Molded bodies and laminates

Abstract

To provide a molded body that can achieve a superior tactile feel. [Solution] A molded body wherein at least a portion of the surface of the molded body is formed from a thermoplastic elastomer composition, a plurality of irregularities are formed on the surface of the molded body, the plurality of irregularities are regularly arranged at intervals of 3 to 15 mm from each other, the depth of the irregularities is 40 to 500 μm, the diameter of the irregularities is 0.5 to 3 mm, and the arithmetic mean roughness (Ra) of the portion where the irregularities are not arranged, as defined in JIS B0601:2013, is greater than 0 and 30 μm or less.

Description

Technical Field

[0001] The present invention relates to a molded body and a laminate.

Background Art

[0002] Resins such as olefin-based thermoplastic elastomers are generally used for interior skin materials such as instrument panels and door trims of automobiles, and for members such as armrests and levers of furniture such as office chairs. To mold a resin such as an olefin-based thermoplastic elastomer into a molded body such as an instrument panel, a door trim, an armrest, or a lever, vacuum molding or injection molding is generally performed.

[0003] Conventionally, urethane foam has been used as an intermediate layer for automobile interior materials. By using urethane foam as the intermediate layer, the touch feeling is improved, but there is a problem that recycling is difficult.

[0004] For example, Patent Document 1 describes a molded body in which at least a part of the surface of the molded body is formed from a thermoplastic elastomer composition.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the conventional molded bodies described in Patent Document 1 and the like, by not using urethane foam as the intermediate layer, the recyclability is improved, but there is still room for further improvement from the perspective of the touch feeling of the molded body.

[0007] An object of the present invention is to provide a molded body and a laminate capable of realizing an excellent touch feeling. [Means for solving the problem]

[0008] The inventors of the present invention have diligently studied to solve the above problems and have found that the above problems can be solved according to the following embodiments, and have completed the present invention. Embodiments of the present invention are shown below.

[0009] [1] A molded body, At least a portion of the surface of the molded article is formed from a thermoplastic elastomer composition, Multiple irregularities are formed on the surface of the molded body. The aforementioned plurality of recesses are regularly arranged at intervals of 3 to 15 mm from each other. The depth of the recess is 40 to 500 μm, and the diameter of the recess is 0.5 to 3 mm. A molded article in which the arithmetic mean roughness (Ra) of the portion where the aforementioned recess is not present is greater than 0 and less than or equal to 30 μm, as defined in JIS B0601:2013. [2] The molded article according to [1], wherein the arithmetic mean roughness (Ra) of the surface of the molded article, as defined in JIS B0601:2013, is 0 to 50 μm. [3] A molded article according to [1] or [2], comprising a thermoplastic elastomer composition. [4] A molded article according to any one of [1] to [3], which is in the form of a sheet with a thickness of 0.5 to 3.0 mm. [5] A molded body described in any of [1] to [4], which is an automotive interior part.

[0010] [6] A laminate comprising a surface material layer made of a molded body described in any of [1] to [5], and a core material layer having a propylene polymer. [7] The laminate according to [6], wherein polyurethane foam is not provided between the surface material layer and the core material layer. [8] The laminate according to [6], in which no other layer is included between the skin material layer and the core material layer. [9] The laminate according to [6], in which the skin material layer and the core material layer are in direct contact with each other.

[0011]

[10] The thermoplastic elastomer composition contains 100 parts by mass of a propylene-based polymer (A), 50 parts by mass or more and 700 parts by mass or less of a rubbery polymer (B), and 5 parts by mass or more and 400 parts by mass or less of a softening agent (C) The molded article according to [3].

[11] The molded article according to

[10] , in which the rubbery polymer (B) contains the following (B-1) and / or (B-2). (B-1) An ethylene-α-olefin copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms (B-2) A hydrogenated product of a block copolymer containing at least one block mainly composed of a conjugated diene monomer unit and at least one block mainly composed of a vinyl aromatic monomer unit [Advantages of the Invention]

[0012] According to the present invention, it is possible to provide a molded article and a laminate capable of realizing an excellent touch feeling. [Brief Description of the Drawings]

[0013] [Figure 1] It is a figure which shows the surface of the molded article shown in order to demonstrate one Embodiment of this invention. [Figure 2] It is an enlarged sectional view shown in order to demonstrate the recessed part by this invention. [Modes for Carrying Out the Invention]

[0014] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0015] [Molded body] The molded article of the present invention is characterized in that at least a portion of the surface of the molded article is formed from a thermoplastic elastomer composition, a plurality of irregularities are formed on the surface of the molded article, the plurality of irregularities are regularly arranged at intervals of 3 to 15 mm from each other, the depth of the irregularities is 40 to 500 μm, the diameter of the irregularities is 0.5 to 3 mm, and the arithmetic mean roughness (Ra) of the portion where the irregularities are not arranged, as defined in JIS B0601:2013, is greater than 0 and 30 μm or less.

[0016] The material of the molded article is not particularly limited as long as at least a portion of the surface of the molded article is formed from a thermoplastic elastomer composition. For example, conventionally known resins can be used, but thermoplastic elastomer compositions are preferred.

[0017] The above-mentioned molded articles are molded using conventionally known molding methods, depending on the intended use of the molded article. Examples of molding methods include press molding, injection molding, extrusion molding, calendering, hollow molding, vacuum molding, and compression molding. Among these molding methods, press molding is preferred because it offers good productivity and can easily form complex shapes.

[0018] Multiple irregularities are formed on the surface of the molded body described above. The method for forming the irregularities is not particularly limited, but when obtaining the molded body using injection molding, the irregularities can be formed on the surface of the molded body by using a flat plate mold with a textured surface having a desired arithmetic mean roughness Ra as the mold used during injection molding.

[0019] The following describes the uneven surface shape formed on the molded body of the present invention, with reference to the figures as appropriate. As shown in Figure 1, a plurality of recesses 2 are formed on the surface of the molded body 1. The space between adjacent recesses 2, 2 constitutes a protrusion 3. The plurality of recesses 2 are arranged regularly, and as shown in Figure 2, the spacing A between the recesses 2, 2 (distance between the centers of adjacent recesses 2, 2) is 3 to 15 mm, preferably 3.3 to 13.0 mm, more preferably 3.5 to 10.0 mm, and even more preferably 4.0 to 7.0 mm.

[0020] The depth E of the recess 2 shown in Figure 2 is 40 to 500 μm, preferably 45 to 300 μm, more preferably 48 to 200 μm, and even more preferably 50 to 100 μm. The diameter D of the recess 2 is 0.5 to 3 mm, preferably 0.8 to 2.8 mm, more preferably 1.0 to 2.7 mm, and even more preferably 1.3 to 2.5 mm.

[0021] The arithmetic mean roughness (Ra, shown as B in Figure 1) of the surface of the above molded article, as defined in JIS B0601:2013, is preferably 0 to 50 μm, more preferably 5 to 45 μm, even more preferably 10 to 43 μm, and particularly preferably 20 to 40 μm. The molded body has a good tactile feel when the spacing between the multiple recesses, the depth of the recesses, the diameter of the recesses, and the Ra of the surface of the molded body are within the above range. The spacing between the multiple recesses, the depth of the recesses, the diameter of the recesses, and the Ra are measured by the method described in the examples.

[0022] The arithmetic mean roughness (Ra) specified in JIS B0601:2013 can be measured using a surface roughness measuring instrument. Whether using a contact-type or non-contact-type surface roughness measuring instrument, the arithmetic mean roughness (Ra) can be calculated in accordance with JIS B0601:2013.

[0023] In the above-described molded article, the arithmetic mean roughness (Ra, shown as C in Figure 1) of the portion where no recess is located, as defined in JIS B0601:2013, is greater than 0 and less than or equal to 30 μm, preferably 0.5 to 25 μm, more preferably 1.5 to 20 μm, and even more preferably 2 to 10 μm. If the Ra value in the area without recesses is within the above range, the molded body has a good tactile feel. The above Ra value is measured by the method described in the examples.

[0024] Thermoplastic elastomer composition The thermoplastic elastomer composition is not particularly limited as long as it contains a thermoplastic elastomer, but it is preferable to include, for example, a propylene polymer (A), a rubbery polymer (B), and a softening agent (C). The above components (A) to (C) and other optional components are described in detail below, but the present invention is not limited to these.

[0025] <Propylene-based polymer (A)> The propylene polymer (A) (hereinafter sometimes referred to as "component (A)") has a content of propylene-derived structural units among the structural units constituting the polymer, preferably 50 mol% or more, and more preferably 90 mol% or more.

[0026] Component (A) may be used alone or in combination of two or more components. Component (A) may be a propylene homopolymer, or a copolymer of propylene and a comonomer other than propylene.

[0027] The structure of component (A) is not particularly limited; for example, the propylene-derived constituent unit may be an isotactic, syndiotactic, or atactic structure, but an isotactic structure is preferred. Furthermore, the copolymer may be random type (also called random PP), block type (also called block PP: bPP), or graft type.

[0028] The above comonomers may be any monomer other than propylene that can copolymerize with propylene, and ethylene and α-olefins having 4 to 10 carbon atoms are preferred. Examples of α-olefins having 4 to 10 carbon atoms include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. The above comonomers may be ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. One comonomer may be used, or two or more may be used.

[0029] The content of comonomer-derived structural units in the above copolymer is preferably 10 mol% or less, from the viewpoint of the flexibility of the thermoplastic elastomer composition. Component (A) may be synthesized by conventionally known methods, or a commercially available product may be used. Examples of commercially available products include polypropylene manufactured by Sun Allomer Co., Ltd., Prime Polypropylene manufactured by Prime Polymer Co., Ltd., Novatec manufactured by Nippon Polypropylene Co., Ltd., and SCG PP manufactured by SCG Plastics Inc.

[0030] Component (A) may contain at least one constituent unit derived from biomass-derived monomers.

[0031] Component (A) may be a crystalline polymer or an amorphous polymer. Here, crystalline means that a melting point (Tm) is observed in differential scanning calorimetry (DSC).

[0032] If component (A) is a crystalline polymer, its melting point (according to the measurement method of JIS K 7121) is preferably 100°C or higher, more preferably 120°C or higher, preferably 180°C or lower, and more preferably 170°C or lower, from the viewpoint of the heat resistance of the thermoplastic elastomer composition.

[0033] The melt flow rate (MFR) of component (A) (according to the measurement method of ASTM D 1238-65T, at 230°C and a 2.16 kg load) is preferably 0.1 to 100 g / 10 min, and more preferably 0.1 to 50 g / 10 min. When the MFR of component (A) is within the above range, the thermoplastic elastomer composition exhibits excellent heat resistance, mechanical strength, fluidity, and moldability.

[0034] <Rubber-like polymer (B)> As the rubbery polymer (B) (which may hereafter be referred to as "component (B)"), for example, polystyrene-based thermoplastic elastomers and polyolefin-based thermoplastic elastomers can be used, but it is preferable that the above rubbery polymer (B) contains the following (B-1) and / or (B-2).

[0035] <Ethylene-α-olefin copolymer (B-1)> Ethylene-α-olefin copolymer (B-1) (hereinafter sometimes referred to as "component (B-1)") is an ethylene-α-olefin copolymer containing constituent units derived from ethylene and constituent units derived from α-olefins having 3 to 20 carbon atoms.

[0036] Component (B-1) can be obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Among these, from the viewpoint of imparting flexibility, α-olefins having 3 to 12 carbon atoms are preferred, propylene, 1-butene, and 1-octene are more preferred, and 1-octene is even more preferred.

[0037] In component (B-1), the constituent units derived from ethylene are preferably in the range of 70 to 99 mol%, more preferably in the range of 80 to 97 mol%, and the constituent units derived from α-olefins having 3 to 20 carbon atoms are preferably in the range of 1 to 30 mol%, more preferably in the range of 3 to 20 mol% (provided that the total amount of constituent units derived from ethylene and α-olefins having 3 to 20 carbon atoms is 100 mol%). When the content ratio of constituent units derived from ethylene is within the above range, a molded article with excellent mechanical strength can be obtained.

[0038] Component (B-1) may optionally be a copolymer obtained by copolymerizing monomers having unsaturated bonds. Preferred monomers having unsaturated bonds include, for example, conjugated diolefins such as butadiene and isoprene; unconjugated diolefins such as 1,4-hexadiene; cyclic diene compounds such as dicyclopentadiene and norbornene derivatives; and acetylenes. Among these, ethylidene norbornene (ENB) and dicyclopentadiene (DCP) are more preferred from the viewpoint of flexibility and other factors.

[0039] Component (B-1) may contain constituent units derived from at least one biomass-derived monomer.

[0040] Component (B-1) has an MFR (measured according to the ASTM D 1238-65T method, 2.16 kg load, temperature 190°C) preferably in the range of 0.1 to 20 g / 10 min, more preferably in the range of 0.3 to 10 g / 10 min. When the MFR is within the above range, a molded article with a better balance between fluidity and mechanical strength can be obtained.

[0041] Component (B-1) has a density (according to the measurement method of ASTM D 1505), preferably 0.8 to 0.9 g / cm³. 3 It is within the range.

[0042] Component (B-1) can be produced using known polymerization catalysts, such as Ziegler-Natta catalysts, vanadium-based catalysts, and metallocene catalysts. The polymerization method is not particularly limited and can be carried out by liquid-phase polymerization methods such as solution polymerization, suspension polymerization, and bulk polymerization, gas-phase polymerization, and other known polymerization methods. Component (B-1) is also available commercially. Examples of commercially available products include Engage 8842 (ethylene-1-octene copolymer) from Dow Chemical, Vistalon® from ExxonMobil, Esprene® from Sumitomo Chemical Co., Ltd., and Mitsui EPT®, Tuffmer P®, and Tuffmer A® from Mitsui Chemicals, Inc.

[0043] <Hydrogenated block copolymer (B-2)> The hydrogenated block copolymer (B-2) (hereinafter sometimes referred to as "component (B-2)") is a hydrogenated block copolymer containing at least one block mainly composed of conjugated diene monomer units and at least one block mainly composed of vinyl aromatic monomer units.

[0044] Component (B-2) is a block copolymer in which at least some conjugated diene monomer units have been hydrogenated. Hereafter, hydrogenation may be referred to as "hydrogenation." The above-mentioned conjugated diene monomer units refer to constituent units derived from polymers resulting from the polymerization of conjugated dienes, which are monomers, and their structure is a molecular structure in which two carbon atoms of an olefin derived from the conjugated diene monomer serve as bonding sites.

[0045] The above-mentioned conjugated diene monomer is a diolefin having one pair of conjugated double bonds. Examples of conjugated diene monomers include 1,3-butadiene (butadiene), 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. Among these, butadiene and isoprene are preferred from the viewpoint of economy and other factors. These may be used individually or in combination of two or more.

[0046] The vinyl aromatic monomer unit mentioned above refers to a constituent unit derived from a polymer produced as a result of polymerizing vinyl aromatic compounds, which are monomers. Its structure is a molecular structure in which the two carbon atoms of a substituted ethylene group derived from a substituted vinyl group serve as the bonding sites.

[0047] The vinyl aromatic monomers mentioned above are not particularly limited, and examples include vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. These may be used individually or in combination of two or more. Among these, styrene is preferred from the viewpoint of economy and other factors.

[0048] In component (B-2), "mainly composed of" means that the polymer block contains 50% by mass or more, preferably 55% by mass or more, of conjugated diene monomer units (or vinyl aromatic monomer units). For example, a polymer block mainly composed of conjugated diene monomer units means a block containing 50% by mass or more, preferably 55% by mass or more, of conjugated diene monomer units.

[0049] The arrangement of each block in component (B-2) is not particularly limited, and any suitable arrangement can be adopted as appropriate. For example, if a polymer block consisting of vinyl aromatic monomer units is represented by S, and a polymer block consisting of units in which at least some conjugated diene monomer units are hydrogenated is represented by B, then the block copolymers include, for example, linear block copolymers represented by SB, S(BS)n1 (where n1 represents an integer from 1 to 3), and S(BSB)n2 (where n2 represents an integer from 1 to 2), as well as copolymers represented by (SB)n3X (where n3 represents an integer from 3 to 6, and X represents a coupling agent residue such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound). Among these, linear block copolymers of type 2 (diblock) represented by SB, type 3 (triblock) represented by SBS, and type 4 (tetrablock) represented by SBSB are preferred.

[0050] Here, polymer block B may be a polymer block consisting only of conjugated diene monomer units, or a polymer block mainly containing conjugated diene monomer units and also containing vinyl aromatic monomer units (conjugated diene monomer units and vinyl aromatic monomer units copolymerized), and in either case, at least some of the conjugated diene monomer units are hydrogenated.

[0051] The content of vinyl aromatic monomer units in component (B-2) is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and even more preferably 30 to 70% by mass, from the viewpoint of heat resistance and dispersibility. By increasing the content of vinyl aromatic monomer units to 10% by mass or more, the mechanical properties can be further improved, and by decreasing it to 80% by mass or less, the low-temperature properties can be further improved. The content of vinyl aromatic monomer units in component (B-2) can be measured by nuclear magnetic resonance spectroscopy (NMR).

[0052] The content of polymer blocks mainly composed of vinyl aromatic monomer units in component (B-2) is preferably 10% by mass or more, and more preferably 10 to 40% by mass, from the viewpoint of mechanical strength, etc. Here, the content of polymer blocks mainly composed of vinyl aromatic monomer units is defined by the following formula, using the mass of polymer blocks mainly composed of vinyl aromatic monomer units obtained by oxidative decomposition of the block copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (the method described in IMKolthoff, et al., J. Polym. Sci. 1, 429 (1946), hereinafter also referred to as the "osmium tetroxide decomposition method") (where polymers mainly composed of vinyl aromatic monomer units with an average degree of polymerization of about 30 or less are excluded).

[0053] Content (mass%) of polymer blocks mainly composed of vinyl aromatic monomer units = [(mass of polymer blocks mainly composed of vinyl aromatic monomer units in the block copolymer before hydrogenation / mass of the block copolymer before hydrogenation)] × 100 The polymer blocks constituting component (B-2) may or may not have the same molecular weight and composition. For example, component (B-2) may contain polymer blocks containing conjugated diene monomer units and vinyl aromatic monomer units, and polymer blocks mainly composed of conjugated diene monomer units. The boundaries and ends of each polymer block do not necessarily need to be clearly distinguishable.

[0054] The distribution of vinyl aromatic monomer units in each polymer block constituting component (B-2) is not particularly limited; they may be uniformly distributed, or they may be distributed in a tapered, step-like, convex, or concave manner. Furthermore, crystalline portions may be present in the polymer block.

[0055] The distribution of vinyl units derived from conjugated diene monomer units in each polymer block constituting component (B-2) is not particularly limited, and for example, the distribution may be biased. Methods for controlling the distribution of vinyl units include adding a vinylizing agent during polymerization and changing the polymerization temperature. Furthermore, the distribution of hydrogenation rates in the conjugated diene monomer units may also be biased. The distribution of hydrogenation rates can be controlled by changing the distribution of vinyl units, or by copolymerizing isoprene and butadiene, then performing hydrogenation using a hydrogenation catalyst described later, and utilizing the difference in hydrogenation rates between isoprene units and butadiene units.

[0056] In component (B-2), from the viewpoint of heat resistance, aging resistance, and weather resistance, preferably 75 mol% or more, more preferably 85 mol% or more, and even more preferably 97 mol% or more of the unsaturated bonds contained in the conjugated diene monomer unit before hydrogenation are hydrogenated.

[0057] The hydrogenation catalyst used for hydrogenation is not particularly limited, and for example, conventionally known (1) A supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, or diatomaceous earth, etc. (2) A so-called Ziegler-type hydrogenation catalyst using organic acid salts of Ni, Co, Fe, and Cr or transition metal salts such as acetylacetone salts and a reducing agent such as organoaluminum, or (3) Homogeneous hydrogenation catalysts such as organometallic compounds including Ti, Ru, Rh, and Zr, etc. You can use it.

[0058] Specific hydrogenation catalysts that can be used include those described in Japanese Patent Publication No. 42-008704, Japanese Patent Publication No. 43-006636, Japanese Patent Publication No. 63-004841, Japanese Patent Publication No. 01-037970, Japanese Patent Publication No. 01-053851, and Japanese Patent Publication No. 02-009041, etc. Among these, preferred hydrogenation catalysts include reducing organometallic compounds such as titanocene compounds.

[0059] As the titanocene compound, for example, the compounds described in Japanese Patent Publication No. 08-109219 can be used. Specific examples of the above titanocene compounds include compounds having at least one ligand with a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride.

[0060] Examples of reducing organometallic compounds include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

[0061] The polymerization method of the block copolymer before hydrogenation described above is not particularly limited, and known methods can be used. Specific examples of methods for polymerizing block copolymers include those described in Japanese Patent Publication No. 36-019286, Japanese Patent Publication No. 43-017979, Japanese Patent Publication No. 46-032415, Japanese Patent Publication No. 49-036957, Japanese Patent Publication No. 48-002423, Japanese Patent Publication No. 48-004106, Japanese Patent Publication No. 56-028925, Japanese Unexamined Patent Publication No. 59-166518, and Japanese Unexamined Patent Publication No. 60-186577, etc.

[0062] If necessary, component (B-2) may have a polar group. Examples of polar groups include hydroxyl groups, carboxyl groups, carbonyl groups, thiocarbonyl groups, acid halide groups, acid anhydride groups, thiocarboxylic acid groups, aldehyde groups, thioaldehyde groups, carboxylic acid ester groups, amide groups, sulfonic acid groups, sulfonic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, amino groups, imino groups, nitrile groups, pyridyl groups, quinoline groups, epoxy groups, thioepoxy groups, sulfide groups, isocyanate groups, isothiocyanate groups, silicon halide groups, alkoxysilicon groups, tin halide groups, boronic acid groups, boron-containing groups, boronic acid bases, alkoxytin groups, and phenyltin groups.

[0063] The vinyl bond content in the conjugated diene monomer units in the block copolymer before hydrogenation is preferably 5 mol% or more from the viewpoint of flexibility and scratch resistance, and preferably 70 mol% or less from the viewpoint of productivity, elongation at break, and scratch resistance. The vinyl bond content in the conjugated diene monomer units is more preferably 10 to 50 mol%, even more preferably 10 to 30 mol%, and still more preferably 10 to 25 mol%.

[0064] Vinyl bond content refers to the proportion of 1,2- and 3,4-bonded structures within the 1,2-, 3,4-, and 1,4-bonded structures of the conjugated diene before hydrogenation. Vinyl bond content can be measured by NMR.

[0065] The weight-average molecular weight of component (B-2) before crosslinking is not particularly limited, but from the viewpoint of scratch resistance, it is preferably 50,000 or more, and from the viewpoint of moldability, it is preferably 400,000 or less, and more preferably 50,000 to 300,000. The molecular weight distribution (Mw / Mn: weight-average molecular weight / number-average molecular weight) is not particularly limited, but from the viewpoint of scratch resistance, it is preferably a value close to 1. The weight-average molecular weight and number-average molecular weight can be determined by gel permeation chromatography (GPC; Shimadzu Corporation, instrument name "LC-10") using tetrahydrofuran (1.0 mL / min) as the solvent and an oven temperature of 40°C, with TSKgelGMHXL columns (4.6 mm ID × 30 cm, 2 columns). The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are calculated as polystyrene-equivalent molecular weight.

[0066] Component (B-2) may contain constituent units derived from at least one biomass-derived monomer.

[0067] The amount of component (B) in the thermoplastic elastomer composition is preferably 50 to 700 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 400 parts by mass, per 100 parts by mass of component (A), from the viewpoint of the flexibility of the thermoplastic elastomer composition and the scratch resistance of the molded article obtained from the thermoplastic elastomer composition.

[0068] <Softener (C)> The softening agent (C) (hereinafter sometimes referred to as "component (C)") is not particularly limited, but plasticizers commonly used in rubber can be used. From the viewpoint of compatibility with the above-mentioned propylene polymer (A) and rubbery polymer (B), a process oil consisting of hydrocarbons such as paraffinic, naphthenic, and aromatic hydrocarbons is preferred. Among these components (C), a process oil mainly composed of paraffinic hydrocarbons is preferred from the viewpoint of weather resistance and colorability, and a process oil mainly composed of naphthenic hydrocarbons is preferred from the viewpoint of compatibility. From the viewpoint of thermal stability and light stability, the content of aromatic hydrocarbons in the process oil is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, in terms of the carbon number ratio specified in ASTM D2140-97.

[0069] The amount of component (C) in the thermoplastic elastomer composition is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of component (A), from the viewpoint of moldability and heat resistance of the thermoplastic elastomer composition. Component (C) may be a softening agent manufactured using at least one type of biomass raw material.

[0070] From the viewpoint of moldability of the thermoplastic elastomer composition and scratch resistance of the molded article obtained from the thermoplastic elastomer composition, the mass ratio (C / B) of component (B) to component (C) is preferably greater than 0 and less than 3, more preferably 0.6 to 2.8, and even more preferably 0.7 to 2.5.

[0071] <Polyorganosiloxane (D)> The thermoplastic elastomer composition preferably contains polyorganosiloxane (D) (hereinafter sometimes referred to as "component (D)") as needed. The structure of component (D) is not particularly limited, but from the viewpoint of abrasion resistance and tactile feel of the molded article obtained from the thermoplastic elastomer composition, it is preferably a linear, branched, or crosslinked polymer structure.

[0072] Component (D) is not particularly limited and known components may be used. Component (D) is preferably a polymer containing siloxane units having substituents such as alkyl groups, vinyl groups, and aryl groups. Among these, polyorganosiloxanes having alkyl groups are particularly preferred, and polyorganosiloxanes having methyl groups are more preferred.

[0073] Specific examples of polyorganosiloxanes having methyl groups include, for example, polydimethylsiloxane, polymethylphenylsiloxane, and polymethylhydrogensiloxane. Among these, polydimethylsiloxane is preferred.

[0074] The kinematic viscosity of component (D) is not particularly limited, but from the viewpoint of wear resistance and scratch resistance of molded articles obtained from the thermoplastic elastomer composition, it is preferable that the kinematic viscosity (25°C) specified in JIS Z8803 is 5,000 centistokes (cSt) or higher. Furthermore, the dispersibility of component (D) in the obtained thermoplastic elastomer composition tends to improve, resulting in a superior appearance of molded articles obtained from the thermoplastic elastomer composition and further improving the quality stability of the thermoplastic elastomer composition during melt extrusion. Therefore, it is preferable that the kinematic viscosity of component (D) is less than 3 million cSt. The kinematic viscosity of component (D) is more preferably 10,000 cSt or more and less than 3 million cSt, and even more preferably 50,000 cSt or more and less than 3 million cSt.

[0075] The amount of component (D) in the thermoplastic elastomer composition is preferably 2 to 30 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 2 to 20 parts by mass, per 100 parts by mass of component (A).

[0076] When the amount of component (D) is 2 parts by mass or more, the effect of improving the scratch resistance of the molded article obtained from the thermoplastic elastomer composition is sufficiently observed, and when it is 30 parts by mass or less, the dispersibility of component (D) in the thermoplastic elastomer composition is excellent.

[0077] <Organic peroxide (E)> The thermoplastic elastomer composition preferably contains an organic peroxide (E) (hereinafter sometimes referred to as "component (E)") as needed. Component (E) acts as a crosslinking initiator for components (A) and (B) by dynamically heat-treating the thermoplastic elastomer composition.

[0078] Specific examples of component (E) include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)butane, and n-butyl-4,4-bis(t-butyl Peroxyketals such as di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, α,α'-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3, etc.; acetylperoxide, isobutylylperoxide, Diacyl peroxides such as octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate Examples include peroxyesters such as t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, and cumyl peroxyoctate; and hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0079] Among these components (E), 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3 are preferred from the viewpoint of thermal decomposition temperature and crosslinking performance.

[0080] Component (E) may be used alone or in combination of two or more types. If the thermoplastic elastomer composition contains component (E), its content is preferably 2 to 6 parts by mass, more preferably 2 to 4 parts by mass, per 100 parts by mass of component (A), from the viewpoint of fluidity during molding of the thermoplastic elastomer composition. If the thermoplastic elastomer composition contains component (E), it is preferable to use the following crosslinking aids in combination.

[0081] <Crosslinking agent> Various known crosslinking aids can be used. Specifically, monofunctional monomers and polyfunctional monomers can be used. Such crosslinking aids can control the rate of the crosslinking reaction.

[0082] Examples of monofunctional monomers include, for example, radically polymerizable vinyl monomers, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, aromatic vinyl monomers, acrylic acid ester monomers, methacrylic acid ester monomers, acrylic acid monomers, methacrylic acid monomers, maleic anhydride monomers, and N-substituted maleimide monomers.

[0083] Examples of monofunctional monomers include styrene, methylstyrene, chloromethylstyrene, hydroxystyrene, tert-butoxystyrene, acetoxystyrene, chlorostyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride, phenyl maleic anhydride, N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N-cetyl maleimide. Among these, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, maleic anhydride, and N-methyl maleimide are preferred from the viewpoint of ease of reaction and versatility. These monofunctional monomers may be used individually or in combination of two or more.

[0084] A polyfunctional monomer is a monomer having multiple radically polymerizable functional groups, and a monomer having a vinyl group is preferred. The number of functional groups in a polyfunctional monomer is preferably two or three.

[0085] Examples of polyfunctional monomers include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, phenylmaleimide, allyl methacrylate, N,N'-m-phenylenebismaleimide, diallyl phthalate, tetraallyloxyethane, and 1,2-polybutadiene. Among these, divinylbenzene and triallyl isocyanurate are preferred. These polyfunctional monomers may be used individually or in combination of two or more.

[0086] If the thermoplastic elastomer composition contains a crosslinking aid, its content is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of component (E).

[0087] The thermoplastic elastomer composition may contain additives such as foaming agents, weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, nucleating agents, decomposing agents, pigments, dyes, plasticizers, hydrochloric acid absorbents, antioxidants, reinforcing agents, fillers, processing aids, activators, hygroscopic agents, adhesives, flame retardants, and mold release agents, to the extent that they do not impair the objectives of the present invention. Additives may be used individually or in combination of two or more. The above-mentioned additive may be an additive manufactured using at least one biomass raw material.

[0088] The thermoplastic elastomer composition may be foamed by adding a blowing agent as needed. Examples of blowing agents include inorganic or organic pyrolysis-type blowing agents (chemical blowing agents), carbon dioxide, nitrogen, and inert gases mainly composed of a mixture of carbon dioxide and nitrogen.

[0089] Examples of inorganic thermal decomposition type blowing agents include inorganic carbonates such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, and ammonium carbonate, and nitrites such as ammonium nitrite.

[0090] Examples of organic pyrolysis-type blowing agents include nitroso compounds such as N,N'-dimethyl-N,N'-dinitrosotelephthalamide and N,N'-dinitrosopentamethylenetetramine; Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p,p'-oxybis(benzenesulfonyl hydrazide), and diphenylsulfone-3,3'-disulfonyl hydrazide; Examples of azide compounds include calcium azide, 4,4'-diphenyldisulfonyl azide, and p-toluenesulfonyl azide.

[0091] When using carbon dioxide or nitrogen, the thermoplastic elastomer composition is melted in a resin plasticizing cylinder at 100-300°C to form a molten foamable thermoplastic elastomer composition in which the thermoplastic elastomer composition and carbon dioxide or nitrogen are in a miscible state.

[0092] The foaming agent is used in a ratio of preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the thermoplastic elastomer composition.

[0093] Additionally, a foaming aid can be added along with the foaming agent as needed. The amount added is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, per 100 parts by weight of the thermoplastic elastomer composition.

[0094] Examples of foaming agents include metal compounds such as zinc, calcium, lead, iron, and barium; higher fatty acids such as stearic acid and their metal salts; and fine inorganic particles such as talc, barium sulfate, and silica. Specifically, examples include mixtures of polycarboxylic acids such as citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, lactic acid, cyclohexane-1,2-dicarboxylic acid, camphoric acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, and nitriloic acid with inorganic carbonate compounds such as sodium bicarbonate, sodium aluminum bicarbonate, and potassium bicarbonate, as well as intermediates produced by these reactions, such as salts of polycarboxylic acids like sodium dihydrogen citrate and potassium oxalate.

[0095] Foaming aids exhibit functions such as lowering the decomposition temperature of the foaming agent, accelerating decomposition, forming foam nuclei, and homogenizing bubbles, and are generally desirable for use. In particular, compounds that decompose at around the extrusion temperature of the raw material pellets or the melting temperature of the foam have the effect of producing fine and uniform foam cells.

[0096] Among the above examples, it is particularly preferable to foam the thermoplastic elastomer composition using an inorganic or organic pyrolysis-type foaming agent and a mixture of polycarboxylic acid and bicarbonate as a foaming aid, specifically a mixture of citric acid and sodium bicarbonate or its reaction intermediate, sodium dihydrogen citrate.

[0097] These foaming agents or foaming aids may be dry-blended before injection molding so that they decompose during injection molding, or they may be melt-blended into the pellets beforehand and then added.

[0098] There are no particular limitations on the method for preparing a foam from a thermoplastic elastomer composition. It can be prepared by extrusion molding, press molding, injection molding, blow molding, extrusion blow molding, injection blow molding, inflation molding, stamping mold molding, compression molding, and bead molding using a molding machine used in known resin processing methods.

[0099] [Laminated structure] The laminate according to the present invention is a laminate comprising a surface material layer made of the molded article of the present invention and a core material layer having a propylene polymer.

[0100] The above-mentioned laminate can be obtained by known manufacturing methods, except that the molded article of the present invention is used as the surface layer. Specific manufacturing methods include, for example, a method of bonding the molded article of the present invention with a core material obtained by various known molding methods, and a method of placing a pre-obtained core material in a mold with a textured surface, and then injection molding the thermoplastic elastomer composition that will become the surface layer to form a laminate.

[0101] The above laminate may contain only a surface material (molded body) and a core material, or it may contain materials other than the surface material and core material. When using the surface material as an interior material for automobiles, it is preferable to use the above laminate rather than using the surface material alone from the viewpoint of mechanical strength, etc.

[0102] From the viewpoint of excellent recyclability, the above laminate preferably does not contain polyurethane foam between the surface material layer and the core material layer, and more preferably does not contain any other layers between the surface material layer and the core material layer, i.e., the surface material layer and the core material layer are in direct contact.

[0103] The core layer in the above laminate contains a propylene polymer. Propylene polymers are preferred as core materials for the core layer because they are lightweight and have excellent rigidity. Examples of propylene polymers include propylene homopolymers, propylene random copolymers, and propylene block copolymers. In addition to the propylene polymers mentioned above, other known core materials can be used as the core material constituting the core layer. Other core materials include, for example, olefin polymers such as ethylene polymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, ionomers, poly-1-butene, and poly-4-methyl-1-pentene; vinyl polymers such as polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and polyvinylpyrrolidone; and nylon 6, nylon 66, nylon 7, nylon 10, nylon 1, nylon 12, nylon 610, and polymetaxylene adipamide. Examples of polyamides include polyesters such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate, and polylactic acid; cellulose resins such as cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate; and thermoplastic resins and polymers such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, polycaprolactone, polyglycolic acid, polybutylene succinate, and polyethylene succinate. Examples of ethylene-based polymers include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), and high-pressure low-density polyethylene (HP-LDPE). The core material may be used alone or in combination of two or more types.

[0104] The core material described above may be a core material manufactured using at least one type of biomass raw material.

[0105] The thickness of the surface material layer in the above laminate is preferably in the range of 0.5 to 3.0 mm, more preferably in the range of 0.7 to 2.0 mm. Laminates using a surface material layer with a thickness of 0.5 mm or more have low flexibility and are therefore difficult to bend. Laminates using a surface material layer with a thickness of 3.0 mm or less have a small mass and are therefore preferable as laminates.

[0106] The thickness of the core material layer in the above laminate is preferably in the range of 1.0 to 20.0 mm, more preferably in the range of 2.0 to 15.0 mm. Laminates using a core material with a thickness of 1.0 mm or more have high durability and are less prone to bending. Laminates using a core material with a thickness of 20.0 mm or less have a low mass and are preferable as laminates.

[0107] The thickness of the laminate is preferably in the range of 1.5 to 23.0 mm, more preferably in the range of 2.7 to 17.0 mm. When the thickness of the laminate is within this range, the mass is small, which is preferable for a laminate.

[0108] <Applications of molded and laminated products> The molded articles and laminates of the present invention can be used in a variety of applications. The above-mentioned molded articles and laminates are not particularly limited in their applications and are suitable for a variety of known uses, such as automotive parts, furniture, civil engineering and building materials, electrical and electronic components, sanitary products, films and sheets, foams, and artificial leather. They are particularly suitable for use in automotive parts such as automotive interior parts and surface materials such as artificial leather. The molded article of the present invention may be used as a sheet-like molded article, and the thickness of the sheet is preferably 0.5 to 3.0 mm, and more preferably 0.7 to 2.0 mm. A sheet-like molded article with a thickness of 0.5 mm or more has low flexibility and is therefore difficult to bend. A sheet-like molded article with a thickness of 3.0 mm or less has a small mass and is therefore preferred as a molded article.

[0109] <Automotive parts> Examples of automotive parts that may use the above-mentioned molded and laminated materials include ceiling materials, interior seats, bumper moldings, side moldings, air spoilers, air duct hoses, cup holders, handbrake grips, shift knob covers, seat adjustment knobs, flapper door seals, wire harness grommets, rack and pinion boots, suspension cover boots, glass guides, inner beltline seals, roof guides, trunk lid seals, molded quarter window gaskets, corner moldings, glass enclosures, hood seals, glass run channels, secondary seals, various gaskets, bumper parts, body panels, side shields, instrument panels (surface), doors (surface), ornaments (surface), garnishes (surface), ceilings (surface), hoses, steering wheels, boots, wire harness covers, and seat adjuster covers.

[0110] <furniture> Examples of furniture that may use the above-mentioned molded and laminated materials include armrests, handles, levers, backrests, buttons, and seats for office chairs; armrests, handles, levers, backrests, buttons, and seats for household chairs; tabletops for office desks; and tabletops for household desks.

[0111] <Civil engineering / building materials supplies> Examples of civil engineering and building materials that can use the above-mentioned molded bodies and laminates include civil engineering materials and building materials such as ground improvement sheets, water intake panels, and noise-blocking walls, as well as various gaskets and sheets for civil engineering and construction, waterproofing materials, joint materials, and building window frames.

[0112] <Electrical and Electronic Components> Examples of electrical and electronic components that may use the above-mentioned molded bodies and laminates include wire insulation materials, connectors, caps, and plugs.

[0113] <Household goods> Examples of lifestyle products that may use the above-mentioned molded and laminated products include sports equipment such as sports shoe soles, ski boots, tennis rackets, ski bindings, and bat grips, as well as general merchandise such as pen grips, toothbrush grips, hairbrushes, fashion belts, various caps, and shoe insoles.

[0114] <Film / Sheet> Examples of films and sheets that can use the above-mentioned molded products and laminates include intravenous fluid bags, medical containers, automotive interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort containers, pipes, transparent substrates, and sealants. [Examples]

[0115] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples.

[0116] The test methods for each component of the raw materials used in the examples and comparative examples are as follows. (1) Hydrogenation rate (%) Nuclear magnetic resonance (NMR) spectroscopy was performed under the following conditions, and the hydrogenation rate was calculated. Equipment: JEOL Ltd. JNM-LA400 Solvent: Deuterated chloroform Chemical shift standard: Tetramethylsilane (TMS) Sample concentration: 50 mg / mL Observation frequency: 400MHz Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Temperature: 26℃

[0117] (2) Content of monomer units and bond units NMR was measured under the following conditions, and the content of vinyl aromatic monomer units, ethylene monomer units, butylene monomer units, and butadiene 1,4-bond units, 1,2-bond units, and 3,4-bond units was calculated. Equipment: JEOL Ltd. JNM-LA400 Solvent: Deuterated chloroform Chemical shift standard: Tetramethylsilane (TMS) Sample concentration: 50 mg / mL Observation frequency: 400MHz Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Temperature: 26℃

[0118] Under the following conditions, 13 ¹¹C-NMR was measured, and the mass fraction (mass%) of each constituent unit contained in component (B) was calculated. Equipment: ECX400P nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. Temperature: 120℃ Solvent: Orthodichlorobenzene / Deuterated benzene = 4 / 1 (by volume) Total number of times: 8000

[0119] (3) Styrene polymer block content (Os value) The styrene-based polymer block content was measured using the method described in IM Kolthoff, et al., J. Polym. Sci. 1, 429 (1946) (osmium tetroxide decomposition method). A 0.1 g / 125 mL tertiary butanol solution of osmium acid was used for the decomposition of the block copolymer before hydrogenation. The styrene-based polymer block content was calculated using the following formula. The styrene-based polymer block content obtained here is referred to as the "Os value". styrene-based polymer block content (Os value; mass%) =[(Mass of styrene-based polymer blocks in the block copolymer before hydrogenation) / (Mass of the block copolymer before hydrogenation)]×100

[0120] (4) Peak temperature of loss tangent (tanδ) The viscoelastic spectrum was measured under the following conditions, the loss tangent (tanδ) was calculated, and the temperature at which the loss tangent was maximum (hereinafter also referred to as the "peak temperature") was determined. Equipment: ARES manufactured by Ta Instruments Strain: 0.1% Frequency: 1Hz

[0121] (5) Weight average molecular weight (Mw) The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC; Shimadzu Corporation, instrument name "LC-10") using tetrahydrofuran as the solvent (flow rate: 1.0 mL / min) at an oven temperature of 40°C, with TSKgelGMHXL columns (4.6 mm ID × 30 cm, 2 columns). The weight-average molecular weight (Mw) was calculated by analyzing the obtained chromatograms using a calibration curve with standard polystyrene samples according to known methods.

[0122] The following polymers were used in the examples and comparative examples.

[0123] [Example 1] [Propylene polymer (A)] As the propylene polymer (A), a propylene homopolymer (homoPP) (trade name Sun Allomer® PL400A, manufactured by Sun Allomer Co., Ltd.) was used (melt flow rate (MFR): 2.0 g / 10 min at 230°C and a 2.16 kg load).

[0124] [Ethylene-α-olefin copolymer (B-1)] As the ethylene-α-olefin copolymer (B-1), ethylene-1-octene copolymer (manufactured by Dow Chemical, trade name "Engage 8842") was used. The ethylene content in the copolymer was 55% by mass, the octene content was 45% by mass, and the MFR under conditions of 190°C and a 2.16 kg load was 1.0 g / 10 min.

[0125] [Hydrogenated block copolymer (B-2)] The following hydrogenated materials (B-2a), (B-2b), and (B-2c) were used as hydrogenated materials (B-2) for the block copolymer (hereinafter also referred to as component (B-2)). Hydrogenated block copolymers (B-2a), (B-2b), and (B-2c) (hereinafter also referred to as "hydrogenated product (B-2a)", "hydrogenated product (B-2b)", and "hydrogenated product (B-2c)", respectively) were prepared, each containing at least one block mainly composed of conjugated diene monomer units and at least one block mainly composed of vinyl aromatic monomer units, as described below.

[0126] <Manufacturing of Hydrogenated Substance (B-2a)> (1) Preparation of hydrogenation catalyst The hydrogenation catalyst used in the hydrogenation reaction of block copolymers was prepared by the following method. In a nitrogen-purged reaction vessel, 1 L of dried and purified cyclohexane was charged, 100 mmol of bis(cyclopentadienyl)titanium dichloride was added, and while stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the reaction was carried out at room temperature for approximately 3 days.

[0127] (2) Production of block copolymers Batch polymerization was carried out using a 10 L stirring device and a jacketed tank reactor. First, 6.4 L of cyclohexane and 75 g of styrene were added to the stirring device and tank reactor, and tetramethylethylenediamine (TMEDA) was added in a molar amount equal to 0.25 times the number of Li moles in the n-butyllithium initiator. Then, n-butyllithium initiator was added to a total of 10 mmol of Li moles, and the first polymerization reaction was carried out at an initial temperature of 65°C. After the first polymerization reaction was completed, a cyclohexane solution containing 470 g of butadiene and 380 g of styrene (monomer concentration 22% by mass) was continuously supplied to the reactor at a constant rate over 60 minutes to carry out the second polymerization reaction. After the second polymerization reaction was completed, a cyclohexane solution containing 75 g of styrene (monomer concentration 22% by mass) was added over 10 minutes to carry out the third polymerization reaction. Then, methanol was added to stop the third polymerization reaction and obtain a copolymer. The styrene content in the obtained copolymer was 53% by mass, the styrene-based block content in the copolymer was 15% by mass, the styrene content in the copolymer block (i.e., the copolymer block containing conjugated diene monomer units and vinyl aromatic monomer units) was 45% by mass, and the vinyl bond content was 23 mol%. The resulting copolymer (block copolymer) was subsequently subjected to the hydrogenation reaction described below in (3).

[0128] (3) Production of hydrogenated block copolymers To the block copolymer obtained in (2) above, the hydrogenation catalyst obtained in (1) above was added at a concentration of 100 ppm of titanium per 100 parts by mass of the block copolymer, and the hydrogenation reaction in the block copolymer was carried out under conditions of a hydrogen pressure of 0.7 MPa and a temperature of 75°C. To the polymer solution containing the hydrogenated block copolymer obtained in the hydrogenation reaction, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer per 100 parts by mass of the hydrogenated block copolymer. The weight-average molecular weight of the obtained hydrogenated block copolymer (B-2a) was 160,000, and the hydrogenation rate of the double bonds of butadiene contained in the hydrogenated block copolymer (B-2a) was 99%. In addition, one of the tanδ peaks obtained by viscoelasticity measurement was present at -15°C.

[0129] <Manufacturing of hydrogenated product (B-2b)> (1) Production of block copolymer Batch polymerization was carried out using a 10 L stirring device and a jacketed tank reactor. First, 6.4 L of cyclohexane and 325 g of styrene were added to the stirring device and tank reactor. TMEDA was added in a quantity equal to 0.40 times the number of Li moles in the n-butyllithium initiator, and then n-butyllithium initiator was added until the number of Li moles was 20 mmol. The first polymerization reaction was then carried out at an initial temperature of 65°C. After the first polymerization reaction was completed, a cyclohexane solution containing 350 g of butadiene (monomer concentration 22% by mass) was continuously supplied to the reactor at a constant rate over 60 minutes to carry out the second polymerization reaction. After the second polymerization reaction was completed, a cyclohexane solution containing 325 g of styrene (monomer concentration 22% by mass) was added over 10 minutes to carry out the third polymerization reaction. Subsequently, methanol was added to stop the third polymerization reaction and obtain a copolymer. The obtained copolymer had a styrene-based block content of 65% by mass and a vinyl bond content of 40 mol%. The resulting copolymer (block copolymer) was subsequently subjected to the hydrogenation reaction described below in (2).

[0130] (2) Production of hydrogenated block copolymers To the block copolymer obtained in (1) above, the hydrogenation catalyst obtained in (1) of "Production of Hydrogenated Product (B-2a)" was added at a titanium equivalent of 100 ppm per 100 parts by mass of the block copolymer. Subsequently, a hydrogenation reaction was carried out in the block copolymer under conditions of a hydrogen pressure of 0.7 MPa and a temperature of 75°C. To the polymer solution containing the hydrogenated block copolymer obtained in the hydrogenation reaction, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer per 100 parts by mass of the hydrogenated block copolymer. The weight-average molecular weight of the obtained hydrogenated block copolymer (B-2b) was 50,000, and the hydrogenation rate of the double bonds of butadiene contained in the hydrogenated block copolymer (B-2b) was 99%.

[0131] <Manufacturing of hydrogenated product (B-2c)> (1) Production of block copolymer Batch polymerization was carried out using a 10 L stirring device and a jacketed tank reactor. First, 6.4 L of dried and purified cyclohexane and 175 g of styrene were added to the stirring device and tank reactor, and TMEDA was added in a quantity equal to 0.30 times the number of Li moles in the n-butyllithium initiator. Then, n-butyllithium initiator was added so that the number of Li moles was 11 mmol. The first polymerization reaction was then carried out at an initial temperature of 65°C. After the first polymerization reaction was completed, a cyclohexane solution containing 650 g of butadiene (monomer concentration 22% by mass) was continuously supplied to the reactor at a constant rate over 60 minutes to carry out the second polymerization reaction. After the second polymerization reaction was completed, a cyclohexane solution containing 175 g of styrene (monomer concentration 22% by mass) was further added over 10 minutes to carry out the third polymerization reaction. Then, methanol was added to stop the third polymerization reaction and obtain a copolymer. The resulting copolymer contained 35% by mass of styrene-based blocks and 36% by mol of vinyl bonds. The resulting copolymer (block copolymer) was subsequently subjected to the hydrogenation reaction described below in (2).

[0132] (2) Production of hydrogenated block copolymers The hydrogenation catalyst obtained in (1) of "Production of Hydrogenated Product (B-2a)" was added to the block copolymer obtained in (1) above at a concentration of 100 ppm of titanium per 100 parts by mass of the block copolymer. The hydrogenation reaction in the block copolymer was carried out under conditions of a hydrogen pressure of 0.7 MPa and a temperature of 75°C to obtain a reaction solution. To the obtained reaction solution, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer per 100 parts by mass of the hydrogenated block copolymer. The weight-average molecular weight of the obtained hydrogenated block copolymer (B-2c) was 150,000, and the hydrogenation rate of the double bonds of butadiene contained in the hydrogenated block copolymer (B-2c) was 99%.

[0133] [Softener (C)] As a softening agent (C), paraffin-based oil (manufactured by Idemitsu Kosan Co., Ltd., product name "Diana Process Oil PW-100") was used.

[0134] [Polyorganosiloxane (D)] As the polyorganosiloxane (D), a masterbatch consisting of 50% by mass of dimethylsiloxane and 50% by mass of polypropylene (manufactured by DuPont-Toray Specialty Materials Ltd., trade name "MB50-001") was used.

[0135] [Organic peroxide (E)] As the organic peroxide (E), a mixture of the following organic peroxide and the following crosslinking aid was used. Organic peroxide: 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (manufactured by NOF Corporation, trade name "Perhexa 25B") Crosslinking agents: Divinylbenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; hereinafter referred to as "DVB"), Triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation; hereinafter referred to as "TAIC")

[0136] <Manufacturing of thermoplastic elastomer compositions> A twin-screw extruder (30 mmφ, L / D=74; manufactured by Kobe Steel, Ltd., "KTX-30") with an oil inlet in the center of the barrel was used as the extruder. A two-screw screw with kneading sections before and after the inlet was used as the screw. The raw materials other than the softener listed in Table 1 were mixed together in the composition ratio (parts by mass) shown in Table 1, and then introduced into the twin-screw extruder (cylinder temperature 200°C) using a quantitative feeder. Subsequently, the amount of softener shown in Table 1 was injected by pump through the inlet in the center of the extruder, and melt extrusion was performed to obtain thermoplastic elastomer composition 1.

[0137] [Table 1]

[0138] <Manufacturing of molded and laminated products> The thermoplastic elastomer composition 1 obtained above was press-molded at 170°C using a flat die with a textured surface featuring periodically arranged recesses, as shown in Table 2. The resulting molded body was used as a molded body sample. Furthermore, a press-molded article of the obtained thermoplastic elastomer composition 1 was bonded to a polypropylene molded article that would serve as the core material layer to obtain a laminate.

[0139] [Measurement of arithmetic mean roughness Ra, depth of depressions, etc.] The arithmetic mean surface roughness Ra, recess depth, recess diameter, and recess spacing of the obtained molded sample were calculated in accordance with JIS B0601:2013 using a one-shot 3D shape measuring instrument (manufactured by Keyence Corporation, non-contact surface roughness measuring instrument). The measurement conditions were set as follows. For Example 1, both the Ra of the portion without recesses and the Ra of the entire surface including recesses were calculated. (Measurement conditions) Measurement length: 40mm Standard length: 8mm Cutoff wavelength: 8mm

[0140] [Tactile evaluation] Six panelists (men and women in their 20s to 40s) conducted a sensory evaluation regarding tactile feel. Each of the six panelists was asked to quantify the tactile sensation when sliding or pressing the surface of the molded sample obtained above with the pad of their index finger, according to the numerical criteria below. Table 2 shows the average of the values ​​obtained from each panelist. A higher number indicates a better tactile sensation. (Quantification criteria) (1) The smooth, moist, and soft feeling when stroked with the index finger 7: Very much so 6: Very much so 5: Somewhat 4: Neither 3: Not really 2: Not at all 1: Not at all (2) Softness of pressure when pressed with the index finger 7: Very much so 6: Very much so 5: Somewhat 4: Neither 3: Not really 2: Not at all 1: Not at all (3) The overall feel when touched with the index finger. 7: Very good 6: Very good 5: Slightly good 4: Neither 3: Slightly bad 2: Very bad 1: Very bad

[0141] [Comparative Example 1] Laminates were fabricated and their tactile properties evaluated in the same manner as in Example 1, except that the thermoplastic elastomer composition 1 obtained above was press-molded using a flat die with a textured surface as shown in Table 2.

[0142] [Comparative Example 2] Laminates were fabricated and their tactile properties evaluated in the same manner as in Example 1, except that the thermoplastic elastomer composition 1 obtained above was press-molded using a flat die with a textured surface as shown in Table 2.

[0143] [Comparative Example 3] The tactile evaluation was performed in the same manner as in Example 1, except that a section cut from the instrument panel of a Japanese SUV was used.

[0144] [Comparative Example 4] The tactile evaluation was performed in the same manner as in Example 1, except that a section of the instrument panel cut from a Japanese SUV2 was used.

[0145] [Comparative Example 5] The tactile evaluation was performed in the same manner as in Example 1, except that a section of the instrument panel cut from a Japanese SUV3 was used.

[0146] [Comparative Example 6] Tactile evaluation was performed in the same manner as in Example 1, except that a section cut from the instrument panel of a European SUV was used.

[0147] [Table 2]

[0148] As shown in Table 2, Example 1 was superior to Comparative Examples 1-6 in terms of smoothness, moisture, and softness, resulting in a better overall tactile feel. [Explanation of symbols]

[0149] 1: Molded body, 2: Recess, 3: Protrusion, A: Spacing between recesses, B: Overall Ra, C: Ra of areas without recesses, D: Diameter of recess, E: Depth of recess

Claims

1. A molded body, At least a portion of the surface of the molded article is formed from a thermoplastic elastomer composition, Multiple irregularities are formed on the surface of the molded body. The aforementioned plurality of recesses are regularly arranged at intervals of 3 to 15 mm from each other. The depth of the recess is 40 to 500 μm, and the diameter of the recess is 0.5 to 3 mm. A molded article in which the arithmetic mean roughness (Ra) of the portion where the recess is not located is greater than 0 and less than or equal to 30 μm, as defined in JIS B0601:2013.

2. The molded article according to claim 1, wherein the arithmetic mean roughness (Ra) of the surface of the molded article, as defined in JIS B0601:2013, is 0 to 50 μm.

3. A molded article according to claim 1, comprising a thermoplastic elastomer composition.

4. The molded article according to claim 1, which is in the form of a sheet with a thickness of 0.5 to 3.0 mm.

5. A molded article according to claim 1, which is an interior part for an automobile.

6. A laminate comprising a surface material layer made of a molded article according to any one of claims 1 to 5, and a core material layer having a propylene polymer.

7. The laminate according to claim 6, wherein polyurethane foam is not included between the surface material layer and the core material layer.

8. The laminate according to claim 6, wherein there is no other layer between the surface material layer and the core material layer.

9. The laminate according to claim 6, wherein the surface material layer and the core material layer are in direct contact.

10. The thermoplastic elastomer composition 100 parts by mass of propylene polymer (A), 50 parts by mass or more and 700 parts by mass or less of rubbery polymer (B), and Softener (C) in amounts of 5 to 400 parts by mass A molded article including the one described in claim 3.

11. The molded article according to claim 10, wherein the rubbery polymer (B) comprises (B-1) and / or (B-2) described below. (B-1) Ethylene-α-olefin copolymer containing constituent units derived from ethylene and constituent units derived from α-olefins having 3 to 20 carbon atoms. (B-2) Hydrogenated block copolymer containing at least one block mainly composed of conjugated diene monomer units and at least one block mainly composed of vinyl aromatic monomer units.

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