Recycled resin composition, method for producing same, and decorative molded body

Abstract

The present disclosure provides a recycled resin composition which is obtained by recycling a decorative molded body that is composed of a plurality of members of heterogeneous resins as it is without separating the members, and which is excellent in terms of mechanical characteristics.　A recycled resin composition according to the present disclosure is composed of a crushed product of a decorative molded body (4) which comprises an adherend (30) containing an olefin-based resin (O) and a decorative film (2), or a processed product of the crushed product, and contains 1-20 mass% of a thermoplastic elastomer (E) which is a block copolymer that has a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and / or a hydrogenated product of the block copolymer, 3-39 mass% of a (meth)acrylic resin (A), and 60-96 mass% of an olefin-based resin (O). At least one thermoplastic elastomer (E) contains an α-methylstyrene unit, and has a retention rate of the tensile elastic modulus of 50-150% and a retention rate of the tensile fracture strain of 50% or more.

Description

Recycled resin composition, its manufacturing method, and decorated molded article

[0001] The present disclosure relates to a recycled resin composition, a method for producing the same, and a decorated molded article.

[0002] Conventionally, in vehicles, for purposes such as surface protection and decoration, paint is applied to the surface of a vehicle exterior member by a spray coating method or the like, and then dried to form a coating. From the viewpoint of reducing environmental impact, solvent-containing paints are being replaced by decorative films having a base film made of a thermoplastic resin and a decorative layer. Under these circumstances, decorative molded bodies in which a decorative film is laminated on at least a portion of the surface of an adherend are becoming mainstream as vehicle exterior members. In addition, in recent years, efforts toward a sustainable society have been progressing, and the recycling of such decorative molded bodies has been considered.

[0003] JP 2002-067078 A JP 2008-120903 A JP 2022-183437 A

[0004] In the decorative molded body for the above-mentioned applications, the constituent resin of the adherend is preferably an olefin-based resin, etc., and the base resin of the decorative film is preferably a (meth)acrylic resin, a fluorine-based resin, etc. However, when such a decorative molded body consisting of a plurality of components of different resins is recycled as is, the compatibility of the plurality of different resins (e.g., olefin-based resin and (meth)acrylic resin) is poor, and the mechanical properties of the resulting recycled resin composition, such as the tensile modulus and tensile breaking strain, tend to be lower than those of virgin materials.

[0005] Patent Document 1 discloses a decorative molded body in which the constituent resin of the adherend and the base resin of the decorative film are the same type of resin (specifically, an olefin-based resin) (claims 1 and 7). This decorative molded body has excellent recyclability because the constituent resin of the adherend and the base resin of the decorative film are the same type. However, the olefin-based resin used as the base resin of the decorative film in Patent Document 1 has inferior scratch resistance and weather resistance compared to (meth)acrylic resins and fluorine-based resins, etc., and is therefore not preferred as a base resin for the decorative film.

[0006] A bonded member in which multiple components made of different resins are bonded via an easily peelable adhesive or pressure-sensitive adhesive layer can be highly recyclable. For example, a bonded member in which multiple components are bonded using the pressure-sensitive adhesive sheet disclosed in Patent Document 2 or the adhesive disclosed in Patent Document 3 can be separated by high-temperature heating and recycled individually. This technology can be applied to decorated molded bodies. However, this technology requires a process of heating the decorated molded body at a high temperature of 100°C or higher to separate the multiple components during recycling, which is undesirable in terms of the number of processes and energy required. In particular, for large vehicle components, recycling requires large heating equipment, making it impractical.

[0007] The present disclosure has been made in consideration of the above circumstances, and aims to provide a recycled resin composition that has excellent mechanical properties and can be obtained by recycling a decorated molded body made of multiple components of different resins without separating them.

[0008] The present disclosure provides a recycled resin composition, a method for producing the same, and a decorated molded article as set forth in the following [1] to

[11] . [1] A recycled resin composition containing crushed pieces of a decorated molded article, or a processed product of the crushed pieces, in which a decorative film is laminated via an adhesive layer on at least a portion of the surface of an adherend containing one or more olefin-based resins (O), the recycled resin composition comprising: 1 to 20 mass% of one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated products of the block copolymers; 3 to 39 mass% of one or more (meth)acrylic resins (A); and 60 to 96 mass% of the one or more olefin-based resins (O), in which the polymer block (x) of the at least one thermoplastic elastomer (E) contains α-methylstyrene units. A recycled resin composition that satisfies the following formulas (1) and (2), where Mv and Sv are the tensile modulus and tensile strain at break measured by the following method on a test piece made of the one or more virgin olefin resins (O) of the virgin materials that are the raw materials for the adherend, respectively, and Mre and Sre are the tensile modulus and tensile strain at break measured by the following method on a test piece made of the recycled resin composition, respectively: 50≦[Mre / Mv]×100[%]≦150 (1) 50≦[Sre / Sv]×100[%] (2) [Method for measuring tensile modulus and tensile strain at break] The tensile modulus and tensile strain at break of a dumbbell 1B test piece were measured in accordance with JIS K7161-1 and JIS K7161-2 at a temperature of 23°C and a pulling rate of 2 mm / min.

[0009] [2] The recycled resin composition of [1], which contains one or more thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers.

[0010] [3] The thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40% by mole, and hydrogenated versions of the block copolymers; one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40% by mole or more, and hydrogenated versions of the block copolymers; The recycled resin composition of [2] contains one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers.

[0011] [4] The recycled resin composition of [3], wherein the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0012] [5] The recycled resin composition according to any one of [1] to [4], wherein the conjugated diene compound units contained in the polymer block (b) are one or more units selected from the group consisting of isoprene units and butadiene units.

[0013] [6] The recycled resin composition according to any one of [1] to [5], wherein the (meth)acrylic resin (A) comprises a non-rubber (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

[0014] [7] The recycled resin composition of any of [1] to [6], wherein the mass ratio (E / A) of the thermoplastic elastomer (E) to the (meth)acrylic resin (A) is 0.70 to 6.67, and the Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the following method on a test piece made of the one or more olefin-based resins (O) of a virgin material that is a raw material of the adherend, are IRv and ILv, respectively, and the Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the following method on a test piece made of the recycled resin composition, are IRre and ILre, respectively, and the recycled resin composition satisfies the following formulas (3) and (4): 50≦[IRre / IRv]×100[%]≦150 (3) 50≦[ILre / ILv]×100[%]≦150 (4) [Method for Measuring Charpy Impact Value] A test piece 80 mm long, 10 mm wide, and 4 mm thick produced by injection molding is formed with a notch having a tip radius of 0.25 mm and a depth of 2 mm, and the Charpy impact value is measured using the edgewise method under a hammer load of 2 J in accordance with JIS K7111-1 / 1eA. Under room temperature conditions, the test piece is left to stand for 24 hours in an environment at a temperature of 23°C and a relative humidity of 50%, and then the Charpy impact value is measured. Under low temperature conditions, the test piece is left to stand for 3 hours in an environment at a temperature of -20°C, and then the Charpy impact value is measured.

[0015] [8] The recycled resin composition according to any one of [1] to [7], wherein the adhesive layer contains at least one thermoplastic elastomer (E) selected from one or more thermoplastic elastomers (E), one or more (meth)acrylic resins (A), and one or more olefin resins (O). [9] The recycled resin composition according to any one of [1] to [8], wherein the decorative film contains one or more (meth)acrylic resins (A) and / or one or more olefin resins (O).

[0016]

[10] A method for producing a recycled resin composition according to any one of [1] to [9], comprising the steps of: crushing the decorative molded body into pieces having a maximum length of 40 mm or less; and melting, kneading, and extruding a resin material containing the crushed pieces using an extruder, and shredding the extruded recycled resin composition into pellets having a maximum length of 5 mm or less, thereby obtaining pellets made of the recycled resin composition.

[0017]

[11] A decorated molded body having a decorative film laminated on at least a portion of the surface of an adherend, wherein the adherend comprises any one of the recycled resin compositions [1] to [9].

[0018] According to the present disclosure, a recycled resin composition having excellent mechanical properties can be provided, which can be obtained by recycling a decorated molded article made of multiple components of different resins as is without separation.

[0019] Fig. 1 is a schematic cross-sectional view showing an example of an adhesive film; Fig. 2 is a schematic cross-sectional view showing an example of a decorative film; Fig. 3 is a schematic cross-sectional view showing an example of a decorative film with an adhesive layer; Fig. 4 is a schematic cross-sectional view showing an example of a decorated molded body.

[0020] In this specification, "virgin material" refers to a molding material that has never been subjected to molding processing in the past, and its form may be pellets, flakes, etc., other than crushed molded products. Generally, the terms "film," "sheet," or "plate" are used for thin film molded products depending on the thickness, but there is no clear definition and no clear distinction between them. In this specification, "film" includes "sheet." In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylonitrile, etc.

[0021] Unless otherwise specified, the weight average molecular weight (Mw) of a (meth)acrylic resin is a weight average molecular weight (Mw) calculated as a standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn). Unless otherwise specified, the weight average molecular weight (Mw) of a resin other than a (meth)acrylic resin (such as a thermoplastic elastomer (E)) is a weight average molecular weight (Mw) calculated as a standard polystyrene by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn).

[0022] [Decorative Molded Body of Material] The decorative molded body, which is the material of the recycled resin composition of the present disclosure, is a body in which a decorative film is laminated on at least a portion of the surface of an adherend via an adhesive layer. The adherend contains one or more olefin-based resins (O) and may further contain one or more optional components as necessary. As the olefin-based resin (O) contained in the adherend, a polypropylene-based resin is preferred from the viewpoints of specific gravity and ease of recycling. The adherend may also be a laminate or composite consisting of multiple components.

[0023] The adhesive layer contains one or more thermoplastic elastomers (E) and, if necessary, may further contain one or more (meth)acrylic resins (A) and / or one or more olefin-based resins (O). The adhesive layer may further contain one or more optional components, if necessary. The adhesive layer may have a single-layer structure or a laminate structure. Examples of adhesive layers include a thermoplastic elastomer-containing layer containing one or more thermoplastic elastomers (E) and, if necessary, one or more olefin-based resins (O), such as polypropylene-based resins; or a laminate of this thermoplastic elastomer-containing layer with one or more other resin layers. From the viewpoints of transparency, weather resistance, surface gloss, and abrasion resistance, a (meth)acrylic resin-containing layer is preferred as the other resin layer. From the viewpoints of moldability and impact resistance, the (meth)acrylic resin-containing layer preferably contains one or more non-rubber (meth)acrylic resins and one or more rubber components selected from the group consisting of acrylic rubber particles (preferably 2-3 layers of acrylic multilayered polymer particles) and acrylic block copolymers.

[0024] An example of a material for the adhesive layer is an adhesive film. FIG. 1 is a schematic cross-sectional view showing an example of an adhesive film. The adhesive film 1 is a three-layer film in which thermoplastic elastomer-containing layers 11A and 11B are laminated on both sides of another resin layer 12 (e.g., a (meth)acrylic resin-containing layer). The configuration of the adhesive film can be appropriately modified, such as a single-layer structure consisting of only the thermoplastic elastomer-containing layer 11A or 11B, or a two-layer structure in which the thermoplastic elastomer-containing layer 11A or 11B is laminated on one side of the other resin layer 12.

[0025] The decorative film may have a substrate film and one or more decorative layers. The substrate film may be a film of a single layer structure or a laminate structure containing one or more thermoplastic resins. From the viewpoint of transparency and solvent resistance, the thermoplastic resin contained in the substrate film is preferably a (meth)acrylic resin; an olefin resin such as a polypropylene resin; a fluorine-based resin such as polyvinylidene fluoride (PVDF); or a combination thereof. (Meth)acrylic resins and fluorine-based resins such as polyvinylidene fluoride (PVDF) are also excellent in weather resistance and scratch resistance and are therefore preferred. The substrate film may preferably contain one or more (meth)acrylic resins (A) and / or one or more olefin resins (O). Specific examples of the substrate film include a (meth)acrylic resin film; an olefin resin film such as a polypropylene resin film; and a laminate film of a (meth)acrylic resin and another thermoplastic resin (e.g., a fluorine-based resin such as polyvinylidene fluoride (PVDF)).

[0026] Examples of decorative layers include metal layers, colored layers, and printed layers. A decorative layer containing a metal layer can impart a metallic appearance and gloss to the film. Examples of metals include Al, Si, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, alloys thereof (such as stainless steel), and combinations thereof. Figure 2 is a schematic cross-sectional view showing an example of a decorative film. In the figure, reference numeral 2 denotes a decorative film, reference numeral 21 denotes a substrate film, and reference numeral 22 denotes a decorative layer.

[0027] Before laminating the decorative film on the adherend, a decorative film 3 with an adhesive layer may be prepared as shown in Fig. 3. The decorative film 3 with an adhesive layer shown in Fig. 3 can be produced by laminating the adhesive film 1 shown in Fig. 1 and the decorative film 2 shown in Fig. 2 by a method such as pressure bonding (preferably thermocompression bonding). By laminating the decorative film 3 with an adhesive layer 3 with an adhesive layer 3 with an adhesive layer 2 ...

[0028] 4 is a schematic cross-sectional view showing an example of a decorative molded body 4. The decorative molded body 4 is formed by laminating a decorative film 2 on at least a portion of the surface of an adherend 30 via an adhesive film (adhesive layer) 1.

[0029] The decorative molded body can be produced by known methods. Examples of production methods include a method in which a decorative film with an adhesive layer is laminated onto at least a portion of the surface of a previously prepared adherend by a molding method such as vacuum forming, pressure forming, vacuum pressure forming, or compression molding, and the like, and the adhesive layer is then secondary-molded simultaneously; an injection molding and simultaneous lamination method is used in which a decorative film with an adhesive layer, which has been secondary-molded (also called pre-molded) as necessary by a vacuum forming method, pressure forming, or the like, is inserted into an injection molding mold, and a thermoplastic resin is then injected into the mold to simultaneously mold the adherend and laminate the decorative film with an adhesive layer onto at least a portion of the surface of the adherend. In the latter method, the adhesive layer decorative film may be pre-molded using an injection molding machine for molding the adherend.

[0030] [Recycled Resin Composition of the Present Disclosure] The recycled resin composition of the present disclosure includes a crushed piece of the above-described decorated molded body, in which a decorative film is laminated via an adhesive layer on at least a portion of the surface of an adherend containing one or more olefin-based resins (O), or a processed product of the crushed piece. Examples of the processed product of the crushed piece include a melt-kneaded product of the crushed piece; strands and pellets obtained from the melt-kneaded product of the crushed piece, etc.

[0031] The recycled resin composition of the present disclosure contains 1 to 20% by mass of one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated products of the block copolymers; 3 to 39% by mass of one or more (meth)acrylic resins (A); and 60 to 96% by mass of one or more olefin resins (O).

[0032] The polymer block (x) of at least one thermoplastic elastomer (E) contains α-methylstyrene (αMSt) units. In the present disclosure, a thermoplastic elastomer (E) having a polymer block (x) containing α-methylstyrene (αMSt) units is also referred to as a thermoplastic elastomer (Eα). The thermoplastic elastomer (Eα) has excellent adhesion to the (meth)acrylic resin (A) and the olefin-based resin (O), and can act as a compatibilizer between one or more thermoplastic elastomers (E), one or more (meth)acrylic resins (A), and one or more olefin-based resins (O). Therefore, even if a decorated molded article made of multiple components of different resins is recycled as is without separation, the multiple different resins (one or more thermoplastic elastomers (E), one or more (meth)acrylic resins (A), and one or more olefin-based resins (O)) are well compatible with each other, and the resulting recycled resin composition has excellent mechanical properties such as tensile modulus and tensile strain at break.

[0033] The content of one or more thermoplastic elastomers (E) in the recycled resin composition of the present disclosure (the total amount when multiple types are used) is 1 to 20% by mass. The lower limit is more preferably 1.5% by mass, even more preferably 2% by mass, particularly preferably 2.5% by mass, and most preferably 3% by mass. The upper limit is more preferably 17% by mass, particularly preferably 15% by mass, and most preferably 12% by mass. If the content of thermoplastic elastomer (E) is equal to or greater than the above-mentioned lower limit, the amount of thermoplastic elastomer (Eα) acting as a compatibilizer can be sufficient, and multiple different resins (one or more thermoplastic elastomers (E), one or more (meth)acrylic resins (A), and one or more olefinic resins (O)) can be well compatible to obtain a recycled resin composition with excellent mechanical properties such as tensile modulus and tensile break strain. If the content of thermoplastic elastomer (E) exceeds the above-mentioned upper limit, the tensile modulus may decrease due to softening caused by excess thermoplastic elastomer (E).

[0034] The content of one or more (meth)acrylic resins (A) in the recycled resin composition of the present disclosure (the total amount when multiple types are used) is 3 to 39% by mass. The lower limit is more preferably 4% by mass, even more preferably 5% by mass, particularly preferably 6% by mass, and most preferably 7% by mass. The upper limit is more preferably 35% by mass, particularly preferably 32% by mass, and most preferably 30% by mass.

[0035] The content of one or more olefin-based resins (O) in the recycled resin composition of the present disclosure (the total amount when multiple types are used) is 60 to 96% by mass. The lower limit is more preferably 65% ​​by mass, even more preferably 70% by mass, particularly preferably 75% by mass, and most preferably 80% by mass. The upper limit is more preferably 95% by mass, particularly preferably 92% by mass, and most preferably 90% by mass.

[0036] The tensile modulus and tensile strain at break measured by the following method for a test piece made of one or more olefin-based resins (O) from a virgin material that is the raw material for the adherend of the decorative molded body, which is the material for the recycled resin composition of the present disclosure, are defined as Mv and Sv, respectively. The tensile modulus and tensile strain at break measured by the following method for a test piece made of the recycled resin composition of the present disclosure are defined as Mre and Sre, respectively. The recycled resin composition of the present disclosure satisfies the following formulas (1) and (2): 50≦[Mre / Mv]×100[%]≦150 (1) 50≦[Sre / Sv]×100[%] (2) [Method for measuring tensile modulus and tensile strain at break] The tensile modulus and tensile strain at break of a dumbbell 1B test piece are measured at a temperature of 23°C and a pulling speed of 2 mm / min in accordance with JIS K7161-1 and JIS K7161-2.

[0037] [Mre / Mv] x 100 [%] is also referred to as "tensile modulus retention." The lower limit of the tensile modulus retention is more preferably 60%, even more preferably 70%, even more preferably 75%, even more preferably 80%, particularly preferably 85%, and most preferably 90%. The upper limit can be 140%, 130%, 120%, or 110%.

[0038] [Sre / Sv] x 100 [%] is also referred to as "tensile breaking strain retention." The lower limit of the tensile breaking strain retention is more preferably 60%, even more preferably 70%, even more preferably 80%, even more preferably 90%, particularly preferably 95%, and most preferably 100%. The upper limit can be 700%, 600%, or 500%.

[0039] (Thermoplastic elastomer (E)) The recycled resin composition of the present disclosure contains one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated products of the block copolymers. The one or more thermoplastic elastomers (E) can be contained in an adhesive layer that constitutes the decorative molded product, which is the material for the recycled resin composition of the present disclosure. The one or more thermoplastic elastomers (E) can impart excellent flexibility and impact resistance to an adhesive film containing the one or more thermoplastic elastomers (E).

[0040] The thermoplastic elastomer (E) contains one or more polymer blocks (a) containing one or more aromatic vinyl compound units. Examples of aromatic vinyl compounds include styrene (St), α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (a) may contain one or more other monomer units other than the aromatic vinyl compound units. Examples of other monomers other than the aromatic vinyl compound include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0041] The content of one or more aromatic vinyl compound units in polymer block (a) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of other monomer units than aromatic vinyl compound units in polymer block (a) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0042] The thermoplastic elastomer (E) contains one or more polymer blocks (b) containing one or more conjugated diene compound units. Examples of conjugated diene compounds include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (b) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (b) may contain one or more other monomer units other than the conjugated diene compound units. Examples of other monomers other than the conjugated diene compounds include styrene (St) and 4-methylstyrene.

[0043] The content of conjugated diene compound units in polymer block (b) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of monomer units other than conjugated diene compound units in polymer block (b) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0044] The bonding form between the polymer block (a) and the polymer block (b) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by a-b, triblock copolymers represented by a-b-a or b-a-b, tetrablock copolymers represented by a-b-a-b, pentablock copolymers represented by a-b-a-b-a or b-a-b-a-b, and (a-b) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by a-b-a are more preferred.

[0045] The content of polymer block (a) in thermoplastic elastomer (E) is not particularly limited, but is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of thermoplastic elastomer (E). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of polymer block (b) in thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of thermoplastic elastomer (E). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (a) and the polymer block (b) in the thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass.

[0046] The thermoplastic elastomer (E) may be an unhydrogenated block copolymer having one or more polymer blocks (a) and one or more polymer blocks (b), or a hydrogenated product thereof. The method for producing the unhydrogenated block copolymer is not particularly limited, and examples thereof include anionic polymerization. Examples include: (i) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, followed by sequentially polymerizing one or more conjugated diene compounds, and, if necessary, further sequentially polymerizing one or more aromatic vinyl compounds; (ii) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, followed by sequentially polymerizing one or more conjugated diene compounds, and then coupling the resulting mixture by adding a coupling agent; and (iii) a method in which a dilithium compound is used as an initiator to sequentially polymerize one or more conjugated diene compounds, followed by sequentially polymerizing one or more aromatic vinyl compounds, and, if necessary, further sequentially polymerizing one or more conjugated diene compounds.

[0047] From the viewpoint of improving heat resistance and weather resistance, the thermoplastic elastomer (E) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (b) containing conjugated diene compound units has been hydrogenated (also referred to as "hydrogenation"). The hydrogenation rate (hydrogenation rate) of the polymer block (b) is not particularly limited and is preferably 80 to 100%. The lower limit is more preferably 85%, and particularly preferably 90%. In this specification, the hydrogenation rate (hydrogenation rate) of the polymer block containing conjugated diene compound units can be determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction. Examples of hydrogenation reactions include a solution in which an unhydrogenated block copolymer is dissolved in a solvent inert to the hydrogenation reaction and the hydrogenation catalyst, or a reaction liquid containing the unhydrogenated block copolymer obtained after the polymerization reaction, and then reacting the unhydrogenated block copolymer with hydrogen in the presence of a hydrogenation catalyst. Commercially available thermoplastic elastomers (E) may also be used.

[0048] The thermoplastic elastomer (E) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary.

[0049] In a preferred embodiment, the one or more thermoplastic elastomers (E) can include one or more thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, and hydrogenated products of the block copolymers.

[0050] The one or more thermoplastic elastomers (E) may further comprise one or more thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of the block copolymers; and / or one or more thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0051] The one or more thermoplastic elastomers (E) may preferably comprise one or more first thermoplastic elastomers (EX), one or more second thermoplastic elastomers (EY), and one or more third thermoplastic elastomers (EZ). In this embodiment, the content of the first thermoplastic elastomer (EX), the content of the second thermoplastic elastomer (EY), and the content of the third thermoplastic elastomer (EZ) are preferably 15 to 55 parts by mass, 25 to 65 parts by mass, and 15 to 35 parts by mass, respectively, per 100 parts by mass of the total amount of the thermoplastic elastomers (E).

[0052] <First Thermoplastic Elastomer (EX)> The first thermoplastic elastomer (EX) can impart excellent flexibility and impact resistance to an adhesive film containing the same. The first thermoplastic elastomer (EX) contains a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and thereby can impart excellent chipping resistance to an adhesive film containing the same. In this specification, "chipping resistance" refers to resistance to damage and / or chipping caused by the impact of small particles such as pebbles and snow-melting salts.

[0053] The first thermoplastic elastomer (EX) contains one or more polymer blocks (xa) containing styrene (St) units. The polymer block (xa) may contain one or more aromatic vinyl compound units other than styrene (St) units. Examples of aromatic vinyl compounds other than styrene (St) include α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (xa) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of other monomers other than aromatic vinyl compounds include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0054] The content of styrene (St) units in the polymer block (xa) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (xa) (the total amount if multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (xa) (the total amount if multiple types are present) is not particularly limited, but is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0055] The first thermoplastic elastomer (EX) contains one or more polymer blocks (xb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the first thermoplastic elastomer (EX) have a total amount of 1,2-bonds and 3,4-bonds of less than 40 mol%. When the first thermoplastic elastomer (EX) contains multiple polymer blocks (xb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (xb) is less than 40 mol%.

[0056] Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (xb) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (xb) may contain one or more other monomer units other than the conjugated diene compound units. Examples of the other monomers other than the conjugated diene compound include styrene (St) and 4-methylstyrene.

[0057] The content of conjugated diene compound units in polymer block (xb) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of monomer units other than conjugated diene compound units in polymer block (xb) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0058] With regard to the bonding form of the conjugated diene compound units in the polymer block (xb), the butadiene units can have 1,2-bonds or 1,4-bonds, and the isoprene units can have 1,2-bonds, 3,4-bonds, or 1,4-bonds. The same applies to the polymer blocks (yb) and (zb). From the viewpoint of chipping resistance, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is less than 40 mol%, preferably 39 mol% or less. The upper limit is more preferably 35 mol%, even more preferably 30 mol%, even more preferably 25 mol%, even more preferably 20 mol%, particularly preferably 15 mol%, and most preferably 10 mol%. The lower limit is 0 mol%.

[0059] The total amount of 1,2-bonds and 3,4-bonds in the conjugated diene compound units in the polymer block containing the conjugated diene compound units is １ Specifically, it can be calculated from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm, which is derived from 1,2-bonded and 3,4-bonded conjugated diene compound units, to the integral value of the second peak at 5.0 to 5.45 ppm, which is derived from 1,4-bonded conjugated diene compound units.

[0060] The bonding form between the polymer block (xa) and the polymer block (xb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by xa-xb, triblock copolymers represented by xa-xb-xa or xb-xa-xb, tetrablock copolymers represented by xa-xb-xa-xb, pentablock copolymers represented by xa-xb-xa-xb-xa or xb-xa-xb-xa-xb, and (xa-xb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by xa-xb-xa are more preferred.

[0061] The content of the polymer block (xa) in the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 5 to 75 mass%. The lower limit is more preferably 10 mass%. The upper limit is more preferably 70 mass%, even more preferably 65 mass%, even more preferably 60 mass%, even more preferably 55 mass%, even more preferably 50 mass%, particularly preferably 45 mass%, and most preferably 40 mass%. The content of the polymer block (xb) in the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 95 to 25 mass%. The upper limit is more preferably 90 mass%. The lower limit is more preferably 30 mass%, even more preferably 35 mass%, even more preferably 40 mass%, even more preferably 45 mass%, even more preferably 50 mass%, particularly preferably 55 mass%, and most preferably 60 mass%. The total content of the polymer block (xa) and the polymer block (xb) in the first thermoplastic elastomer (EX) is not particularly limited, but is preferably 95 to 100% by mass. The lower limit is more preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass.

[0062] The first thermoplastic elastomer (EX) may be an unhydrogenated block copolymer having one or more polymer blocks (xa) and one or more polymer blocks (xb), or a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the first thermoplastic elastomer (EX) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (xb) containing a conjugated diene compound unit is hydrogenated (also referred to as hydrogenation). The hydrogenation rate (hydrogenation rate) of the polymer block (xb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0063] The first thermoplastic elastomer (EX) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary.

[0064] The weight average molecular weight (Mw) (standard polystyrene equivalent) of the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the mechanical properties and moldability of the first thermoplastic elastomer (EX), it is preferably 30,000 to 500,000. The lower limit is more preferably 50,000, even more preferably 60,000, particularly preferably 70,000, and most preferably 80,000. The upper limit is more preferably 400,000, even more preferably 300,000, even more preferably 200,000, particularly preferably 190,000, and most preferably 180,000.

[0065] Since the effects of the first thermoplastic elastomer (EX) (such as providing chipping resistance) are effectively exhibited, the content of the first thermoplastic elastomer (EX) is preferably 15 to 55 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 20 parts by mass, and particularly preferably 35 parts by mass. The upper limit is more preferably 50 parts by mass, and particularly preferably 45 parts by mass.

[0066] <Second Thermoplastic Elastomer (EY)> The second thermoplastic elastomer (EY) contains a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and thus can impart excellent adhesion to non-polar resins to an adhesive film containing this.

[0067] The second thermoplastic elastomer (EY) contains one or more polymer blocks (ya) containing styrene (St) units. The polymer block (ya) may contain one or more aromatic vinyl compound units other than styrene (St) units. The polymer block (ya) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of aromatic vinyl compounds other than styrene (St) and other monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0068] The content of styrene (St) units in the polymer block (ya) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (ya) (the total amount if multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (ya) (the total amount if multiple types are present) is not particularly limited, but is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0069] The second thermoplastic elastomer (EY) contains one or more polymer blocks (yb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the second thermoplastic elastomer (EY) have a total content of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the second thermoplastic elastomer (EY) contains multiple polymer blocks (yb), the total content of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (yb) is 40 mol% or more. The polymer block (yb) may contain one or more types of other monomer units other than the conjugated diene compound units. Examples of conjugated diene compounds, preferred embodiments, and examples of other monomers are the same as those for the polymer block (xb). The content of the conjugated diene compound units in the polymer block (yb) (the total amount when multiple types are contained) is not particularly limited, and is preferably 80 to 100 mass%. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than the conjugated diene compound units in the polymer block (yb) is not particularly limited and is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0070] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0071] The 1,2-bonds and 3,4-bonds of the conjugated diene compound units can be increased by adding one or more organic Lewis bases to the reaction solution during anionic polymerization. Furthermore, the total amount of 1,2-bonds and 3,4-bonds can be easily controlled by adjusting the amount of organic Lewis base added. Examples of organic Lewis bases include esters such as ethyl acetate; amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; amides such as dimethylacetamide; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; sulfoxides such as dimethyl sulfoxide; and ketones such as acetone and methyl ethyl ketone.

[0072] The bonding form between the polymer block (ya) and the polymer block (yb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by ya-yb, triblock copolymers represented by ya-yb-ya or yb-ya-yb, tetrablock copolymers represented by ya-yb-ya-yb, pentablock copolymers represented by ya-yb-ya-yb-ya or yb-ya-yb-ya-yb, and (ya-yb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by ya-yb-ya are more preferred.

[0073] The content of the polymer block (ya) in the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 5 to 75 mass%. The lower limit is more preferably 10 mass%. The upper limit is more preferably 70 mass%, even more preferably 65 mass%, even more preferably 60 mass%, even more preferably 55 mass%, even more preferably 50 mass%, particularly preferably 45 mass%, and most preferably 40 mass%. The content of the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 95 to 25 mass%. The upper limit is more preferably 90 mass%. The lower limit is more preferably 30 mass%, even more preferably 35 mass%, even more preferably 40 mass%, even more preferably 45 mass%, even more preferably 50 mass%, particularly preferably 55 mass%, and most preferably 60 mass%. The total content of the polymer block (ya) and the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited, but is preferably 95 to 100% by mass, and the lower limit is more preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass.

[0074] The second thermoplastic elastomer (EY) may be an unhydrogenated block copolymer having one or more polymer blocks (ya) and one or more polymer blocks (yb), or a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the second thermoplastic elastomer (EY) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (yb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (yb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0075] The second thermoplastic elastomer (EY) may contain, as necessary, one or more functional groups, such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group, in the molecular chain and / or at the molecular chain terminals. The weight average molecular weight (Mw) (standard polystyrene equivalent) of the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoints of the mechanical properties and moldability of the second thermoplastic elastomer (EY), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0076] Since the functional effects of the second thermoplastic elastomer (EY) (such as excellent adhesion to non-polar resins) are effectively exhibited, the content of the second thermoplastic elastomer (EY) is preferably 25 to 65 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 30 parts by mass, and particularly preferably 35 parts by mass. The upper limit is more preferably 60 parts by mass, particularly preferably 55 parts by mass, and most preferably 50 parts by mass.

[0077] <Third Thermoplastic Elastomer (EZ)> The third thermoplastic elastomer (EZ) contains a polymer block (za) containing α-methylstyrene (αMSt) units, which can impart rigidity and excellent adhesion to polar resins to an adhesive film containing the same. The third thermoplastic elastomer (EZ) contains a polymer block (zb) containing conjugated diene compound units having a total content of 1,2-bonds and 3,4-bonds of 40 mol% or more, which can impart excellent adhesion to non-polar resins to an adhesive film containing the same. The third thermoplastic elastomer (EZ) can act as a compatibilizer in the recycled resin composition of the present disclosure.

[0078] The third thermoplastic elastomer (EZ) contains one or more polymer blocks (za) containing α-methylstyrene (αMSt) units. The polymer block (za) may contain one or more aromatic vinyl compound units other than α-methylstyrene (αMSt) units. Examples of aromatic vinyl compounds other than α-methylstyrene (αMSt) include styrene (St), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (za) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of other monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0079] The content of α-methylstyrene (αMSt) units in the polymer block (za) is not particularly limited, and is preferably 80 to 100% by mass from the viewpoint of the rigidity of an adhesive film containing the same and excellent adhesion to polar resins. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing α-methylstyrene (αMSt) units in the polymer block (za) (the total amount if multiple types are present) is not particularly limited, and is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (za) (the total amount if multiple types are present) is not particularly limited, and is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0080] The third thermoplastic elastomer (EZ) contains one or more polymer blocks (zb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the third thermoplastic elastomer (EZ) have a total content of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the third thermoplastic elastomer (EZ) contains multiple polymer blocks (zb), the total content of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (zb) is 40 mol% or more. The polymer block (zb) may contain one or more types of other monomer units other than the conjugated diene compound units. Examples of conjugated diene compounds, preferred embodiments, and examples of other monomers are the same as those for the polymer block (xb).

[0081] The content of conjugated diene compound units in polymer block (zb) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of other monomer units than conjugated diene compound units in polymer block (zb) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0082] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (zb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0083] The bonding form between the polymer block (za) and the polymer block (zb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by za-zb, triblock copolymers represented by za-zb-za or zb-za-zb, tetrablock copolymers represented by za-zb-za-zb, pentablock copolymers represented by za-zb-za-zb-za or zb-za-zb-za-zb, and (za-zb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by za-zb-za are more preferred.

[0084] The content of the polymer block (za) in the third thermoplastic elastomer (EZ) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the third thermoplastic elastomer (EZ), it is preferably 5 to 75 mass%. The lower limit is more preferably 10 mass%. The upper limit is more preferably 70 mass%, even more preferably 65 mass%, even more preferably 60 mass%, even more preferably 55 mass%, even more preferably 50 mass%, particularly preferably 45 mass%, and most preferably 40 mass%. The content of the polymer block (zb) in the third thermoplastic elastomer (EZ) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the third thermoplastic elastomer (EZ), it is preferably 95 to 25 mass%. The upper limit is more preferably 90 mass%. The lower limit is more preferably 30 mass%, even more preferably 35 mass%, even more preferably 40 mass%, even more preferably 45 mass%, even more preferably 50 mass%, particularly preferably 55 mass%, and most preferably 60 mass%. The total content of the polymer block (za) and the polymer block (zb) in the third thermoplastic elastomer (EZ) is not particularly limited, but is preferably 95 to 100% by mass, and the lower limit is more preferably 97% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass.

[0085] The third thermoplastic elastomer (EZ) may be an unhydrogenated block copolymer having one or more polymer blocks (za) and one or more polymer blocks (zb), or a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the third thermoplastic elastomer (EZ) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (zb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (zb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0086] The third thermoplastic elastomer (EZ) may contain, as necessary, one or more functional groups, such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group, in the molecular chain and / or at the molecular chain terminals. The weight average molecular weight (Mw) (standard polystyrene equivalent) of the third thermoplastic elastomer (EZ) is not particularly limited, and from the viewpoints of the mechanical properties and moldability of the third thermoplastic elastomer (EZ), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0087] Since the effects of the third thermoplastic elastomer (EZ) (imparting rigidity, excellent adhesion to polar resins, excellent adhesion to non-polar resins, etc., and acting as a compatibilizer in the recycled resin composition of the present disclosure) are effectively exhibited, the content of the third thermoplastic elastomer (EZ) is preferably 15 to 35 parts by mass per 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 17 parts by mass, particularly preferably 18 parts by mass, and most preferably 19 parts by mass. The upper limit is more preferably 30 parts by mass, particularly preferably 27 parts by mass, and most preferably 25 parts by mass.

[0088] ((Meth)acrylic resin (A)) The recycled resin composition of the present disclosure contains one or more (meth)acrylic resins (A). The one or more (meth)acrylic resins (A) can be contained in one or more of the adhesive layer constituting the decorated molded body, which is the material for the recycled resin composition of the present disclosure, and the base film of the decorative film. The (meth)acrylic resin (A) contains one or more non-rubber (meth)acrylic resins (AX), and can further contain one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers, as necessary.

[0089] Examples of non-rubber (meth)acrylic resins (AX) include homopolymers or copolymers containing (meth)acrylic acid units and / or (meth)acrylic acid ester units; modified products thereof, and the like. The (meth)acrylic resin (AX) is preferably a homopolymer or copolymer containing structural units derived from one or more (meth)acrylic acid esters, including methyl methacrylate (MMA). The hydrocarbon group in the (meth)acrylic acid ester may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group, or a propyl group; an alicyclic hydrocarbon group; or an aromatic hydrocarbon group such as a phenyl group. From the viewpoint of transparency, the content of (meth)acrylic acid ester monomer units in the (meth)acrylic resin (AX) (the total amount in the case of multiple types, unless otherwise specified) is preferably 90 to 100% by mass. The lower limit is more preferably 95% by mass, and particularly preferably 98% by mass.

[0090] Examples of monomers other than MMA include methyl acrylate (MA), ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, trifluoromethyl (meth)acrylate, trifluoroethyl (meth)acrylate, pentaerythritol, and the like. (meth)acrylic acid esters such as methyltrifluoroethyl, glycidyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and 3-dimethylaminoethyl (meth)acrylate; unsaturated carboxylic acids such as (meth)acrylic acid, maleic anhydride, maleic acid, and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; aromatic vinyl compounds such as styrene (St), α-methylstyrene (αMSt), and o-, m-, or p-methylstyrene; (meth)acrylamide, (meth)acrylonitrile; vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride. Among these, from the viewpoint of availability, MA, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, etc. are preferred, MA and ethyl (meth)acrylate, etc. are more preferred, and MA is particularly preferred. The content of structural units derived from other monomers in the (meth)acrylic resin (AX) (unless otherwise specified, the total amount in the case of multiple types) is preferably 0 to 10 mass%.The upper limit is more preferably 5% by mass, and particularly preferably 2% by mass.

[0091] The (meth)acrylic resin (AX) is preferably obtained by polymerizing one or more (meth)acrylic acid esters containing MMA, and, if necessary, other monomers. When using multiple types of monomers, the multiple types of monomers are usually mixed to prepare a monomer mixture, and then polymerization is carried out. The polymerization method is not particularly limited, and from the viewpoint of productivity, radical polymerization methods such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization are preferred. The (meth)acrylic resin (AX) may also be a modified (meth)acrylic resin obtained by further modifying the (meth)acrylic resin obtained by the above polymerization method using a known method.

[0092] From the viewpoints of moldability, impact resistance, etc., the (meth)acrylic resin (A) preferably contains one or more (meth)acrylic resins (AX) and one or more rubber components selected from the group consisting of acrylic rubber particles (preferably acrylic multilayer structure polymer particles having 2 to 3 layers) and acrylic block copolymers. Known acrylic rubber particles (preferably acrylic multilayer structure polymer particles having 2 to 3 layers) and acrylic block copolymers can be used.

[0093] In the recycled resin composition disclosed herein, the thermoplastic elastomer (E) functions as a compatibilizer by forming a layer of polymer block (a) containing aromatic vinyl compound units at the interface between the (meth)acrylic resin (A) and the olefinic resin (O), which are poorly compatible. As a result, a recycled resin composition can be provided that exhibits excellent mechanical properties, such as tensile modulus and tensile strain at break, as well as excellent impact resistance at room temperature (20-30°C) and low temperatures (e.g., -30 to 0°C). However, if the mass ratio of the thermoplastic elastomer (E) to the (meth)acrylic resin (A) is too high, the tensile modulus may decrease due to softening caused by the excess thermoplastic elastomer (E). If the mass ratio of the (meth)acrylic resin (A) to the thermoplastic elastomer (E) is too high, the presence of the excess (meth)acrylic resin (A) may prevent the thermoplastic elastomer (E) from fully fulfilling its compatibilizing function, potentially resulting in brittle fracture of the (meth)acrylic resin (A), resulting in reduced impact resistance. From the viewpoints of mechanical properties such as tensile modulus and tensile strain at break, as well as impact resistance at room temperature (20 to 30°C) and low temperatures (e.g., -30 to 0°C), the mass ratio (E / A) of the thermoplastic elastomer (E) (total amount, if multiple types) to the (meth)acrylic resin (A) (total amount, if multiple types) is preferably 0.10 to 6.67. The lower limit is more preferably 0.20, even more preferably 0.30, even more preferably 0.40, even more preferably 0.50, even more preferably 0.60, even more preferably 0.70, even more preferably 0.80, even more preferably 0.90, particularly preferably 1.00, and most preferably 1.10. The upper limit is more preferably 6.00, even more preferably 5.00, even more preferably 4.00, even more preferably 3.00, even more preferably 2.00, particularly preferably 1.90, and most preferably 1.80.

[0094] The Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the following method, of a test piece made of one or more olefin-based resins (O) of virgin material that is the raw material of the adherend, are defined as IRv and ILv, respectively. The Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the following method, of a test piece made of the recycled resin composition of the present disclosure, are defined as IRre and ILre, respectively. The recycled resin composition of the present disclosure preferably satisfies the following formulas (3) and (4). 50≦[IRre / IRv]×100[%]≦150 (3) 50≦[ILre / ILv]×100[%]≦150 (4) [Method for Measuring Charpy Impact Value] A test piece 80 mm long, 10 mm wide, and 4 mm thick produced by injection molding is formed with a notch having a tip radius of 0.25 mm and a depth of 2 mm, and the Charpy impact value is measured using the edgewise method under a hammer load of 2 J in accordance with JIS K7111-1 / 1eA. Under room temperature conditions, the test piece is left to stand for 24 hours in an environment at a temperature of 23°C and a relative humidity of 50%, and then the Charpy impact value is measured. Under low temperature conditions, the test piece is left to stand for 3 hours in an environment at a temperature of -20°C, and then the Charpy impact value is measured.

[0095] [IRre / IRv] x 100 [%] is also referred to as "retention of Charpy impact value at room temperature." The lower limit of the retention of Charpy impact value at room temperature is more preferably 60%, even more preferably 70%, even more preferably 75%, even more preferably 80%, particularly preferably 85%, and most preferably 90%. The upper limit can be 140%, 130%, 120%, or 110%.

[0096] [ILre / ILv] x 100 [%] is also referred to as "Charpy impact value retention at low temperature." The lower limit of the Charpy impact value retention at room temperature is more preferably 60%, even more preferably 70%, even more preferably 75%, even more preferably 80%, particularly preferably 85%, and most preferably 90%. The upper limit can be 140%, 130%, 120%, or 110%.

[0097] (Olefin-based resin (O)) The recycled resin composition of the present disclosure contains one or more types of olefin-based resin (O). The one or more types of olefin-based resin (O) can be contained in one or more of the adherend, adhesive layer, and base film of the decorative film that constitute the decorated molded body that is the material for the recycled resin composition of the present disclosure. The olefin-based resin (O) is a homopolymer or copolymer containing one or more types of α-olefin units. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and cyclohexene. Examples of the olefin-based resin (O) include ethylene-based resins, propylene-based resins, polybutene, and poly-4-methylpentene-1. Examples of the olefin copolymer include copolymers containing ethylene units and / or α-olefin units having 3 or more carbon atoms (preferably 3 to 20 carbon atoms), such as propylene-ethylene block copolymers and propylene-ethylene-butene-1 block copolymers.

[0098] The olefin resin (O) contained in the adherend that constitutes the decorative molded article, which is the material for the recycled resin composition of the present disclosure, can contain one or more propylene polymers (P). The propylene polymer (P) is a homopolymer or copolymer containing propylene units and, as needed, one or more other monomer units. Examples of propylene copolymers include propylene-ethylene block copolymers and propylene-ethylene-butene-1 block copolymers. The adherend that constitutes the decorative molded article, which is the material for the recycled resin composition of the present disclosure, may include a layer or member made of the recycled resin composition of the present disclosure.

[0099] The adherend constituting the decorative molded article, which is the material for the recycled resin composition of the present disclosure, can contain one or more fillers in an amount of 0 to 50% by weight, preferably 5 to 50% by weight. Fillers can improve the mechanical strength of the adherend and reduce the shrinkage rate during molding. The filler can be inorganic particles, organic particles, organic-inorganic composite particles, or a combination thereof. Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, aluminum oxide, aluminum hydroxide, silica (silicon dioxide), calcined calcium silicate, calcined kaolin, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, glass, talc, clay, mica, carbon black, and white carbon, with talc being preferred. Examples of organic particles include resin particles such as crosslinked styrene-based resin particles, high-molecular-weight styrene-based resin particles, and crosslinked siloxane-based resin particles. The filler may be coated particles obtained by coating the surface of the above-exemplified particles with aluminum and titanium oxide, or surface-treated particles obtained by surface-treating the above-exemplified particles with a fatty acid or the like.

[0100] The adhesive layer constituting the decorative molded body, which is the material for the recycled resin composition of the present disclosure, can contain one or more olefin-based resins (O). The olefin-based resin (O) that can be contained in the adhesive layer can contain one or more propylene-based polymers (P). From the viewpoint of adhesiveness to various materials (polar resins, non-polar resins, or metals), the olefin-based resin (O) that can be contained in the adhesive layer preferably contains a combination of one or more first polypropylene-based polymers (PX) that do not have polar groups (also referred to as polar-group-free polypropylene-based polymers) and one or more second polypropylene-based polymers (PY) that have polar groups (also referred to as polar-group-containing polypropylene-based polymers).

[0101] Examples of methods for producing polar group-free polypropylene-based polymers include copolymerizing propylene and, if necessary, one or more other monomers by a known method. Examples of other monomers include α-olefins other than propylene, specific examples of which include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The form of copolymerization is not particularly limited, and examples include random copolymerization and block copolymerization.

[0102] Examples of polar groups contained in the polar group-containing polypropylene-based polymer include polar atoms such as oxygen, nitrogen, and sulfur atoms; (meth)acryloyloxy groups; hydroxyl groups; amide groups; carboxyl groups; acid anhydride groups; and halogen atoms such as chlorine atoms. A first method for producing a polar group-containing polypropylene-based polymer includes copolymerizing propylene, a polar group-containing monomer, and, if necessary, one or more other monomers using a known method. The copolymerization form is not particularly limited, and examples include random copolymerization and block copolymerization. A second method for producing a polar group-containing polypropylene-based polymer includes graft copolymerizing a polar group-containing monomer onto a polypropylene-based polymer (non-polar polypropylene-based polymer) that contains propylene units and, if necessary, one or more other monomer units but does not have polar groups. Among the above methods, graft copolymerization is preferred. The polar group-containing polypropylene-based polymer produced by the first or second production method includes propylene units and polar group-containing monomer units, and may further include, if necessary, one or more other monomer units.

[0103] Examples of polar group-containing monomers include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, unsaturated carboxylic acids or their esters or anhydrides, and (meth)acrylamide. Among these, unsaturated carboxylic acids or their esters or anhydrides are preferred, and carboxylic acid (anhydrides) such as maleic acid (anhydride) are more preferred. In this specification, carboxylic acid (anhydride) is a general term for carboxylic acids and carboxylic acid anhydrides.

[0104] As the polar group-containing polypropylene polymer, polypropylene having a carboxy group or a carboxylic acid anhydride group as the polar group is preferred from the viewpoint of adhesiveness to various materials. Among them, polypropylene polymers obtained by graft copolymerizing a polypropylene polymer having no polar group (non-polar polypropylene polymer) with a carboxylic acid (anhydride) to modify the polypropylene polymer (also referred to as a (carboxylic acid anhydride)-modified polypropylene polymer) are preferred. Among them, maleic acid (anhydride)-modified polypropylene polymers are more preferred.

[0105] The polar groups contained in the polar-group-containing polypropylene polymer produced by the first or second production method may be post-treated after the polymerization reaction. Polar groups such as (meth)acrylic acid groups and carboxyl groups may be neutralized with metal ions to form ionomers, or may be esterified with alcohols such as methanol and ethanol. Polar groups such as vinyl acetate groups may also be hydrolyzed.

[0106] A third method for producing a polar group-containing polypropylene-based polymer includes a method in which a polypropylene-based polymer containing propylene units and, if necessary, one or more other monomer units but not having a polar group (non-polar polypropylene-based polymer) is oxidized or halogenated (e.g., chlorinated) by a known method.

[0107] (Optional Components) The recycled resin composition of the present disclosure may contain one or more other polymers in addition to those described above. Examples of other polymers include styrene-based resins such as polystyrene, high-impact polystyrene, methyl methacrylate-styrene copolymer (MS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-maleic anhydride-methyl methacrylate copolymer (SMM resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, acrylic-acrylonitrile-styrene (AAS) resin, acrylonitrile-chlorinated ethylene-styrene (ACS) resin, and methacrylic butadiene styrene (MBS) resin; polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6; nylon 8; nylon 9; nylon 10; nylon 11; 66 and polyamide elastomers; polycarbonate resins; other thermoplastic resins such as polyphenylene sulfide, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, ethylene-vinyl acetate copolymer, phenoxy resin, and ethylene-based ionomer; thermosetting resins such as epoxy resin, phenol resin, melamine resin, and silicone resin; polyurethane and chlorinated polyurethane resin; modified polyphenylene ether; silicone-modified resin; silicone rubber; silicone rubber; olefin-based rubber such as IR, EPR, and EPDM.

[0108] The recycled resin composition of the present disclosure may optionally contain one or more additives, such as fillers, tackifying resins, softeners, antioxidants, lubricants, heat stabilizers, heat degradation inhibitors, light stabilizers, polymer processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, silicone oils, antiblocking agents, UV absorbers, release agents, foaming agents, antifoaming agents, antibacterial agents, antifungal agents, fragrances, and metals.

[0109] Examples of tackifying resins include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, rosin ester resins, hydrogenated rosin ester resins, terpene phenol resins, hydrogenated terpene phenol resins, terpene resins, hydrogenated terpene resins, aromatic hydrocarbon-modified terpene resins, coumarone-indene resins, phenol resins, and xylene resins.

[0110] Examples of softeners include paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; oligomers of ethylene and α-olefins; paraffin wax; liquid paraffin; polybutene; low molecular weight polybutadiene; low molecular weight polyisoprene; and the like. Examples of antioxidants include hindered phenolic, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, a combination of a hindered phenolic antioxidant and a phosphorus-based antioxidant is preferred. The metal that can be contained in the recycled resin composition of the present disclosure can be contained in a metal layer as a decorative layer contained in a decorative film that constitutes a decorative molded product that is the material for the recycled resin composition of the present disclosure.

[0111] As described above, according to the present disclosure, a recycled resin composition having excellent mechanical properties can be provided, which can be obtained by recycling a decorated molded body made of multiple components of different resins without separating them.

[0112] [Method for Producing the Recycled Resin Composition of the Present Disclosure] The method for producing the recycled resin composition of the present disclosure is not particularly limited and may include the steps of (S1) crushing a decorated molded article, which comprises one or more olefin-based resins (O) and a decorative film laminated via an adhesive layer on at least a portion of the surface of an adherend, into pieces with a maximum length of 40 mm or less, and (S2) melt-kneading and extruding the resulting resin material containing the crushed material using an extruder, and shredding the extruded recycled resin composition into pellets with a maximum length of 5 mm or less, to obtain pellets of the recycled resin composition of the present disclosure. The resin material fed into the extruder may optionally contain one or more optional components other than the crushed material. Optional components include virgin olefin-based resins (O).

[0113] (Washing step) The decorated molded body before step (S1) and / or the crushed material obtained after step (S1) can be washed batchwise or continuously using liquids such as water, detergent, neutralizing agent, and alkaline aqueous solution, as needed. After washing, the decorated molded body and / or crushed material are preferably dehydrated (preferably by centrifugal dehydration) and / or dried (preferably by hot air drying).

[0114] (Step (S1)) The decorated molded body can be crushed using a crusher such as a jaw crusher, impact crusher, cutter mill, stamp mill, ring mill, roller mill, jet mill, or hammer mill. The maximum length of the crushed material obtained after step (S1) is preferably 1 to 40 mm. The lower limit is more preferably 2 mm, particularly preferably 5 mm, and most preferably 8 mm. The upper limit is more preferably 30 mm, even more preferably 25 mm, even more preferably 20 mm, particularly preferably 15 mm, and most preferably 10 mm.

[0115] (Step (S2)) One or more optional components can be added to the crushed material before, at, or during step (S2), as needed. The crushed decorated molded body and optional components can be mixed before step (S2) begins using a Henschel mixer, tumbler, disperser, or the like. The crushed material obtained after step (S1) can be melt-kneaded and extruded into strands using an extruder such as a single-screw extruder, twin-screw extruder, or multi-screw extruder. The extruded strands can be cooled and cut into pellets with a maximum length of 5 mm or less using a pelletizer. A hot-cut method may be used instead of the above-described strand-cut method. After step (S2), pellets made from the recycled resin composition of the present disclosure can be obtained. The shape of the pellets is not particularly limited, and examples include rods, particles, cubes, rectangular parallelepipeds, and irregular shapes. The maximum length of the pellets is preferably 1 to 5 mm.

[0116] [Decorated Molded Body of the Present Disclosure] The recycled resin composition of the present disclosure can be used for any application and can be used as a material for the adherend of the decorated molded body. The decorated molded body of the present disclosure comprises an adherend containing the recycled resin composition of the present disclosure, and a decorative film is laminated on at least a portion of the surface thereof. The adherend may include a layer or member made of the recycled resin composition of the present disclosure, or may be a layer or member made entirely of the recycled resin composition of the present disclosure. Examples of methods for molding the adherend include solution casting, extrusion molding, compression molding (also known as press molding), injection molding, inflation molding, blow molding, calendar molding, solution casting, vacuum molding, and pressure molding. Examples of adherends include planar objects with single-layer or laminated structures such as films, sheets, and plates; pipes, tubes, rods; and any three-dimensional structures. The adherend may also be a laminate or composite comprising a layer or member made of the recycled resin composition of the present disclosure and a layer or member made of other resins or various materials other than resins.

[0117] [Applications] The recycled resin composition of the present disclosure and the decorated molded article containing the same can be used in any application, and are preferably used in various applications requiring design. Suitable applications include automobile interior components, and transportation-related parts such as automobile exterior components such as side visors, rear visors, head wings, headlight covers, and bumpers.

[0118] Examples and comparative examples according to the present invention will be described. Unless otherwise specified, the resin material used was virgin material. [Evaluation Items and Evaluation Methods] The evaluation items and evaluation methods are as follows. (Polymerization Conversion Rate) The polymerization conversion rate was determined by gas chromatography analysis. A Shimadzu Gas Chromatograph GC-14A was connected to a GL Sciences INERTCAP1 column (film thickness 0.4 μm, inner diameter 0.25 mmφ, length 60 m). Analysis was performed under the following conditions, and the polymerization conversion rate was calculated from the obtained data. Injection temperature: 250°C, Detector temperature: 250°C, Temperature profile: Hold at 60°C for 5 minutes → Heat to 250°C at a rate of 10°C / min → Hold at 250°C for 10 minutes.

[0119] (Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin were determined by gel permeation chromatography (GPC) analysis. The measurement device used was a GPC device "HLC-8320" manufactured by Tosoh Corporation. The separation column used was a series connection of "TSKguardcolumnSuperHZ-H", "TSKgelHZM-M", and "TSKgelSuperHZ4000" manufactured by Tosoh Corporation. A differential refractive index detector (RI detector) was used as the detector. A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran. The column oven temperature was set to 40°C. Tetrahydrofuran was used as the eluent, and the eluent flow rate was set to 0.35 ml / min. 20 μl of sample solution was injected into the instrument and a chromatogram was measured. Ten standard polystyrene or standard polymethyl methacrylate (PMMA) samples with molecular weights ranging from 400 to 5,000,000 were subjected to GPC measurement, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw, Mn, and Mw / Mn of the resin to be measured, converted to standard polystyrene or standard PMMA, were determined.

[0120] (Hydrogenation Rate) The hydrogenation rate of the polymer block containing conjugated diene compound units was determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0121] (Total amount of 1,2-bonds and 3,4-bonds) of a thermoplastic elastomer containing a polymer block containing a conjugated diene compound unit １ H-NMR measurement was performed. The total amount of 1,2-bonds and 3,4-bonds was calculated from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm, which is derived from 1,2-bonded and 3,4-bonded conjugated diene compound units, to the integral value of the second peak at 5.0 to 5.45 ppm, which is derived from 1,4-bonded conjugated diene compound units.

[0122] (Melting Point) The melting point of the polypropylene polymer was measured using a differential scanning calorimeter (Shimadzu Corporation, "DSC-50 (product number)"). Approximately 5 mg of a polypropylene film sample was placed in an aluminum pan and set in the above-mentioned apparatus. After nitrogen substitution for 30 minutes or more, the sample was heated from room temperature (20-25°C) to 200°C at a rate of 10°C / min in a nitrogen stream of 10 ml / min, held for 5 minutes, and then cooled to 40°C at a rate of 10°C / min (primary scan). Next, the sample was heated to 200°C at a rate of 10°C / min (secondary scan) to obtain a calorimetry curve of fusion. The maximum peak temperature of fusion (°C) was determined as the melting point (Tm).

[0123] (Melt Tension) The melt tension of the polypropylene-based polymer was measured using a capillary rheometer ("Capillograph 1D" manufactured by Toyo Seiki Seisakusho, Ltd.) equipped with a pulley-type tension measurement unit. The polypropylene-based polymer was placed in a cylinder with a diameter of 9.55 mmφ heated to a temperature of 230°C. The molten polypropylene-based polymer was extruded through an orifice with a diameter of 2.0 mmφ and a length of 40 mm at an extrusion speed of 20 mm / min, and taken up by a pair of take-up rolls at a take-up speed of 4.0 m / min. The tension applied to the pulley-type tension measurement jig was measured as the melt tension (N).

[0124] (Tensile Modulus and Tensile Breaking Strain) In each example and comparative example, in accordance with JIS K7161-1 and JIS K7161-2, a dumbbell 1B-type test piece was punched from the center of the planar view of the adherend (PP-M) (injection-molded plate) molded using virgin material as the material for the decorative molded body, and the tensile modulus (Mv) and tensile breaking strain (Sv) were measured at a temperature of 23 ° C and a tensile speed of 2 mm / min. In each example and comparative example, the pellets of the obtained recycled resin composition were injection-molded at 230 ° C using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., "SG-100") to obtain an injection-molded plate measuring 100 mm long x 40 mm wide x 3 mm thick. The tensile modulus (MRe) and tensile breaking strain (Sre) of the injection-molded plate made of this recycled resin composition were measured in the same manner as above. The retention of the tensile modulus and the retention of the tensile breaking strain were calculated based on the following formula. [Retention rate of tensile modulus] = [Mre / Mv] × 100 [%] [Retention rate of tensile breaking strain] = [Sre / Sv] × 100 [%]

[0125] (Charpy Impact Value) In each example and comparative example, a Charpy impact test was carried out on the virgin olefin resin (O) used as the raw material for the adherend and the resulting recycled resin composition using a "Digital Impact Tester DG-CB" manufactured by Toyo Seiki Co., Ltd. Using an injection molding machine ("M-100C" manufactured by Meiki Seisakusho Co., Ltd.), the resin composition to be measured was injection molded under conditions of a cylinder temperature of 200°C, a mold temperature of 50°C, and an injection speed of 25 mm / sec, to obtain an unnotched test piece having a length (l) of 80 mm, a width (b) of 10 mm, and a thickness (h) of 4 mm. A notch with a tip radius (rN) of 0.25±0.05 mm and a depth of 2 mm (i.e., the remaining width (bN) of the notched test piece = 8 mm) was formed in the unnotched test piece using a notching machine ("Notching Tool (registered trademark) A-4" manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7111-1 / 1eA, to obtain a notched test piece. The Charpy impact values ​​(kJ / m) of the obtained notched test piece under room temperature conditions and low temperature conditions were measured. ２) was measured in accordance with JIS K7111-1 / 1eA using the edgewise method with a hammer load of 2 J. At room temperature, the notched test specimen was left to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, after which the Charpy impact value was measured. At low temperature, the notched test specimen was left to stand for 3 hours in an environment with a temperature of -20°C, after which the Charpy impact value was measured. Using the above method, the Charpy impact value (IRv) at room temperature and the Charpy impact value (ILv) at low temperature were determined for notched test specimens made from virgin olefin-based resin (O), and the Charpy impact value (IRre) at room temperature and the Charpy impact value (ILre) at low temperature were determined for notched test specimens made from recycled resin compositions. The Charpy impact value retention rate at room temperature and the Charpy impact value retention rate at low temperature were calculated based on the following formula: [Charpy impact value retention rate at room temperature] = [IRre / IRv] x 100 [%] [Charpy impact value retention rate at low temperature] = [ILre / ILv] x 100 [%]

[0126] [Materials] <Methacrylic resin (M)> The following methacrylic resin (M1) was produced by a conventional method: (M1) Methyl methacrylate (MMA)-methyl acrylate (MA) copolymer (MMA unit content: 93.6% by mass, MA unit content: 6.4% by mass, Mw (standard PMMA equivalent) = 120,000, Mw / Mn = 2.1).

[0127] <Multilayered Polymer Particles (R)> The following multilayered polymer particles (R1) and (R2) were produced. (R1) A reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet, a monomer inlet tube, and a reflux condenser was charged with 100 parts by mass of deionized water, and 0.019 parts by mass of a surfactant (polyoxyethylene alkyl ether sodium acetate (NIKKOL-ECT-3NEX, manufactured by Nikko Chemicals Co., Ltd.)) and 0.10 parts by mass of sodium carbonate were added and dissolved. The atmosphere inside the reactor was purged with nitrogen gas to create a substantially oxygen-free state, and the aqueous solution was heated to 80°C. 0.04 parts by mass of potassium persulfate was added to the aqueous solution and stirred for 5 minutes, after which a mixture of 32.6 parts by mass of methyl methacrylate (MMA), 2.1 parts by mass of methyl acrylate (MA), and 0.07 parts by mass of allyl methacrylate was continuously added dropwise over 50 minutes. After completion of the addition, the mixture was held for 40 minutes to achieve a polymerization rate of 98% or higher, and emulsion polymerization was carried out. Next, 0.05 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 36.6 parts by mass of n-butyl acrylate (n-BA), 7.9 parts by mass of styrene (St), and 0.89 parts by mass of allyl methacrylate was continuously added dropwise over 60 minutes. After completion of the addition, the mixture was held for 90 minutes to achieve a polymerization rate of 98% or higher, and seed emulsion polymerization was carried out. At this point, the volume average particle size (D50) of the polymer particles in the latex was measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer and found to be 0.09 μm. Next, 0.02 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 18.6 parts by mass of methyl methacrylate (MMA), 1.2 parts by mass of methyl acrylate (MA), and 0.04 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 30 minutes. After the addition was completed, the mixture was maintained for 60 minutes until the polymerization rate reached 98% or more, and seed emulsion polymerization was carried out. The final latex was placed in a vessel equipped with a stirrer, and an aqueous magnesium sulfate solution was added to the stirred latex to cause salting-out coagulation. The coagulated material obtained was washed with water, dehydrated, and dried to obtain acrylic multilayer structure polymer particles (acrylic rubber particles) (R1).

[0128] (R2) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 100 parts by mass of deionized water, and 0.019 parts by mass of a surfactant ("Pelex SS-H" manufactured by Kao Corporation) and 0.5 parts by mass of sodium carbonate were added and dissolved. The atmosphere inside the reactor was purged with nitrogen gas to create a substantially oxygen-free state, and the aqueous solution was heated to 80°C. 0.02 parts by mass of potassium persulfate was added to the aqueous solution and stirred for 5 minutes. A mixture of 9.4 parts by mass of methyl methacrylate (MMA), 0.6 parts by mass of methyl acrylate (MA), and 0.02 parts by mass of allyl methacrylate was then added dropwise continuously over 20 minutes. After the addition was completed, the mixture was maintained for 30 minutes to achieve a polymerization rate of 98% or higher, and emulsion polymerization was then carried out. Next, 0.07 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 41.1 parts by mass of n-butyl acrylate (n-BA), 8.9 parts by mass of styrene (St), and 2.0 parts by mass of allyl methacrylate was continuously added dropwise over 80 minutes. After completion of the addition, the mixture was held for 60 minutes to achieve a polymerization rate of 98% or higher, and seed emulsion polymerization was carried out. At this point, the volume average particle size (D50) of the polymer particles in the latex was measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer and found to be 0.21 μm. Next, 0.07 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 37.6 parts by mass of methyl methacrylate (MMA), 2.4 parts by mass of methyl acrylate (MA), and 0.12 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 60 minutes. After the addition was completed, the mixture was maintained for 60 minutes until the polymerization rate reached 98% or more, and seed emulsion polymerization was carried out. The final latex was placed in a vessel equipped with a stirrer, and an aqueous magnesium sulfate solution was added to the stirred latex to cause salting-out coagulation. The coagulated material obtained was washed with water, dehydrated, and dried to obtain acrylic multilayer structure polymer particles (acrylic rubber particles) (R2).

[0129] <Block Copolymer (B)> The following block copolymer (B1) was produced by a conventional method. (B1) Acrylic triblock copolymer, methyl methacrylate (MMA) polymer block (b1))-(n-butyl acrylate (n-BA) polymer block (b2))-(methyl methacrylate (MMA) polymer block (b1), b1:b2:b1 (mass ratio) = 14.3:50.0:35.7, MMA unit:n-BA unit (mass ratio) = 50:50, weight average molecular weight (Mw, standard PMMA equivalent) = 70,000.

[0130] <Methacrylic Resin Composition (MR)> The following methacrylic resin composition (MR1) was produced. (MR1) 55.7 parts by mass of pellets of methacrylic resin (M1), 33.6 parts by mass of pellets of multilayer structure polymer particles (R1), 6.7 parts by mass of pellets of multilayer structure polymer particles (R2), and 4 parts by mass of pellets of block copolymer (B1) were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of methacrylic resin composition (MR1).

[0131] <Thermoplastic Elastomer (E)> The following thermoplastic elastomers (EX-1), (EY-1), and (EZ-1) were produced. (First Thermoplastic Elastomer (EX-1)) A pressure-resistant vessel whose interior had been replaced with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 61.1 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (6.42 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. The solution was heated to 50°C, and 0.81 kg of styrene (St) was added and polymerized for 1 hour. Subsequently, 10.87 kg of isoprene was added and polymerized for 2 hours. Subsequently, 0.81 kg of styrene (St) was added and polymerized for 1 hour. In this manner, a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Palladium carbon (palladium loading: 5% by mass) was added as a hydrogenation catalyst to this reaction solution in an amount of 5% by mass relative to the block copolymer, and the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150°C. After cooling and pressure release, the palladium carbon was removed by filtration, and the filtrate was concentrated and vacuum dried to obtain thermoplastic elastomer (EX-a) (a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in thermoplastic elastomer (EX-a) was 7 mol%.

[0132] Separately, a pressure-resistant vessel whose interior had been purged with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 420.0 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (44.1 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. After heating this solution to 50°C, 2.83 kg of styrene (St) was added and polymerization was allowed for 1 hour, followed by the addition of 19.81 kg of isoprene and polymerization for 2 hours. In this manner, a reaction solution containing a polystyrene-polyisoprene diblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as above to obtain thermoplastic elastomer (EX-b) (a hydrogenated product of polystyrene-polyisoprene diblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks of thermoplastic elastomer (EX-b) was 7 mol%.

[0133] The obtained thermoplastic elastomers (EX-a) and (EX-b) were melt-kneaded using a twin-screw extruder ("ZSK26 MegaCompounder" manufactured by Coperion) (ratio of effective screw length (L) to screw diameter (D) (L / D) = 54) at a screw rotation speed of 300 rpm and a melt-kneading temperature of 200°C, to obtain a first thermoplastic elastomer (EX-1). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the first thermoplastic elastomer (EX-1) was 7 mol%.

[0134] (Second Thermoplastic Elastomer (EY-1)) A pressure vessel whose interior had been replaced with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent, 94.1 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (9.9 g of sec-butyllithium) as an anionic polymerization initiator, and 300 g of tetrahydrofuran as a Lewis base, and mixed. After heating this solution to 50°C, 1.25 kg of styrene (St) was added and polymerized for 1 hour, followed by the addition of 10.00 kg of isoprene and polymerization for 2 hours, followed by the addition of 1.25 kg of styrene (St) and polymerization for 1 hour. In this way, a reaction liquid containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as in Production Example 1, to obtain a second thermoplastic elastomer (EY-1) (a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the second thermoplastic elastomer (EY-1) was 55 mol %.

[0135] (Third Thermoplastic Elastomer (EZ-1)) 4.29 kg of α-methylstyrene (αMSt), 6.25 kg of cyclohexane, 1.18 kg of methylcyclohexane, and 0.15 kg of tetrahydrofuran were charged into a pressure vessel whose interior had been replaced with nitrogen and dried, and then mixed. 0.42 L of a 1.3 M cyclohexane solution of sec-butyllithium was added to this solution, and polymerization was carried out at −10°C for 5 hours. Three hours after the start of polymerization, the weight-average molecular weight (Mw, in standard polystyrene terms) of poly(α-methylstyrene) (block S) was 6,600, and the polymerization conversion of α-methylstyrene was 90%. Next, 0.88 kg of butadiene was added to this reaction solution, and polymerization was carried out at −10°C for 30 minutes, after which 41.8 kg of cyclohexane was added. The polymerization conversion of butadiene at this point was 90%. After this process, a poly(α-methylstyrene) block (S)-polybutadiene block (t1) copolymer was obtained. The polybutadiene block (t1) had a weight average molecular weight (Mw, calculated as standard polystyrene) of 3,700 and a 1,2-bond content of 81 mol %.

[0136] To the reaction mixture was further added 7.71 kg of butadiene, and polymerization was carried out at 50°C for 2 hours to obtain a poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer. The weight-average molecular weight (Mw, calculated as standard polystyrene) of the polybutadiene block (t2) was 29,800, and the 1,2-bond content was 40 mol%.

[0137] To the reaction mixture, 0.54 L of a 0.5 M toluene solution of dichlorodimethylsilane was added, and a coupling reaction was carried out at 50°C for 1 hour. After this reaction, a poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2)-X-polybutadiene block (t2)-polybutadiene block (t1)-poly(α-methylstyrene) block (S) copolymer) was produced as a coupling product. Here, X represents a coupling residue. The resulting poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer had a poly(α-methylstyrene) block content of 31% by mass, and the 1,4-bond content in the total polybutadiene blocks (t1 + t2) was 55 mol%. The coupling product and the block copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer) that had not undergone the coupling reaction were subjected to GPC analysis, and the coupling efficiency was determined from the ratio of the UV absorption peak integral values ​​to be 94%.

[0138] A Ziegler hydrogenation catalyst consisting of nickel octylate and triethylaluminum was added to the reaction solution under a hydrogen atmosphere, and a hydrogenation reaction was carried out for 5 hours at a hydrogen pressure of 0.8 MPa and 80°C to obtain a third thermoplastic elastomer (EZ-1). The third thermoplastic elastomer (EZ-1) was mainly composed of a hydrogenated poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (a hydrogenated product of the above-mentioned coupling product), and its content was 94% by mass. The third thermoplastic elastomer (EZ-1) had a weight-average molecular weight (Mw, calculated as standard polystyrene) of 79,500, a number-average molecular weight (Mn, calculated as standard polystyrene) of 78,700, and Mw / Mn of 1.01. The hydrogenation rate of the entire polybutadiene block (t1 + t2) was 97.5%, and the combined proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block was 45 mol%.

[0139] <Polypropylene-based polymer (P)> The following polypropylene-based polymers (PX-1), (PX-2), (PY-1), and (PY-2) were prepared. (PX-1) "Waymax (registered trademark) MFX8" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18 N: 1.1 g / 10 min, melt tension: 24.5 × 10 －２ N, (PX-2) "Waymax (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18N: 9.0 g / 10 min, melt tension: 4.9 × 10 －２ N, (PY-1) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., "UMEX (registered trademark) 5500", melting point 123°C, (PY-2) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., "UMEX (registered trademark) 5202W", melting point 115°C.

[0140] [Examples E1-E11, Comparative Examples EC1-EC4] <Base Film (BF) of Decorative Film> The following thermoplastic resin films with a single-layer structure or laminate structure (single-layer structure unless otherwise specified) were prepared or manufactured as the base film of the decorative film. (BF1) Polypropylene (PP) film, "Pure Thermo" manufactured by Idemitsu Unitech Co., Ltd., thickness: 50 μm or 200 μm. (BF2) Using a vented 50 mmφ single-screw extruder, pellets of the methacrylic resin composition (MR1) were melt-kneaded at 260°C and extruded through a 500 mm wide T-die. The extruded resin in the molten state was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by wrapping around the third cooling roll. The cooled film was taken up by a pair of take-up rolls. In this way, a single-layer methacrylic resin film (BF2) with a width of 500 mm and a thickness of 50 μm or 75 μm was produced. (BF3) A laminated film of polyvinylidene fluoride (PVDF) and (meth)acrylic resin, "KFC Film FT50Y" manufactured by Kureha Extron Co., Ltd., thickness: 50 μm. The type, specific gravity, and thickness of the substrate film used in each example and comparative example are shown in Tables 1 to 3.

[0141] <Decorative Film (DF)> In each example and comparative example, a decorative film (DF) ((DF1), (DF2), or (DF3)) having a laminated structure of a base film (BF) ((BF1), (BF2), or (BF3)) and an indium layer (decorative layer, metal layer) was obtained. As a vacuum deposition apparatus, a "VE-2030" (resistance heating type) manufactured by Vacuum Device Co., Ltd. was used. As an evaporation source, indium particles with a purity of 99.99% and a particle size of 1 mm were used. A basket heater (alumina 92%) was used for resistance heating. The deposition conditions were a vacuum degree of 7 x 10 －３ The deposition was carried out at a pressure of 0.2 Pa and a rate of 0.8 Å / sec for 10 minutes. A 50 nm thick indium layer was vacuum-deposited as a decorative layer (metal layer) on the entire surface of one of the surfaces of the base film (BF) ((BF1), (BF2), or (BF3)) (in the case of the base film (BF3), the surface of the (meth)acrylic resin layer).

[0142] <Adhesive Film (AF) or (AFC)> The following adhesive films were produced. (AF1) 40 parts by mass of a first thermoplastic elastomer (EX-1), 40 parts by mass of a second thermoplastic elastomer (EY-1), 20 parts by mass of a third thermoplastic elastomer (EZ-1), 7.5 parts by mass of a first polypropylene-based polymer (PX-2), and 10 parts by mass of a second polypropylene-based polymer (PY-2) were melt-kneaded at 230°C using a twin-screw extruder ("TEM-28" manufactured by Toshiba Machine Co., Ltd.) and extruded into strands. The strands were cut using a pelletizer to obtain pellets (ER1) of an elastomer resin composition. Three single-screw extruders were prepared. Elastomer resin composition pellets (ER1), methacrylic resin composition (MR1), and elastomer resin composition pellets (ER1) were each loaded into the hoppers of separate extruders and melt-kneaded at 230°C. These resin compositions were then co-extruded through a 400mm-wide multi-manifold die. The thermoplastic resin laminate extruded in a molten state was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by being wrapped around the third cooling roll. The cooled film was taken up by a pair of take-up rolls. In this manner, a two-kind, three-layer adhesive film (AF1) (width: 300mm) consisting of a first elastomer resin composition layer (ER1), a methacrylic resin composition layer (MR1), and a second elastomer resin composition layer (ER1) was obtained. The thickness of the first elastomer resin composition layer and the thickness of the second elastomer resin composition layer were set to be the same, and the thickness of each layer was adjusted by the extrusion flow rate of each resin composition.

[0143] (AFC2) Elastomer resin composition pellets (ER2) were obtained in the same manner as for the elastomer resin composition pellets (ER1), except that the raw material composition of the elastomer resin composition was changed to 50 parts by mass of the first thermoplastic elastomer (EX-1), 50 parts by mass of the second thermoplastic elastomer (EY-1), 7.5 parts by mass of the first polypropylene-based polymer (PX-1), and 10 parts by mass of the second polypropylene-based polymer (PY-1). A comparative adhesive film (AFC1) (width: 300 mm) consisting of a two-kind, three-layer structure of a first elastomer resin composition layer (ER2) / a methacrylic resin composition layer (MR1) / a second elastomer resin composition layer (ER2) was obtained in the same manner as for the adhesive film (AF1), except that the elastomer resin composition pellets (ER2) were used instead of the elastomer resin composition pellets (ER1).

[0144] (AFC3) Using a vented 50 mm diameter single-screw extruder, pellets of maleic anhydride-modified polypropylene (Umex (registered trademark) 5202W manufactured by Sanyo Chemical Industries, Ltd., melting point 115°C) were melt-kneaded at 260°C and extruded through a 500 mm wide T-die. The resin extruded in a molten state was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by being wrapped around the third cooling roll. The film obtained after cooling was taken up by a pair of take-up rolls. In this way, a comparative adhesive film (AFC3) with a width of 500 mm and a thickness of 50 μm was produced, having a single-layer structure made of maleic anhydride-modified polypropylene.

[0145] The type of adhesive film used in each example and comparative example and the specific gravity and thickness of each layer are shown in Tables 1 to 3. In the tables, the "thickness of elastomer resin composition layer" is the total thickness of the first elastomer resin composition layer and the second elastomer resin composition layer.

[0146] <Decorative film with adhesive layer (ADF)> In each example and comparative example, a thermal lamination device ("VAII-700 type" manufactured by Taisei Laminator Co., Ltd.) was used, and a pair of heating rolls set at 110 ° C. was used to thermocompress the adhesive film (AF) or (AFC) ((AF1), (AFC2), or (AFC3)) and the decorative film (DF) ((DF1), (DF2), or (DF3)). The thermocompression bonding was performed so that the adhesive film (AF) or (AFC) and the indium layer (decorative layer, metal layer) contained in the decorative film (DF) were in contact with each other. After thermocompression bonding, the adhesive film (AF) or (AFC) became an adhesive layer. In this manner, a decorative film with an adhesive layer (ADF) (length 100 mm x width 40 mm) having a laminated structure of base film (BF) / indium layer (decorative layer, metal layer) / adhesive layer was obtained.

[0147] <Adherend> The following adherends were prepared. (PP-M) Injection-molded plates with a length of 100 mm, a width of 40 mm, and a thickness of 650 μm, 1500 μm, 1650 μm, or 3000 μm were obtained by injection molding a polypropylene resin (Prime Polymer Co., Ltd.'s "J709QG") at 230°C using an injection molding machine (Sumitomo Heavy Industries, Ltd.'s "SG-100"). The type, specific gravity, and thickness of the adherends used in each example and comparative example are shown in Tables 1 to 3.

[0148] <Decorated Molded Body (DM)> In each example and comparative example, a vacuum pressure molding machine ("NGF-0406-T" manufactured by Fuse Vacuum Co., Ltd.) was used to laminate a decorative film with an adhesive layer (ADF) onto one surface of an adherend (PP-M) by known three-dimensional surface decorative molding to obtain a decorated molded body (DM). The degree of vacuum was 0.5 kPa, and the heating temperature of the decorative film with an adhesive layer (ADF) was 130 ° C. Molding was performed so that the adherend (PP-M) and the adhesive layer included in the decorative film with an adhesive layer (ADF) were in contact with each other. The temperature of the decorative film with an adhesive layer (ADF) was measured with a radiation thermometer. In this way, a decorated molded body (DM) having a laminated structure of base film (BF) / indium layer (decorative layer, metal layer) / adhesive layer / adherend was obtained.

[0149] <Recycled Resin Composition> In each example and comparative example, the resulting decorated molded body (DM) was crushed into pieces with a maximum length of 10 mm or less using a single-screw low-speed crusher (STORZ "SCUTTER S3-18X 24") to obtain crushed material. The resulting crushed material was melt-kneaded at 230°C using a twin-screw extruder and extruded into strands. The resulting strands were cooled and cut into pieces with a maximum length of 5 mm or less using a pelletizer to obtain pellets of the recycled resin composition. Tables 1 to 3 show the content (total amount if multiple types) of thermoplastic elastomer (E), the content (total amount if multiple types) of (meth)acrylic resin (A), the content (total amount if multiple types) of olefin resin (O), and the mass ratio (E / A) of thermoplastic elastomer (E) to (meth)acrylic resin (A) in the recycled resin compositions obtained in each example and comparative example. The evaluation results of the obtained recycled resin compositions are shown in Tables 1 to 3.

[0150]

[0151]

[0152]

[0153] [Summary of Results] In Examples E1 to E11, a decorative film was laminated onto the surface of an adherend containing an olefin-based resin (O) via an adhesive layer, and a decorated molded body consisting of multiple components of different resins was recycled as is without separation to obtain a recycled resin composition. Each of the recycled resin compositions obtained contained 1 to 20% by mass of one or more thermoplastic elastomers (E), 3 to 39% by mass of one or more (meth)acrylic resins (A), and 60 to 96% by mass of one or more olefin-based resins (O). Each of the recycled resin compositions obtained contained a thermoplastic elastomer (EZ) containing α-methylstyrene (αMSt) units. Each of the recycled resin compositions obtained had a tensile modulus retention rate of 50 to 150%, a tensile break strain retention rate of 50% or more, and good mechanical properties.

[0154] The recycled resin compositions obtained in Examples E2, E3, E5, and E6 to E10 all had Charpy impact value retention rates of 50 to 150% at room temperature and at low temperatures, and also had good impact resistance properties at room temperature and low temperatures. In particular, the recycled resin compositions obtained in Examples E6 to E10, in which the mass ratio (E / A) of the thermoplastic elastomer (E) to the (meth)acrylic resin (A) was 0.70 to 6.67, had high and excellent impact resistance properties at room temperature and low temperatures.

[0155] In Comparative Example EC1, the same adhesive film as in Examples E1 to E11 was used, but the adhesive film was thin at 30 μm, and the content of one or more thermoplastic elastomers (E) in the resulting recycled resin composition was less than 1 mass %. The resulting recycled resin composition had poor compatibility between the (meth)acrylic resin (A) and the olefin resin (O), and the tensile break strain retention rate was less than 50%, resulting in poor mechanical properties.

[0156] In Comparative Example EC2, the same adhesive film as in Examples E1 to E11 was used, but the adhesive film was as thick as 1000 μm, and the content of one or more thermoplastic elastomers (E) in the resulting recycled resin composition exceeded 20% by mass. The resulting recycled resin composition had poor mechanical properties, with a tensile modulus retention rate of less than 50% due to softening caused by the excess thermoplastic elastomer (E).

[0157] In Comparative Examples EC3 and EC4, a comparative adhesive film was used that did not contain a thermoplastic elastomer (EZ) containing α-methylstyrene (αMSt) units. In all of the obtained recycled resin compositions, the (meth)acrylic resin (A) and the olefin resin (O) were not well compatible with each other, and the retention rate of tensile break strain was less than 50%, resulting in poor mechanical properties.

[0158] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention.

[0159] This application claims priority based on Japanese Patent Application No. 2024-091866, filed on June 6, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0160] REFERENCE SIGNS LIST 1 adhesive film 2 decorative film 3 decorative film with adhesive layer 4 decorated molded body 11A, 11B thermoplastic elastomer-containing layer 12 other resin layer 21 substrate film 22 decorative layer 30 adherend

Claims

1. A recycled resin composition comprising crushed pieces of a decorated molded body, or a processed product of said crushed pieces, in which a decorative film is laminated via an adhesive layer on at least a portion of the surface of an adherend containing one or more olefin-based resins (O), the composition comprising 1 to 20 mass% of one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated products of said block copolymers; 3 to 39 mass% of one or more (meth)acrylic resins (A); and 60 to 96 mass% of one or more olefin-based resins (O), in which the polymer block (x) of at least one thermoplastic elastomer (E) contains α-methylstyrene units, A recycled resin composition that satisfies the following formulas (1) and (2), where Mv and Sv are the tensile modulus and tensile strain at break measured by the following method on a test piece made of the one or more olefin-based resins (O) of a virgin material that is the raw material of the adherend, respectively, and Mre and Sre are the tensile modulus and tensile strain at break measured by the following method on a test piece made of the recycled resin composition, respectively: 50≦[Mre / Mv]×100[%]≦150 (1) 50≦[Sre / Sv]×100[%] (2) [Method for measuring tensile modulus and tensile strain at break] The tensile modulus and tensile strain at break of a dumbbell 1B test piece are measured in accordance with JIS K7161-1 and JIS K7161-2 at a temperature of 23°C and a pulling rate of 2 mm / min.

2. The recycled resin composition according to claim 1, comprising one or more thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of said block copolymers.

3. The thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40% by mole, and hydrogenated versions of the block copolymers; and one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40% by mole or more, and hydrogenated versions of the block copolymers. The recycled resin composition according to claim 2, comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers.

4. The recycled resin composition according to claim 3, wherein the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

5. The recycled resin composition according to claim 1, wherein the conjugated diene compound units contained in polymer block (b) are one or more units selected from the group consisting of isoprene units and butadiene units.

6. The recycled resin composition according to claim 1, wherein the (meth)acrylic resin (A) comprises a non-rubber-like (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

7. The recycled resin composition according to claim 1, wherein the mass ratio (E / A) of the thermoplastic elastomer (E) to the (meth)acrylic resin (A) is 0.70 to 6.67, and the following formulas (3) and (4) are satisfied when the Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the method below for a test piece made of the one or more olefin-based resins (O) of a virgin material that is the raw material of the adherend, are IRv and ILv, respectively, and the Charpy impact value at room temperature and the Charpy impact value at low temperature, measured by the method below for a test piece made of the recycled resin composition, are IRre and ILre, respectively. 50≦[IRre / IRv]×100[%]≦150 (3) 50≦[ILre / ILv]×100[%]≦150 (4) [Method for Measuring Charpy Impact Value] A test piece 80 mm long, 10 mm wide, and 4 mm thick produced by injection molding is formed with a notch having a tip radius of 0.25 mm and a depth of 2 mm, and the Charpy impact value is measured using the edgewise method under a hammer load of 2 J in accordance with JIS K7111-1 / 1eA. Under room temperature conditions, the test piece is left to stand for 24 hours in an environment at a temperature of 23°C and a relative humidity of 50%, and then the Charpy impact value is measured. Under low temperature conditions, the test piece is left to stand for 3 hours in an environment at a temperature of -20°C, and then the Charpy impact value is measured.

8. The recycled resin composition according to claim 1, wherein the adhesive layer contains at least one thermoplastic elastomer (E) selected from one or more thermoplastic elastomers (E), one or more (meth)acrylic resins (A), and one or more olefin resins (O).

9. The recycled resin composition according to claim 1, wherein the decorative film contains one or more (meth)acrylic resins (A) and / or one or more olefin resins (O).

10. A method for producing a recycled resin composition according to any one of claims 1 to 9, comprising the steps of: crushing the decorative molded body into pieces having a maximum length of 40 mm or less; and using an extruder to melt-knead and extrude a resin material containing the crushed pieces, and shredding the extruded recycled resin composition into pellets having a maximum length of 5 mm or less, thereby obtaining pellets consisting of the recycled resin composition.

11. A decorated molded body having a decorative film laminated on at least a portion of the surface of an adherend, wherein the adherend contains the recycled resin composition described in any one of claims 1 to 9.

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