Elastomer resin composition, film, laminate, and molded article

Abstract

The present invention provides an elastomer resin composition having good process trafficability, film forming properties, adhesiveness to various materials, and chipping resistance. This elastomer resin composition contains thermoplastic elastomers (EX)-(EZ) and polypropylene-based polymers (PX) and (PY). EX has a block containing an St unit and a block containing a conjugated diene compound unit in which the total amount of 1, 2-bonds and 3, 4-bonds is less than 40 mol%. EY has a block containing an St unit and a block containing a conjugated diene compound unit in which the total amount of 1, 2-bonds and 3, 4-bonds is 40 mol% or more. The block (EZ) has a block containing an [alpha] MSt unit and a block containing a conjugated diene compound unit in which the total amount of 1, 2-bonds and 3, 4-bonds is 40 mol% or more. PX does not have a polar group and has a melt tension of 2.5 * 10 <-2 > N or more. And (PY) has a polar group and has a melting point of 130 DEG C or less.

Description

Technical Field

[0001] This invention relates to elastomeric resin compositions, films, laminates, and molded articles. Background Technology

[0002] For purposes such as surface protection and decoration, coatings are sometimes applied to the surface of vehicle exterior components by spraying or other methods and then dried to form a film. For such coatings, localized damage and / or defects can sometimes occur due to impacts from small particles such as pebbles and de-icing salt, resulting in partial exposure of the substrate and preventing the desired function from being achieved. In this specification, the damage and defects described above are collectively referred to as "cracking," and the resistance to such damage and defects is referred to as "cracking resistance."

[0003] In vehicle exterior components, especially bumpers, there is a tendency for them to crack, requiring higher crack resistance in their coatings. Previously, polypropylene polymers were widely used as materials for vehicle bumpers due to their high impact resistance, low density, and low material cost. However, non-polar polypropylene polymers typically repel coatings, making it difficult to form a well-adhered coating. Reduced coating adhesion leads to decreased crack resistance, thus making them a less desirable choice.

[0004] In addition, the method of using coatings requires a large drying oven and a lot of energy, which is costly.

[0005] Decorative films have been proposed as an alternative to coatings for solving the aforementioned problems.

[0006] Patent documents 1 to 3 can be cited as related technologies of this invention.

[0007] Patent documents 1 and 2 disclose an elastomer resin composition containing a thermoplastic elastomer and a polypropylene polymer containing polar groups. The thermoplastic elastomer is a block copolymer or a hydrogenation thereof having polymer blocks containing aromatic vinyl compound units and polymer blocks containing conjugated diene compound units (claim 1 of Patent Document 1 and claim 1 of Patent Document 2).

[0008] Patent document 3 discloses an elastomer resin composition containing a thermoplastic elastomer and a polypropylene polymer having specific uniaxial tensile viscosity characteristics, more preferably containing a polypropylene polymer containing polar groups, wherein the thermoplastic elastomer is a block copolymer or a hydride thereof having polymer blocks containing aromatic vinyl compound units and polymer blocks containing conjugated diene compound units (claims 1, 4, 5, paragraph 0033).

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: International Publication No. 2013 / 105392

[0012] Patent Document 2: International Publication No. 2016 / 031550

[0013] Patent Document 3: International Publication No. 2020 / 179923 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] The elastomeric resin compositions disclosed in Patent Documents 1 and 2 exhibit good adhesion and flexibility to various materials such as metals and resins. The elastomeric resin composition disclosed in Patent Document 1 also exhibits good insert molding properties. However, if the elastomeric resin compositions disclosed in these documents are extruded into a film, sometimes insufficient melt tension results in a film width narrower than the die width of the T-die.

[0016] The elastomeric resin composition disclosed in Patent Document 3, by adding a polypropylene polymer with specific uniaxial tensile viscosity characteristics (e.g., a polypropylene polymer with a long-chain branched structure), can suppress shrinkage during extrusion molding without reducing adhesion (paragraph 0010).

[0017] However, the inventors have found that the elastomeric resin compositions disclosed in Patent Documents 1 to 3 have the following characteristics: they have a high viscosity and are difficult to separate from the cooling roller or conveying roller during the film-making process, resulting in poor process passability.

[0018] Furthermore, patent documents 1 to 3 do not describe the anti-cracking properties, nor do they disclose the composition of materials suitable for use as decorative films.

[0019] The present invention was made in view of the above circumstances, and its object is to provide an elastomer resin composition with good processability, film-forming properties, adhesion to various materials such as metals and resins, and anti-cracking properties.

[0020] Methods for solving problems

[0021] The present invention provides the following [1] to

[16] films, laminates and molded articles.

[0022] [1] An elastomer resin composition comprising a thermoplastic elastomer (E) and a polypropylene polymer (P) and satisfying the following conditions 1 to 3.

[0023] (Condition 1)

[0024] Thermoplastic elastomer (E) comprises: One or more first thermoplastic elastomers (EX) selected from the group consisting of a polymer block (xa) having a polymer block (xb) containing styrene units and a polymer block (xb) containing 1,2- and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of less than 40 mol% and hydrides of the block copolymer. The second thermoplastic elastomer (EY) selected from the group consisting of a block copolymer having a polymer block (Ya) containing styrene units and a polymer block (Yb) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more, and a hydride of the block copolymer, and The third thermoplastic elastomer (EZ) is selected from the group consisting of a block copolymer having a polymer block (ZA) containing α-methylstyrene units and a polymer block (ZB) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more.

[0025] (Condition 2)

[0026] Polypropylene polymers (P) comprise a first polypropylene polymer (PX) and a second polypropylene polymer (PY). The first polypropylene polymer (PX) lacks polar groups and has a melt tension of 2.5 × 10⁻⁶ measured at 230°C and a traction speed of 4.0 m / min. -2 The second polypropylene polymer (PY) has a polar group and a melting point below 130°C.

[0027] (Condition 3)

[0028] Relative to 100 parts by mass of the total thermoplastic elastomer (E), 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, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass.

[0029] [2] According to the elastomeric resin composition of [1], wherein the melt tension of the first polypropylene polymer (PX) measured at 230°C and a traction speed of 4.0 m / min is 50 × 10⁻⁶. -2 Below N.

[0030] [3] The elastomeric resin composition according to [1] or [2], wherein the melting point of the second polypropylene polymer (PY) is above 100°C.

[0031] [4] The elastomeric resin composition according to any one of [1] to [3] further comprises two or more antioxidants (AO) including phenolic antioxidants (AO-F) and phosphorus antioxidants (AO-P). The content of phenolic antioxidants (AO-F) is 0.10 to 5.00 parts by weight relative to a total of 100 parts by weight of thermoplastic elastomer (E) and polypropylene polymers (P), and the content of phosphorus antioxidants (AO-P) is 0.01 to 5.00 parts by weight.

[0032] [5] A membrane comprising a layer of an elastomeric resin composition of any one of [1] to [4].

[0033] [6] The membrane according to [5] further comprises a layer containing (meth)acrylic resin.

[0034] [7] The membrane according to [6], wherein the layer containing (meth)acrylic resin comprises (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

[0035] [8] The membrane according to any one of [5] to [7] further comprises a metal layer.

[0036] [9] The membrane according to any one of [5] to [7] further comprises a decorative layer.

[0037]

[10] A laminate comprising a layer made of an elastomeric resin composition of any one of [1] to [4].

[0038]

[11] A molded body comprising a layer or component made of an elastomeric resin composition of any one of [1] to [4].

[0039]

[12] The molded body according to

[11] , wherein at least a portion of the surface of the adherend has a layer composed of the above-described elastomeric resin composition and a metal layer in sequence.

[0040]

[13] The molded body according to

[12] further comprises a layer containing (meth)acrylic resin on the metal layer.

[0041]

[14] The molded body according to

[11] , wherein at least a portion of the surface of the adhered object has a layer and a decorative layer composed of the above-described elastomeric resin composition in sequence.

[0042]

[15] The molded body according to

[14] further comprises a layer containing (meth)acrylic resin on the above-mentioned decorative layer.

[0043]

[16] The molded article according to

[13] or

[15] , wherein the layer containing (meth)acrylic resin comprises (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

[0044] Invention Effects

[0045] According to the present invention, an elastomer resin composition with good processability, film-forming properties, adhesion to various materials such as metals and resins, and anti-cracking properties can be provided. Attached Figure Description

[0046] Figure 1 This is a schematic cross-sectional view of a membrane according to one embodiment of the present invention.

[0047] Figure 2 This is a schematic cross-sectional view showing an example of a film containing a metal layer.

[0048] Figure 3 This is a schematic cross-sectional view illustrating a decorative film according to one embodiment of the present invention.

[0049] Figure 4 This is a schematic cross-sectional view illustrating a decorative molded body according to one embodiment of the present invention. Detailed Implementation

[0050] Generally, for thin film molded articles, terms such as "film," "sheet," or "plate" are used depending on the thickness, but there is no clear definition and no clear distinction between them. The term "film" as used in this specification also includes "sheet."

[0051] In this specification, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid, and the same applies to (meth)acrylonitrile, etc.

[0052] In this specification, "adhesion" is a general term for both pressure-sensitive adhesive and adhesive bonding.

[0053] Unless otherwise specified, the weight-average molecular weight (Mw) of (meth)acrylic resins in this specification is the weight-average molecular weight (Mw) converted from that of standard polymethyl methacrylate (PMMA) determined by gel permeation chromatography (GPC). The same applies to the number-average molecular weight (Mn).

[0054] Unless otherwise specified, the weight-average molecular weight (Mw) of resins other than (meth)acrylic resins (thermoplastic elastomers (E), etc.) in this specification is the weight-average molecular weight (Mw) converted from that of standard polystyrene determined by gel permeation chromatography (GPC). The same applies to the number-average molecular weight (Mn).

[0055] [Elastomer Resin Composition]

[0056] The elastomeric resin composition of the present invention contains a thermoplastic elastomer (E) and a polypropylene polymer (P) and satisfies the following conditions 1 to 3.

[0057] (Condition 1)

[0058] Thermoplastic elastomer (E) comprises: One or more first thermoplastic elastomers (EX) selected from the group consisting of a polymer block (xa) having a polymer block (xb) containing styrene (St) units and a polymer block (xb) containing less than 40 mol% of conjugated diene compound units with 1,2- and 3,4- bonds, and hydrides of the block copolymers. The second thermoplastic elastomer (EY) selected from the group consisting of a block copolymer having a polymer block (Ya) containing styrene (St) units and a polymer block (Yb) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more, and hydrides of the block copolymer, and The third thermoplastic elastomer (EZ) is selected from the group consisting of a polymer block (za) having a polymer block (zb) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more.

[0059] (Condition 2)

[0060] The polypropylene polymer (P) comprises a first polypropylene polymer (PX) and a second polypropylene polymer (PY). The first polypropylene polymer (PX) does not have polar groups and has a melt tension of 2.5 × 10⁻⁶ measured at 230°C and a traction speed of 4.0 m / min. -2 The second polypropylene polymer (PY) has a polar group and a melting point below 130°C.

[0061] (Condition 3)

[0062] Relative to 100 parts by mass of the total thermoplastic elastomer (E), 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, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass.

[0063] (First thermoplastic elastomer (EX))

[0064] The elastomeric resin composition of the present invention contains one or more first thermoplastic elastomers (EX) selected from the group consisting of a block copolymer having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing less than 40 mol% of conjugated diene compound units with 1,2-bonding and 3,4-bonding.

[0065] The first thermoplastic elastomer (EX) is one of the matrix components of the elastomeric resin composition, which can impart excellent softness and impact resistance to the elastomeric resin composition. The first thermoplastic elastomer (EX) can impart excellent crack resistance to the elastomeric resin composition by comprising polymer blocks (xb) containing less than 40 mol% of conjugated diene compound units with 1,2-bonded and 3,4-bonded structures.

[0066] <Polymer Block (xa)>

[0067] The first thermoplastic elastomer (EX) comprises one or more polymer blocks (xa) containing styrene (St) units.

[0068] The polymer block (xa) may also 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.

[0069] The polymer block (xa) may also contain one or more monomer units other than aromatic vinyl compound units. Examples of monomers other than aromatic vinyl compounds include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0070] 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.

[0071] The content of one or more aromatic vinyl compound units including styrene (St) units in the polymer block (xa) is not particularly limited (total in the case of two or more units), but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass.

[0072] The content of monomer units other than aromatic vinyl compound units in the polymer block (xa) (total quantity in the case of two or more) 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.

[0073] <Polymer Block (xb)>

[0074] The first thermoplastic elastomer (EX) comprises one or more polymer blocks (xb), each polymer block (xb) containing one or more conjugated diene compound units. The total stoichiometry of 1,2-bonded and 3,4-bonded components of the one or more conjugated diene compound units contained in the first thermoplastic elastomer (EX) is less than 40 mol%. It should be noted that when the first thermoplastic elastomer (EX) comprises two or more polymer blocks (xb), the total stoichiometry of 1,2-bonded and 3,4-bonded components of the one or more conjugated diene compound units contained in all polymer blocks (xb) is less than 40 mol.

[0075] Examples of conjugated diene compounds 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 more preferably composed of butadiene units and / or isoprene units.

[0076] The polymer block (xb) may also contain one or more monomer units other than the conjugated diene compound unit. Examples of monomers other than the conjugated diene compound include styrene (St) and 4-methylstyrene.

[0077] The content of conjugated diene compound units in the polymer block (xb) (total amount in the case of two or more) 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.

[0078] The content of monomer units other than the conjugated diene compound unit in the polymer block (xb) (total quantity in the case of two or more) 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.

[0079] Regarding the bonding mode of the conjugated diene compound units in the polymer block (xb), the butadiene unit can be 1,2-bonded or 1,4-bonded, and the isoprene unit can be 1,2-bonded, 3,4-bonded, or 1,4-bonded. The same applies to the polymer blocks (yb) and (zb).

[0080] From the viewpoint of resistance to breakage, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is less than 40 mol%, preferably less than 39 mol%. The upper limit is more preferably 35 mol%, further 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%.

[0081] The total stoichiometry of 1,2-bonding and 3,4-bonding of conjugated diene units in polymer blocks containing conjugated diene units can be obtained by... 1 The results were calculated using H-NMR measurements. Specifically, the results can be calculated based on the ratio of the integral value of the first peak present in the range of 4.2–5.0 ppm from 1,2-bonded and 3,4-bonded conjugated diene units to the integral value of the second peak present in the range of 5.0–5.45 ppm from 1,4-bonded conjugated diene units.

[0082] The bonding mode between polymer blocks (xa) and polymer blocks (xb) is not particularly limited, and can include linear, branched, radial, and combinations thereof, with linear bonding being preferred. Examples of linear bonding modes 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 X-type copolymers (where X represents coupling residues and n represents an integer greater than 2) and combinations thereof. Among them, triblock copolymers are preferred, and triblock copolymers represented by xa-xb-xa are more preferred.

[0083] The content of polymer blocks (xa) in the first thermoplastic elastomer (EX) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 5 to 75% by mass. The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, further preferably 65% ​​by mass, further preferably 60% by mass, further preferably 55% by mass, further preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass.

[0084] The content of polymer blocks (xb) in the first thermoplastic elastomer (EX) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 95 to 25% by mass. The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, further preferably 35% by mass, further preferably 40% by mass, further preferably 45% by mass, further preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass.

[0085] The total content of polymer blocks (xa) and polymer blocks (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, particularly preferably 98% by mass, and most preferably 99% by mass.

[0086] 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 it may be a hydrogenated form thereof.

[0087] There are no particular limitations on the method for manufacturing unhydrogenated block copolymers, and anionic polymerization methods can be listed. For example, the following methods can be listed: (i) using an alkyl lithium compound as an initiator to sequentially polymerize one or more aromatic vinyl compounds containing styrene (St), followed by sequentially polymerizing one or more conjugated diene compounds, and further, as needed, sequentially polymerizing one or more aromatic vinyl compounds containing styrene (St); (ii) using an alkyl lithium compound as an initiator to sequentially polymerize one or more aromatic vinyl compounds containing styrene (St), followed by sequentially polymerizing one or more conjugated diene compounds, and then adding a coupling agent for coupling; (iii) using a dilithium compound as an initiator to sequentially polymerize one or more conjugated diene compounds, followed by sequentially polymerizing one or more aromatic vinyl compounds containing styrene (St), and further, as needed, sequentially polymerizing one or more conjugated diene compounds; etc.

[0088] From the viewpoint of improving heat resistance and weather resistance, the first thermoplastic elastomer (EX) is preferably a hydrogenated block copolymer obtained by hydrogenating (also called hydrogenating) at least a portion of the polymer block (xb) containing conjugated diene compound units. The hydrogenation rate (hydrogenation rate) of the polymer block (xb) is not particularly limited, but is preferably 80-100%. A lower limit of 85% is more preferred, and particularly preferably 90%.

[0089] In this specification, the hydrogenation rate (hydrogenation rate) of polymer blocks containing conjugated diene compound units can be determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0090] As a hydrogenation reaction, the following methods can be listed: prepare a solution obtained by dissolving the unhydrogenated block copolymer in a solvent that is inert to the hydrogenation reaction and the hydrogenation catalyst, or a reaction solution containing the unhydrogenated block copolymer obtained after the polymerization reaction, and then react the unhydrogenated block copolymer with hydrogen in the presence of the hydrogenation catalyst.

[0091] The first thermoplastic elastomer (EX) can also be commercially available.

[0092] The first thermoplastic elastomer (EX) may, as needed, contain one or more functional groups selected from carboxyl, hydroxyl, anhydride, amino, and epoxy groups in and / or at the ends of the molecular chain.

[0093] The weight-average molecular weight (Mw) of the first thermoplastic elastomer (EX) (converted from standard polystyrene) is not particularly limited, but from the viewpoint of the mechanical properties and processability of the first thermoplastic elastomer (EX), it is preferably 30,000 to 500,000. The lower limit is more preferably 50,000, further preferably 60,000, particularly preferably 70,000, and most preferably 80,000. The upper limit is more preferably 400,000, further preferably 300,000, further preferably 200,000, particularly preferably 190,000, and most preferably 180,000.

[0094] From the perspective of effectively demonstrating the effects (such as imparting crack resistance) brought about by the first thermoplastic elastomer (EX), the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass relative to 100 parts by mass of the total amount of thermoplastic elastomer (E). A lower limit is more preferably 20 parts by mass, and particularly preferably 35 parts by mass. An upper limit is more preferably 50 parts by mass, and particularly preferably 45 parts by mass.

[0095] (Second thermoplastic elastomer (EY))

[0096] The elastomeric resin composition of the present invention contains one or more second thermoplastic elastomers (EY) selected from the group consisting of a block copolymer having a polymer block (Ya) containing styrene (St) units and a polymer block (Yb) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more, and hydrides of the block copolymers.

[0097] The second thermoplastic elastomer (EY) is one of the matrix components of the elastomeric resin composition. The second thermoplastic elastomer (EY), by comprising polymer blocks (yb) containing 40 mol% or more of conjugated diene compound units with 1,2- and 3,4-bonds, can impart excellent adhesion to non-polar resins to the elastomeric resin composition.

[0098] <Polymer Block (ya)>

[0099] The second thermoplastic elastomer (EY) comprises one or more polymer blocks (ya) containing styrene (St) units.

[0100] The polymer block (ya) may also contain one or more aromatic vinyl compound units other than styrene (St) units. The polymer block (ya) may also contain one or more monomer units other than aromatic vinyl compound units. Examples of aromatic vinyl compounds other than styrene (St) and monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0101] 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.

[0102] The content of one or more aromatic vinyl compound units including styrene (St) units in the polymer block (ya) is not particularly limited (total in the case of two or more units), but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass.

[0103] The content of monomer units other than aromatic vinyl compound units in the polymer block (ya) (total quantity in the case of two or more) 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.

[0104] <Polymer Block (yb)>

[0105] The second thermoplastic elastomer (EY) comprises one or more polymer blocks (yb) containing one or more conjugated diene compound units. The total stoichiometry of 1,2-bonding and 3,4-bonding of the one or more conjugated diene compound units contained in the second thermoplastic elastomer (EY) is 40 mol% or more. It should be noted that when the second thermoplastic elastomer (EY) comprises two or more polymer blocks (yb), the total stoichiometry of 1,2-bonding and 3,4-bonding of the one or more conjugated diene compound units contained in all polymer blocks (yb) is 40 mol% or more.

[0106] The polymer block (yb) may also contain one or more monomer units other than the conjugated diene compound unit. Examples and preferred embodiments of the conjugated diene compound and examples of other monomers are the same as those for the polymer block (xb).

[0107] The content of conjugated diene compound units in the polymer block (yb) (total amount in the case of two or more) 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.

[0108] The content of monomer units other than the conjugated diene compound unit in the polymer block (yb) is not particularly limited (total amount in the case of two or more), and is 20% to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0109] From the viewpoint of excellent adhesion to non-polar resins, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is 40 mol% or more. 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%.

[0110] The 1,2- and 3,4-bonds of the conjugated diene compound units can be increased by adding one or more organoLewis bases to the reaction solution during anionic polymerization. Furthermore, the total amount of 1,2- and 3,4-bonds can be easily controlled by adjusting the amount of organoLewis base added.

[0111] 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.

[0112] The bonding mode between polymer blocks (ya) and polymer blocks (yb) is not particularly limited, and can include linear, branched, radial, and combinations thereof, with linear bonding being preferred. Examples of linear bonding modes 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 X-type copolymers (where X represents coupling residues and n represents an integer greater than 2) and combinations thereof. Among them, triblock copolymers are preferred, and triblock copolymers represented by ya-yb-ya are more preferred.

[0113] The content of polymer blocks (ya) in the second thermoplastic elastomer (EY) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 5 to 75% by mass. The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, further preferably 65% ​​by mass, further preferably 60% by mass, further preferably 55% by mass, further preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass.

[0114] The content of polymer blocks (yb) in the second thermoplastic elastomer (EY) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 95 to 25% by mass. The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, further preferably 35% by mass, further preferably 40% by mass, further preferably 45% by mass, further preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass.

[0115] The total content of polymer blocks (ya) and polymer blocks (yb) in the second thermoplastic elastomer (EY) is not particularly limited, but is preferably 95 to 100% by mass. The lower limit is more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0116] The second thermoplastic elastomer (EY) can be an unhydrogenated block copolymer having one or more polymer blocks (ya) and one or more polymer blocks (yb), or it can be a hydrogenated form thereof.

[0117] From the viewpoint of improving heat resistance and weather resistance, the second thermoplastic elastomer (EY) is preferably a hydrogenated block copolymer obtained by hydrogenating at least a portion of the polymer block (yb) containing conjugated diene compound units. The hydrogenation rate (hydrogenation rate) of the polymer block (yb) is not particularly limited, but is preferably 80-100%. A lower limit of 85% is more preferred, and particularly preferred is 90%.

[0118] The manufacturing method of the second thermoplastic elastomer (EY) is the same as that of the first thermoplastic elastomer (EX). Commercially available products can also be used for the second thermoplastic elastomer (EY).

[0119] The second thermoplastic elastomer (EY) may contain one or more functional groups, such as carboxyl, hydroxyl, anhydride, amino, and epoxy groups, in the molecular chain and / or at the molecular chain ends, as needed.

[0120] There are no particular restrictions on the weight-average molecular weight (Mw) (converted from standard polystyrene) of the second thermoplastic elastomer (EY). From the viewpoint of the mechanical properties and processability of the second thermoplastic elastomer (EY), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0121] From the perspective of effectively demonstrating the effects of the second thermoplastic elastomer (EY) (such as imparting excellent adhesion to non-polar resins), the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E). A lower limit is more preferably 30 parts by mass, particularly preferably 35 parts by mass. An upper limit is more preferably 60 parts by mass, particularly preferably 55 parts by mass, and most preferably 50 parts by mass.

[0122] (Third thermoplastic elastomer (EZ))

[0123] The elastomeric resin composition of the present invention contains one or more third thermoplastic elastomers (EZ) selected from the group consisting of a block copolymer having a polymer block (Za) containing α-methylstyrene (αMSt) units and a polymer block (Zb) containing 1,2-bonded and 3,4-bonded conjugated diene compound units in a total stoichiometric amount of 40 mol% or more, and hydrides of the block copolymers.

[0124] Third thermoplastic elastomers (EZ) are one of the matrix components of elastomeric resin compositions. By comprising polymer blocks (za) containing α-methylstyrene (αMSt) units, third thermoplastic elastomers (EZ) can impart rigidity and excellent adhesion to polar resins to elastomeric resin compositions. By comprising polymer blocks (zb) containing 40 mol% or more of conjugated diene compound units with 1,2- and 3,4-bonded structures, third thermoplastic elastomers (EZ) can impart excellent adhesion to non-polar resins to elastomeric resin compositions.

[0125] <Polymer Block (za)>

[0126] The third thermoplastic elastomer (EZ) comprises one or more polymer blocks (za) containing α-methylstyrene (αMSt) units.

[0127] The polymer block (za) may also contain one or more aromatic vinyl compound units other than the α-methylstyrene (αMSt) unit. 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.

[0128] Polymer blocks (za) may also contain one or more monomer units other than aromatic vinyl compounds. Examples of monomers other than aromatic vinyl compounds are the same as those for polymer blocks (xa).

[0129] The content of α-methylstyrene (αMSt) units in the polymer block (za) is not particularly limited, but from the viewpoint of the rigidity of the elastomer resin composition and excellent adhesion to polar resins, it is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass.

[0130] The content of one or more aromatic vinyl compound units including α-methylstyrene (αMSt) units in the polymer block (za) is not particularly limited (the total amount is used when there are two or more), but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass.

[0131] The content of monomer units other than aromatic vinyl compound units in the polymer block (za) (total quantity in the case of two or more) 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.

[0132] <Polymer Block (zb)>

[0133] The third thermoplastic elastomer (EZ) comprises one or more polymer blocks (zb) containing one or more conjugated diene compound units. The total stoichiometry of the 1,2-bonded and 3,4-bonded components of the one or more conjugated diene compound units contained in the third thermoplastic elastomer (EZ) is 40 mol% or more. It should be noted that when the third thermoplastic elastomer (EZ) comprises two or more polymer blocks (zb), the total stoichiometry of the 1,2-bonded and 3,4-bonded components of the one or more conjugated diene compound units contained in all polymer blocks (zb) is 40 mol% or more.

[0134] The polymer block (zb) may also contain one or more monomer units other than the conjugated diene compound unit. Examples and preferred embodiments of the conjugated diene compound and examples of other monomers are the same as those for the polymer block (xb).

[0135] The content of conjugated diene compound units in the polymer block (zb) (total amount in the case of two or more) 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.

[0136] The content of monomer units other than the conjugated diene compound unit in the polymer block (zb) is not particularly limited (total amount in the case of two or more), and is 20% to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0137] From the viewpoint of excellent adhesion to non-polar resins, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (ZB) is 40 mol% or more. 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%.

[0138] The bonding mode between polymer blocks (za) and polymer blocks (zb) is not particularly limited, and can include linear, branched, radial, and combinations thereof, with linear bonding being preferred. Examples of linear bonding modes 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) nX-type copolymers (where X represents coupling residues and n represents an integer greater than 2) and combinations thereof. Among them, triblock copolymers are preferred, and triblock copolymers represented by za-zb-za are more preferred.

[0139] The content of polymer blocks (za) in the third thermoplastic elastomer (EZ) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the third thermoplastic elastomer (EZ), it is preferably 5 to 75% by mass. The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, further preferably 65% ​​by mass, further preferably 60% by mass, further preferably 55% by mass, further preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass.

[0140] The content of polymer blocks (zb) in the third thermoplastic elastomer (EZ) is not particularly limited, but from the viewpoint of the softness and mechanical properties of the third thermoplastic elastomer (EZ), it is preferably 95 to 25% by mass. The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, further preferably 35% by mass, further preferably 40% by mass, further preferably 45% by mass, further preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass.

[0141] The total content of polymer blocks (za) and polymer blocks (zb) in the third thermoplastic elastomer (EZ) is not particularly limited, but is preferably 95 to 100% by mass. The lower limit is more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0142] The third thermoplastic elastomer (EZ) can be an unhydrogenated block copolymer having one or more polymer blocks (za) and one or more polymer blocks (zb), or it can be a hydrogenated form thereof.

[0143] From the viewpoint of improving heat resistance and weather resistance, the third thermoplastic elastomer (EZ) is preferably a hydrogenated block copolymer obtained by hydrogenating at least a portion of the polymer block (ZB) containing conjugated diene compound units. The hydrogenation rate (hydrogenation rate) of the polymer block (ZB) is not particularly limited, but is preferably 80-100%. A lower limit of 85% is more preferred, and particularly preferred is 90%.

[0144] The manufacturing method of the third thermoplastic elastomer (EZ) is the same as that of the second thermoplastic elastomer (EY). Commercially available products can also be used for the third thermoplastic elastomer (EZ).

[0145] Third thermoplastic elastomers (EZ) may contain one or more functional groups, such as carboxyl, hydroxyl, anhydride, amino, and epoxy groups, in the molecular chain and / or at the molecular chain ends, as needed.

[0146] There are no particular restrictions on the weight-average molecular weight (Mw) (converted from standard polystyrene) of the third thermoplastic elastomer (EZ). From the viewpoint of the mechanical properties and processability of the third thermoplastic elastomer (EZ), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0147] From the perspective of effectively exhibiting the effects of the third thermoplastic elastomer (EZ) (such as imparting rigidity, excellent adhesion to polar resins, and excellent adhesion to non-polar resins), the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E). A lower limit is more preferably 17 parts by mass, particularly preferably 18 parts by mass, and most preferably 19 parts by mass. An upper limit is more preferably 30 parts by mass, particularly preferably 27 parts by mass, and most preferably 25 parts by mass.

[0148] (First polypropylene polymer (PX))

[0149] The elastomeric resin composition of the present invention contains one or more first polypropylene polymers (PX) (nonpolar polypropylene polymers) that do not have polar groups.

[0150] The first polypropylene polymer (PX) tends to have a higher melt tension as its melt flow rate (MFR) decreases. The melt tension of the first polypropylene polymer (PX) measured at 230°C and a traction speed of 4.0 m / min was 2.5 × 10⁻⁶. -2 N or more. A lower limit value is more preferably 3.0 × 10⁻⁶. -2 N, more preferably 3.5 × 10 -2 N, preferably 4.0 × 10 -2 N, the optimal value is 4.5 × 10 -2 N. There is no particular limit to the upper limit, but it is preferably 50 × 10⁻⁶. -2 N, more preferably 40×10 -2 N, preferably 30×10 -2 N.

[0151] The elastomeric resin composition of the present invention further comprises a first polypropylene polymer (PX) with a melt tension of at least the aforementioned lower limit, exhibiting appropriate viscosity and good sliding properties relative to metal. Therefore, the elastomeric resin composition of the present invention can be smoothly separated from the cooling roller and the conveying roller during the film-forming process, resulting in good process throughput.

[0152] The elastomeric resin composition of the present invention contains a first polypropylene polymer (PX) with a melt tension of at least the aforementioned lower limit value, exhibits good film-forming properties in extrusion molding and the like, and the film obtained by extrusion molding and the like has good film thickness stability and other properties.

[0153] The MFR of the first polypropylene polymer (PX) is not particularly limited, but is preferably 0.1 to 20 g / 10 min. The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min. The upper limit is preferably 15 g / 10 min, more preferably 10 g / 10 min.

[0154] Unless otherwise specified, the MFR of polypropylene polymers in this specification is determined according to JIS K7210 using a melt index meter at a temperature of 230°C and a load of 21.18 N.

[0155] The first type of polypropylene polymer (PX) is a homopolymer or copolymer containing propylene units and one or more other monomer units that do not have polar groups as required.

[0156] Other monomers include α-olefins other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene.

[0157] The proportion of propylene units relative to all structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 55 to 100 mol%. The lower limit is more preferably 65 mol%, further preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%.

[0158] The proportion of monomer units other than the propylene unit relative to all structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 45 to 0 mol%. The upper limit is more preferably 35 mol%, further preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0159] Examples of polypropylene polymers (PX) having the melt tension specified above include those with crosslinked structures, long-chain branched structures, high molecular weight components, or combinations thereof. From the viewpoint of maintaining membrane flexibility, polypropylene polymers with long-chain branched structures are preferred. Methods for manufacturing polypropylene polymers with long-chain branched structures include graft copolymerization of free radical polymerizable monomers with polypropylene (Macromolecules 26(1993)3467), copolymerization of propylene with polyenes (Japanese Patent Application Laid-Open No. 5-194778), macromonomer copolymerization using metallocene catalysts (Japanese Patent Application Laid-Open No. 2009-057542), and melt-mixing of polypropylene, conjugated diene compounds, and free radical polymerization initiators (Japanese Patent Application Laid-Open No. 2015-098542). From the viewpoint of suppressing gel formation, macromonomer copolymerization using metallocene catalysts is preferred.

[0160] The melting point (Tm) of the first polypropylene polymer (PX) is not particularly limited, but from the viewpoint of the heat resistance of the elastomer resin composition, it is preferably 100°C or higher. The lower limit is more preferably 110°C. The upper limit is preferably 170°C, more preferably 160°C, and most preferably 150°C.

[0161] From the viewpoint of balancing excellent processability and film-forming properties (film thickness stability, etc.) of the elastomer resin composition with good adhesion to various materials, the content of the first polypropylene polymer (PX) is 3 to 15 parts by weight relative to 100 parts by weight of the thermoplastic elastomer (E). The lower limit is preferably 5 parts by weight, more preferably 6 parts by weight, and particularly preferably 7 parts by weight. The upper limit is preferably 12 parts by weight, more preferably 10 parts by weight, and particularly preferably 8 parts by weight.

[0162] When the content of the first polypropylene polymer (PX) is less than the lower limit mentioned above, the process passability and film-forming properties (film thickness stability, etc.) of the elastomer resin composition may be reduced. When it exceeds the upper limit mentioned above, the adhesion of the elastomer resin composition to polar resins, non-polar resins, or metals may be reduced.

[0163] (Second polypropylene polymer (PY))

[0164] The elastomeric resin composition of the present invention contains one or more second polypropylene polymers (PY) having polar groups. The second polypropylene polymer (PY) can impart excellent adhesion to metals to the elastomeric resin composition.

[0165] As polar groups, examples include: polar atoms such as oxygen, nitrogen, and sulfur; (meth)acryloyloxy; hydroxyl; amide; carboxyl; acid anhydride; halogen atoms such as chlorine.

[0166] As a primary method for manufacturing polypropylene polymers containing polar groups, methods for copolymerizing propylene, a monomer containing polar groups, and one or more other monomers as needed, using known methods can be cited. There are no particular limitations on the copolymerization method; random copolymerization and block copolymerization, among others, can be cited.

[0167] As a second method for manufacturing polypropylene polymers containing polar groups, one example is a method of graft copolymerizing a monomer containing polar groups with a polypropylene polymer (non-polar polypropylene polymer) containing propylene units and one or more other monomer units as needed, but without polar groups.

[0168] Of the above, graft copolymerization is preferred.

[0169] The polypropylene polymer containing polar groups manufactured by the first or second manufacturing method described above may contain propylene units and monomer units containing polar groups, and may further contain one or more other monomer units as needed.

[0170] Examples of monomers containing polar groups include: vinyl acetate, vinyl chloride; ethylene oxide, propylene oxide; unsaturated carboxylic acids or their esters or anhydrides; (meth)acrylamide, etc. Among these, unsaturated carboxylic acids or their esters or anhydrides are preferred, including (meth)acrylic acid, (meth)acrylates, maleic acid (anhydride), fumaric acid (anhydride), itaconic acid (anhydride), and nadic acid (anhydride), etc. Among these, carboxylic acids (anhydrides) such as maleic acid (anhydride) are more preferred.

[0171] In this specification, carboxylic acid (anhydride) is a general term for both carboxylic acids and carboxylic anhydrides.

[0172] Other monomers include α-olefins other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene.

[0173] The total percentage of propylene units and monomer units containing polar groups relative to the total number of structural units in the polypropylene polymer containing polar groups is not particularly limited, but is preferably 55 to 100 mol%. A lower limit is more preferably 65 mol%, further preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%.

[0174] The proportion of α-olefin units other than propylene units relative to all structural units of polypropylene polymers containing polar groups is not particularly limited, but is preferably 45 to 0 mol%. The upper limit is more preferably 35 mol%, further preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0175] From the viewpoint of adhesion to various materials, polypropylene containing polar groups is preferred as a type of polypropylene.

[0176] Preferably, the polypropylene polymer modified by graft copolymerization of carboxylic acid (anhydride) with a non-polar polypropylene polymer (also known as carboxylic acid (anhydride) modified polypropylene polymer) is preferred. Maleic acid (anhydride) modified polypropylene polymer is even more preferred.

[0177] The polar groups contained in the polypropylene polymers manufactured by the first or second manufacturing method described above can be post-processed after the polymerization reaction. Polar groups such as (meth)acrylate and carboxyl groups can be neutralized with metal ions to form ionomers, or esterified with alcohols such as methanol and ethanol. In addition, polar groups such as vinyl acetate groups can also be hydrolyzed.

[0178] As a third method for manufacturing polypropylene polymers containing polar groups, one example is the method of oxidizing or halogenating (e.g., chlorinating) a polypropylene polymer (non-polar polypropylene polymer) containing propylene units and one or more other monomer units as needed but without polar groups by a known method.

[0179] From the viewpoint of excellent adhesion of the elastomeric resin composition to metals, the melting point (Tm) of the second polypropylene polymer (PY) is 130°C or lower. There is no particular limitation on the lower limit, but from the viewpoint of the heat resistance of the elastomeric resin composition, 100°C is preferred, more preferably 105°C, and particularly preferably 110°C. The upper limit is more preferably 125°C.

[0180] From the viewpoint of balancing excellent adhesion to metals and heat resistance, the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass relative to 100 parts by mass of the thermoplastic elastomer (E). The lower limit is preferably 8 parts by mass, more preferably 9 parts by mass, and particularly preferably 10 parts by mass. The upper limit is preferably 17.5 parts by mass, more preferably 15 parts by mass.

[0181] When the content of the second polypropylene polymer (PY) is above the lower limit mentioned above, the elastomer resin composition exhibits good adhesion to metals; when the content of the second polypropylene polymer (PY) is below the upper limit mentioned above, the elastomer resin composition exhibits good heat resistance.

[0182] (Optional ingredients)

[0183] Antioxidants (AO)

[0184] The elastomeric resin composition of the present invention may contain one or more antioxidants (AO). Examples of antioxidants (AO) include phenolic antioxidants, phosphorus antioxidants, lactone antioxidants, and hydroxyl antioxidants. Preferably, the elastomeric resin composition of the present invention contains two or more antioxidants (AO) including phenolic antioxidants (AO-F) and phosphorus antioxidants (AO-P).

[0185] Generally, thermoplastic elastomers and polypropylene polymers containing aromatic vinyl compound units and conjugated diene compound units have poor thermal stability. If the heating and melting time is prolonged, oxidative degradation may occur, leading to decomposition and / or crosslinking. Therefore, if the residence time in the molten state during the manufacture and molding of elastomer resin compositions containing these resins is prolonged, thermal decomposition of the thermoplastic elastomers and / or polypropylene polymers may occur, resulting in an increase in the amount of residual monomers in the resin composition and a decrease in heat resistance. Furthermore, foreign matter such as oxidative degradation products of the thermoplastic elastomers and / or polypropylene polymers may be generated, resulting in poor appearance.

[0186] Typically, in the oxidative degradation mechanism of resin compositions, firstly, a CH bond in the carbon chain decomposes due to heat, generating a free radical. This free radical immediately reacts with oxygen to become a peroxide radical (ROO·). This peroxide radical then abstracts a hydrogen atom from a nearby carbon chain, generating a new free radical and a peroxide. Oxidation based on this free radical chain reaction is also called primary oxidation.

[0187] Furthermore, the self-destruction of the peroxides generated in the above reactions also produces new free radicals, leading to a free radical chain reaction. Oxidation based on this free radical chain reaction is also called secondary oxidation.

[0188] According to the inventor's research, the following information has been obtained.

[0189] Phenolic antioxidants (AO-F), acting as primary antioxidants (also known as primary oxidation inhibitors), capture peroxide radicals, converting them into peroxides and becoming phenoxy radicals themselves, which can then capture other peroxide radicals. However, unstable peroxides can potentially revert to peroxide radicals due to heat, initiating a free radical chain reaction in the presence of oxygen. Phosphorus antioxidants (AO-P), acting as secondary antioxidants (also known as secondary oxidation inhibitors), can decompose unstable peroxides into stable alcohols.

[0190] By combining appropriate amounts of phenolic antioxidants (AO-F) as primary antioxidants and appropriate amounts of phosphoric antioxidants (AO-P) as secondary antioxidants, the thermal stability of thermoplastic elastomers (E) and polypropylene polymers (P) can be effectively improved during prolonged heating and melting, and oxidative degradation and decomposition can be effectively suppressed. Therefore, according to the technique of the present invention using these antioxidants (AO), the thermal stability and heat decomposition resistance of the elastomer resin composition can be effectively improved. Furthermore, according to the technique of the present invention using these antioxidants (AO), the formation of foreign matter such as oxidative degradation products of thermoplastic elastomers and / or polypropylene polymers can be suppressed during prolonged heating and melting, and the occurrence of undesirable appearance can be suppressed.

[0191] As phenolic antioxidants (AO-F), one or more known phenolic antioxidants can be used. Examples include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, stearate 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-butylenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and pentaerythritol. Tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propionate]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl) and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl), etc.

[0192] As a phenolic antioxidant (AO-F), one of the above commercially available products can be used.

[0193] Phenolic antioxidants (AO-F) preferably include hindered phenolic antioxidants.

[0194] The phenolic antioxidant (AO-F) preferably contains a quaternary carbon and has a molecular weight of 250 to 1500. More preferably, the molecular weight is 700 to 1200.

[0195] Phenolic antioxidants (AO-F) preferably contain hindered phenolic antioxidants having a quaternary carbon and a molecular weight of 250 to 1500.

[0196] In the elastomeric resin composition of the present invention, the content of phenolic antioxidants (AO-F) (in cases where there are two or more, the total amount is used) is preferably 0.10 to 5.00 parts by weight relative to a total of 100 parts by weight of the thermoplastic elastomer (E) and the polypropylene polymer (P). The lower limit is more preferably 0.15 parts by weight, particularly preferably 0.20 parts by weight. The upper limit is more preferably 4.00 parts by weight, further preferably 3.00 parts by weight, particularly preferably 2.00 parts by weight, and most preferably 1.50 parts by weight.

[0197] As a phosphorus antioxidant (AO-P), one or more known phosphorus antioxidants can be used. Examples include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxane, tris(2,4-di-tert-butylphenyl)phosphite, trinonylphenyl hypophosphite, diphenylisodecyl phosphite, and triphenylphosphite biphenyl-4,4'-diylbis[bis(2,4-di-tert-butylphenoxy)phosphite], etc.

[0198] As a phosphorus-based antioxidant (AO-P), one of the above commercially available products can be used.

[0199] As a phosphorus antioxidant (AO-P), commercially available multi-component phosphorus antioxidants containing two or more phosphorus antioxidants can also be used.

[0200] The phosphorus-based antioxidant (AO-P) preferably comprises a phosphorus-based antioxidant having a spiro or biphenyl structure and a molecular weight of 500 to 1500. More preferably, the molecular weight is 500 to 1200.

[0201] In the elastomeric resin composition of the present invention, the content of phosphorus antioxidant (AO-P) (in the case of two or more, the total amount is used unless otherwise specified) is preferably 0.01 to 5.00 parts by mass relative to a total of 100 parts by mass of thermoplastic elastomer (E) and polypropylene polymer (P).

[0202] The lower limit is more preferably 0.05 parts by mass, particularly preferably 0.10 parts by mass, and most preferably 0.15 parts by mass. The upper limit is more preferably 4.00 parts by mass, further preferably 3.00 parts by mass, particularly preferably 2.00 parts by mass, and most preferably 1.50 parts by mass.

[0203] The elastomeric resin composition of the present invention, containing phenolic antioxidants (AO-F) and phosphorus antioxidants (AO-P), exhibits excellent resistance to thermal decomposition. Regarding thermal decomposition resistance, for example, when heated to 240°C in air and held at that temperature, the time to reach 240°C and the weight loss (also referred to as the 5% weight loss time) are used as indicators. The 5% weight loss time can be measured using a thermogravimetric analyzer. The 5% weight loss time of the elastomeric resin composition of the present invention, containing phenolic antioxidants (AO-F) and phosphorus antioxidants (AO-P), can be 10 minutes or more, 15 minutes or more, 20 minutes or more, or 25 minutes or more.

[0204] <Other polymers>

[0205] The elastomeric resin composition of the present invention may contain one or more other polymers besides those described above. Examples of other polymers include: polyethylene, polypropylene polymers other than polypropylene polymers (PX) and (PY), polyolefin resins such as poly-1-butene, poly-4-methyl-1-pentene, and polynorbornene; (meth)acrylic resins; styrene 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, acrylate-acrylonitrile-styrene (AAS) resin, acrylonitrile-vinyl chloride-styrene (ACS) resin, and butadiene-methacrylate-styrene (MBS) resin; polyethylene terephthalate (PET) resin; and poly(ethylene terephthalate) resin. Polyester resins such as glycol esters and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; polycarbonate resins; other thermoplastic resins such as polyphenylene sulfide, polyetheretherketone, polysulfone, polyphenylene ether, polyimide, polyetherimide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, ethylene-vinyl acetate copolymer, phenoxy resins, and ethylene ionomers; thermosetting resins such as epoxy resins, phenolic resins, melamine resins, and polysiloxane resins; polyurethane and chlorinated polyurethane resins; modified polyphenylene ether; polysiloxane modified resins; acrylic rubber and silicone rubber; acrylic rubber and silicone rubber; acrylic thermoplastic elastomers such as diblock copolymers and triblock copolymers of methyl methacrylate polymer blocks and n-butyl acrylate polymer blocks; olefin rubbers such as IR, EPR, and EPDM, etc.

[0206] <Other Additives>

[0207] The elastomeric resin composition of the present invention may contain one or more additives other than antioxidants (AO) as needed. Examples of additives include tackifying resins, softeners, lubricants, heat stabilizers, heat deterioration resistant agents, light stabilizers, polymer processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, silicone oils, antiblocking agents, ultraviolet absorbers, release agents, foaming agents, defoamers, antibacterial agents, mildew inhibitors, and fragrances.

[0208] 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 phenolic resins, hydrogenated terpene phenolic resins, terpene resins, hydrogenated terpene resins, aromatic hydrocarbon-modified terpene resins, coumarone-indene resins, phenolic resins, and xylene resins.

[0209] As a plasticizer, plasticizers commonly used in rubber or plastics can be used. Examples include: alkanes, cycloalkanes, and aromatic processing oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; oligomers of ethylene and α-olefins; solid paraffin wax; liquid paraffin wax; polybutene; low molecular weight polybutadiene; low molecular weight polyisoprene, etc.

[0210] The addition of other polymers and additives that may be contained in the elastomer resin composition of the present invention may be during or after the manufacture of one or more of the thermoplastic elastomers (EX) to (EZ) and polypropylene polymers (PX) and (PY), or it may be during the manufacture of the elastomer resin composition.

[0211] As described above, according to the present invention, an elastomer resin composition with good processability, film-forming properties, adhesion to various materials such as metals and resins, and anti-cracking properties can be provided.

[0212] [Method for manufacturing elastomer resin composition]

[0213] The method for manufacturing the elastomeric resin composition of the present invention is not particularly limited. From the viewpoint of dispersibility and compatibility of each component, a method of melt-blending thermoplastic elastomers (EX) to (EZ), polypropylene polymers (PX) and (PY), and one or more optional components as needed is preferred. Melt-blending can be performed using known mixing or blending equipment such as extruders, kneaders, mixing rollers, and Banbury mixers. From the viewpoint of blending and compatibility, extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred, and twin-screw extruders are more preferred. The melt-blending temperature is sufficient to be above the melting temperature of the thermoplastic elastomers (EX) to (EZ) and polypropylene polymers (PX) and (PY), preferably 150 to 300°C, and more preferably 200 to 300°C.

[0214] The form of the elastomeric resin composition of the present invention is not particularly limited, and granules and powders are examples.

[0215] [molded body]

[0216] The molded body of the present invention comprises a layer or component made of the elastomeric resin composition of the present invention described above, or may be integrally composed of a layer or component made of the elastomeric resin composition of the present invention described above.

[0217] Examples of forming methods include solution casting, extrusion molding, compression molding (also known as press molding), injection molding, blow molding, blow molding, calendering, solution casting, vacuum forming, and air forming.

[0218] Examples of molded bodies include: planar structures such as films, sheets, and plates, either single-layer or multi-layered; fibers, pipes, tubes, and rods; particles; and any three-dimensional structures. Molded bodies can also be laminates or composites comprising layers or components made of the elastomeric resin composition of this invention, or layers or components made of other resins or various materials other than resins. For molded bodies obtained by known molding methods, surface treatments such as printing, coating, plating, vapor deposition, and sputtering can be performed as needed; shape processing such as bending, folding, and cutting (also known as secondary molding) can be applied.

[0219] [membrane]

[0220] The membrane of the present invention comprises a layer (also referred to as an elastomeric resin composition layer) made of the elastomeric resin composition described above, or may be an integral layer (elastomeric resin composition layer) made of the elastomeric resin composition described above. The membrane of the present invention is a monolayer membrane or a laminated membrane comprising one or more layers made of the elastomeric resin composition described above.

[0221] Unless otherwise specified in this specification, "elastomeric resin composition layer" refers to a resin layer composed of the elastomeric resin composition of the present invention.

[0222] The layer (elastomeric resin composition layer) formed by the elastomeric resin composition of the present invention can function as an adhesive layer and an impact-absorbing layer, etc. Preferably, at least one elastomeric resin composition layer is disposed on the outermost layer in the laminated film.

[0223] The membranes of the present invention, with their single-layer or multi-layer structures, can be used as adhesive membranes and shock-absorbing membranes, etc.

[0224] Methods for forming the membrane according to the present invention include solution casting, extrusion molding, compression molding (press molding), blow molding, blow molding, calendering, and melt casting, with extrusion molding and compression molding (press molding) being preferred. Among these, extrusion molding is preferred, and T-die molding is more preferred.

[0225] The following describes the film-forming method for single-layer films based on the T-die method.

[0226] The elastomeric resin composition of the present invention is melt-blended using an extruder and extruded in a molten state from a T-die having a wide discharge port. Examples of extruders include single-screw extruders, twin-screw extruders, multi-screw extruders, and combinations thereof. The melting temperature is higher than the glass transition temperature (Tg) of the elastomeric resin composition, preferably 150–300°C, more preferably 200–300°C. From the viewpoint of suppressing coloration, melt blending is preferably performed under reduced pressure at the vent or under a nitrogen flow.

[0227] To remove foreign matter, it is preferable to use a filter to melt-filter the molten resin before extrusion. By using the melt-filtered molten resin to form a membrane, a membrane with fewer defects caused by foreign matter and gelation can be obtained. The filter media can be appropriately selected based on factors such as operating temperature, viscosity, and filtration precision. Examples include: nonwoven fabrics made of glass fibers, sheets made of cellulose impregnated with phenolic resin, sintered sheets of metal fiber nonwoven fabrics, sintered sheets of metal powder, metal mesh, and combinations thereof. From the viewpoint of heat resistance and durability, filters made by stacking two or more sintered sheets of metal fiber nonwoven fabrics are preferred. The filtration precision of the filter is not particularly limited, but is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

[0228] To improve the accuracy of film thickness, a gear pump can be installed on the extrusion molding production line for film production.

[0229] Molten resin extruded in film form from a T-die can be cooled using two or more cooling rollers. Examples of cooling rollers include rigid metal rollers and elastic metal rollers.

[0230] Metal rigid rollers are inelastic rollers made of metals such as stainless steel; examples include perforated rollers and spiral rollers. From the perspective of producing films with high surface smoothness, the surface of a metal rigid roller is preferably mirror-like.

[0231] A metal elastic roller is a roller with an elastic outer cylinder made of a metal film on its outer periphery. A metal elastic roller typically includes, for example, a metal roller made of stainless steel or the like, a metal film (elastic outer cylinder) made of stainless steel or the like covering the outer periphery of the roller, and a fluid sealed between the roller and the metal film (elastic outer cylinder), which allows it to exhibit elasticity through the presence of the fluid. Examples of fluids include water and oil.

[0232] The thickness of the metal film in the metal elastic roller is not particularly limited, but is preferably about 2 mm to about 8 mm. The metal film preferably has flexibility and is flexible in nature, and is preferably a seamless structure without weld seams. The metal elastic roller with such a metal film has excellent durability, and can be processed in the same way as a conventional mirror roller by simply mirroring the metal film, so that a film with a high surface smoothness can be produced.

[0233] The resulting single-layer film, after cooling, is drawn by traction rollers. The extrusion, cooling, and traction processes described above are performed continuously.

[0234] The film of the present invention can be a co-extruded film comprising two or more layers made of the elastomeric resin composition of the present invention, or a co-extruded film comprising a layer made of the elastomeric resin composition of the present invention and other resin layers. In co-extrusion molding, the constituent resins (compositions) of each layer are melt-blended using an extruder and co-extruded in a film form from a T-die having a wide discharge port in the desired laminated structure. Examples of lamination methods include a feed block method where lamination is performed before flowing into the T-die and a multi-manifold method where lamination is performed inside the T-die. From the viewpoint of improving the smoothness of the interlayer interfaces, the multi-manifold method is preferred. The molten thermoplastic resin laminate co-extruded from the T-die is pressed and cooled using two or more cooling rollers. The laminated film obtained after cooling is drawn by a pair of traction rollers. The above extrusion, cooling, and drawing processes are performed continuously.

[0235] It should be noted that in this specification, the object in the heated and molten state is mainly described as a "thermoplastic resin laminate" and the cured product is described as a "thermoplastic resin laminate film", but there is no clear boundary between the two.

[0236] The thickness of the membrane of the present invention can be designed according to the application, etc., and is preferably 10 to 700 μm. A lower limit is more preferably 30 μm, particularly preferably 50 μm. An upper limit is more preferably 500 μm, further preferably 400 μm, further preferably 300 μm, particularly preferably 200 μm, and most preferably 150 μm. When the thickness is above the above lower limit, the membrane is easy to manufacture and exhibits excellent impact resistance and reduced warpage during heating. When the thickness is below the above upper limit, the membrane has good film-forming properties or film-forming stability.

[0237] In the membrane of the present invention, the layer (elastomeric resin composition layer) composed of the elastomeric resin composition of the present invention can function as an adhesive layer, and the membrane of the present invention can be an adhesive membrane.

[0238] The film of the present invention can be held in place by a pair of release films as needed during or after film formation. Examples of release films include films on which at least one surface of a substrate composed of thermoplastic resin, paper, metal foil, or combinations thereof has been subjected to release treatment. Examples of thermoplastic resins include: polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; ethylene-vinyl acetate copolymer saponification; polyvinyl chloride, polyvinylidene chloride; polyethylene, polypropylene; poly4-methyl-1-pentene; polycarbonate resins; polyamide resins such as polyamide 6, polyamide 66, and polyamide 12. Examples of metal foils include aluminum foil and iron foil. The thickness of the release film is not particularly limited, and is typically from about 5 μm to about 100 μm.

[0239] [Composite film, decorative film]

[0240] In one embodiment, the film of the present invention can be a composite film having one or more layers (elastomeric resin composition layers) composed of the elastomeric resin composition of the present invention and one or more metal layers. The metal layers can function as decorative layers.

[0241] In another embodiment, the film of the present invention can be a decorative film having one or more layers (elastomeric resin composition layers) composed of the elastomeric resin composition of the present invention and one or more decorative layers. Examples of decorative layers include metallic layers, coloring layers, printing layers, nonwoven fabrics, artificial leather, natural leather, and combinations thereof. Decorative layers containing metallic layers can impart a metallic hue and luster to the film. The thickness of the decorative layer is not particularly limited, but from the viewpoints of processability and economy, it is preferable to be thinner than the layers (elastomeric resin composition layers) composed of the elastomeric resin composition of the present invention.

[0242] As described above, the layer (elastomeric resin composition layer) formed by the elastomeric resin composition of the present invention can function as an adhesive layer and an impact-absorbing layer, etc. Preferably, at least one elastomeric resin composition layer is disposed on the outermost layer in the composite film and decorative film of the present invention.

[0243] The layer composed of the elastomeric resin composition of the present invention (elastomeric resin composition layer) exhibits good adhesion to metals. Therefore, the composite film and decorative film of the present invention can contain a metal layer with good adhesive strength. Examples of metals include Al, Si, Ti, Cr, Ni, Zn, Ga, Y, Zr, Nb, In, Sn, Hf, Ta, W, alloys thereof, and combinations thereof.

[0244] The layer (elastomeric resin composition layer) made of the elastomeric resin composition of the present invention has good adhesion to various materials, therefore the decorative film of the present invention can contain decorative layers made of any raw materials.

[0245] The membrane of the present invention may contain one or more resin layers other than the layer (elastomeric resin composition layer) made of the elastomeric resin composition of the present invention as a substrate layer, decorative layer, protective layer of metal layer, or protective layer of decorative layer, etc.

[0246] Resins that form other resin layers include: (meth)acrylic resins; polyolefin resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and polynorbornene; styrene resins such as acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene (ABS) resin; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; polycarbonate resins; polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; polyacetal; polyurethane; and combinations thereof, etc., thermoplastic resins.

[0247] From the perspectives of transparency, weather resistance, surface gloss, and scratch resistance, layers containing (meth)acrylic resins are preferred as other resin layers.

[0248] From the viewpoints of processability and impact resistance, the layer containing (meth)acrylic resin preferably comprises one or more (meth)acrylic resins and one or more rubber components selected from the group consisting of acrylic rubber particles (preferably 2 to 3 layers of acrylic multilayer polymer particles) and acrylic block copolymers.

[0249] (Meth)acrylic resins are homopolymers or copolymers containing one or more (meth)acrylate units, and known (meth)acrylic resins can be used. Preferably, the methacrylic resin is a homopolymer or copolymer containing one or more methacrylate units comprising methyl methacrylate (MMA) units.

[0250] As acrylic rubber particles (preferably 2 to 3 layers of acrylic multilayer polymer particles) and acrylic block copolymers, known acrylic rubber particles and acrylic block copolymers can be used.

[0251] Other resin layers may contain one or more additives as needed. Examples of additives are the same as those for the elastomeric resin compositions of the present invention.

[0252] The composite film of the present invention may have other resin layers, such as a layer containing (meth)acrylic resin, on the metal layer as a substrate layer and / or a protective layer of the metal layer.

[0253] The decorative film of the present invention may have other resin layers, such as a layer containing (meth)acrylic resin, as the substrate layer and / or protective layer of the decorative layer.

[0254] Other resin layers can be either uncolored or colored. Examples of methods for coloring resin films used as other resin layers include: methods that color the resin before film formation by containing pigments and / or dyes; dyeing methods that color the resin film by immersing it in a dye dispersion; and so on.

[0255] The resin film of other resin layers may have a printed layer on at least one surface containing patterns, text, graphics, colors, and combinations thereof.

[0256] The resin film of other resin layer materials may have a metal layer on at least one surface. The metal layer may be made of metal foil. In addition, the metal layer can be formed on the resin film by vapor phase methods such as vacuum evaporation, sputtering, ion plating (IP), laser ablation, thermochemical vapor deposition, chemical vapor deposition (CVD), and plasma chemical vapor deposition (plasma CVD).

[0257] From the viewpoint of suppressing stress whitening during molding, the resin film is preferably free from whitening when bent at 180°.

[0258] The composite film and decorative film of the present invention can be manufactured by known methods. Examples of manufacturing methods for the composite film and decorative film of the present invention include laminating a single-layer film or laminated film comprising a layer (elastomeric resin composition layer) made of the elastomeric resin composition of the present invention with a film containing a metal layer or decorative layer having a metal layer or decorative layer on at least one surface of the resin film by pressing (preferably hot pressing).

[0259] Figure 1 This is a schematic cross-sectional view of a membrane according to one embodiment of the present invention.

[0260] In this embodiment, the membrane 1 is a three-layer structure in which layers (elastomeric resin composition layers) 11A and 11B, composed of the elastomeric resin composition of the present invention, are respectively stacked on both sides of other resin layers 12 (preferably layers containing (meth)acrylic resin). The composition and thickness of the elastomeric resin composition layer 11A and the elastomeric resin composition layer 11B may be the same or different.

[0261] The composition of the membrane of the present invention can be appropriately designed and modified to include a single-layer membrane containing only a layer (elastomeric resin composition layer) 11A or 11B made of the elastomeric resin composition of the present invention, or a two-layer membrane having a layer (elastomeric resin composition layer) 11A or 11B made of the elastomeric resin composition of the present invention laminated on one side of other resin layers 12, etc.

[0262] Figure 2 This is a schematic cross-sectional view showing an example of a film containing a metal layer.

[0263] In the figure, symbol 2 represents a film containing a metal layer, symbol 21 represents a substrate layer, and symbol 22 represents a metal layer. The film 2 containing a metal layer has a substrate layer 21 composed of a resin layer such as a layer containing methacrylic resin, and a metal layer 22 formed on one surface of the substrate layer 21 by a vapor deposition method or the like. The metal layer 22 can function as a decorative layer.

[0264] Figure 3 This is a schematic cross-sectional view illustrating a decorative film according to one embodiment of the present invention.

[0265] Decorative film 3 in Figure 1 The membrane 1 shown has an elastomer resin composition layer 11B on which is laminated. Figure 2 The membrane 2 shown contains a metal layer.

[0266] By Figure 1 The membrane 1 shown is Figure 2 The metal-layered film 2 shown is laminated using methods such as pressing (preferably hot pressing) to manufacture... Figure 3 The decorative film 3 shown. By laminating the metal layer 22 with the substrate layer 21 covering the surface of the metal layer 22, the substrate layer 21 can function as a protective layer for the metal layer 22.

[0267] [Composite molded bodies, decorative molded bodies]

[0268] In one embodiment, the molded body of the present invention can be a composite molded body having, in sequence, a layer composed of an elastomeric resin composition of the present invention and a metal layer on at least a portion of the surface of the adherend.

[0269] In one embodiment, the molded body of the present invention can be a decorative molded body having, in sequence, a layer composed of the elastomeric resin composition of the present invention and a decorative layer on at least a portion of the surface of the adherend.

[0270] The layer (elastomeric resin composition layer) formed by the elastomeric resin composition of the present invention can bond the adherend to the metal layer or decorative layer well.

[0271] Materials that can be used as adhesives include: organic materials such as thermoplastic or thermosetting resins and processed products of trees or other plants (e.g., kenaf); inorganic materials such as metals, metal compounds, ceramics, carbon, and stone (e.g., marble); and combinations thereof.

[0272] Examples of thermoplastic resins are similar to those of other resin layers that may be included in the composite films and decorative films of the present invention, with polypropylene resins and ABS resins being preferred. Examples of thermosetting resins include epoxy resins, phenolic resins, and melamine resins.

[0273] As metals, examples 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, their alloys (such as stainless steel), and combinations thereof.

[0274] The composite molded articles and decorative molded articles of the present invention can be manufactured using the composite film or decorative film of the present invention described above by known methods.

[0275] Examples of manufacturing methods include: a method of simultaneously laminating the composite film or decorative film of the present invention onto at least a portion of the surface of a pre-prepared adherend using forming methods such as vacuum forming, pneumatic forming, vacuum pneumatic forming, and compression forming; and a method of simultaneously molding and bonding the composite film or decorative film of the present invention by inserting the composite film or decorative film of the present invention, which has undergone secondary forming (also called pre-forming) as required by vacuum forming and pneumatic forming, into an injection molding mold, and then injecting thermoplastic resin into the mold, thereby simultaneously molding the adherend and laminating the composite film or decorative film of the present invention onto at least a portion of the surface of the adherend. In the latter method, the pre-forming of the composite film or decorative film of the present invention may also be performed using an injection molding machine for forming the adherend.

[0276] Figure 4 This is a schematic cross-sectional view illustrating a decorative molded body according to one embodiment of the present invention.

[0277] Decorative molded body 4 has at least a portion of the surface of the adherend 30 laminated with Figure 3 Decorative film 3 is shown.

[0278] [use]

[0279] The elastomeric resin composition of the present invention and films, laminates, or molded articles comprising the elastomeric resin composition can be used for any application. The elastomeric resin composition of the present invention exhibits good film-forming properties, processability, adhesion to various materials, and anti-cracking properties, making it suitable for applications such as decorative films and decorative molded articles. The decorative films and decorative molded articles of the present invention are preferably used for various applications requiring aesthetic appeal.

[0280] Suitable applications include: advertising towers, freestanding signs, protruding signs, lintel signs, roof signs, and other sign components or marking films; shop windows, partitions, shop stands, and other display stand components; fluorescent lamp shades, ambient lighting shades, lampshades, lumen ceilings, light walls, chandeliers, and other lighting components; furniture, wallpaper, chandeliers, and mirrors, and other interior decoration components; doors, window frames, domes, safety window glass, partitions, stair skirts, balcony skirts, roofs of leisure buildings, and other architectural components; aircraft windshields, pilot sun visors, motorcycle windshields, speedboat windshields, bus sun visors, car side sun visors, rear sun visors, front wings, headlight covers, automotive interior components, and bumpers, and other automotive exterior components. Components for conveyor systems; electronic devices such as mobile phones and personal computers; various household appliance components such as television protective covers; solar cell components such as backsheets for solar cells and frontsheets for flexible solar cells; audio-visual signs and stereo covers; vending machines; medical equipment components such as incubators and X-ray machine components; equipment-related components such as clock panels, mechanical covers, measuring instrument covers, experimental devices, dials, and observation windows; traffic-related components such as road signs, guide boards, curved mirrors, and soundproof walls; bathroom and sanitary components such as bathtubs; greenhouses, large water tanks, and water tanks; stationery such as rulers and table mats; game parts, toys, and musical instruments; decorative and protective films on surfaces such as face masks used for welding.

[0281] Example

[0282] The embodiments and comparative examples of the present invention will be described.

[0283] [Evaluation Items and Evaluation Methods]

[0284] The evaluation items and evaluation methods are as follows.

[0285] (Aggregation Conversion Rate)

[0286] The polymerization conversion rate was determined by gas chromatography. A GL Sciences Inc.-manufactured "INERTCAP1" column (0.4 μm film thickness, 0.25 mm inner diameter) was connected as the column in a Shimadzu GC-14A gas chromatograph. (Length 60m). The analysis was conducted under the following conditions, and the polymerization conversion rate was calculated from the obtained data.

[0287] Injection temperature: 250℃ Detector temperature: 250℃ Temperature distribution: Hold at 60℃ for 5 minutes → Increase temperature to 250℃ at a rate of 10℃ / minute → Hold at 250℃ for 10 minutes.

[0288] (Weight-average molecular weight (Mw), Number-average molecular weight (Mn), Molecular weight distribution (Mw / Mn))

[0289] 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). The GPC apparatus "HLC-8320" manufactured by Tosoh Corporation was used as the assay device. A separation column consisting of "TSKguardcolumSuperHZ-H", "TSKgelHZM-M", and "TSKgelSuperHZ4000" manufactured by Tosoh Corporation, connected in series, was used as the separation column. A differential refractive index detector (RI detector) was used as the detector.

[0290] A sample solution was prepared by dissolving 4 mg of the target resin in 5 ml of tetrahydrofuran. The column oven temperature was set to 40 °C. Using tetrahydrofuran as the eluent, the eluent flow rate was set to 0.35 ml / min. 20 μl of the sample solution was injected into the apparatus, and the chromatogram was measured. GPC measurements were performed on 10 points of standard polystyrene or standard polymethyl methacrylate (PMMA) with molecular weights in the range of 400–5,000,000 to construct a standard curve showing the relationship between retention time and molecular weight. Based on this standard curve, the Mw, Mn, and Mw / Mn values ​​of the target resin (converted from standard polystyrene or standard PMMA) were determined.

[0291] (Hydrogenation rate)

[0292] The hydrogenation rate of polymer blocks containing conjugated diene compound units is determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0293] (The sum of 1,2-bond amount and 3,4-bond amount)

[0294] Thermoplastic elastomers comprising polymer blocks containing conjugated diene compound units 1 ¹H-NMR determination. The summation of 1,2-bonded and 3,4-bonded amounts was calculated based on the ratio of the integral value of the first peak present in the range of 4.2–5.0 ppm from 1,2-bonded and 3,4-bonded conjugated diene units to the integral value of the second peak present in the range of 5.0–5.45 ppm from 1,4-bonded conjugated diene units.

[0295] (Melting point)

[0296] The melting point of polypropylene polymers was determined using a differential scanning calorimeter (DSC-50, product number 600000, manufactured by Shimadzu Corporation). Approximately 5 mg of a polypropylene film sample was placed in an aluminum dish and then placed in the apparatus. After nitrogen purging for at least 30 minutes, the temperature was temporarily increased from room temperature (20–25 °C) to 200 °C at a rate of 10 °C / min in a nitrogen flow of 10 ml / min, held for 5 minutes, and then decreased to 40 °C at a rate of 10 °C / min (single scan). Next, the temperature was increased to 200 °C at a rate of 10 °C / min (second scan), and the heat of fusion curve was obtained. The melting point (Tm) was used to determine the maximum melting peak temperature (°C).

[0297] (melt tension)

[0298] The melt tension of polypropylene polymers was measured using a capillary rheometer (Toyo Seiki Co., Ltd. "Capello Graff 1D") equipped with a wheeled tension measuring unit. The polypropylene polymer was added to a 9.55 mm diameter tube heated to 230°C. The molten polypropylene polymer is fed into a barrel at a feed rate of 20 mm / min from a diameter of 2.0 mm. The extrusion is carried out through a 40mm orifice at a traction speed of 4.0m / min using a pair of traction rollers. The tension applied to the pulley-type tension measuring fixture is determined as the melt tension (N).

[0299] (Slippery)

[0300] A 100mm × 200mm test piece was cut from a single-layer film (E-Ex) (150μm thick) composed of an elastomeric resin composition. The test piece was pressed and adhered by hand to the surface of a smooth stainless steel plate (SUS plate) that was horizontally positioned relative to the ground and larger than the single-layer film (E-Ex). A 100g metal plate was then placed on top of the plate. In this state, the single-layer film (E-Ex) was stretched by hand, and the results were evaluated according to the following criteria.

[0301] Good (〇): The single-layer film does not stick and can slide smoothly.

[0302] Defect (×): The single-layer film can slide, but there is adhesion.

[0303] (Film thickness stability)

[0304] Test pieces measuring 120 mm × 200 mm were cut from a single-layer film (E-Ex) (150 μm thick) composed of an elastomeric resin composition. It should be noted that the long axis of the test piece follows the extrusion direction (resin flow direction) during molding. Along the central axis parallel to the long axis, the thickness was measured at five points (50 mm intervals) at positions 0 mm, 50 mm, 100 mm, 150 mm, and 200 mm from the center of one of the short sides. The difference between the maximum and minimum values ​​(also known as the maximum film thickness difference) was calculated and evaluated according to the following criteria.

[0305] Good (〇): Maximum film thickness difference is less than 25 μm. Defect (×): Maximum film thickness difference greater than 25 μm.

[0306] (Adhesion strength of the elastomer resin composition to polypropylene (PP))

[0307] A test piece measuring 25 mm in length and 150 mm in width was cut from the laminated film (E-PP) having a laminated structure of an elastomer resin composition layer / polyimide layer / polypropylene layer and including a direct joint between the elastomer resin composition layer and the polypropylene layer.

[0308] According to JIS K6854-2, a peel test was conducted using an Autograph ("GS-X" manufactured by Shimadzu Corporation) under the conditions of a peel angle of 180°, a tensile speed of 300 mm / min, and an ambient temperature of 23°C.

[0309] Starting from the area where the polyimide film serves as a non-adhesive spacer, the peel strength of the elastomeric resin composition layer from the polypropylene layer at the direct bonding portion is measured. This peel strength is used as data for the adhesive strength of the elastomeric resin composition to polypropylene (PP), and is evaluated according to the following criteria.

[0310] Good (〇): Bond strength is above 20N / 25mm. Poor (×): Bond strength less than 20N / 25mm.

[0311] It should be noted that, since the elastomeric resin composition layer and the polypropylene layer are not directly bonded, peel tests can be easily performed by peeling from the area where the polyimide layer is located. The same applies to the evaluation of the adhesion strength of the elastomeric resin composition to methacrylic resins and to indium, as described later. The polyimide layer is used as a starting layer for easily performing peel tests and is not a necessary layer in actual decorative films and molded decorative articles.

[0312] (Adhesion strength of elastomer resin composition to methacrylic resin)

[0313] A test piece measuring 25 mm longitudinally and 150 mm transversely was cut from a laminated film (EM) having a laminated structure of an elastomer resin composition layer / polyimide layer / methacrylic resin composition layer and including a direct joint between the elastomer resin composition layer and the methacrylic resin composition layer.

[0314] A peel test was performed using the same method as described above for "adhesion strength of the elastomeric resin composition to polypropylene (PP)".

[0315] Starting from the area where the polyimide film serves as a non-adhesive spacer, the peel strength of the elastomeric resin composition layer from the methacrylic resin composition layer at the direct bonding portion is measured. This peel strength is used as data for the adhesive strength of the elastomeric resin composition to the methacrylic resin, and is evaluated according to the following criteria.

[0316] Good (〇): Bond strength is above 50N / 25mm. Poor (×): Bond strength less than 50N / 25mm.

[0317] (Adhesion strength of the elastomeric resin composition to indium)

[0318] A test piece measuring 25 mm in length and 100 mm in width was cut from the decorative film (DF2) having a laminated structure of a methacrylic resin composition layer / indium layer / polyimide layer / second elastomer resin composition layer / methacrylic resin composition layer / first elastomer resin composition layer and including a direct joint between the indium layer and the second elastomer resin composition layer.

[0319] A peel test was performed using the same method as described above for "adhesion strength of the elastomeric resin composition to polypropylene (PP)".

[0320] Starting from the area where the polyimide film serves as a non-adhesive spacer, the peel strength of the second elastomeric resin composition layer is measured at the direct bonding portion between the indium layer and the second elastomeric resin composition layer. This peel strength is used as data on the adhesive strength of the elastomeric resin composition to indium and is evaluated according to the following criteria.

[0321] Good (〇): Bond strength is above 10N / 25mm. Poor (×): Bond strength less than 10N / 25mm.

[0322] (Resistance to breakage)

[0323] Using a gravel impact tester (manufactured by Suga Testing Equipment Co.), 50g of No. 7 gravel was impacted onto the surface of the indium layer (decorative layer) of a plate-shaped decorative molded body (DM) from a distance of 350mm at a test piece temperature of -20°C, a test piece installation angle of 90° relative to the spray axis of the sprayed material, and an air pressure of 0.4MPa. The surface of the decorative molded body after the test was visually observed and evaluated according to the following criteria.

[0324] Good (〇): No cracking (damage and / or defects) was observed.

[0325] Defective (×): More than one crack (damage and / or defect) was observed.

[0326] (5% weight reduction time)

[0327] Using a thermogravimetric analyzer (Shimadzu Corporation's "TGA-50"), 5 mg of the test resin was heated from room temperature (20–25 °C) to 240 °C at a heating rate of 10 °C / min in air, and held at that temperature for 45 minutes to obtain the TG curve. The moment when 240 °C was reached was taken as the baseline time (0 minutes), and the weight at that moment was taken as the baseline weight (100%). The time when the weight loss rate reached 5% (5% weight loss time) was then calculated.

[0328] [Preparation or manufacture of resin (composition)]

[0329] The resin (composition) manufactured or prepared is as described below.

[0330] (Manufacturing Example 1) (Manufacturing of the First Thermoplastic Elastomer (EX-1))

[0331] In a pressure vessel that has been purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 61.1 g of a 10.5% by mass cyclohexane solution (6.42 g of sec-butyllithium) as an anionic polymerization initiator are added and mixed. The solution is heated to 50°C, 0.81 kg of styrene (St) is added and polymerization is carried out for 1 hour, followed by the addition of 10.87 kg of isoprene and polymerization for 2 hours, and then the addition of 0.81 kg of styrene (St) and polymerization for 1 hour. This yields a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer. Palladium on carbon (palladium loading: 5% by mass) as a hydrogenation catalyst is added to this reaction solution at 5% by mass relative to the above block copolymer, and the reaction is carried out for 10 hours at a hydrogen pressure of 2 MPa and a temperature of 150°C. After cooling and depressurization, palladium on carbon was removed by filtration, the filtrate was concentrated, and vacuum dried to obtain thermoplastic elastomer (EX-a) (a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer). The total stoichiometric ratio of 1,2-bonded and 3,4-bonded components in the polyisoprene blocks of thermoplastic elastomer (EX-a) is 7 mol.

[0332] In addition, in a pressure vessel that has been purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 420.0 g of a 10.5% by mass cyclohexane solution (44.1 g of sec-butyllithium) as an anionic polymerization initiator were added and mixed. The solution was heated to 50°C, 2.83 kg of styrene (St) was added and polymerization was carried out for 1 hour, followed by the addition of 19.81 kg of isoprene and polymerization for 2 hours. This yielded a reaction solution containing a polystyrene-polyisoprene diblock copolymer. Next, hydrogenation, palladium removal by filtration on carbon, and vacuum drying were performed using the same method as above to obtain a thermoplastic elastomer (EX-b) (a hydrogenated form of the polystyrene-polyisoprene diblock copolymer). The total stoichiometric ratio of 1,2-bonded and 3,4-bonded segments in the polyisoprene blocks of the thermoplastic elastomer (EX-b) was 7 mol.

[0333] Thermoplastic elastomers (EX-a) and (EX-b) were melt-blended using a twin-screw extruder (Coperon ZSK26 MegaCompounder, with an effective screw length (L) to screw diameter (D) ratio (L / D) = 54) at a screw speed of 300 rpm and a melt-blending temperature of 200°C to obtain a first thermoplastic elastomer (EX-1). The polyisoprene blocks in the first thermoplastic elastomer (EX-1) had a total stoichiometric ratio of 7 mol for 1,2-bonded and 3,4-bonded segments.

[0334] (Manufacturing Example 2) (Manufacturing of the Second Thermoplastic Elastomer (EY-1))

[0335] In a pressure vessel that has been purged with nitrogen and dried, 50.0 kg of cyclohexane as a solvent, 94.1 g of a 10.5% by mass cyclohexane solution (9.9 g of sec-butyllithium) as an anionic polymerization initiator, and 300 g of tetrahydrofuran as a Lewis base were added and mixed. The solution was heated to 50°C, 1.25 kg of styrene (St) was added and polymerization was carried out for 1 hour, followed by the addition of 10.00 kg of isoprene and polymerization for 2 hours, and then the addition of 1.25 kg of styrene (St) and polymerization for 1 hour. This yielded a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer. Then, using the same method as in Manufacturing Example 1, hydrogenation, palladium removal by filtration on carbon, and vacuum drying were performed to obtain a second thermoplastic elastomer (EY-1) (a hydrogenated form of the polystyrene-polyisoprene-polystyrene triblock copolymer). The total stoichiometric ratio of 1,2-bonded and 3,4-bonded segments in the polyisoprene blocks of the second thermoplastic elastomer (EY-1) is 55 mol.

[0336] (Manufacturing Example 3) (Manufacturing of the Third Thermoplastic Elastomer (EZ-1))

[0337] In a pressure vessel that has been purged with nitrogen and dried, 4.29 kg of α-methylstyrene (αMSt), 6.25 kg of cyclohexane, 1.18 kg of methylcyclohexane, and 0.15 kg of tetrahydrofuran were added and 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, converted to standard polystyrene) of poly(α-methylstyrene) (block S) was 6600, and the polymerization conversion rate of α-methylstyrene was 90%. Next, 0.88 kg of butadiene was added to the reaction solution, and after polymerization at -10°C for 30 minutes, 41.8 kg of cyclohexane was added. At this point, the polymerization conversion rate of butadiene was 90%. This process yielded a poly(α-methylstyrene) block (S)-polybutadiene block (t1) copolymer. The weight-average molecular weight (Mw, converted from standard polystyrene) of the polybutadiene block (t1) is 3700, and the 1,2-bonding amount is 81 mol.

[0338] 7.71 kg of butadiene was further added to the above reaction solution, 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, converted from standard polystyrene) of the polybutadiene block (t2) was 29800, and the 1,2-bonding amount was 40 mol%.

[0339] 0.54 L of a 0.5 M toluene solution of dichlorodimethylsilane was added to the above reaction solution, and a coupling reaction was carried out at 50 °C for 1 hour. After this reaction, the resulting coupling product was 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). Here, X represents a coupling residue.

[0340] The obtained poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer contains 31% poly(α-methylstyrene) blocks by mass and 55 mol of 1,4-bonds in all polybutadiene blocks (t1+t2).

[0341] It should be noted that GPC analysis was performed on the above-mentioned coupling compound and the unreacted coupling block copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer), and the coupling efficiency was determined by the ratio of the peak integral values ​​of UV absorption, which was 94%.

[0342] In the above reaction solution, a Ziegler-based hydrogenation catalyst composed of nickel octanoate and triethylaluminum was added under a hydrogen atmosphere, and the hydrogenation reaction was carried out for 5 hours at a hydrogen pressure of 0.8 MPa and a temperature of 80°C to obtain the third thermoplastic elastomer (EZ-1). The main component of the third thermoplastic elastomer (EZ-1) is the hydrogenation product of poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (the hydrogenation product of the above coupling), with a content of 94% by mass.

[0343] The third thermoplastic elastomer (EZ-1) has a weight-average molecular weight (Mw, converted to standard polystyrene) of 79,500, a number-average molecular weight (Mn, converted to standard polystyrene) of 78,700, a Mw / Mn ratio of 1.01, a hydrogenation rate of 97.5% for all polybutadiene blocks (t1+t2), and a total stoichiometric ratio of 1,2-bonds and 3,4-bonds in the polybutadiene blocks of 45 moles.

[0344] (First polypropylene polymer (PX) or (PXC))

[0345] (PX-1) "Waymark MFX8" manufactured by Polypro Co., Ltd. of Japan, with an MFR of 1.1g / 10 minutes at 230°C and 21.18N, and a melt tension of 24.5×10⁻⁶. -2 N; (PX-2) "Waymax (registered trademark) MFX3" manufactured by Polypro Co., Ltd. of Japan, with an MFR of 9.0g / 10 minutes at 230℃ and 21.18N, and a melt tension of 4.9×10⁻⁶. -2 N; (PXC-3) (For comparison) "WINTEC (registered trademark) WSX03" manufactured by Polypro Co., Ltd. of Japan, at 230℃ and 21.18N, has an MFR of 7.0g / 10 minutes and a melt tension of 0.4×10⁻⁶. -2 N.

[0346] (Second polypropylene polymer (PY) or (PYC))

[0347] (PY-1) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries Co., Ltd., "Eumex (registered trademark) 5200", melting point 124℃; (PY-2) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries Co., Ltd., "Eumex (registered trademark) 5500", melting point 123℃; (PY-3) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., “Eumex (registered trademark) 5202W”, melting point 115℃; (PYC-4) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., “Eumex (registered trademark) 1001”, melting point 142℃; (PYC-5) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., “Eumex (registered trademark) 1010”, melting point 135℃; (PYC-6) Maleic anhydride modified polypropylene, manufactured by Mitsui Chemicals Co., Ltd., "ADMER (registered trademark) QF551", melting point 147℃.

[0348] (Polypropylene film)

[0349] (PP-F) Non-polar polypropylene film, "Nobatet MA3" manufactured by Polypro Co., Ltd. of Japan.

[0350] (Object to be glued)

[0351] As the substrate (PP-M), a sheet-shaped polypropylene molded product with a length of 100mm × width of 40mm × thickness of 3mm is prepared by injection molding non-polar polypropylene (J708UG manufactured by Polymer Co., Ltd.) at 230°C using an injection molding machine (SG-100 manufactured by Sumitomo Heavy Industries, Ltd.).

[0352] (Manufacturing Example 4) (Manufacturing of Methacrylic Resin (M))

[0353] The following methacrylic resins (M1) and (M2) are manufactured using conventional methods.

[0354] (M1) Methyl methacrylate (MMA)-methyl acrylate (MA) copolymer (MMA unit content: 93.6% by mass, MA unit content: 6.4% by mass, Mw (conversion from standard PMMA) = 120000, Mw / Mn = 2.1); (M2) Methyl methacrylate (MMA)-methyl acrylate (MA) copolymer (MMA unit content: 99.3% by mass, MA unit content: 0.7% by mass, Mw (conversion from standard PMMA) = 84000, Mw / Mn = 2.1).

[0355] (Manufacturing Example 5) (Manufacturing of Multilayer Polymer Particles (R1))

[0356] In a reactor equipped with a stirrer, thermometer, nitrogen inlet, monomer inlet pipe, and reflux cooler, 100 parts by weight of deionized water, 0.019 parts by weight of surfactant (sodium polyoxyethylene alkyl ether acetate (NIKKOL-ECT-3NEX manufactured by Nikko Kemikazu Co., Ltd.)) and 0.10 parts by weight of sodium carbonate were added and dissolved. After purging the reactor with nitrogen to create a substantially oxygen-free environment, the aqueous solution was heated to 80°C.

[0357] After adding 0.04 parts by mass of potassium persulfate to the above aqueous solution and stirring for 5 minutes, 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 the addition was completed, emulsion polymerization was carried out for 40 minutes to maintain a polymerization rate of over 98%.

[0358] Next, 0.05 parts by mass of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, 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 added dropwise over 60 minutes. After the addition was completed, seed emulsion polymerization was carried out for 90 minutes to achieve a polymerization rate of over 98%. At this point, the volume average particle size of the multilayer polymer particles in the latex was determined by dynamic light scattering using a laser diffraction / scattering particle size distribution measuring device, and the result was 0.09 μm.

[0359] Next, 0.02 parts by weight of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, a mixture of 18.6 parts by weight of methyl methacrylate (MMA), 1.2 parts by weight of methyl acrylate (MA), and 0.04 parts by weight of n-octyl mercaptan (n-OM) was continuously added dropwise over 30 minutes. After the addition was completed, seed emulsion polymerization was carried out for 60 minutes to achieve a polymerization rate of over 98%.

[0360] The final latex was added to a container equipped with a mixer. A magnesium sulfate aqueous solution was then added to the stirred latex to induce salting-out and coagulation. The resulting coagulated material was washed with water, dehydrated, and dried to obtain acrylic multilayer polymer particles (R1).

[0361] (Manufacturing Example 6) (Manufacturing of Multilayer Polymer Particles (R2))

[0362] In a reactor equipped with a stirrer, thermometer, nitrogen inlet, monomer inlet pipe, and reflux cooler, 100 parts by weight of deionized water, 0.019 parts by weight of surfactant (Perex SS-H manufactured by Kao Corporation), and 0.5 parts by weight of sodium carbonate were added and dissolved. After purging the reactor with nitrogen to create a substantially oxygen-free environment, the aqueous solution was heated to 80°C.

[0363] After adding 0.02 parts by mass of potassium persulfate to the above aqueous solution and stirring 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 added dropwise over 20 minutes. After the addition was complete, emulsion polymerization was carried out for 30 minutes to achieve a polymerization rate of over 98%. The volume average particle size at this point was 0.21 μm.

[0364] Next, 0.07 parts by weight of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, a mixture of 41.1 parts by weight of n-butyl acrylate (n-BA), 8.9 parts by weight of styrene (St), and 2.0 parts by weight of allyl methacrylate was continuously added dropwise over 80 minutes. After the addition was completed, seed emulsion polymerization was carried out for 60 minutes to achieve a polymerization rate of over 98%.

[0365] Next, 0.07 parts by weight of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, a mixture of 37.6 parts by weight of methyl methacrylate (MMA), 2.4 parts by weight of methyl acrylate (MA), and 0.12 parts by weight of n-octyl mercaptan (n-OM) was continuously added dropwise over 60 minutes. After the addition was completed, seed emulsion polymerization was carried out for 60 minutes to achieve a polymerization rate of over 98%.

[0366] The final latex was added to a container equipped with a mixer. A magnesium sulfate aqueous solution was then added to the stirred latex to induce salting-out and coagulation. The resulting coagulated material was washed with water, dehydrated, and dried to obtain acrylic multilayer polymer particles (R2).

[0367] (Manufacturing Example 7) (Manufacturing of Multilayer Polymer Particles (R3))

[0368] In a reactor equipped with a stirrer, thermometer, nitrogen inlet, monomer inlet pipe and reflux cooler, add 200 parts by mass of deionized water, 1 part by mass of sodium dodecylbenzenesulfonate and 0.05 parts by mass of sodium carbonate. After the reactor is fully replaced with nitrogen to become a substantially oxygen-free state, the aqueous solution is heated to 80°C.

[0369] After adding 0.01 parts by mass of potassium persulfate to the above aqueous solution and stirring for 5 minutes, a mixture of 9.48 parts by mass of methyl methacrylate (MMA), 0.5 parts by mass of n-butyl acrylate (n-BA), and 0.02 parts by mass of allyl methacrylate was added dropwise over 20 minutes. After the addition was complete, emulsion polymerization was carried out for 30 minutes to maintain a polymerization rate of over 98%.

[0370] Next, 0.03 parts by weight of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, a mixture of 1.45 parts by weight of methyl methacrylate (MMA), 27.67 parts by weight of n-butyl acrylate (n-BA), and 0.88 parts by weight of allyl methacrylate was added dropwise over 40 minutes. After the addition was completed, seed emulsion polymerization was carried out for 30 minutes to achieve a polymerization rate of over 98%.

[0371] Next, 0.06 parts by mass of potassium persulfate were added to the obtained latex and stirred for 5 minutes. Then, a mixture of 53.73 parts by mass of methyl methacrylate (MMA), 5.97 parts by mass of n-butyl acrylate (n-BA), and 0.3 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 100 minutes. After the addition was completed, seed emulsion polymerization was carried out for 60 minutes to achieve a polymerization rate of over 98%, resulting in a latex containing multilayer polymer particles (R3). The volume average particle size of the multilayer polymer particles (R3) was 0.10 μm.

[0372] Next, the latex containing the multilayer polymer particles (R3) was frozen at -30°C for 4 hours. The frozen latex was then added to twice the volume of 80°C warm water and stirred to form a slurry, which was kept at 80°C for 20 minutes. The slurry was then dehydrated and dried at 70°C to obtain acrylic multilayer polymer particles (R3).

[0373] (Manufacturing Example 8) (Manufacturing of Block Copolymer (B-1))

[0374] The following block copolymer (B-1) is manufactured using conventional methods.

[0375] (B-1) 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, converted from standard PMMA) = 70000.

[0376] (Manufacturing Example 9) (Manufacturing of Methacrylic Acid Resin Composition (MR1))

[0377] 55.7 parts by weight of methacrylic resin granules (M1), 33.6 parts by weight of multilayer polymer particles (R1), 6.7 parts by weight of multilayer polymer particles (R2), and 4 parts by weight of block copolymer (B-1) granules were melt-blended using a twin-screw extruder and extruded in filaments. The filaments were then cut using a granulator to obtain granules of the methacrylic resin composition (MR1).

[0378] (Manufacturing Example 10) (Manufacturing of Methacrylic Acid Resin Composition (MR2))

[0379] Ten parts by weight of methacrylic resin (M2) and 90 parts by weight of multilayer polymer particles (R3) were melt-blended at 230°C using a twin-screw extruder and extruded in filaments. The filaments were then cut using a granulator to obtain granules of the methacrylic resin composition (MR2).

[0380] (Phenolic antioxidants (AO-F))

[0381] (AO-F1) Hindered phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], BASF Japan's "Irganox 1010", molecular weight: 1178 (AO-F2) Hindered phenolic antioxidant, bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propionic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), "Adekastab AO-80" manufactured by ADEKA, molecular weight: 741.

[0382] (Phosphorus antioxidants (AO-P))

[0383] (AO-P1) is a multi-component phosphorus antioxidant containing the following 5 compounds, namely "HOSTANOX P-EPQ" manufactured by Clariant Japan Co., Ltd., with a molecular weight of 595 to 1035.

[0384]

[0385] (AO-P2) Phosphorus antioxidant, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, "Adekastab PEP-8" manufactured by ADEKA, molecular weight: 733.

[0386] [Examples E1-E5, Comparative Examples EC1-EC11]

[0387] (Preparation of the elastomer resin composition)

[0388] In Examples E1 to E5 and Comparative Examples EC1 to EC11, one or more thermoplastic elastomers (E) and one or more polypropylene polymers (P) were melt-blended at 230°C using a twin-screw extruder (Toshiba Machine Co., Ltd.'s "TEM-28") with the formulations described in Table 1 or Table 2, and then extruded in filament form. The filaments were cut using a granulator to obtain granules (EP) of the elastomer resin composition.

[0389] In Tables 1 and 2, EP1 to EP5 and EPC1 to EPC11 are elastomeric resin compositions (elastic resin compositions without added antioxidants) obtained in each embodiment and comparative example, which are composed of a mixture of one or more thermoplastic elastomers (E) and one or more polypropylene polymers (P).

[0390] The unit for the amount of compounding in Tables 1 and 2 is "parts by mass".

[0391] (Manufacturing of a single-layer film (E-Ex) composed of an elastomeric resin composition)

[0392] In Examples E1 to E5 and Comparative Examples EC1 to EC11, 20mm was used. A single-screw extruder (manufactured by OCS) is used to melt-blend the resulting elastomeric resin composition granules (EP) at 230°C and extrude them through a 150mm wide T-die. The molten resin composition is sandwiched between adjacent first and second cooling rollers, wound onto the second cooling roller, sandwiched between the second and third cooling rollers, and wound onto the third cooling roller for cooling. The resulting film is then drawn using a pair of traction rollers. In this way, a single-layer film (E-Ex) composed of the elastomeric resin composition with a width of 120mm and a thickness of 150μm is produced.

[0393] (Manufacturing of a laminated film (E-PP) comprising an elastomer resin composition layer and a polypropylene layer)

[0394] In Examples E1 to E5 and Comparative Examples EC1 to EC11, a compression molding machine was used at 200°C and a load of 50 kgf / cm. 2 Under certain conditions, the granules (EP) of the obtained elastomeric resin composition were compressed and molded for 2 minutes to obtain a single-layer film (E-HP) composed of the elastomeric resin composition.

[0395] On a single-layer membrane (E-HP) (150mm longitudinally × 150mm transversely × 0.5mm thick) made of an elastomeric resin composition, a polyimide membrane (“Capton” (registered trademark) manufactured by Toray DuPont, 75mm longitudinally × 150mm transversely × 0.05mm thick) and a non-polar polypropylene membrane (PP-F) (150mm longitudinally × 150mm transversely × 0.4mm thick) are stacked sequentially. It should be noted that the central axes of each membrane are aligned.

[0396] As a spacer, a metal frame with an inner size of 150mm × 150mm and a thickness of 0.8mm was prepared. The obtained temporary laminated films were embedded in the metal frame and clamped with a pair of polytetrafluoroethylene (PTFE) films (release films), and then clamped from the outside with a pair of metal plates. A compression molding machine was used at 200℃ and a load of 50kgf / cm². 2 Under the conditions of heating and pressurizing the obtained temporary laminate for 2 minutes, a pair of metal plates, a pair of PTFE films and a metal frame are removed.

[0397] The above operation yields a laminated film (E-PP) (150 mm longitudinally × 150 mm transversely) with a laminated structure consisting of an elastomer resin composition layer (0.5 mm thick), a polyimide layer (0.05 mm thick), and a polypropylene (PP) layer (0.4 mm thick).

[0398] (Manufacturing of a laminated film (EM) comprising an elastomer resin composition layer and a methacrylic resin composition layer)

[0399] By compressing granules of a methacrylic resin composition (MR1) into a single layer (M-HP) using the same method as for a single layer film (E-HP) composed of an elastomeric resin composition (MR1), a single layer film (M-HP) composed of a methacrylic resin composition (MR1) is obtained.

[0400] In Examples E1 to E5 and Comparative Examples EC1 to EC11, a single-layer film (M-HP) (150 mm longitudinally × 150 mm transversely × 0.4 mm thick) composed of a methacrylic resin composition (MR1) was used instead of a non-polar polypropylene film (PP-F). Otherwise, the process was the same as for the laminated film (E-PP) to obtain a laminated film (EM) (150 mm longitudinally × 150 mm transversely) with a laminated structure of an elastomer resin composition layer (0.5 mm thick) / a polyimide layer (0.05 mm thick) / a methacrylic resin composition layer (0.4 mm thick).

[0401] (Manufacturing of films with decorative layers (films with metal layers) (M-In))

[0402] In Examples E1 to E5 and Comparative Examples EC1 to EC11, a 50mm... A single-screw extruder with an exhaust port melt-blends granules of a methacrylic resin composition (MR1) at 260°C and extrudes them through a 500mm wide T-die. The molten resin is sandwiched between adjacent first and second cooling rollers, wound onto the second cooling roller, sandwiched between the second and third cooling rollers, and wound onto the third cooling roller for cooling. The resulting film is then drawn using a pair of traction rollers. This produces a single-layer film (M-Ex) of the methacrylic resin composition (MR1) with a width of 500mm and a thickness of 75μm.

[0403] Using a vacuum evaporation apparatus (VE-2030, manufactured by Vacuum Equipment Company, resistance heating method) and indium particles with a purity of 99.99% and a particle size of 1 mm, a 50 nm thick indium layer was vacuum-deposited as a decorative layer (metal layer) on the entire surface of a monolayer film (M-Ex) composed of a methacrylic resin composition (MR1). A basket heater (92% alumina) was used for resistance heating. The evaporation conditions were set at a vacuum degree of 7 × 10⁻⁶. -3 The test was conducted at Pa and a speed of 0.8 Å / s for 10 minutes.

[0404] Following the above steps, a laminated film containing a decorative layer (film containing a metal layer) (M-In) is obtained, consisting of a methacrylic resin composition layer (substrate layer and protective layer) (75 μm thick) and an indium layer (decorative layer, metal layer) (50 nm thick). (Please refer to...) Figure 2 ).

[0405] (Manufacturing of decorative film)

[0406] In Examples E1-E5 and Comparative Examples EC1-EC11, granules of the obtained elastomer resin composition (EP), granules of the methacrylic resin composition (MR2), and granules of the obtained elastomer resin composition (EP) were melt-blended using a single-screw extruder (GMENGINEERING's "VGM25-28EX"). These molten resins were stacked in a multi-manifold die, and a three-layer thermoplastic resin laminate was co-extruded from a T-die at 240°C and a flow rate of 5 kg / h. This thermoplastic resin laminate was sandwiched between adjacent first and second cooling rollers, wound onto the second cooling roller, sandwiched between the second and third cooling rollers, and wound onto the third cooling roller for cooling. The resulting cooled film was then drawn using a pair of traction rollers.

[0407] Following the above steps, a laminated film (EME) with a width of 300 mm and a total thickness of 300 μm is obtained, comprising a first elastomeric resin composition layer (50 μm thick, adhesive layer and impact-absorbing layer), a methacrylic resin composition layer (200 μm thick, substrate layer), and a second elastomeric resin composition layer (50 μm thick, adhesive layer and impact-absorbing layer). (Please refer to...) Figure 1 ).

[0408] It should be noted that the first elastomeric resin composition layer and the second elastomeric resin composition layer have the same composition and thickness and are not particularly distinguished; both can function as adhesive bonding layers and impact absorption layers.

[0409] Next, using a heat lamination apparatus (VAII-700 type manufactured by Taisei Ramuneter Co., Ltd.), a pair of heated rollers set to 110°C are used to heat-press the laminated film (EME) (100mm longitudinal x 40mm transverse x 300μm thickness) with the film containing the decorative layer (film containing the metal layer) (M-In) (100mm longitudinal x 40mm transverse x approximately 75μm thickness). It should be noted that the heat pressing is performed so that the second elastomeric resin composition layer (adhesive layer and impact-absorbing layer) contained in the laminated film (EME) and the indium layer (decorative layer, metal layer) contained in the film containing the decorative layer (film containing the metal layer) (M-In) come into contact with each other.

[0410] Following the above steps, a decorative film (DF1) with a laminated structure consisting of a methacrylic resin composition layer (substrate layer and protective layer), an indium layer (decorative layer and metal layer), a second elastomer resin composition layer (adhesive layer and impact absorption layer), a methacrylic resin composition layer, and a first elastomer resin composition layer (adhesive layer and impact absorption layer) is obtained (100mm longitudinally and 40mm transversely). (Please refer to...) Figure 3 ).

[0411] Additionally, a polyimide film (Toray DuPont's "Capton" film, 30mm x 40mm x 0.05mm thick) is placed between a laminated film (EME) (100mm x 40mm x 75μm thick) and a film containing a decorative layer (including a metal layer) (M-In) (100mm x 40mm x 75μm thick). This is then heat-pressed using the same method as described above to obtain a decorative film (DF2) with a laminated structure consisting of a methacrylic resin composition layer (substrate layer and protective layer), an indium layer (decorative layer and metal layer), a polyimide layer, a second elastomeric resin composition layer (adhesive layer and impact-absorbing layer), a methacrylic resin composition layer, and a first elastomeric resin composition layer (adhesive layer and impact-absorbing layer). It should be noted that the central axes of each film are aligned. This decorative film is used to measure adhesive strength.

[0412] (Manufacturing of decorative molded objects)

[0413] Using a vacuum forming machine (NGF-0406-T manufactured by Buse Vacuum Corporation), a three-dimensional surface decoration molding process was performed by covering one surface of a substrate (PP-M) with a decorative film (DF1) using a known method, resulting in a decorative molded body (DM). The vacuum level was set to 0.5 kPa, and the heating temperature of the decorative film (DF1) was set to 130°C. The molding process was carried out by bringing the substrate (PP-M) into contact with the first elastomeric resin composition layer (adhesive layer and impact-absorbing layer) contained in the decorative film (DF1). It should be noted that the temperature of the decorative film (DF1) was measured using a radiation thermometer.

[0414] As described above, a decorative molded body (DM) with a laminated structure of a methacrylic resin composition layer (substrate layer and protective layer), an indium layer (decorative layer and metal layer), a second elastomer resin composition layer (adhesive layer and impact-absorbing layer), a methacrylic resin composition layer, a first elastomer resin composition layer (adhesive layer and impact-absorbing layer), and an adherend is obtained (please refer to...). Figure 4 ).

[0415] [Results Summary]

[0416] The evaluation results are shown in Tables 1 and 2.

[0417] [Table 1]

[0418] In Examples E1 to E5, an elastomer resin composition was manufactured comprising a first thermoplastic elastomer (EX), a second thermoplastic elastomer (EY), a third thermoplastic elastomer (EZ), a first polypropylene polymer (PX), and a second polypropylene polymer (PY). Relative to 100 parts by mass of the total thermoplastic elastomer (E), the content of the first thermoplastic elastomer (EX) was 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) was 25 to 65 parts by mass, the content of the third thermoplastic elastomer (EZ) was 15 to 35 parts by mass, the content of the first polypropylene polymer (PX) was 3 to 15 parts by mass, and the content of the second polypropylene polymer (PY) was 7.5 to 20 parts by mass.

[0419] The elastomeric resin compositions obtained in these examples all exhibited appropriate viscosity, good sliding properties relative to metals, and good process passability.

[0420] The films obtained in these embodiments have good average film thickness stability and good film-forming properties.

[0421] The elastomeric resin compositions obtained in these examples all exhibit good adhesion to various materials, including non-polar resins (such as non-polar polypropylene), polar resins (such as methacrylic resins), and metals (such as indium).

[0422] The decorative molded articles comprising resin layers and decorative layers made of the elastomeric resin compositions obtained in these embodiments exhibit good resistance to chipping and are suitable for decorative applications such as vehicle exterior components.

[0423] In Comparative Example EC1, the content of the third thermoplastic elastomer (EZ) is less than 15 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E). The elastomer resin composition obtained in this comparative example has poor adhesion to polar resins (such as methacrylic resins).

[0424] In Comparative Example EC2, a third thermoplastic elastomer (EZ) was not used. The elastomer resin composition obtained in this comparative example had high viscosity, poor sliding properties relative to metals, and poor process passability. In addition, it had poor adhesion to polar resins (such as methacrylic resins).

[0425] In Comparative Example EC3, the first thermoplastic elastomer (EX) was not used, and the content of the third thermoplastic elastomer (EZ) exceeded 35 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E), and the content of the first polypropylene polymer (PX) exceeded 15 parts by mass. The elastomer resin composition obtained in this comparative example exhibited poor adhesion to metals (such as In) and poor resistance to chipping.

[0426] In Comparative Example EC4, the first polypropylene polymer (PX) was not used. The elastomer resin composition obtained in this comparative example had high viscosity, poor lubrication relative to metals, and poor process passability. Furthermore, it exhibited poor film thickness stability and poor film-forming properties. Additionally, it had poor adhesion to metals (such as In).

[0427] In Comparative Example EC5, a polymer with a melt tension of less than 2.5 × 10⁻⁶, measured at 230°C and a traction speed of 4.0 m / min, was used instead of the first polypropylene polymer (PX). -2 The comparative example used a polypropylene polymer (PXC). The elastomer resin composition obtained in this comparative example exhibited high viscosity, poor lubrication relative to metal, and poor process passability. Furthermore, it showed poor film thickness stability and poor film-forming properties.

[0428] In Comparative Example EC6, the content of the first polypropylene polymer (PX) was less than 3 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E), and a comparative polypropylene polymer (PYC) with a melting point exceeding 130°C was used instead of the second polypropylene polymer (PY). The elastomer resin composition obtained in this comparative example exhibited poor film thickness stability and poor film-forming properties. Furthermore, it showed poor adhesion to metals (such as In).

[0429] In Comparative Example EC7, the content of the second polypropylene polymer (PY) is less than 7.5 parts by mass relative to 100 parts by mass of the total thermoplastic elastomer (E). The elastomer resin composition obtained in this comparative example exhibits poor adhesion to metals (such as In).

[0430] In Comparative Examples EC8-11, a comparative polypropylene polymer (PYC) with a melting point exceeding 130°C was used instead of the second polypropylene polymer (PY). The elastomeric resin compositions obtained in these comparative examples all exhibited poor adhesion to metals (such as In). Furthermore, the elastomeric resin composition obtained in Comparative Example EC8 exhibited poor adhesion to non-polar resins (such as non-polar polypropylene).

[0431] The elastomeric resin compositions obtained in Comparative Examples EC1 to 11 are not suitable for decorative applications such as vehicle exterior components.

[0432] [Examples E3-1 to E3-10]

[0433] In Examples E3-1 to E3-10, the elastomer resin composition (EP3) without added antioxidant obtained in Example E3 and one or more antioxidants (AO) were melt-mixed at 230°C for 4 minutes using a test mixer (Labo Plustmill manufactured by Toyo Seiki Co., Ltd.) to obtain an elastomer resin composition with added antioxidant.

[0434] The formulation and evaluation results for each example are shown in Table 3. In Table 3, ">45.0" indicates a 5% weight reduction time exceeding 45.0 minutes.

[0435]

[0436] [Results Summary]

[0437] In Examples E3-1 to E3-3, for the antioxidant-free elastomeric resin composition (EP3) consisting of one or more thermoplastic elastomers (E), a first polypropylene polymer (PX), and a second polypropylene polymer (PY), no phosphorus antioxidant (AO-P) was added, but 0.10 to 5.00 parts by weight (total amount in the case of two or more) of one or more phenolic antioxidants (AO-F) were added. The 5% weight reduction time of the elastomeric resin compositions obtained in these examples was 8.8 to 9.7 minutes.

[0438] In Examples E3-4 to E3-10, for an antioxidant-free elastomer resin composition (EP3) consisting of one or more thermoplastic elastomers (E), a first polypropylene polymer (PX), and a second polypropylene polymer (PY), 0.10 to 5.00 parts by weight (total amount in cases of two or more) of one or more phenolic antioxidants (AO-F) and 0.01 to 5.00 parts by weight (total amount in cases of two or more) of one or more phosphorus antioxidants (AO-P) were added. The elastomer resin compositions obtained in these examples all exhibited a 5% weight reduction time of 10 minutes or more and high thermal decomposition resistance.

[0439] It is believed that in these embodiments, the synergistic effect of appropriate amounts of phenolic antioxidants (AO-F) and phosphorus antioxidants (AO-P) effectively inhibits the thermal degradation and thermal decomposition of thermoplastic elastomers (E) and polypropylene polymers (P) when held in the molten state.

[0440] This invention is not limited to the above-described embodiments and examples. As long as the spirit of this invention is not departed, appropriate design changes can be made.

[0441] This application claims priority based on Japanese Patent Application No. 2023-120616, filed July 25, 2023, and Japanese Patent Application No. 2024-018382, filed February 9, 2024, the entire disclosure of which is incorporated herein by reference.

Claims

1. An elastomer resin composition containing a thermoplastic elastomer (E) and a polypropylene-based polymer (P) and satisfying the following conditions 1 to 3, (Condition 1) 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 a conjugated diene compound unit having a total amount of 1,2-linkage and 3,4-linkage of less than 40 mol%, and hydrogenates 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 a conjugated diene compound unit having a total amount of 40 mol% or more of 1,2-linkage and 3,4-linkage, and hydrogenates of the block copolymers, and one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit having a total amount of 40 mol% or more of 1,2-linkage and 3,4-linkage, and hydrogenates of the block copolymers; (Condition 2) The polypropylene-based polymer (P) comprises a first polypropylene-based polymer (PX) having no polar group and a melt tension of 2.5 x 10 -2 N or more, the second polypropylene-based polymer (PY) has a polar group and a melting point of 130°C or less; (Condition 3) 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, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene-based polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene-based polymer (PY) is 7.5 to 20 parts by mass, with respect to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

2. The elastomer resin composition according to claim 1, wherein, The first polypropylene-based polymer (PX) has a melt tension of 50 x 10 -2 Nbelow.

3. The elastomer resin composition according to claim 1, wherein, The melting point of the second polypropylene-based polymer (PY) is 100°C or higher.

4. The elastomer resin composition according to claim 1, further containing two or more antioxidants (AO) comprising a phenolic antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P), the content of the phenolic antioxidant (AO-F) is 0.10 to 5.00 parts by mass, and the content of the phosphorus-based antioxidant (AO-P) is 0.01 to 5.00 parts by mass, with respect to 100 parts by mass of the total of the thermoplastic elastomer (E) and the polypropylene-based polymer (P).

5. A film comprising a layer composed of the elastomer resin composition according to claim 1.

6. The film according to claim 5, further comprising a (meth)acrylic resin-containing layer.

7. The film of claim 6, wherein, The (meth)acrylic resin-containing layer contains a (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

8. The film according to claim 5 or 6, further comprising a metal layer.

9. The film according to claim 5 or 6, further comprising a decorative layer.

10. A laminate comprising a layer composed of the elastomer resin composition according to claim 1.

11. A molded body comprising a layer or a member composed of the elastomer resin composition according to claim 1.

12. The shaped body of claim 11, wherein, A layer composed of the elastomer resin composition and a metal layer are sequentially provided on at least a part of the surface of the adherend.

13. The shaped body of claim 12, wherein, A layer containing a (meth)acrylic resin is further provided on the metal layer.

14. The shaped body of claim 11, wherein, A layer composed of the elastomer resin composition and a decorative layer are sequentially provided on at least a part of the surface of the adherend.

15. The shaped body of claim 14, wherein, A layer containing a (meth)acrylic resin is further provided on the decorative layer.

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