 mol% or more of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups.

[0772] 1. Melt flow rate (MFR(A)): (a1)

[0773] The melt flow rate (MFR) of the polypropylene resin (A) contained in the sealing layer (I) (at 230°C and 2.16 kg load) is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. Within the aforementioned range, sufficient relaxation occurs during the thermoforming of the three-dimensional decorative material, making it easier to achieve sufficient adhesive strength. There is no upper limit to the MFR (A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of adhesive strength due to reduced physical properties will not occur.

[0774] 2. Melting peak temperature (Tm(A))

[0775] The melting peak temperature (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, the formability during three-dimensional decorative thermoforming is good. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[0776] 3. Resin Composition

[0777] In the fifth embodiment, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[0778] [Thermoplastic Resins (E)]

[0779] The thermoplastic resin (E) used in the sealing layer (I) of the fifth embodiment contains a component in the polypropylene resin (A) that slows down the crystallization of the polypropylene resin (A). By slowing down the crystallization rate of the polypropylene resin (A), it is possible to prevent the sealing layer resin from crystallizing (curing) and reducing the adhesive strength before the sealing layer (I) is heat-fused to the substrate surface during decorative molding. As a result, strong adhesive strength is easily exhibited even if the heating time of the decorative film is shortened. The effect of slowing down the crystallization of the polypropylene resin (A) is evaluated by the isothermal crystallization time of the resin composition (XX5) described later.

[0780] 1. Resin composition: (e1)

[0781] The thermoplastic resin (E) of this invention preferably contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group. By giving the thermoplastic resin (E) the aforementioned characteristics, when mixed with the aforementioned polypropylene resin (A), it exhibits the effect of slowing down the crystallization of the polypropylene resin (A), resulting in high adhesion to the matrix and minimal damage to the matrix surface. Specifically, examples of alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituent derivatives, condensed cyclizations, cross-linked structures, etc., with cyclopentyl and cyclohexyl being particularly preferred. Examples of aromatic hydrocarbon groups include phenyl, methylphenyl, biphenyl, indene, fluorenyl, and their substituent derivatives, fused cyclizations, etc., with phenyl, biphenyl, and indene being particularly preferred. In addition, the alicyclic hydrocarbon group may also be obtained by hydrogenating the aromatic hydrocarbon group contained in the resin.

[0782] It should be noted that as a thermoplastic resin (E), it can be appropriately selected and used as long as the above necessary conditions (e1) are met. Styrene-based elastomers or alicyclic hydrocarbon resins are particularly suitable for use, and both may be included.

[0783] Examples of styrene-based elastomers include: styrene-butadiene-styrene triblock copolymer elastomers (SBS), styrene-isoprene-styrene triblock copolymer elastomers (SIS), styrene-ethylene-butene copolymer elastomers (SEB), styrene-ethylene-propylene copolymer elastomers (SEP), styrene-ethylene-butene-styrene copolymer elastomers (SEBS), styrene-ethylene-butene-ethylene copolymer elastomers (SEBC), hydrogenated styrene-butadiene elastomers (HSBR), styrene-ethylene-propylene-styrene copolymer elastomers (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer elastomers (SEEPS), and styrene-butadiene-butene-styrene copolymer elastomers (SBBS), etc., and in particular, hydrogenated styrene-based elastomers can be appropriately used.

[0784] Commercially available products include the DYNARON series manufactured by JSR Corporation, the Kraton G series manufactured by Kraton Polymers Japan Ltd., and the Tuftec series manufactured by Asahi Kasei Corporation.

[0785] Examples of alicyclic hydrocarbon resins include: hydrocarbon resins obtained by polymerizing one or more dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene as the main raw material; hydrogenated coumarone-indene resin; hydrogenated C9 petroleum resin; hydrogenated C5 petroleum resin; C5 / C9 copolymer petroleum resin; hydrogenated terpene resin; and hydrogenated rosin resin. Furthermore, commercially available products can be used; specifically, the ARKON series manufactured by Arakawa Chemical Co., Ltd. can be cited.

[0786] Resin Composition (XX5)

[0787] In the fifth embodiment, the resin composition (XX5) constituting the sealing layer (I) includes polypropylene resin (A) and thermoplastic resin (E) as main components, and can be a mixture of polypropylene resin (A) and thermoplastic resin (E) or a melt compound.

[0788] 1. Weight ratio of polypropylene resin (A) to thermoplastic resin (E)

[0789] In the resin composition (XX5), the weight ratio ((A):(E)) of the polypropylene resin (A):(E) is preferably selected in the range of 97:3 to 5:95, more preferably 95:5 to 10:90, and even more preferably 93:7 to 20:80. Various polypropylene resins (A) or thermoplastic resins (E) may be included here. For example, if thermoplastic resin (E1) and thermoplastic resin (E2) are included, the total of thermoplastic resin (E1) and thermoplastic resin (E2) is taken as the weight of thermoplastic resin (E). Within the aforementioned range, sufficient adhesive strength can be achieved during three-dimensional decorative thermoforming, and the heating time of the film can be shortened. Consequently, the adhesion between the sealing layer (I) and the layer (II) is good.

[0790] 2. Isothermal crystallization time (t(XX5)): (xx1)

[0791] For the resin composition (XX5), the isothermal crystallization time (t(XX5)) (seconds) of the resin composition (XX5) determined by differential scanning calorimetry (DSC) preferably satisfies the following formula (x-1), more preferably satisfies formula (x-2), and even more preferably satisfies formula (x-3).

[0792] t(XX5)≥1.5×t(A)···Equation (x-1)

[0793] t(XX5)≥2.0×t(A)···Equation (x-2)

[0794] t(XX5)≥2.5×t(A)···Equation (x-3)

[0795] (In the formula, t(A) represents the isothermal crystallization time (in seconds) of polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A), and t(XX5) represents the isothermal crystallization time (in seconds) of resin composition (XX5) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A).)

[0796] If the isothermal crystallization time (t(XX5)) of the resin composition (XX5) is within the aforementioned range, then during decorative molding, the time until the sealing layer (I) of the decorative film is thermally fused with the substrate surface can be saved, resulting in high adhesion.

[0797] There is no particular upper limit to the isothermal crystallization time (t(XX5)), but when 30t(A)≥t(XX5), the film has good formability.

[0798] (Determination of isothermal crystallization time based on differential scanning calorimetry (DSC))

[0799] The isothermal crystallization time in this invention is a value measured using a differential scanning calorimeter (DSC) according to JIS-K7121 (2012) "Method for determination of conversion temperature of plastics".

[0800] Specifically, 5 mg of a sample of polypropylene resin (A) was placed in an aluminum holder and heated from 40 °C to 200 °C at a rate of 10 °C / min under a nitrogen atmosphere. After holding at 200 °C for 10 minutes, the sample was cooled to 40 °C at a rate of 10 °C / min to allow crystallization. The initial crystallization temperature was then determined and calculated based on the DSC curve at this point.

[0801] Next, 5 mg of a sample of polypropylene resin (A) or resin composition (XX5) was placed in an aluminum holder, and the temperature was increased from 40°C to 200°C at a rate of 10°C / min under a nitrogen atmosphere, and held for 10 minutes to allow the sample to melt. Then, the sample was cooled at a rate of 40°C / min to a temperature 10°C higher than the initial crystallization temperature of the polypropylene resin (A) determined by the above method (hereinafter sometimes referred to as the "test temperature"). The sample was then held at the test temperature, and the crystallization and heating behavior of the sample was measured. The time from when the sample temperature reaches the test temperature to the heating peak is defined as the isothermal crystallization time. Here, since it is believed that during decorative molding, even slight crystallization of the sealing layer (I) of the decorative film significantly reduces the adhesive strength, if there are more than two heating peaks in the isothermal crystallization measurement, the time up to the first heating peak is defined as the isothermal crystallization time.

[0802] Furthermore, depending on the type of polypropylene resin (A), in measurements taken at a temperature 10°C higher than the initial crystallization temperature, the isothermal crystallization time of the polypropylene resin (A) may be very short (e.g., less than 120 seconds) or very long (e.g., more than 3000 seconds). In such cases, the isothermal crystallization time can be measured at a temperature 10 ± 2°C higher than the initial crystallization temperature. However, when performing such a measurement, the isothermal crystallization time of the resin composition (XX5) must also be measured in accordance with the measurement temperature of the polypropylene resin (A).

[0803] <Sixth Implementation>

[0804] In the sixth embodiment, the polypropylene resin (A) used as the sealing layer (I) is a resin composition (XX6) containing a propylene-ethylene block copolymer (F). By providing such a sealing layer (I), good adhesion is achieved even when the molding time of the three-dimensional decorative thermoforming is shortened, thus making it easier to suppress the reduction of surface gloss and / or weather resistance by completing the molding before the nucleating agent and / or weather-resistant agent evaporates.

[0805] Propylene-ethylene block copolymer (F)

[0806] The propylene-ethylene block copolymer (F) used in the sixth embodiment contains: a component (F1) comprising a propylene homopolymer or a propylene-ethylene random copolymer, and a component (F2) comprising a propylene-ethylene random copolymer containing more ethylene than component (F1). The adhesive strength to the resin molded body (matrix) is improved by the component (F2) in the propylene-ethylene block copolymer (F) which acts as a rubber component. The propylene-ethylene block copolymer (F) is obtained as follows: in the first polymerization step, propylene is homopolymerized or the component (F1) comprising a propylene-ethylene random copolymer is (co)polymerized; and in the second polymerization step, the component (F2) comprising a propylene-ethylene random copolymer containing more ethylene than component (F1) is gradually copolymerized.

[0807] 1. The ratio of component (F1) and component (F2): (f2)

[0808] Regarding the mixing ratio of components (F1) and (F2) constituting the propylene-ethylene block copolymer (F) in the sixth embodiment, component (F1) is preferably 5-97% by weight and component (F2) is 3-95% by weight. More preferably, component (F1) is 30-95% by weight and component (F2) is 5-70% by weight. Even more preferably, component (F1) is 52-92% by weight and component (F2) is 8-48% by weight. If the ratio of components (F1) and (F2) is within the aforementioned range, sufficient adhesive strength can be achieved. In addition, when within the aforementioned range, the film is not sticky and has good film formability.

[0809] 2. Melt flow rate (MFR(F)): (a1)

[0810] The melt flow rate (MFR) of the propylene-ethylene block copolymer (F) at 230°C and 2.16 kg load is preferably more than 0.5 g / 10 min, more preferably more than 1 g / 10 min, and particularly preferably more than 2 g / 10 min. If the MFR is within the aforementioned range, the relaxation of the propylene-ethylene block copolymer (F) during three-dimensional decorative thermoforming is sufficient, making it easier to achieve adequate adhesive strength. There is no upper limit to the MFR, but it is preferably less than 100 g / 10 min. If it is within the aforementioned range, the deterioration of adhesive strength due to a decrease in physical properties will not occur.

[0811] 3. Melting peak temperature (Tm(F)): (f1)

[0812] The melting point (melting peak temperature) Tm(F) of the propylene-ethylene block copolymer (F) is preferably 110–170°C. More preferably, it is 113–169°C, and even more preferably, it is 115–168°C. If Tm(F) is within the aforementioned range, the formability during three-dimensional decorative thermoforming is good. The melting peak temperature mainly originates from the component with low ethylene content (F1), i.e., the component with high crystallinity (F1), and can be changed by adjusting the ethylene content in the copolymer.

[0813] 4. Ethylene content (E(F)) in propylene-ethylene block copolymer (F): (f3)

[0814] The ethylene content (hereinafter referred to as "E(F)") in the propylene-ethylene block copolymer (F) is preferably 0.15 to 85% by weight. More preferably, it is 0.5 to 75% by weight, and even more preferably, it is 2 to 50% by weight. When E(F) is in the aforementioned range, sufficient adhesive strength can be achieved, and in addition, good adhesion to the decorative film layer (II) and excellent film formability are also achieved.

[0815] 5. Ethylene content (E(F1)): (f4) of component (F1)

[0816] The component (F1) is preferably a propylene homopolymer or a propylene-ethylene random copolymer with a relatively high melting point and an ethylene content (hereinafter referred to as "E(F1)") in the range of 0 to 6% by weight. More preferably, it is 0 to 5% by weight. If E(F1) is within the aforementioned range, the formability during three-dimensional decorative thermoforming is good, and the film has less stickiness and excellent film formability.

[0817] 6. Ethylene content (E(F2)): (f5) of component (F2)

[0818] For component (F2), its ethylene content (hereinafter referred to as "E(F2)") is higher than that of component (F1) E(F1). Furthermore, a propylene-ethylene random copolymer with E(F2) in the range of 5 to 90% by weight is preferred. E(F2) is more preferably 7 to 80% by weight, and even more preferably 9 to 50% by weight. If E(F2) is within the aforementioned range, sufficient adhesive strength can be achieved.

[0819] [(Method for manufacturing propylene-ethylene block copolymer (F))]

[0820] The propylene-ethylene block copolymer (F) used in this invention, and the components constituting it, including propylene homopolymer or propylene-ethylene random copolymer (F1) and propylene-ethylene random copolymer (F2), are preferably manufactured using the following raw materials and polymerization methods. The manufacturing method of the propylene-ethylene block copolymer (F) used in this invention will be described below.

[0821] Raw materials used

[0822] As a catalyst used in manufacturing the propylene-ethylene block copolymer (F) used in this invention, the following can be used: a magnesium-supported catalyst with magnesium, halogen, titanium, and an electron donor as catalyst components; a catalyst containing a solid catalyst component with titanium trichloride as a catalyst and an organoaluminum; or a metallocene catalyst. There are no particular limitations on the specific method of catalyst manufacturing. Examples include the Ziegler catalyst disclosed in Japanese Patent Application Publication No. 2007-254671 and the metallocene catalyst disclosed in Japanese Patent Application Publication No. 2010-105197.

[0823] In addition, the olefins used for polymerization are propylene and ethylene. Other olefins, such as 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc., may be used as needed without impairing the purpose of the present invention.

[0824] Polymerization process

[0825] The polymerization process carried out in the presence of the aforementioned catalyst includes multiple stages: a first polymerization process for manufacturing component (F1) and a second polymerization process for manufacturing component (F2).

[0826] First polymerization process

[0827] The first polymerization step is as follows: propylene alone or a mixture of propylene and ethylene is supplied to a polymerization system incorporating the aforementioned catalyst to produce a propylene homopolymer or a propylene-ethylene random copolymer, forming a component (F1) in an amount equivalent to 5 to 97% by weight of the total polymer.

[0828] The MFR (hereinafter referred to as "MFR(F1)") of component (F1) can be adjusted by using hydrogen as a chain transfer agent. Specifically, increasing the concentration of hydrogen as a chain transfer agent increases the MFR(F1) of component (F1). Conversely, the MFR(F1) also decreases. Increasing the hydrogen concentration in the polymerization tank is simply a matter of increasing the amount of hydrogen supplied to the polymerization tank, which is extremely easy for those skilled in the art. Furthermore, when component (F1) is a propylene-ethylene random copolymer, controlling the amount of ethylene supplied to the polymerization tank is a simple method for controlling the ethylene content. Specifically, increasing the ratio of ethylene to propylene supplied to the polymerization tank (ethylene supply amount ÷ propylene supply amount) increases the ethylene content of component (F1). Conversely, the same applies. The relationship between the ratio of propylene to ethylene supplied to the polymerization tank and the ethylene content of component (F1) varies depending on the type of catalyst used, and obtaining component (F1) with a target ethylene content by appropriately adjusting the supply ratio is extremely easy for those skilled in the art.

[0829] Second polymerization process

[0830] The second polymerization step is as follows: following the first polymerization step, a propylene / ethylene mixture is introduced to produce a propylene-ethylene random copolymer, forming a component (F2) in an amount equivalent to 3 to 95% by weight of the total polymer.

[0831] The MFR (hereinafter referred to as "MFR(F2)") of component (F2) can be adjusted by using hydrogen as a chain transfer agent. The specific control method is the same as that for component (F1). As a method for controlling the ethylene content of component (F2), controlling the amount of ethylene supplied to the polymerization tank is simple. The specific control method is the same as that for the case where component (F1) is a propylene-ethylene random copolymer.

[0832] Next, the control methods for the parameters of propylene-ethylene block copolymer (F) will be explained.

[0833] First, the method for controlling the weight ratio of component (F1) to component (F2) will be explained. The weight ratio of component (F1) to component (F2) is controlled by the production amount in the first polymerization step of component (F1) and the production amount in the second polymerization step of component (F2). For example, to increase the amount of component (F1) and thus reduce the amount of component (F2), it is sufficient to reduce the production amount in the second polymerization step while maintaining the production amount in the first polymerization step. This can be achieved by shortening the residence time in the second polymerization step or lowering the polymerization temperature. Alternatively, it can be controlled by adding polymerization inhibitors such as ethanol or oxygen, or by increasing the amount of such inhibitors added if they are already present. Conversely, the same applies.

[0834] Typically, the weight ratio of component (F1) to component (F2) is defined by the amount produced in the first polymerization step of component (F1) and the amount produced in the second polymerization step of component (F2). The formula is shown below.

[0835] Weight of component (F1) : Weight of component (F2) = W(F1) : W(F2)

[0836] W(F1) = Production quantity of the first polymerization step ÷ (Production quantity of the first polymerization step + Production quantity of the second polymerization step)

[0837] W(F2) = Production quantity of the second polymerization process ÷ (Production quantity of the first polymerization process + Production quantity of the second polymerization process)

[0838] W(F1) + W(F2) = 1

[0839] (Here, W(F1) and W(F2) are the weight ratios of component (F1) to component (F2) in the propylene-ethylene block copolymer (F).)

[0840] For industrial manufacturing equipment, the production volume is determined by the heat balance and material balance of each polymerization tank. Furthermore, when the crystallinity of components (F1) and (F2) is completely different, analytical methods such as TREF (temperature elution fractionation) can be used to separate and identify them and determine their ratio. The method of evaluating the crystallinity distribution of polypropylene by TREF determination is well known to those skilled in the art, and detailed determination methods are shown in references such as G. Glokner, J. Appl. Polym. Sci: Appl. Poly. Symp.; 45, 1-24 (1990), L. Wild, Adv. Polym. Sci.; 98, 1-47 (1990), JBP Soares, AE Hamielec, Polymer; 36, 8, 1639-1654 (1995).

[0841] Next, the method for controlling the ethylene content will be explained. The propylene-ethylene block copolymer (F) is a mixture of a component (F1) containing propylene homopolymer or propylene-ethylene random copolymer and a component (F2) containing propylene-ethylene random copolymer, and therefore the following relationship exists between their respective ethylene contents.

[0842] E(F)=E(F1)×W(F1)+E(F2)×W(F2)

[0843] (Here, E(F), E(F1), and E(F2) represent the ethylene content of the propylene-ethylene block copolymer (F), the ethylene content of the component containing propylene homopolymer or propylene-ethylene random copolymer (F1), and the ethylene content of the component containing propylene-ethylene random copolymer (F2), respectively. W(F1) and W(F2) are the same as above.)

[0844] This formula shows the material balance related to ethylene content.

[0845] Therefore, if the weight ratio of component (F1) to component (F2) is determined, that is, if W(F1) and W(F2) are determined, E(F) can be uniquely determined by E(F1) and E(F2). In other words, E(F) can be controlled by controlling the three factors: the weight ratio of component (F1) to component (F2), E(F1), and E(F2). For example, to increase E(F), either E(F1) or E(F2) can be increased. Furthermore, if it is noted that E(F2) is higher than E(F1), it is easy to understand that W(F1) can be decreased and W(F2) increased. The reverse control method works similarly.

[0846] It should be noted that the directly measurable values ​​are actually E(F) and E(F1), and E(F2) is calculated using these two values. Therefore, assuming that when performing an operation to increase E(F), the operation to increase E(F2), i.e., increasing the amount of ethylene supplied to the second polymerization step, is chosen as the method, the directly measurable value is E(F) rather than E(F2). The reason why E(F) increases is because E(F2) increases, which is obvious.

[0847] Finally, the control method of MFR(F) is described. In this application, MFR(F2) is defined by the following formula.

[0848] MFR(F2)=exp{(loge[MFR(F)]-W(F1)×loge[MFR(F1)])÷W(F2)}

[0849] (Here, loge is the logarithm to the base e. MFR(F), MFR(F1), and MFR(F2) are respectively: the MFR of the propylene-ethylene block copolymer (F), the MFR of the component containing propylene homopolymer or propylene-ethylene random copolymer (F1), and the MFR of the component containing propylene-ethylene random copolymer (F2). W(F1) and W(F2) are the same as above.)

[0850] This formula is usually: an empirical formula known as the logarithmic addition rule of viscosity.

[0851] The modified loge[MFR(F)] = W(F1) × loge[MFR(F1)] + W(F2) × loge[MFR(F2)] is commonly used in this field.

[0852] Because it is defined by this formula, the weight ratio of component (F1) to component (F2), MFR(F), MFR(F1), and MFR(F2) are not independent. Therefore, to control MFR(F), these three factors—the weight ratio of component (F1) to component (F2), MFR(F1), and MFR(F2)—can be controlled. For example, to increase MFR(F), either MFR(F1) or MFR(F2) can be increased. Furthermore, when MFR(F2) is lower than MFR(F1), it is easy to understand that increasing W(F1) and decreasing W(F2) can also increase MFR(F). The reverse control method is similar.

[0853] It should be noted that the directly measurable values ​​are MFR(F) and MFR(F1), and MFR(F2) is calculated using these two values. Therefore, assuming that when increasing MFR(F), the method chosen is to increase MFR(F2), i.e., to increase the amount of hydrogen supplied to the second polymerization step, the directly measurable value is MFR(F), not MFR(F2). The reason why MFR(F) increases is that MFR(F2) increases is obvious.

[0854] The polymerization process of propylene-ethylene block copolymers can be implemented using either batch or continuous methods. In this case, methods can be employed such as: polymerization in inert hydrocarbon solvents like hexane or heptane; methods that substantially do not use inert solvents but use propylene as the solvent; methods that substantially do not use liquid solvents but polymerize in gaseous monomers; and combinations thereof. Furthermore, the first and second polymerization steps can use the same polymerization tank or separate polymerization tanks.

[0855] (1) Determination of ethylene content in copolymer

[0856] The ethylene content of each component in the propylene-ethylene block copolymer (F) was determined. Specifically, the ethylene content of the component (F1) containing propylene homopolymer or propylene-ethylene random copolymer obtained at the end of the first polymerization step and the propylene-ethylene block copolymer (F) obtained after the second polymerization step were determined by proton decoupling under the following conditions. 13 The results are obtained by analyzing the C-NMR spectrum.

[0857] Model: GSX-400 or equivalent device manufactured by Nippon Electronics Co., Ltd. (carbon nucleus resonance frequency above 100MHz)

[0858] Solvent: o-dichlorobenzene + hydroxybenzene (4:1 (volume ratio))

[0859] Concentration: 100 mg / mL

[0860] Temperature: 130℃

[0861] Pulse angle: 90°

[0862] Pulse interval: 15 seconds

[0863] Total number of times: 5,000 or more

[0864] For the assignment of spectra, references can be made, for example, to Macromolecules 17, 1950 (1984). The assignments of spectra measured under the above conditions are shown in the table below. For the notation Sαα in the table, according to the notation of Carman et al. (Macromolecules 10, 536 (1977)), P represents methyl carbon, S represents methylene carbon, and T represents methine carbon.

[0865] [Table 1]

[0866] Chemical shift (ppm) Belonging 45～48 <![CDATA[S αα ]]> 37.8～37.9 <![CDATA[S αγ ]]> 37.4～37.5 <![CDATA[S αδ ]]> 33.1 <![CDATA[T δδ ]]> 30.9 <![CDATA[T βδ ]]> 30.6 <![CDATA[S γγ <!-- 50 -->]]> 30.2 <![CDATA[S γδ ]]> 29.8 <![CDATA[S δδ ]]> 28.7 <![CDATA[T ββ ]]> 27.4～27.6 <![CDATA[S βδ ]]> 24.4～24.7 <![CDATA[S ββ ]]> 19.1～22.0 P

[0867] Hereinafter, when “P” is set as the propylene unit in the copolymer chain and “E” is set as the ethylene unit, six triads can exist in the chain: PPP, PPE, EPE, PEP, PEE, and EEE. As recorded in Macromolecules 15, 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are related by the following formulas (f-1) to (f-6).

[0868] [PPP]=k×I(Tββ)···(f-1)

[0869] [PPE]=k×I(Tβδ)···(f-2)

[0870] [EPE]=k×I(Tδδ)···(f-3)

[0871] [PEP]=k×I(Sββ)···(f-4)

[0872] [PEE]=k×I(Sβδ)···(f-5)

[0873] [EEE]=k×{I(Sδδ) / 2+I(Sγδ) / 4}···(f-6)

[0874] Here, brackets [] represent the fractions of a three-unit group. For example, [PPP] represents the fraction of the PPP three-unit group out of all three-unit groups. Therefore, it is...

[0875] [PPP]+[PPE]+[EPE]+[PEP]+[PEE]+[EEE]=1···(f-7).

[0876] In addition, k is a constant, and I represents the spectral intensity. For example, I(Tββ) refers to the peak intensity at 28.7 ppm attributable to Tββ. By using the relationships (1) to (7) above, the fraction of each ternary unit group is obtained, and then the ethylene content is obtained by the following formula (f-8).

[0877] Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100···(f-8)

[0878] It should be noted that the conversion from mol% to wt% of ethylene content is performed using the following formula (f-9).

[0879] Ethylene content (wt%) = (28×X / 100) / {28×X / 100+42×(1-X / 100)}×100···(f-9)

[0880] Here, X represents the ethylene content expressed in mole percent.

[0881] [Other components of the sealing layer (I)]

[0882] In the basic embodiments described above, and in embodiments 1 to 6, the resin compositions (XX) constituting the sealing layer (I) (resin compositions (XX1) to (XX6)) may contain the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc., as long as the effects of the present invention are not impaired. However, the total amount of the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc., is preferably 50% by weight or less relative to the resin composition. As other additives, the aforementioned additives, etc., may be used.

[0883] When the resin composition (XX) contains a polypropylene resin (A), the resin composition (XX) preferably has the aforementioned properties of the polypropylene resin (A).

[0884] For the resin composition (XX), it can be manufactured by the following methods: a method of melt-kneading a polypropylene resin (A) (in the basic embodiment, and in the first and second embodiments), a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) (in the third embodiment), a polypropylene resin (A) and a thermoplastic elastomer (D) (in the fourth embodiment), a polypropylene resin (A) and a thermoplastic resin (E) (in the fifth embodiment), or a propylene-ethylene block copolymer (F) (in the sixth embodiment) with the aforementioned additives, other additives other than the aforementioned additives, fillers, other resin components, etc.; in the third to fifth embodiments, a method of dry-blending an ethylene-α-olefin random copolymer (C), a thermoplastic elastomer (D), or a thermoplastic resin (E) in a product obtained by melt-kneading a polypropylene resin (A) and the aforementioned additives, other additives other than the aforementioned additives, fillers, other resin components, etc.; a method of adding a polypropylene resin (A) to an ethylene-α-olefin random copolymer (C), a thermoplastic elastomer (D), or a thermoplastic resin (E), and dry-blending with a masterbatch in which the aforementioned additives, other additives other than the aforementioned additives, fillers, other resin compositions, etc. are highly dispersed in a carrier resin, etc.

[0885] <Basic embodiment of layer (II)>

[0886] The layer (II) contained in the decorative film in the third and fourth aspects of the present invention includes: a resin composition (YY) containing a polypropylene resin (B). Layer (II) can be the aforementioned base material layer. By providing layer (II) in the decorative film, it becomes easier to suppress the occurrence of film breakage or appearance defects caused by roughness during three-dimensional decorative thermoforming. Thus, the decorative film may not contain a thermosetting resin layer having excellent thermoformability for improving thermoformability.

[0887] 《Polypropylene resin (B)》

[0888] Next, the polypropylene resin (B) constituting layer (II) will be described. The polypropylene resin (B) is preferably a resin that is less likely to melt and relax compared to the aforementioned polypropylene resin (A).

[0889] 1. Melt flow rate (MFR(B)): (b1)

[0890] The melt flow rate (at 230 °C, 2.16 kg load) (MFR(B)) of the polypropylene resin (B) is preferably lower than the MFR(A) of the polypropylene resin (A). That is, it is preferably to satisfy the following relational expression (b-1).

[0891] MFR(B) < MFR(A) ··· Formula (b-1)

[0892] Regarding the ratio of the MFR of polypropylene resin (B) to the MFR of polypropylene resin (A), that is, MFR(B) / MFR(A), it is preferably less than 1 (i.e., MFR(B) < MFR(A)), preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less, and particularly preferably 0.25 or less. When MFR(B) / MFR(A) is within the aforementioned range, the thermoformability becomes good. There is no limit to the lower limit of MFR(B) / MFR(A), and it is preferably 0.01 or more.

[0893] When MFR(B) is within the aforementioned range, there is no particular limitation, and it is preferably 0.1 g / 10 minutes or more, more preferably 0.2 g / 10 minutes or more. When within the aforementioned range, the ductility of the decorative film during thermoforming is good. In addition, MFR(B) is preferably 20 g / 10 minutes or less, more preferably 15 g / 10 minutes or less.

[0894] 2. Melting peak temperature (Tm(B)): (b2)

[0895] The melting peak temperature Tm(B) in the DSC measurement of polypropylene resin (B) is not particularly limited, and it is preferably 150 °C or more, more preferably 155 °C or more. When Tm(B) is within the aforementioned range, the heat resistance, scratch resistance, and solvent resistance become good.

[0896] In addition, the melting peak temperature (Tm(B)) of polypropylene resin (B) is preferably higher than the melting peak temperature (Tm(A)) of polypropylene resin (A), and preferably satisfies the following relational expression (b-2).

[0897] Tm(B) > Tm(A) ··· Formula (b-2)

[0898] When within the aforementioned range, the thermoformability becomes good.

[0899] 3. Crystallization temperature (Tc(B)): (b3)

[0900] The crystallization temperature (Tc(B)) in the DSC measurement of polypropylene resin (B) is preferably higher than the crystallization temperature (Tc(A)) of polypropylene resin (A), and preferably satisfies the following relational expression (b-3).

[0901] Tc(B) > Tc(A) ··· Formula (b-3)

[0902] When within the aforementioned range, the thermoformability becomes good.

[0903] When Tc(B) is within the aforementioned range, there is no particular limitation, and it is preferably 95 °C or more, more preferably 100 °C or more.

[0904] 4. Resin composition

[0905] The polypropylene resin (B) can be selected from: metallocene catalyst-based propylene polymers, Ziegler-Natta catalyst-based propylene polymers, etc. Ziegler-Natta catalyst-based propylene polymers are preferred.

[0906] The polypropylene resin (B) in this invention can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene-α-olefin block copolymers (block polypropylene), or combinations thereof. Preferably, the propylene polymer contains at least 50 mol% of polymerization units derived from propylene monomers.

[0907] In this invention, the preferred combination with the sealing layer (I) is as follows.

[0908] In the first embodiment, layer (II) preferably satisfies the above-mentioned necessary conditions (b1) and (b2); in the second embodiment, layer (II) preferably satisfies the above-mentioned necessary conditions (b1) and (b3); and in the third to sixth embodiments, layer (II) preferably satisfies the above-mentioned necessary condition (b1).

[0909] [Other components of layer (II)]

[0910] The resin composition (YY) constituting layer (II) may contain, in addition to the polypropylene resin (B), the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components. That is, it can be a resin composition (polypropylene resin composition) comprising: a propylene polymer (polypropylene resin (B)) and the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components. The total amount of the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components is preferably 50% by weight or less relative to the polypropylene resin composition. Other additives illustrated in the first and second embodiments can be used as other additives.

[0911] The resin composition (YY) can be manufactured by the following methods: a method of melt-blending a propylene polymer with the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc.; a method of dry-blending other resin components into a product obtained by melt-blending a propylene polymer with the aforementioned additives, other additives besides the aforementioned additives, fillers, etc.; a method of dry-blending a masterbatch, in which the aforementioned additives, other additives besides the aforementioned additives, fillers, etc., are dispersed in a carrier resin at a high concentration, based on a propylene polymer and other resin components.

[0912] When the resin composition (YY) contains a polypropylene resin (B), the resin composition (YY) preferably has the aforementioned properties of the polypropylene resin (B).

[0913] Additionally, coloring can be applied to impart aesthetic appeal, using various colorants such as inorganic pigments, organic pigments, and dyes. Furthermore, luminescent materials such as aluminum flakes, titanium dioxide flakes, and (synthetic) mica can be used.

[0914] When the decorative molded body of the present invention is formed into a colored molded body, the colorant is only used in the decorative film. Therefore, compared with the case where the entire resin molded body is colored, the use of expensive colorants can be suppressed. In addition, the changes in physical properties associated with the mixing of colorants can be suppressed.

[0915] <Decorative films of the third and fourth embodiments of the present invention>

[0916] The decorative film in the third and fourth embodiments of the present invention comprises a sealing layer (I) containing polypropylene resin (A) and a layer (II) containing polypropylene resin (B). Besides the sealing layer (I) and layer (II), the decorative film can have various other compositions. That is, the decorative film can be a two-layer film composed of the sealing layer (I) and layer (II), or it can be a multi-layer film composed of three or more layers, including the sealing layer (I), layer (II), and other layers. It should be noted that the sealing layer (I) is adhered along the resin molding body (substrate). Furthermore, the decorative film can be textured, embossed, printed, sandblasted, scratched, etc., on its surface.

[0917] In addition to the sealing layer (I) and layer (II), the multilayer film may also include a surface layer, a surface decoration layer (III), a printing layer, a light-shielding layer, a coloring layer, a substrate layer, a barrier layer, and a connecting layer that can be disposed between these layers. The layer (II) containing polypropylene resin (B) can be any layer other than the sealing layer among the layers constituting the multilayer film.

[0918] In the multilayer film, layers other than the sealing layer (I) and layer (II) are preferably layers containing thermoplastic resins, and more preferably layers containing polypropylene resins. There are no particular limitations on the MFR (230°C, 2.16 kg load) of the polypropylene resin constituting the layers, as long as the layers other than the sealing layer (I) and layer (II) can be identified as sealing layer (I) and layer (II). Each layer is preferably a layer that does not contain thermosetting resins. By using thermoplastic resins, recyclability is improved, and by using polypropylene resins, the complexity of the layer composition can be suppressed, thereby further improving recyclability.

[0919] When the decorative film is a two-layer film, the sealing layer (I) forms the bonding surface to the resin molded body, and the layer (II) forms the surface layer opposite to the bonding surface to the resin molded body. In this case, layer (II) preferably contains a nucleating agent and / or a weather-resistant agent.

[0920] Figure 1 (a)~ Figure 1 (c) An explanatory diagram illustrating a cross-section of an embodiment of the decorative film. Figure 1 (a)~ Figure 1 In (c), the configuration of sealing layer (I) 3 and layer (II) 2 is described specifically for ease of understanding, but the layer composition of the decorative film is not limited to these examples. In this specification, reference numeral 1 in the figures indicates the decorative film, reference numeral 2 indicates layer (II), reference numeral 3 indicates sealing layer (I), and reference numeral 4 indicates surface decorative layer (III). Figure 1 (a) is an example of decorative film 1 comprising two layers of film, with layer (II) 2 stacked on sealing layer (I) 3. Figure 1 (b) The decorative film 1 includes a sealing layer (I) 3, a layer (II) 2 and a surface layer, with the layer (II) 2 and the surface layer stacked sequentially on the sealing layer (I) 3. Figure 1 (c) The decorative film 1 includes a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4, wherein the layer (II) 2 and the surface decorative layer (III) 4 are stacked sequentially on the sealing layer (I) 3.

[0921] Figure 8 (a)~ Figure 8 (c) An explanatory diagram illustrating a cross-section of a decorative molded body 6 formed by attaching a decorative film 1 to a resin molded body 5. Figure 8 (a)~ Figure 8 In (c), the configuration of the sealing layer (I) and the layer (II) is described in a specific way for ease of understanding, but the layer composition of the decorative film 1 is not limited to these examples for explanation. Figure 8 (a) is an example of a decorative film 1 comprising two films, wherein a sealing layer (I) 3 is attached to a resin molded body 5 and a layer (II) 2 is stacked on the sealing layer (I) 3. Figure 8 (b) The decorative film 1 includes a sealing layer (I) 3, a layer (II) 2 and a surface layer. The sealing layer (I) 3 is attached to the surface of the resin molded body 5, and the layer (II) 2 and the surface layer are stacked on the sealing layer (I) 3 in sequence. Figure 8 (c) The decorative film 1 includes a sealing layer (I) 3, a layer (II) 2 and a surface decorative layer (III) 4. The sealing layer (I) 3 is attached to the surface of the resin molded body 5, and the layer (II) 2 and the surface decorative layer (III) 4 are stacked on the sealing layer (I) 3 in sequence.

[0922] Another preferred embodiment of the decorative film is a multilayer film in which the outermost surface of the side opposite to the side facing the resin molded body contains a surface decorative layer (III) comprising a surface decorative layer resin.

[0923] The resin for the surface decorative layer is preferably a thermoplastic resin, more preferably a polypropylene resin (H). Furthermore, the surface decorative layer (III) preferably contains a nucleating agent and / or a weather-resistant agent.

[0924] In this invention, the melt flow rate (230°C, 2.16 kg load) (MFR(H)) of the polypropylene resin (H) preferably satisfies MFR(H) > MFR(B). By setting it within the range of the above values, a more beautiful surface gloss and texture can be achieved.

[0925] The polypropylene resin (H) in this invention can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene-α-olefin block copolymers (block polypropylene), or combinations thereof. The propylene polymer preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The propylene polymer preferably does not contain polymerization units derived from monomers containing polar groups. For the polypropylene resin (H), polypropylene is preferred from the viewpoints of oil resistance, solvent resistance, and scratch resistance. Furthermore, propylene-α-olefin copolymers are preferred from the viewpoints of gloss and transparency. In this invention, the polypropylene resin (H) constituting the surface decoration layer (III) can be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

[0926] The polypropylene resin (H) may contain the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components. That is, it can be a resin composition (polypropylene resin composition) of a propylene polymer and the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components. The total amount of the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components is preferably 50% by weight or less relative to the polypropylene resin composition.

[0927] Other additives exemplified in the first and second methods may be used as other additives.

[0928] Polypropylene resin compositions can be manufactured by the following methods: a method of melt-blending a propylene polymer with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components; a method of dry-blending other resin components into a product obtained by melt-blending a propylene polymer with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc.; and a method of dry-blending a masterbatch, in which the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc., are dispersed in a carrier resin at a high concentration, based on a propylene polymer and other resin components.

[0929] When the polypropylene resin (H) constituting the surface decorative layer (III) is a polypropylene resin composition, the polypropylene resin composition may be the same as or different from a polypropylene resin composition with polypropylene resin (A) as a component, wherein the polypropylene resin (A) constitutes the sealing layer (I).

[0930] {{Fifth and Sixth Embodiments of the Invention}}

[0931] The decorative film of the fifth and sixth embodiments of the present invention is characterized in that it comprises: a layer containing at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, the decorative film comprising: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a resin composition (B'), the resin composition (B') comprising a polypropylene resin (B), the aforementioned polypropylene resin (A) satisfying the following necessary condition (a'1), the aforementioned resin composition (B') satisfying the following necessary conditions (b'1) and (b'2), preferably satisfying the following necessary conditions (b'1') and (b'2'), more preferably satisfying the following necessary conditions (b'1") and (b'2").

[0932] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[0933] (b'1) Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 40 g / 10 min.

[0934] (b'2) The strain hardening degree λ is 1.1 or higher.

[0935] (b'1') Melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 20 g / 10 min.

[0936] (b'2') The strain hardening degree λ is 1.8 or higher.

[0937] (b'1") The melt flow rate (230°C, 2.16 kg load) (MFR(B')) is less than 12 g / 10 min.

[0938] (b'2") The strain hardening degree λ is 2.3 or higher.

[0939] For the decorative films of the fifth and sixth embodiments of the present invention, by using a layer (II) containing a resin composition (B') of a polypropylene resin (B) having a specific melt flow rate (MFR) and a specific strain hardness, a decorative molded body with excellent thermoformability during three-dimensional decorative thermoforming and a good product appearance can be obtained even without a thermosetting resin layer.

[0940] Furthermore, by including the aforementioned decorative film with a sealing layer (adhesive layer) (I), adhesion to the resin molded body (substrate) can be achieved with a short heating time. Therefore, the decorative molding is completed before the aforementioned additives evaporate, which can suppress the reduction of gloss and / or weather resistance and obtain a high-gloss decorative molded body. The sealing layer (adhesive layer) (I) contains at least one additive selected from nucleating agents, hindered amine light stabilizers and ultraviolet absorbers, and contains a polypropylene resin with a specific melt flow rate (MFR).

[0941] By utilizing the aforementioned sealing layer (I), a decorative film can be adhered to a polar substrate, and the decorative molded body made from the decorative film and the substrate containing the polar resin material exhibits particularly excellent water resistance and chemical resistance.

[0942] According to the fifth and sixth embodiments of the present invention, a beautiful decorative molded body can be obtained, which has no pores or wrinkles on its surface, no air entrapment between the decorative film and the resin molded body, and suppressed reduction in gloss and / or weather resistance. Furthermore, for the decorative molded body obtained in this way, since the decorative film is composed of polypropylene resin (A) and polypropylene resin (B), and does not contain or may not contain a thermosetting resin layer, the reduction in appearance and performance during recycling is small, and the recycling adaptability is high.

[0943] <Basic Implementation of Layer (II)>

[0944] In the basic embodiments of the fifth and sixth aspects of the present invention, the decorative film contains a layer (II) comprising a resin composition (B') of a polypropylene resin (B), wherein the resin composition (B') has a specific melt flow rate (MFR(B')) satisfying the necessary condition (b'1) described later and a strain hardening degree in a tensile viscosity measurement satisfying the necessary condition (b'2) described later.

[0945] By setting layer (II), it is possible to suppress the occurrence of film breakage or roughness leading to poor appearance during (three-dimensional decoration) thermoforming. As a result, the thermoformability of the decorative film is improved, so it is not necessary to contain a thermosetting resin layer with excellent thermoformability, thus improving recyclability.

[0946] Furthermore, by improving the formability of the resin composition (B') containing polypropylene resin (B), it is possible to use a decorative film with an extremely simple configuration of layer (II) and sealing layer (I), and with such a configuration, the manufacture of a decorative film under (co)extrusion can be achieved.

[0947] [Resin composition (B') containing polypropylene resin (B)]

[0948] The decorative film comprises a layer (II) containing a resin composition (B') comprising a polypropylene resin (B). The layer (II) may consist of only the polypropylene resin (B), or it may consist of a variety of polypropylene resins comprising the polypropylene resin (B), or it may be any mixture of polypropylene resin (B) and other polypropylene resins.

[0949] All resin compositions (B') satisfy the necessary conditions (b'1) and (b'2) described below. When resin composition (B') consists only of polypropylene resin (B), the polypropylene resin (B) satisfies the necessary conditions (b'1) and (b'2). Furthermore, when resin composition (B') is composed of a mixture of polypropylene resin (B) and other polypropylene resins, it is preferable that in addition to resin composition (B') satisfying the necessary conditions (b'1) and (b'2), the polypropylene resin (B) also satisfies the necessary conditions (b'1) and (b'2). There are no particular limitations on the mixing of polypropylene resin (B) and other polypropylene resins; it can be any of the following: mixing of granules and / or powders, melt mixing, or solution mixing, or a combination thereof.

[0950] In this invention, if the viscosity of the resin composition (B') containing polypropylene resin (B) is excessively reduced, sufficient molding stability cannot be obtained. Therefore, the resin composition (B') must have a certain viscosity. In this invention, the melt flow rate (MFR) (230°C, 2.16 kg load) is specified as an indicator of this viscosity.

[0951] In this specification, the MFR (230°C, 2.16 kg load) of the resin composition (B') containing polypropylene resin (B) is defined as MFR(B'). MFR(B') preferably satisfies the following necessary condition (b'1), preferably satisfies necessary condition (b'1'), and more preferably satisfies necessary condition (b'1”). By setting the MFR(B') of the resin composition (B') to a value below the following, a decorative molded article with a good appearance can be obtained.

[0952] (b'1)MFR(B') is less than 40g / 10 minutes.

[0953] (b'1')MFR(B') is less than 20g / 10 minutes.

[0954] (b'1”)MFR(B') is less than 12g / 10 minutes.

[0955] There is no particular limitation on the lower limit of the MFR(B') of the resin composition (B'), but it is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. By setting the MFR(B') to the above value or above, the formability during the manufacture of the decorative film is improved, and the appearance defects such as sharkskin-like roughness on the film surface can be suppressed.

[0956] In this specification, the determination of each MFR for polypropylene resins and resin compositions is carried out according to ISO 1133:1997 Conditions M, under conditions of 230°C and 2.16 kg load. The unit is g / 10 minutes.

[0957] The strain hardening degree λ of the resin composition (B') containing polypropylene resin (B) preferably satisfies the following necessary condition (b'2), more preferably satisfies the necessary condition (b'2'), and more preferably satisfies the necessary condition (b'2”). By setting the strain hardening degree of the resin composition (B') to a value within the following range, it is possible to obtain a decorative molded body with good formability and good appearance during decorative thermoforming.

[0958] (b'2) The strain hardening degree λ is 1.1 or higher.

[0959] (b'2') The strain hardening degree λ is 1.8 or higher.

[0960] (b'2") The strain hardening degree λ is 2.3 or higher.

[0961] There is no particular upper limit to the strain hardening degree of the resin composition (B'), but it is preferably 50 or less, more preferably 20 or less. By setting the strain hardening degree to a value within the above range, a good appearance of the decorative film can be achieved.

[0962] The strain hardening degree of the resin composition (B') is determined based on the determination of strain hardening property in tensile viscosity determination. The strain hardening degree λ can be calculated by the same method as described in the first and second embodiments of the present invention regarding the resin composition (X).

[0963] Conventional crystalline polypropylene is a linear polymer and typically does not exhibit strain hardening properties. In contrast, the polypropylene resin (B) used in this invention is preferably a polypropylene resin (BL) with a long-branched structure as described in the first and second embodiments of this invention, thereby enabling the resin composition (B') containing the polypropylene resin (B) to exhibit better strain hardening properties.

[0964] In the decorative films of the fifth and sixth embodiments, if the polypropylene resin (B) contains gel, the appearance of the film deteriorates; therefore, it is preferable to use a resin composition (B') that does not contain gel. In particular, the aforementioned polypropylene resin (BL) with a long branched structure is preferred, and it is a polypropylene resin with less gel produced by a method other than crosslinking. More preferably, a resin produced by the following method is preferred: using a metallocene catalyst with a specific structure, a macromolecular monomer with terminal unsaturated bonds is produced, and it is copolymerized with propylene, thereby forming a long branched structure.

[0965] In particular, the branching index g' when the absolute molecular weight Mabs is 1 million as described above preferably satisfies 0.3 or more and less than 1.0, more preferably 0.55 or more and less than 0.98, further preferably 0.75 or more and less than 0.96, and most preferably 0.78 or more and less than 0.95.

[0966] It should be noted that in this invention, "low gel content" refers to the branching index g' of a polypropylene resin with an absolute molecular weight of 1 million Mabs being within the aforementioned range. When the branching index g' is within this range, highly cross-linked components are not formed, there is no gel formation, or very little gel formation. Therefore, especially when the surface of the article is composed of a layer (II) containing a polypropylene resin (BL) with a long branched structure, the appearance will not be deteriorated.

[0967] As described in the first and second embodiments of the present invention, by means of 13 C-NMR can distinguish between short-branched and long-branched structures.

[0968] For such a polypropylene resin (BL) with a long branched structure, the resin composition (B') containing the polypropylene resin (B) only needs to contain an amount sufficient to impart strain hardening properties. Preferably, the polypropylene resin (BL) with a long branched structure contains 1 to 100% by weight, and more preferably 5% by weight or more, in 100% by weight of the resin composition (B').

[0969] In the fifth and sixth embodiments, the polypropylene resin (BL) with a long branched structure can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), propylene block copolymers (block polypropylene), or combinations thereof. Preferably, the polypropylene resin contains at least 50 mol% polymeric units derived from propylene monomers.

[0970] For the polypropylene resin (B) in the fifth and sixth embodiments of the present invention, from the viewpoints of heat resistance, scratch resistance, and solvent resistance, a high degree of crystallinity is preferred. The melting point (DSC melting peak temperature) of the polypropylene resin (B) is preferably 130°C or higher, more preferably 140°C or higher, further preferably 140–170°C, even more preferably 145–170°C, and 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. Furthermore, even with a high melting point, if it contains components with low crystallinity, scratch resistance and solvent resistance are reduced; therefore, the polypropylene resin (B) preferably does not contain an ethylene-α-olefin copolymer with an ethylene content of 50–70% by weight.

[0971] Furthermore, the melting peak temperature (Tm(B')) in the DSC measurement of polypropylene resin (B) is preferably higher than the melting peak temperature (Tm(A)) in the DSC measurement of polypropylene resin (A). That is, it is preferable to satisfy the following necessary condition (b3).

[0972] (b'3)Tm(B') satisfies the following relation (b'-3) with respect to Tm(A).

[0973] Tm(B')>Tm(A)···Equation (b'-3)

[0974] If it falls within the aforementioned range, the thermoformability becomes good.

[0975] The resin composition (B') containing polypropylene resin (B) may contain the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, other resin components, etc. In this case, the total amount of the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, other resin components, etc., is preferably 50% by weight or less relative to the resin composition (B') containing polypropylene resin (B) containing them.

[0976] When the decorative molded body of the present invention is formed into a colored molded body, the colorant is only used in the decorative film. Therefore, compared with the case where the entire resin molded body is colored, the use of expensive colorants can be suppressed. In addition, the changes in physical properties associated with the mixing of colorants can be suppressed. Various colorants such as inorganic pigments, organic pigments, and dyes can be used in the coloring process. In addition, luminescent materials such as aluminum flakes, titanium dioxide flakes, and (synthetic) mica can be used.

[0977] Other additives exemplified in the first and second methods may be used as other additives.

[0978] A resin composition (B') containing a polypropylene resin (B) can be manufactured by the following methods: a method of melt-blending a polypropylene resin with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components; a method of dry-blending other resin components in a product obtained by melt-blending a polypropylene resin with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc.; and a method of dry-blending a masterbatch, in which the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc., are dispersed in a carrier resin at a high concentration, based on a polypropylene resin and other resin components.

[0979] <Basic Implementation Method of Sealing Layer (I)>

[0980] [1. Sealing layer (I) containing polypropylene resin (A)]

[0981] The decorative film of the fifth and sixth embodiments of the present invention comprises: a sealing layer (I) containing a polypropylene resin (A) that satisfies the following necessary condition (a'1).

[0982] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[0983] By including a sealing layer (I) containing polypropylene resin (A) on the bonding surface of the resin molded body (substrate), sufficient adhesive strength is achieved even with a shortened film heating time during three-dimensional decorative thermoforming. This allows the molding to be completed before the nucleating agent and / or weathering agent evaporates, suppressing the reduction of surface gloss and / or weather resistance.

[0984] The melt flow rate (MFR(A)) of the polypropylene resin (A) at 230°C and a load of 2.16 kg is preferably greater than 2.0 g / 10 min, more preferably greater than 3.0 g / 10 min, and particularly preferably greater than 4.0 g / 10 min. Within the aforementioned range, sufficient relaxation occurs during the thermoforming of the three-dimensional decorative material, resulting in adequate bond strength. There is no upper limit to the MFR(A), but it is preferably less than 100 g / 10 min. Within the aforementioned range, deterioration of bond strength due to a decrease in physical properties will not occur.

[0985] For the determination of MFR of polypropylene resins (A) and resin compositions containing them, the determination shall be carried out according to ISO 1133:1997 Conditions M, at 230°C and under a load of 2.16 kg. The unit is g / 10 min.

[0986] The polypropylene resin (A) can be selected from various types of propylene polymers, such as propylene homopolymers (homogeneous polypropylene), propylene-α-olefin copolymers (random polypropylene), and propylene block copolymers (block polypropylene), or combinations thereof. The polypropylene resin (A) preferably contains at least 50 mol% of polymerization units derived from propylene monomers. The polypropylene resin (A) preferably does not contain polymerization units derived from monomers containing polar groups.

[0987] The melting point (DSC melting peak temperature) of the polypropylene resin (A) is preferably 100-170°C, more preferably 115-165°C.

[0988] For polypropylene resins (A), from a sealing point of view, propylene-α-olefin copolymers are preferred. Generally, compared with propylene homopolymers, propylene-α-olefin copolymers have lower crystallization temperatures as their melting points decrease, so they exhibit good adhesion even with short-term heating in three-dimensional decorative molding.

[0989] [2. Sealing layer (I) containing polypropylene resin (A)]

[0990] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, it is preferred that the polypropylene resin (A) satisfies the above-mentioned necessary conditions (a'1) and further satisfies the following necessary conditions (a'2) to (a'4), and the aforementioned resin composition (B') containing the polypropylene resin (B) further satisfies the following necessary condition (b'3).

[0991] (a'2) is a metallocene catalyst-based propylene polymer.

[0992] (a'3) Melting peak temperature (Tm(A)) is below 150℃.

[0993] (a'4) The molecular weight distribution (Mw / Mn(A)) measured by GPC was 1.5 to 3.5.

[0994] (b'3)Tm(B') satisfies the following relation (b'-3) with respect to Tm(A).

[0995] Tm(B')>Tm(A)···Equation (b'-3)

[0996] The necessary condition (a'1) is as described above in [1. Sealing layer (I) containing polypropylene resin (A)]. The necessary conditions (a'2) to (a'4) are respectively equivalent to the necessary conditions (a2) to (a4) in the first embodiment of the third and fourth embodiments, as described therein.

[0997] The melting peak temperature (Tm(B')) in the DSC measurement of the resin composition (B') containing polypropylene resin (B) is preferably higher than Tm(A), and more preferably Tm(B') > Tm(A) (necessary condition (b'3)). If it is within the aforementioned range, the thermoformability becomes good.

[0998] The melting point (Tm(B')) (melting peak temperature in DSC measurement) of the resin composition (B') is preferably 140°C or higher, more preferably 145–170°C, and 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. Furthermore, even with a high melting point, if it contains components with low crystallinity, scratch resistance and solvent resistance are reduced; therefore, the resin composition (B') preferably does not contain an ethylene-α-olefin copolymer with an ethylene content of 50–70% by weight.

[0999] [3. A sealing layer (I) of a resin composition (XX'3) containing a polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) in a weight ratio of 97:3 to 5:95]

[1000] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, the sealing layer (I) preferably contains a resin composition (XX'3) of a weight ratio of polypropylene resin (A) to ethylene-α-olefin random copolymer (C) of 97:3 to 5:95, wherein the polypropylene resin (A) satisfies the following necessary condition (a'1) and the ethylene-α-olefin random copolymer (C) satisfies the following necessary conditions (c'1) to (c'3).

[1001] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[1002] (c'1) Ethylene content [E(C)] is 65% by weight or more.

[1003] (c'2) Density is 0.850~0.950 g / cm³ 3 .

[1004] (c'3) Melt flow rate (230℃, 2.16kg load) (MFR(C)) is 0.1~100g / 10min.

[1005] The necessary condition (a'1) is as described above in [1. Sealing layer (I) containing polypropylene resin (A)]. The necessary condition for the ethylene-α-olefin random copolymer (C) is as described in the third embodiment of the third and fourth embodiments of the "ethylene-α-olefin random copolymer (C)". The necessary condition for the resin composition (XX'3) is equivalent to the necessary condition for the resin composition (XX3) in the third embodiment of the third and fourth embodiments, as described therein.

[1006] Melting peak temperature (Tm(A))

[1007] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point" in this specification) (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, good formability is achieved during three-dimensional decorative thermoforming. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[1008] In this method, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[1009] [4. A sealing layer (I) of a resin composition (XX'4) containing a polypropylene resin (A) and a thermoplastic elastomer (D) in a weight ratio of 97:3 to 5:95]

[1010] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, the sealing layer (I) preferably contains a resin composition (XX'4) in which the weight ratio of polypropylene resin (A) to thermoplastic elastomer (D) is 97:3 to 5:95, wherein the polypropylene resin (A) satisfies the following necessary condition (a'1) and the thermoplastic elastomer (D) satisfies the following necessary conditions (d'1) to (d'4).

[1011] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[1012] (d'1) is a thermoplastic elastomer with at least one of propylene and butene as its main components.

[1013] (d'2) Density is 0.850~0.950 g / cm³ 3 .

[1014] (d'3) Melt flow rate (230℃, 2.16kg load) (MFR(D)) is 0.1~100g / 10min.

[1015] (d'4) has a smaller tensile modulus than polypropylene resin (A).

[1016] The necessary condition (a'1) is as described above in [1. Sealing layer (I) containing polypropylene resin (A)]. The necessary condition for the thermoplastic elastomer (D) is as described in the fourth embodiment of the third and fourth embodiments, "Thermoplastic Elastomer (D)". The necessary condition for the resin composition (XX'4) is equivalent to the necessary condition for the resin composition (XX4) in the fourth embodiment of the third and fourth embodiments, as described therein.

[1017] Melting peak temperature (Tm(A))

[1018] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point" in this specification) (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, good formability is achieved during three-dimensional decorative thermoforming. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[1019] In this method, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[1020] [5. A sealing layer (I) of a resin composition (XX'5) containing a polypropylene resin (A) and a thermoplastic resin (E) in a weight ratio of 97:3 to 5:95]

[1021] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, the sealing layer (I) preferably contains a resin composition (XX'5) in which the weight ratio of polypropylene resin (A) to thermoplastic resin (E) is 97:3 to 5:95, wherein the polypropylene resin (A) satisfies the following necessary condition (a'1), the thermoplastic resin (E) satisfies the following necessary condition (e'1), and the resin composition (XX'5) satisfies the following necessary condition (xx'1).

[1022] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(A)) exceeds 2.0 g / 10 min.

[1023] (e'1) contains at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[1024] (xx'1) The isothermal crystallization time (t(XX'5)) (seconds) obtained by differential scanning calorimetry (DSC) satisfies the following formula (x'-1).

[1025] t(XX'5)≥1.5×t(A)···Formula (x'-1)

[1026] (In the formula, t(A) represents the isothermal crystallization time (seconds) of polypropylene resin (A) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A), and t(XX'5) represents the isothermal crystallization time (seconds) of resin composition (XX'5) measured at a temperature 10°C higher than the initial crystallization temperature of polypropylene resin (A).)

[1027] The necessary condition (a'1) is as described above in [1. Sealing layer (I) containing polypropylene resin (A)]. The necessary condition for the thermoplastic resin (E) is as described in the fifth embodiment of the third and fourth embodiments, "Thermoplastic Resin (E)". The necessary condition for the resin composition (XX'5) is equivalent to the necessary condition for the resin composition (XX5) in the fifth embodiment of the third and fourth embodiments, as described therein.

[1028] Melting peak temperature (Tm(A))

[1029] The melting peak temperature (DSC melting peak temperature, sometimes referred to as "melting point" in this specification) (Tm(A)) of the polypropylene resin (A) is preferably 110°C or higher, more preferably 115°C or higher, and even more preferably 120°C or higher. Within the aforementioned range, good formability is achieved during three-dimensional decorative thermoforming. There is no upper limit to the melting peak temperature, but it is preferably 170°C or lower; within the aforementioned range, sufficient adhesive strength can be achieved.

[1030] In this method, the polypropylene resin (A) can be a resin polymerized using a Ziegler catalyst, a metallocene catalyst, or the like. That is, the polypropylene resin (A) can be a Ziegler catalyst-based propylene polymer or a metallocene catalyst-based propylene polymer.

[1031] [6. Sealing layer (I) containing propylene-ethylene block copolymer (F)]

[1032] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, the sealing layer (I) contains propylene-ethylene block copolymer (F) as polypropylene resin (A), and the propylene-ethylene block copolymer (F) preferably satisfies the following necessary conditions (a'1), (f'1) and (f'2), and more preferably the propylene-ethylene block copolymer (F) satisfies (f'3), (f'4) and / or (f'5).

[1033] (a'1) Melt flow rate (230°C, 2.16 kg load) (MFR(F)) exceeds 2.0 g / 10 min.

[1034] (f'1) contains: 5 to 97% by weight of component (F1) which contains propylene homopolymer or propylene-ethylene random copolymer, and 3 to 95% by weight of component (F2) which contains propylene-ethylene random copolymer and has a higher ethylene content than the aforementioned component (F1).

[1035] (f'2) The melting peak temperature (Tm(F)) is 110~170℃.

[1036] (f'3) The ethylene content in the propylene-ethylene block copolymer (F) is 0.15–85% by weight.

[1037] (f'4) The ethylene content of the aforementioned component (F1) is in the range of 0 to 6% by weight.

[1038] (f'5) The ethylene content of the aforementioned component (F2) is in the range of 5 to 90% by weight.

[1039] The necessary condition (a'1) is as described above in [1. Sealing layer (I) containing polypropylene resin (A)]. In addition to the necessary condition (a'1), the necessary conditions for the propylene-ethylene block copolymer (F) are also as described in the sixth embodiment of the third and fourth embodiments of "Propylene-ethylene Block Copolymer (F)".

[1040] The polypropylene resin (A) in embodiments 1 to 6 described above may include the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc. That is, it may be a resin composition (polypropylene resin composition) of polypropylene resin and the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc. In this case, the total amount of the aforementioned additives, other additives besides the aforementioned additives, fillers, other resin components, etc., is preferably 50% by weight or less relative to the polypropylene resin composition.

[1041] Other additives, fillers, and resin components may be used as examples of the first and second methods.

[1042] [7. Sealing layer (I) containing polyolefin adhesive resin (G)]

[1043] As one aspect of the decorative film of the fifth and sixth embodiments of the present invention, the sealing layer (I) comprises: a sealing layer (I) containing a polyolefin adhesive resin (G), wherein the polyolefin adhesive resin (G) preferably satisfies the following necessary conditions (g'1) and (g'2).

[1044] (g'1) is a polyolefin resin having a polar functional group containing at least one heteroatom.

[1045] (g'2) Melt flow rate (230℃, 2.16kg load) (MFR(G)) is less than 100g / 10min.

[1046] Melt flow rate (MFR(G)): (g'2)

[1047] The melt flow rate (MFR(G)) of the polyolefin adhesive resin (G) in this method is preferably 100 g / 10 min or less, preferably 50 g / 10 min or less, and more preferably 20 g / 10 min or less. By setting the MFR(G) of the polyolefin adhesive resin (G) to the above-mentioned value or less, a sealing layer (I) containing the polyolefin adhesive resin (G) can be laminated onto a layer (II) containing a resin composition (B') comprising a polypropylene resin (B) by extrusion molding.

[1048] There is no particular limitation on the lower limit of the MFR(G) of the polyolefin adhesive resin (G), but it is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. By setting the MFR(G) of the polyolefin adhesive resin (G) to the above value or above, the following problems can be suppressed in the co-extrusion molding of the resin composition (B') containing the polypropylene resin (B) and the polyolefin adhesive resin (G): interfacial roughness at the lamination interface and failure of the polyolefin adhesive resin (G) to be laminated to the film end.

[1049] Polar functional groups containing heteroatoms: (g'1)

[1050] From the viewpoint of improving the adhesion to the layer (II) containing a resin composition (B') comprising a polypropylene resin (B), the polyolefin adhesive resin (G) in this embodiment is a polyolefin resin having a polar functional group containing at least one heteroatom.

[1051] Examples of polar functional groups having at least one heteroatom include: epoxy, carbonyl, ester, ether, hydroxyl, carboxyl or its metal salt, alkoxy, aryloxy, acyl, acyloxy, acid anhydride, amino, imide, amide, nitrile, mercapto, sulfonyl, isocyanate, and halogen. More preferably, the polyolefin adhesive resin (G) is a polyolefin resin having at least one functional group selected from the group consisting of epoxy, hydroxyl, carboxyl, acid anhydride, amino, imide, amide, nitrile, mercapto, isocyanate, and halogen.

[1052] Specific examples of polyolefins possessing such polar functional groups include: maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, acrylic acid-modified polypropylene, and other acid-modified polypropylene; ethylene / vinyl chloride copolymers, ethylene / vinylidene chloride copolymers, ethylene / acrylonitrile copolymers, ethylene / methacrylonitrile copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylamide copolymers, ethylene / methacrylamide copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / maleic acid copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / isopropyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / isobutyl acrylate copolymers, ethylene / 2-ethylhexyl acrylate copolymers, and ethylene / methyl methacrylate copolymers. ethylene or α-olefin / vinyl monomer copolymers, including ethylene / ethyl methacrylate copolymers, ethylene / isopropyl methacrylate copolymers, ethylene / butyl methacrylate copolymers, ethylene / isobutyl methacrylate copolymers, ethylene / 2-ethylhexyl methacrylate copolymers, ethylene / maleic anhydride copolymers, ethylene / ethyl acrylate / maleic anhydride copolymers, ethylene / metal acrylate copolymers, ethylene / metal methacrylate copolymers, ethylene / vinyl acetate copolymers or their saponifications, ethylene / vinyl propionate copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / ethyl acrylate / glycidyl methacrylate copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers, etc.; chlorinated polyolefins such as chlorinated polypropylene and chlorinated polyethylene, etc.

[1053] In addition, these resins can be used alone or in mixtures of two or more. Furthermore, they can be mixed with other resins or rubbers, tackifiers, the aforementioned additives, other additives besides those mentioned above, fillers, etc., as needed.

[1054] In polyolefin resins with polar functional groups, from the viewpoint of adhesion to layer (II), as commercially available products, it is appropriate to use the trade name "ADMER" manufactured by Mitsui Chemicals Co., Ltd., the trade name "MODIC" manufactured by Mitsubishi Chemical Co., Ltd., and the trade name "UMEX" manufactured by Sanyo Chemical Co., Ltd.

[1055] Other resins or rubbers mentioned above include, for example: polypentene-1, polymethylpentene-1 and other poly-α-olefins; propylene / butene-1 copolymer and other ethylene or α-olefin / α-olefin copolymers; ethylene / propylene / 5-ethylidene-2-norbornene copolymer and other ethylene or α-olefin / α-olefin / diene monomer copolymers; polybutadiene, polyisoprene and other polydiene copolymers; styrene / butadiene random copolymers, styrene / isoprene random copolymers and other vinyl monomer / diene monomer random copolymers; styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene block copolymers and other vinyl monomer / diene monomer / vinyl monomer block copolymers; hydrogenated (styrene / butadiene random copolymers), hydrogenated (styrene / isoprene random copolymers) and other hydrogenated... This includes vinyl polymers such as vinyl monomer / diene monomer random copolymers, hydrogenated styrene / butadiene / styrene block copolymers, hydrogenated styrene / isoprene / styrene block copolymers, acrylonitrile / butadiene / styrene graft copolymers, methyl methacrylate / butadiene / styrene graft copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, ethyl polyacrylate, butyl polyacrylate, polymethyl methacrylate, polystyrene, vinyl chloride / acrylonitrile copolymers, vinyl chloride / vinyl acetate copolymers, acrylonitrile / styrene copolymers, and methyl methacrylate / styrene copolymers.

[1056] Examples of the aforementioned tackifiers include, for instance, rosin-based resins (such as rosin resin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleic rosin, rosin esters, etc.), terpene phenol resins, terpene resins (polymers such as α-pinene, β-pinene, and limonene), aromatic hydrocarbon-modified terpene resins, petroleum resins (aliphatic, alicyclic, and aromatic resins, etc.), coumarone-indene resins, styrene-based resins, phenolic resins (alkylphenols, phenol-xylene-formaldehyde, rosin-modified phenolic resins, etc.), and xylene resins. These can be used alone or in combination of two or more. Among these, from the viewpoint of thermal stability, rosin-based resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, and hydrogenated petroleum resins are preferred. From the perspective of compatibility with the polyolefin adhesive resin (G) of the present invention and its ability to facilitate adhesion to polar resins, rosin-based resins and terpene phenol resins are particularly preferred.

[1057] Other additives besides those mentioned above may include other additives exemplified in the first and second embodiments, such as phosphorus-based processing stabilizers, metal soaps, acid adsorbents, crosslinking agents, chain transfer agents, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, and fluorescent whitening agents, which may be added within the scope that does not impair the effects of the present invention.

[1058] The resin composition of the sealing layer in the fifth and sixth embodiments can be manufactured by the following methods: a method of melt-blending the resin of embodiments 1 to 7 with the aforementioned additives, additives other than the aforementioned additives, fillers, and other resin components; a method of dry-blending other resin components in a product obtained by melt-blending the resin of embodiments 1 to 7 with the aforementioned additives, additives other than the aforementioned additives, fillers, etc.; a method of dry-blending a masterbatch in which the aforementioned additives, additives other than the aforementioned additives, fillers, etc., are dispersed in a carrier resin at a high concentration, based on the resin of embodiments 1 to 7 and other resin components.

[1059] <Decorative films of the fifth and sixth embodiments of the present invention>

[1060] The decorative film in the fifth and sixth embodiments of the present invention comprises a layer (II) and a sealing layer (I). That is, the decorative film can be a two-layer film comprising a layer (II) and a sealing layer (I), or it can be a multilayer film comprising three or more layers including a layer (II), a sealing layer (I), and other layers. The decorative film in the fifth and sixth embodiments can also have various other configurations besides layer (II) and sealing layer (I). It should be noted that the sealing layer (I) is attached along the resin molding body (substrate). Furthermore, the decorative film of the present invention can be textured, embossed, printed, sandblasted, scratched, etc., on its surface.

[1061] In addition to the sealing layer (I) and layer (II), the multilayer film may also include a substrate layer, a surface layer, a surface decoration layer (III), a printing layer, a light-shielding layer, a coloring layer, a barrier layer, and a connecting layer that can be disposed between these layers. The layer (II) containing the resin composition (B') can be any layer in the multilayer film except for the sealing layer.

[1062] When the decorative film is a two-layer film comprising a layer (II) and a sealing layer (I), layer (II) forms a surface layer opposite to the bonding surface facing the resin molded body, and sealing layer (I) forms the bonding surface to the resin molded body. In this case, layer (II) preferably contains a nucleating agent and / or a weather-resistant agent.

[1063] It can also be a multilayer film composed of more complex layers, similarly including layer (II) and sealing layer (I).

[1064] Furthermore, as another preferred embodiment of a multilayer film containing more than two layers than layer (II) and sealing layer (I), the layers other than layer (II) and sealing layer (I) are preferably layers containing thermoplastic resin, and more preferably layers containing polypropylene resin. The MFR (230°C, 2.16 kg load) of the polypropylene resin constituting the layers other than layer (II) and sealing layer (I) is not particularly limited, as long as the layers can be identified as layer (II) and sealing layer (I). Each layer is preferably a layer that does not contain thermosetting resin. By using thermoplastic resin, recyclability is improved; by using polypropylene resin, the complexity of the layer structure can be suppressed, thereby further improving recyclability.

[1065] Figure 1 (a)~ Figure 1 (c) An explanatory diagram illustrating a cross-section of an embodiment of a decorative film comprising layer (II) and a sealing layer (I), wherein layer (II) contains a resin composition (B') comprising a polypropylene resin (B). Figure 8 (a)~ Figure 8 (c) An explanatory diagram illustrating a cross-section of the aforementioned decorative film adhered to the resin molded body. The description of the drawing is as described in the third and fourth embodiments.

[1066] As a preferred embodiment of the multilayer film, the layers other than the sealing layer (I) and layer (II) are preferably layers containing thermoplastic resins, more preferably layers containing polypropylene resins other than polypropylene resins (B). Each layer is preferably a layer that does not contain thermosetting resins. By using thermoplastic resins, recyclability is improved. Furthermore, by using polypropylene resins other than polypropylene resins (B), the complexity of the layer structure can be suppressed, and recyclability is further improved.

[1067] Another preferred embodiment of the decorative film is a multilayer film in which a surface decorative layer (III) comprising a surface decorative layer resin is contained on the side opposite to the side that is bonded to the resin molded body, and more preferably on the outermost surface of the opposite side. The surface decorative layer resin is preferably a thermoplastic resin, and more preferably a polypropylene-based resin (H') with an MFR (230°C, 2.16 kg load) exceeding 2.0 g / 10 min. That is, by further providing a surface decorative layer (III) containing a polypropylene-based resin (H') on the surface layer of the decorative film, gloss and embossing transferability can be improved without significantly reducing thermoformability. Furthermore, by using a polypropylene-based resin (H'), the complexity of the layer structure and the reduction of recyclability can be suppressed. Moreover, by using a polypropylene-based resin (H') in the surface decorative layer (III) of the decorative film, excellent solvent resistance and other properties can be achieved. Furthermore, by using a polypropylene-based resin (H') in the surface decoration layer, the surface transferability during the manufacturing and thermoforming of the decorative film is improved. When using a mirror roller during thermoforming, a high-gloss decorative film can be produced. Moreover, by including the nucleating agent of this invention in the surface decoration layer, an even higher surface gloss can be achieved.

[1068] The polypropylene resin (H') in this embodiment can be selected from various types of propylene polymers, such as propylene homopolymer (homogeneous polypropylene), propylene-α-olefin copolymer (random polypropylene), and propylene block copolymer (block polypropylene), or combinations thereof. The polypropylene resin (H') preferably contains at least 50 mol% of polymeric units derived from propylene monomers. The polypropylene resin (H') preferably does not contain polymeric units derived from monomers containing polar groups. For the polypropylene resin (H'), homopolymere is preferred from the viewpoints of oil resistance, solvent resistance, and scratch resistance. Furthermore, propylene-α-olefin copolymer is preferred from the viewpoints of gloss and transparency (color development). In this embodiment, the polypropylene resin (H') constituting the surface decoration layer (III) can be the same as or different from the polypropylene resin (A) constituting the sealing layer (I).

[1069] In this method, the strain hardening degree of the polypropylene resin (H') is preferably less than 1.1, more preferably less than 1.0. By ensuring that the strain hardening degree of the polypropylene resin (H') is less than 1.1, the appearance of the decorative molded article can be improved. The strain hardening degree of the polypropylene resin (H') can be determined by the aforementioned method.

[1070] The MFR (Mean Free Rate) of the polypropylene resin (H') (at 230°C and 2.16 kg load) is preferably greater than 2.0 g / 10 min, more preferably 5.0 g / 10 min or more, and even more preferably 9.0 g / 10 min or more. By setting the MFR of the polypropylene resin (H') within the above-mentioned range, it is possible to easily improve the gloss of the decorative film and the embossing transferability, and to obtain a decorative molded body with a good appearance for the desired surface shape (gloss, matte, embossed, etc.).

[1071] There is no particular upper limit to the MFR of polypropylene resins (H'), but it is preferably 100 g / 10 min or less, and more preferably 50 g / 10 min or less. By setting the MFR to the range of the above values, good oil resistance, solvent resistance, scratch resistance, etc., can be achieved.

[1072] The polypropylene resin (H') may contain the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components. That is, it can be a resin composition (polypropylene resin composition) of the polypropylene resin (H') and the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components. The total amount of the aforementioned additives, other additives besides those mentioned above, fillers, colorants, and other resin components is preferably 50% by weight or less relative to the polypropylene resin composition.

[1073] Other additives, fillers, and resin components may be used as examples of the first and second methods.

[1074] Resin compositions containing polypropylene resin (H') can be manufactured by the following methods: a method of melt-blending polypropylene resin (H') with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, and other resin components; a method of dry-blending other resin components into a product obtained by melt-blending polypropylene resin (H') with the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc.; and a method of dry-blending a masterbatch, in which the aforementioned additives, other additives besides the aforementioned additives, fillers, colorants, etc., are dispersed in a carrier resin at a high concentration, based on polypropylene resin (H') and other resin components.

[1075] When the surface decorative layer (III) is a polypropylene resin composition containing a polypropylene resin (H'), this polypropylene resin composition may be the same as or different from a polypropylene resin composition with polypropylene resin (A) as a component, wherein the polypropylene resin (A) constitutes the sealing layer (I). When both polypropylene resin compositions are the same, it has the advantage that the sealing layer (I) and the surface decorative layer (III) can be formed using a feed block or similar device in a single extruder.

[1076] [Thickness of decorative film]

[1077] The thickness of the decorative film in the first to sixth embodiments of the present invention is preferably about 20 μm or more, more preferably about 50 μm or more, and even more preferably about 80 μm or more. By making the thickness of the decorative film at such a value or more, the appearance effect is improved, the stability during molding is also improved, and a better decorative molded article 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 even more preferably about 0.8 mm or less. By making the thickness of the decorative film at such a value or less, the heating time required during thermoforming can be shortened, thereby improving productivity and making it easier to cut off unwanted parts.

[1078] In the decorative films of the third to sixth embodiments of the present invention, the thickness of the sealing layer (I) preferably accounts for 1 to 70% of the total thickness of the decorative film, and the thickness of the layer (II) preferably accounts for 30 to 99%. When the thickness of the sealing layer (I) accounts for a proportion within the above-mentioned range of values ​​in the total thickness of the decorative film, sufficient adhesive strength can be achieved, damage to the resin molded body (matrix) can be suppressed from surfacing, and the decorative molding can be completed before the nucleating agent and / or weathering agent evaporate. In addition, when the thickness of the layer (II) accounts for a proportion within the above-mentioned range of values ​​in the total thickness of the decorative film, insufficient thermoformability of the decorative film can be avoided.

[1079] Furthermore, in the multilayer films in which a surface decorative layer (III) containing polypropylene resin (H) or (H') is provided on the outermost surface of the decorative film of the third to sixth embodiments of the present invention, the proportion of the thickness of the surface decorative layer (III) in the decorative film is preferably 30% or less relative to the overall thickness of the decorative film.

[1080] [Manufacturing of Decorative Films]

[1081] The decorative film of the present invention can be manufactured by a variety of known forming methods.

[1082] For example, in the case of multilayer films, the following methods can be listed: co-extrusion molding (e.g., in the third and fourth methods, co-extrusion molding of a sealing layer (I) containing a resin composition (XX) and a layer (II) containing a resin composition (YY), or co-extrusion molding of the sealing layer (I), layer (II), and other layers. In the fifth and sixth methods, co-extrusion molding of various sealing layers (I) and a layer (II) containing a resin composition (B') containing a polypropylene resin (B), or co-extrusion molding of the sealing layer (I), layer (II), and other layers).); hot lamination method, in which heat and pressure are applied to one side of a pre-extruded layer to bond other layers; dry lamination method and wet lamination method, in which bonding is achieved by means of an adhesive; extrusion lamination method, sandwich lamination method, etc., in which resin is melt-extruded to one side of a pre-extruded layer. As an apparatus for forming decorative films, known (co)extrusion T-die forming machines and known lamination forming machines can be used. From a productivity perspective, a co-extrusion T-die forming machine can be appropriately used.

[1083] Methods for cooling the molten decorative film extruded from the mold include: a method of contacting the molten decorative film with a cooling roller by means of air discharged from an air knife unit or an air chamber unit; and a method of pressing and cooling with multiple cooling rollers.

[1084] When imparting gloss to the decorative film of the present invention, a mirror-finishing method is performed by transferring a mirror-shaped cooling roller surface onto the outer surface of the decorative film article.

[1085] Furthermore, the decorative film of the present invention can have an embossed shape on its surface. Such a decorative film can be manufactured by methods such as: directly pressing molten resin extruded from a die onto a smooth roller to transfer the embossed shape; or pressing a smooth film onto a heated roller with an embossed shape and a smooth (cooling) roller to transfer the embossed shape. Examples of embossed shapes include satin, leather, brushed, and charcoal finishes.

[1086] The decorative film of the present invention can be heat-treated after film formation. Examples of heat treatment methods include heating with a hot roller, heating with a heating furnace, heating with a far-infrared heater, and blowing hot air.

[1087] [Decorative Molded Forms]

[1088] As the decorated resin molded body (decoration object) in this invention, various molded bodies (hereinafter sometimes referred to as "matrix") preferably containing thermoplastic resin, more preferably containing polyolefin resin, and even more preferably containing polypropylene resin or a polypropylene resin composition can be used. There are no particular limitations on the molding method of the molded body; examples include injection molding, blow molding, compression molding, extrusion molding, etc.

[1089] Polypropylene resins are non-polar and therefore difficult to bond. However, the decorative films in the third and fourth embodiments of the present invention, by comprising a sealing layer (I) containing a resin composition (XX) and a layer (II) containing a resin composition (YY), achieve very high adhesive strength when the decorative object containing the polypropylene resin is bonded to the decorative film, allowing the decorative molding to be completed before the nucleating agent and / or weathering agent evaporates. Furthermore, the decorative films in the fifth and sixth embodiments of the present invention, by comprising various sealing layers (I) and a layer (II) containing a resin composition (B') containing a polypropylene resin (B), achieve very high adhesive strength when the decorative object containing the polypropylene resin is bonded to the decorative film, allowing the decorative molding to be completed before the nucleating agent and / or weathering agent evaporates.

[1090] For the polypropylene resin and the base resin of the polypropylene resin composition used as the decorative object, various types of base resins based on a variety of known propylene monomers can be selected, such as propylene homopolymer (homopolymer), propylene-α-olefin copolymer, or propylene block copolymer. Furthermore, without impairing the effects of the present invention, fillers such as talc for imparting rigidity and elastomers for imparting impact resistance may be included. Additionally, similar to the polypropylene resin composition that can constitute the above-mentioned decorative film, the aforementioned additives, other additives besides the aforementioned additives, and other resin components may be included.

[1091] As decorative molded bodies (decorative objects) in the fifth and sixth embodiments of the present invention, various molded bodies containing polar resin materials can also be used. In such cases, it is preferable to use various molded bodies containing polar resin materials 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. Furthermore, additives such as inorganic fillers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, and lubricants can be added to these resins. These additives can be used alone or in combination of two or more. There are no particular limitations on the molding method; examples include injection molding, blow molding, compression molding, and extrusion molding.

[1092] For the aforementioned polar resin materials, non-polar polypropylene resins are difficult to bond, and therefore, they are generally not heat-bonded. In contrast, the decorative films in the fifth and sixth embodiments of the present invention, by containing a polyolefin adhesive resin (G) in the sealing layer (I), enable heat bonding between the decorative object and the decorative film, resulting in high adhesive strength. As the polyolefin adhesive resin (G), a modified polyolefin resin grafted with α,β-unsaturated carboxylic acids is preferably exemplified.

[1093] Decorative molded bodies obtained by attaching the decorative film of the present invention to various molded bodies formed in three-dimensional shapes are suitable for use as automotive components, home appliances, vehicles (railways, etc.), building materials, daily necessities, etc., due to the significant reduction in VOCs contained in coatings and adhesives.

[1094] [Manufacturing of Decorative Molded Components]

[1095] The method for manufacturing a decorative molded body according to the present invention is characterized by comprising the following steps: preparing the aforementioned decorative film, preparing a resin molded body, placing the aforementioned resin molded body and the aforementioned decorative film in a depressurization chamber, depressurizing the aforementioned chamber, heating and softening the aforementioned decorative film, pressing the aforementioned decorative film onto the aforementioned resin molded body, and restoring or pressurizing the aforementioned depressurized chamber to atmospheric pressure.

[1096] According to the method for manufacturing decorative molded articles of the present invention, there is no air entrapment between the decorative film and the resin molded article, resulting in a beautiful decorative molded article with good reproducibility of textures such as embossing. For decorative molded articles obtained using decorative films of the third to sixth methods, the constituent material of the decorative film is a polypropylene resin, which does not contain or may not contain a thermosetting resin layer. Therefore, even if recycled, the degradation of appearance and performance is small, and the recycling adaptability is high.

[1097] Three-dimensional decorative thermoforming has the following basic steps, involving the attachment of a thin film under reduced pressure: a resin molded body and a decorative film are placed in a chamber capable of depressurization; the film is heated and softened while the chamber is under reduced pressure; the softened decorative film is pressed onto the resin molded body; the chamber is then restored to atmospheric pressure, thereby attaching the decorative film to the surface of the resin molded body. This results in a beautiful decorative molded body that does not accumulate air. In the manufacturing method of this invention, all known techniques can be used, provided that the apparatus and conditions are suitable for three-dimensional decorative thermoforming.

[1098] That is, the chamber can be an object that houses the resin molded body and the decorative film, as well as the mechanism for pressing them and the device for heating the decorative film, all in one, or it can be multiple objects divided based on the decorative film.

[1099] In addition, the mechanism for pressing the resin molded body and the decorative film can be any type of mechanism that moves the resin molded body, mechanism that moves the decorative film, or mechanism that moves both.

[1100] The following examples illustrate representative forming methods in more detail.

[1101] Hereinafter, with reference to the figures, an exemplary method for attaching a decorative film to a resin molded body using a three-dimensional decorative thermoforming machine will be described.

[1102] like Figure 2 As shown, the three-dimensional decorative thermoforming machine of this embodiment has upper and lower chambers 11 and 12, and the decorative film 1 is thermoformed in the two chambers 11 and 12. Vacuum circuit (not shown) and air circuit (not shown) are respectively piped to the upper and lower chambers 11 and 12.

[1103] Additionally, a clamp 13 for fixing the decorative film 1 is provided between the upper and lower chambers 11 and 12. Furthermore, a movable worktable 14 is provided in the lower chamber 12, on which the resin molded object (decorative object) 5 is mounted (either by means of a clamp or directly). A heater 15 is installed in the upper chamber 11, through which the decorative film 1 is heated. The resin molded object 5 may be based on an acrylic resin composition.

[1104] As such a three-dimensional decorative thermoforming machine, commercially available forming machines (such as the NGF series manufactured by Fuse Vacuum Co., Ltd.) can be used.

[1105] like Figure 3 As shown, firstly, with the upper and lower chambers 11 and 12 open, a resin molding body 5 is placed on a worktable 14 inside the lower chamber 12, so that the worktable 14 is in a lowered state. Next, a decorative film 1 is placed in a film fixing clamp 13 between the upper and lower chambers 11 and 12, with the bonding surface facing the resin molding body 5.

[1106] like Figure 4 As shown, the upper chamber 11 is lowered, the upper and lower chambers 11 and 12 are joined, and the aforementioned housing is closed. Then, the respective chambers 11 and 12 are in a vacuum state, and the decorative film 1 is heated by the heater 15.

[1107] After the decorative film 1 is heated and softened, as follows: Figure 5As shown, while maintaining a vacuum in the upper and lower chambers 11 and 12, the worktable 14 inside chamber 12 is raised. The decorative film 1 is pressed onto the resin molded body 5, thereby covering the resin molded body 5. Then, as... Figure 6 As shown, the upper chamber 11 is opened to atmospheric pressure or compressed air is supplied through a compressor tank, thereby sealing the decorative film 1 with the resin molded body 5 with greater force.

[1108] Next, the upper and lower chambers 11 and 12 are opened to atmospheric pressure, and the decorative molded body 6 is removed from the lower chamber 12. Finally, as... Figure 7 For example, the edges of the unwanted decorative film 1 located around the decorative molded body 6 are trimmed off.

[1109] [Forming conditions]

[1110] For the decompression in chambers 11 and 12, it is sufficient to prevent air accumulation. The pressure in the chamber is preferably 10 kPa or less, more preferably 3 kPa or less, and even more preferably 1 kPa or less.

[1111] In addition, in the two chambers 11 and 12 divided into upper and lower sections by the decorative film 1, as long as the pressure in the chamber on the side where the resin molded body 5 is attached to the decorative film 1 is within this range, the drooping of the decorative film 1 can also be suppressed by changing the pressure in the upper and lower chambers 11 and 12.

[1112] At this time, films containing polypropylene resins may sometimes deform significantly and break due to the decrease in viscosity during heating and slight pressure changes.

[1113] The decorative film 1 of the third to sixth embodiments of the present invention comprises a layer (II) containing a specific polypropylene resin (B) or a resin composition (B') containing a specific polypropylene resin (B), thus it is not only not prone to drooping, but also resistant to film deformation caused by pressure changes.

[1114] The heating of the decorative film 1 is controlled by the heater temperature (power) and heating time. Alternatively, the surface temperature of the film can be measured using a thermometer such as a radiation thermometer, and appropriate target conditions can be set.

[1115] In this invention, in order to attach the decorative film 1 to the resin molded body 5, the surface of the resin molded body 5 and the decorative film 1 must be sufficiently softened or melted.

[1116] Therefore, the heater temperature must be higher than the melting temperature of the resin constituting the resin molded body 5 and the resin constituting the decorative film 1. In the case of a polypropylene decorative film, the heater temperature is preferably 160°C or higher, more preferably 180°C or higher, and most preferably 200°C or higher.

[1117] The higher the heater temperature, the shorter the heating time. However, the temperature on the heater side becomes too high until the interior of the decorative film 1 (or the side opposite to the heater in the case of a heater on only one side) is sufficiently heated. This not only leads to the deterioration of formability but also to the thermal degradation of the resin. Therefore, the heater temperature is preferably 500°C or less, more preferably 450°C or less, and most preferably 400°C or less.

[1118] The appropriate heating time varies depending on the heater temperature, and the decorative film must be sufficiently softened or melted. In the case of polypropylene decorative films, it is preferable that the decorative film is heated until a rebound, known as springback, begins. In the basic embodiments of the third and fourth embodiments of the present invention, the first embodiment, the second embodiment, and the fifth and sixth embodiments, it is preferable to heat for a period of 2 seconds after the end of the springback or for a period exceeding that time.

[1119] That is, the polypropylene decorative film, after being heated by the heater, is heated from a solid state, thereby causing thermal expansion. As the crystal melts, it temporarily relaxes. If the crystal melting proceeds as a whole, the molecules relax, and a rebound is temporarily observed. Subsequently, it exhibits a drooping behavior due to its own weight. After the rebound, the crystals of the decorative film completely melt, and the molecules relax sufficiently, thus resulting in good thermoforming properties and sufficient adhesive strength.

[1120] Furthermore, surprisingly, the decorative films of the third to sixth embodiments of the present invention can be firmly bonded to the substrate even when decorative thermoforming is performed before the rebound ends. This shortens the thermoforming time and allows forming to be completed before the nucleating agent and / or weather-resistant agent contained in the decorative film evaporates. Additionally, there is a significant effect on suppressing embossing recovery.

[1121] On the other hand, if the heating time becomes too long, the film will sag due to its own weight and deform due to the pressure difference between the upper and lower chambers. Therefore, in the first and second embodiments of the present invention, the heating time is preferably less than 120 seconds after the rebound ends, and in the third to sixth embodiments of the present invention, the heating time is preferably less than 30 seconds after the rebound ends.

[1122] When decorating molded bodies with complex, uneven shapes and achieving higher adhesion to ensure the decorative film adheres tightly to the substrate, compressed air is preferably supplied. The pressure in the upper chamber when introducing compressed air is 150 kPa or more, preferably 200 kPa or more, and more preferably 250 kPa or more. There is no particular upper limit, but if the pressure is too high, there is a concern that it may damage the machine; therefore, it can be 450 kPa or less, preferably 400 kPa or less.

[1123] In this invention, some or all of the necessary conditions of the first to sixth methods can be applied to other methods. Alternatively, some or all of the necessary conditions of each method can be combined with some or all of other methods and then applied to another method. In this case, the necessary conditions of the application source can be appropriately modified according to the form of the application target.

[1124] Example

[1125] The present invention will now be described in more detail by way of embodiments, but the present invention is not limited to these embodiments.

[1126] [Examples A and B]

[1127] 1. Methods for determining various physical properties

[1128] (i) Atomization test

[1129] The haze value (HAZE) of the glass plate covering the mouth of the sample bottle after the following atomization test according to ISO 6452 was measured using a haze meter (NDH5000 type, manufactured by Nippon Electronics Industries, Ltd.), and the change in haze value after the atomization test was calculated according to the following formula.

[1130] Change in haze value after fogging test = Haze value of glass plate after fogging test - Haze value of glass plate before fogging test

[1131] It should be noted that the haze value of the glass plate before the atomization test was 0.23.

[1132] <Atomization Test>

[1133] One g (±0.01 g) of an additive selected from nucleating agents, hindered amine light stabilizers, and ultraviolet absorbers was placed in a glass sample vial (83 mm inner diameter, 190 mm height). The vial was capped with a glass plate (3.0 mm thick) and heated at 150°C for 1 hour, causing the glass plate to fog (atomize). The fogging tester used was a WF-2 windshield fogging tester (manufactured by Suga Test Instruments Co., Ltd.). The glass sample vials and glass plates were provided by SugaTest Instruments Co., Ltd.

[1134] (ii) Melt Flow Rate (MFR)

[1135] The determination was performed according to ISO 1133:1997 Conditions M, at 230°C and a load of 2.16 kg. The unit is g / 10 minutes.

[1136] (iii) Strain hardening degree λ

[1137] The strain hardening degree λ is determined according to the method described above. Here, η*(0.01), used as the shear viscosity value, and ηe(3.5), used as the tensile viscosity value, are determined by the following method. Furthermore, the samples used in this measurement are flat plates with thicknesses of 0.7 mm and 2 mm, formed by pressing at 180°C and 10 MPa for 1 hour. The 0.7 mm thick sample is used for tensile viscosity measurement, and the 2 mm thick sample is used in the dynamic frequency scanning experiment.

[1138] (iii-1) Shear viscosity η*(0.01)

[1139] Dynamic frequency sweep experiments were performed using an ARES device manufactured by Rheometric Scientific. A parallel circular plate with a diameter of 25 mm was used for measurement geometry. Measurements were conducted using the TAOrchestrator software in Dynamic Frequency Sweep Test mode. The sample was a 2 mm thick pressed molded body prepared using the method described above. The measurement temperature was set to 180 °C. For the angular frequency ω, measurements were taken at 5 points per digit at equal intervals on a logarithmic scale, ranging from 0.01 to 100 rad / s.

[1140] As an indicator of the viscosity of a sample at low shear rates, the complex viscosity η*(0.01) [unit: Pa·s] at ω = 0.01 rad / s is used. It should be noted that the complex viscosity η* is calculated from the complex modulus G* [unit: Pa] and ω using η* = G* / ω.

[1141] (iii-2) Tensile viscosity ηe (3.5)

[1142] Tensile viscosity was measured using an ARES measuring fixture manufactured by Rheometric Scientific and an ExtensionalViscosity Fixture manufactured by TA Instruments Inc. The measurement was performed using the TAOrchestrator software in ExtensionalViscosityTest mode. A 0.7 mm thick test piece, formed using the method described above, was used. The test piece was 10 mm wide and 18 mm long. The strain rate was 1.0 s⁻¹. -1 The measurement temperature was 180℃. Other measurement parameters were set as follows.

[1143] Sampling Mode: log

[1144] Points per Zone: 200

[1145] Solid density: 0.9

[1146] Melt density: 0.8

[1147] Prestretch Rate: 0.05s -1

[1148] Relaxation after prestretch: 30 seconds

[1149] Under these conditions, data were collected up to 3.7 seconds after the start of the measurement. The time-dependent data of the tensile viscosity were obtained using software. The tensile viscosity value at 3.5 seconds (i.e., strain 3.5) of the obtained tensile viscosity curve was denoted as ηe(3.5) [unit: Pa·s].

[1150] (iv) Determination of the branching index g' when the absolute molecular weight Mabs is 1 million:

[1151] Based on the aforementioned method, the measurement was performed using a GPC detector equipped with a light scattering meter and a viscometer, and the branching index g' was calculated based on the aforementioned analytical method.

[1152] (v) use 13 Detection of long-branched structures by C-NMR:

[1153] Based on the aforementioned method, using 13 The presence or absence of long-branched structures was determined by C-NMR.

[1154] 2. Materials used

[1155] (1) Additives

[1156] (i) Nucleating agents

[1157] (A-1): Organometallic salt nucleating agent (change in haze value after atomization test = 12.9), manufactured by ADEKA Co., Ltd., trademarked as "ADK STAB NA-11"

[1158] (A-2): Organometallic salt nucleating agent (change in haze value after atomization test = 31.4), manufactured by ADEKA Co., Ltd., trademarked as "ADK STAB NA-21"

[1159] (A-3): Amide-based nucleating agent (change in haze value after atomization test = 13.1), manufactured by BASF Japan Ltd., trademark name "IRGACLEARXT386".

[1160] (A-4): Amide-based nucleating agent (change in haze value after atomization test = 7.0), manufactured by Shin Nippon Rika Co., Ltd., trademark name "PC-1"

[1161] (A-5): Sorbitol-based nucleating agent (change in haze value after atomization test = 49.6), manufactured by Milliken Japan, trademark name "MilladNX8000J"

[1162] (A-6): Sorbitol-based nucleating agent (change in haze value after atomization test = 49.5), manufactured by Shin Nippon Rika Co., Ltd., trademarked as "GEL All MD".

[1163] (ii) Hindered amine light stabilizers and ultraviolet absorbers

[1164] (A'-1): Hindered amine light stabilizer (change in HAZE value after atomization test = 3.78, molecular weight = approximately 3000), manufactured by BASF Corporation, trade name "Chimassorb 944"

[1165] (A'-2): Hindered amine light stabilizer (change in HAZE value after fogging test = 5.13, molecular weight = approximately 791), manufactured by ADEKA Co., Ltd., trade name "LA-57".

[1166] (A'-3): Hindered amine light stabilizer (change in HAZE value after fogging test = 3.98, molecular weight = approximately 1900), manufactured by ADEKA Co., Ltd., trade name "LA-68".

[1167] (A'-4): Hindered amine light stabilizer (change in HAZE value after fogging test = 49.59, molecular weight = 480), manufactured by BASF Corporation, trade name "Tinuvin 770"

[1168] (A'-5): Ultraviolet absorber (change in HAZE value after fogging test = 22.12, molecular weight = 659), manufactured by ADEKA Co., Ltd., trademarked as "ADK STAB LA-31G".

[1169] (2) Polypropylene resin

[1170] Use the following polypropylene resins.

[1171] (B-1): A propylene homopolymer without long branches (MFR = 10 g / 10 min, strain hardening degree λ = 1.0), manufactured by Japan Polypropylene Corporation, trade name "Novatec (registered trademark) FA3KM", branching index g' = 1.0 at an absolute molecular weight of 1 million Mabs, through... 13 C-NMR measurements confirmed that it did not have a long-branched structure.

[1172] (B-1-1): A polypropylene resin composition prepared by mixing 0.2 parts by weight of nucleating agent (A-1) with 100 parts by weight of polypropylene resin (B-1) (MFR = 10 g / 10 min).

[1173] (B-1-2): A polypropylene resin composition prepared by mixing 0.2 parts by weight of nucleating agent (A-2) with 100 parts by weight of polypropylene resin (B-1) (MFR = 10 g / 10 min).

[1174] (B-1-3): A polypropylene resin composition prepared by mixing 0.2 parts by weight of nucleating agent (A-3) with 100 parts by weight of polypropylene resin (B-1) (MFR...

Claims

1. A decorative film for thermoforming and adhering to a resin molded body under vacuum, the decorative film containing at least one additive selected from a nucleating agent, a hindered amine light stabilizer, and an ultraviolet absorber, The decorative film comprises: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), The surface layer of the decorative film contains the additive, and the additive satisfies the following requirements, Requirements: For a glass plate after the following fogging test is carried out by the method according to ISO6452, the change amount of the haze value measured by the method according to JIS-K7136 is 40 or less, Fogging test: Put 1 g of the additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150 °C for 1 hour to cause the glass plate to fog up, The polypropylene resin (A) satisfies the following requirement (a1), and the polypropylene resin (B) satisfies the following requirement (b1), (a1) The melt flow rate (MFR(A)) at 230 °C and a load of 2.16 kg exceeds 0.5 g / 10 min, (b1) The melt flow rate (MFR(B)) at 230 °C and a load of 2.16 kg and MFR(A) satisfy the relational expression (b-1), MFR(B) < MFR(A) ··· Expression (b-1), The sealing layer (I) contains a resin composition (XX3), and the resin composition (XX3) contains only the polypropylene resin (A) and an ethylene-α-olefin random copolymer (C) as resin components, and the weight ratio of the polypropylene resin (A) to the ethylene-α-olefin random copolymer (C) is 97:3 to 5:95, The ethylene-α-olefin random copolymer (C) satisfies the following requirements (c1) to (c3), (c1) The ethylene content is 65% by weight or more, (c2) Density: 0.850~0.950g / cm 3 , (c3) The melt flow rate (MFR(C)) at 230 °C and a load of 2.16 kg is 0.1 to 100 g / 10 min.

2. A decorative film for thermoforming and adhering to a resin molded body under vacuum, the decorative film containing at least one additive selected from a nucleating agent, a hindered amine light stabilizer, and an ultraviolet absorber, The decorative film comprises: a sealing layer (I) containing a polypropylene resin (A) and a layer (II) containing a polypropylene resin (B), The surface layer of the decorative film contains the additive, and the additive satisfies the following requirements, Requirements: For a glass plate after the following fogging test is carried out by the method according to ISO6452, the change amount of the haze value measured by the method according to JIS-K7136 is 40 or less, Fogging test: Put 1 g of the additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150 °C for 1 hour to cause the glass plate to fog up, The polypropylene resin (A) satisfies the following requirement (a1), and the polypropylene resin (B) satisfies the following requirement (b1), (a1) The melt flow rate (MFR(A)) at 230 °C and a load of 2.16 kg exceeds 0.5 g / 10 min, (b1) The melt flow rate (MFR(B)) at 230 °C and a load of 2.16 kg and MFR(A) satisfy the relational expression (b-1), MFR(B) < MFR(A) ··· Expression (b-1), The sealing layer (I) contains a resin composition (XX4), and the resin composition (XX4) contains only a propylene-based resin (A) and a thermoplastic elastomer (D) as resin components, and the weight ratio of the propylene-based resin (A) to the thermoplastic elastomer (D) is 97:3 to 5:95, The thermoplastic elastomer (D) is at least one copolymer selected from the group consisting of a butene-ethylene copolymer having an ethylene content of less than 50 wt%, a propylene-ethylene-butene copolymer having an ethylene content of less than 50 wt%, a propylene-butene copolymer, and a butene homopolymer, The thermoplastic elastomer (D) satisfies the following necessary conditions (d1) to (d4), (d1) A thermoplastic elastomer mainly composed of at least one of propylene and butene, (d2) Density: 0.850~0.950g / cm 3 , (d3) The melt flow rate (MFR(D)) at 230 °C and a load of 2.16 kg is 0.1 to 100 g / 10 min, (d4) The tensile elastic modulus is smaller than that of the polypropylene-based resin (A).

3. A decorative film, which is used for thermoforming and adhering to a resin molded body under vacuum, and the decorative film contains at least one additive selected from a nucleating agent, a hindered amine light stabilizer, and an ultraviolet absorber, The decorative film includes: a sealing layer (I) containing a polypropylene-based resin (A) and a layer (II) containing a polypropylene-based resin (B), The surface layer of the decorative film contains the additive, and the additive satisfies the following necessary conditions, Necessary condition: For a glass plate after the following fogging test is carried out by the method according to ISO6452, the change amount of the haze value measured by the method according to JIS-K7136 is 40 or less, Fogging test: Put 1 g of the additive into a glass sample bottle, cover the sample bottle with a glass plate, and heat at 150 °C for 1 hour to cause the glass plate to fog, The polypropylene-based resin (A) satisfies the following necessary condition (a1), and the polypropylene-based resin (B) satisfies the following necessary condition (b1), (a1) The melt flow rate (MFR(A)) at 230 °C and a load of 2.16 kg exceeds 0.5 g / 10 min, (b1) The melt flow rate (MFR(B)) at 230 °C and a load of 2.16 kg and MFR(A) satisfy the relational expression (b-1), MFR(B) < MFR(A) ··· Expression (b-1), The sealing layer (I) contains: a resin composition (XX5) in which the weight ratio of the polypropylene-based resin (A) to the thermoplastic resin (E) is 97:3 to 5:95, The thermoplastic resin (E) satisfies the following necessary condition (e1), and the resin composition (XX5) satisfies the following necessary condition (xx1), (e1) a styrene-based elastomer containing at least one of an alicyclic hydrocarbon group and an aromatic hydrocarbon group, (xx1) The isothermal crystallization time t(XX5) of the resin composition (XX5) determined by differential scanning calorimetry (DSC) satisfies the following formula (x-1): t(XX5)≥1.5×t(A)···Formula (x-1) In the formula, t(A) represents the isothermal crystallization time of the polypropylene resin (A) measured at a temperature 10°C higher than the crystallization starting temperature of the polypropylene resin (A), and t(XX5) is the isothermal crystallization time of the resin composition (XX5) measured at a temperature 10°C higher than the crystallization starting temperature of the polypropylene resin (A), and the unit of the isothermal crystallization time is seconds.

4. The decorative film according to any one of claims 1 to 3, wherein The nucleating agent is selected from any one or more of aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, nonitol derivatives, amide compounds and metal salts of rosin.

5. The decorative film according to any one of claims 1 to 3, wherein The polypropylene resin (A) further satisfies the following requirements (a2) to (a4), and the polypropylene resin (B) further satisfies the following requirement (b2), (a2) is a metallocene catalyst-based propylene polymer, (a3) the melting peak temperature (Tm(A)) is lower than 150°C, (a4) the molecular weight distribution Mw / Mn(A) measured by GPC is 1.5 to 3.5, (b2) The melting peak temperatures Tm(B) and Tm(A) satisfy the relationship (b-2), Tm(B)>Tm(A)···Formula (b-2).

6. The decorative film according to any one of claims 1 to 3, wherein The polypropylene resin (A) further satisfies the following requirement (a5), and the polypropylene resin (B) further satisfies the following requirement (b3), (a5) the crystallization temperature Tc(A) is lower than 100°C, (b3) The crystallization temperatures Tc(B) and Tc(A) satisfy the relationship (b-3), Tc(B)>Tc(A)···Formula (b-3).

7. The decorative film according to any one of claims 1 to 3, wherein The polypropylene resin (A) is a propylene-ethylene block copolymer (F) satisfying the following necessary conditions (f1) and (f2), wherein (f1) has a melting peak temperature (Tm(F)) of 110 to 170°C, (f2) contains: 5 to 97 wt% of a component (F1) comprising a propylene homopolymer or a propylene-ethylene random copolymer, and 3 to 95 wt% of a component (F2) comprising a propylene-ethylene random copolymer having a higher ethylene content than the component (F1).

8. The decorative film according to any one of claims 1 to 3, wherein The polypropylene-based resin (A) is a propylene-α-olefin copolymer.

9. The decorative film according to claim 5, wherein: The Tm(A) is 140°C or lower.

10. The decorative film according to claim 1, wherein: The ethylene-α-olefin random copolymer (C) further satisfies at least one of the following requirements (c4) and (c5), (c4) melting peak temperature (Tm(C)) is 30 to 130°C, (c5) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

11. The decorative film according to claim 2, wherein: The thermoplastic elastomer (D) further satisfies the following necessary condition (d5), (d5) The melting peak temperature (Tm(D)) is 30 to 170°C.

12. The decorative film according to claim 7, wherein: The propylene-ethylene block copolymer (F) further satisfies at least one of the following requirements (f3) to (f5), (f3) The ethylene content of 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.

13. The decorative film according to any one of claims 1 to 3, wherein The layer (II) has a surface decorative layer (III) on the side opposite to the side to be bonded to the resin molded body, wherein the surface decorative layer (III) comprises a surface decorative layer resin containing a nucleating agent.

14. The decorative film according to claim 13, wherein: The surface decorative layer (III) comprises a polypropylene resin (H) satisfying the following necessary condition (h1): (h1) The melt flow rate (MFR(H)) and MFR(B) at 230°C and 2.16 kg load satisfy the relationship (h-1). MFR(H)>MFR(B)···Formula (h-1).

15. A method for manufacturing a decorative molded body, comprising the following steps: a step of preparing the decorative film described in any one of claims 1 to 14; a step of preparing a resin molded body; a step of placing the resin molded body and the decorative film in a chamber capable of reducing pressure; a step of reducing pressure in the chamber; a step of heating and softening the decorative film; a step of pressing the decorative film against the resin molded body; and a step of restoring or pressurizing the reduced pressure chamber to atmospheric pressure.

16. The method for producing a decorative molded body according to claim 15, wherein: The resin molded article includes a propylene-based resin composition.

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