Solid composition and method for producing the same

Abstract

To provide a solid composition excellent in shock resistance at a low temperature, and to provide a production method of the same.SOLUTION: A solid composition which contains a propylene-based polymer B and a polymer A satisfies requirements (1)-(3) as follows: requirement (1): the propylene-based polymer B forms a continuous phase, and the polymer A forms a dispersion phase; requirement (2): a glass-transition temperature (Tg) of the polymer A is less than 0°C; and requirement (3): a crystal orientation degree of the solid composition represented by following formula is 60-80%. The crystal orientation degree (%)={(180-hw040) / 180}×100... (1) [in the formula (1), hw040 is a half-value width (degree) of the maximum peak in a distribution curve to an azimuthal angle with respect to a scattering intensity of a surface of an α crystal (040) of a propylene-based polymer, obtained from a two-dimensional wide angle x-ray scattering image of a central part of the solid composition.]SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a solid composition and a method for producing the same. [Background technology]

[0002] Solid compositions obtained by molding resin compositions containing propylene-based polymers have been used for automobile parts and home appliance parts. These solid compositions contain not only propylene-based polymers but also copolymers of ethylene and α-olefins having 3 or more carbon atoms, inorganic fillers, and the like.

[0003] For example, Patent Document 1 describes a resin composition comprising an isotactic propylene polymer and a propylene-ethylene-α-olefin copolymer, which contains 84 to 50 mol % of structural units derived from propylene, 15 to 30 mol % of structural units derived from ethylene, and 1 to 20 mol % of structural units derived from an α-olefin having 4 to 20 carbon atoms, has an isotactic triad fraction (mm) calculated by C-NMR of 85% or more, and has no melting point observed by DSC. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5020524 Summary of the Invention [Problem to be solved by the invention]

[0005] Meanwhile, there is a demand for further improvement in the impact resistance at low temperatures in solid compositions that mainly contain propylene polymers.

[0006] The present invention has been made in view of the above problems, and an object of the present invention is to provide a solid composition having excellent impact resistance at low temperatures and a method for producing the same. [Means for solving the problem]

[0007] The solid composition according to the present invention is a solid composition containing a propylene polymer B and a polymer A, and satisfies the following requirements (1) to (3). Requirement (1): The propylene-based polymer B forms a continuous phase, and the polymer A forms a dispersed phase. Requirement (2): The glass transition temperature (Tg) of the polymer A is lower than 0°C. Requirement (3): The degree of crystalline orientation of the solid composition, represented by the following formula, is 60 to 80%. Crystal orientation degree (%)={(180-hw040) / 180}×100 … (1) [In formula (1), hw040 is the half-value width (degrees) of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α-crystal of the propylene polymer B versus the azimuth angle, obtained from a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition.]

[0008] Here, when the total of the propylene polymer B and the polymer A is 100 parts by weight, the propylene polymer B can account for 50.1 to 99.9 parts by weight, and the polymer A can account for 0.1 to 49.9 parts by weight.

[0009] The polymer A may have a glass transition temperature (Tg) of −30° C. or lower.

[0010] The polymer A may be an ethylene copolymer.

[0011] The ethylene copolymer may be at least one selected from the group consisting of an ethylene-propylene copolymer, an ethylene-1-butene copolymer, and an ethylene-1-octene copolymer.

[0012] In addition, the polymer A in the solid composition may have a melt mass flow rate of 0.01 to 35 g / 10 minutes under conditions of a temperature of 190° C. and a load of 2.16 kgf.

[0013] A method for producing a solid composition according to the present invention includes a step of fluidizing a solid raw material containing a thermoplastic resin and a polymer A by applying pressure at a temperature equal to or lower than the melting point (°C) of the thermoplastic resin + 10°C to obtain a solid composition, In the solid composition, the thermoplastic resin forms a continuous phase and the polymer A forms a dispersed phase, The glass transition temperature (Tg) of the polymer A is less than 0°C, A method for producing a solid composition, wherein the degree of crystal orientation in the solid composition, as represented by the following formula, is 60 to 80%. Crystal orientation degree (%)={(180-hw040) / 180}×100 … (1) [In formula (1), hw040 is the half-width (degrees) of the maximum peak in the distribution curve of the scattering intensity at a scattering angle 2θ' versus the azimuth angle β obtained from a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition, and the scattering angle 2θ' is the angle that gives the maximum peak in the scattering angle 2θ range of 16° to 18°.] [Effects of the Invention]

[0014] According to the present invention, there are provided a solid composition having excellent impact resistance at low temperatures and a method for producing the same. [Brief explanation of the drawings]

[0015] [Figure 1] 1(a) and 1(b) are schematic diagrams sequentially illustrating a method for producing a solid composition according to an embodiment of the present invention, and FIG. 1(c) is a side view of the obtained solid composition, and FIG. 1(d) is a top view of the obtained solid composition. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, several embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0017] The solid composition of the present embodiment is a solid composition containing a propylene polymer B and a polymer A, and satisfies the following requirements (1) to (3). Requirement (1): Propylene-based polymer B forms a continuous phase, and polymer A forms a dispersed phase. Requirement (2): The glass transition temperature (Tg) of polymer A is lower than 0°C. Requirement (3): The degree of crystalline orientation of the solid composition calculated by the following formula (1) is 60 to 80%. Formula (1)...Crystal orientation degree (%)={(180-hw040) / 180}×100 [In formula (1), hw040 is the half-value width (degrees) of the maximum peak in the azimuthal angle distribution curve of the scattering intensity of the (040) plane of the propylene polymer B, obtained from a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition.]

[0018] (Propylene Polymer B) The propylene polymer B of the present invention is a polymer containing a structural unit derived from propylene, and can be (1) a propylene homopolymer, (2) a propylene random copolymer, or (3) a propylene multi-stage polymerization material (heterophasic propylene polymerization material). The propylene polymer B may be one of these, or a mixture of two or more of them. In this specification, the term "structural unit" can be rephrased as "monomer unit."

[0019] <(1) Propylene homopolymer> A propylene homopolymer is a polymer consisting only of structural units derived from propylene.

[0020] <(2) Propylene random copolymer> The propylene random copolymer is (2-1) A random copolymer containing structural units derived from propylene and structural units derived from ethylene; (2-2) A random copolymer containing a structural unit derived from propylene and a structural unit derived from an α-olefin having 4 to 10 carbon atoms, or (2-3) A random copolymer containing structural units derived from propylene, structural units derived from ethylene, and structural units derived from an α-olefin having 4 to 10 carbon atoms.

[0021] Examples of the α-olefin having 4 to 10 carbon atoms used in the random copolymer (2-2) or (2-3) include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and preferred are 1-butene, 1-hexene, and 1-octene.

[0022] Examples of the random copolymer (2-2) include propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, and propylene-1-decene random copolymer.

[0023] Examples of the random copolymer (2-3) include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene, and propylene-ethylene-1-decene copolymer.

[0024] The content of structural units derived from ethylene contained in the random copolymer (2-1) is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, and even more preferably 0.1 to 10% by weight. The content of structural units derived from propylene contained in the random copolymer (2-1) is preferably 99.9 to 70% by weight, more preferably 99.9 to 80% by weight, and even more preferably 99.9 to 90% by weight (where the total weight of the random copolymer (2-1) is taken as 100% by weight).

[0025] The content of structural units derived from an α-olefin having 4 to 10 carbon atoms contained in the random copolymer (2-2) is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, and even more preferably 0.1 to 10% by weight. The content of structural units derived from propylene contained in the random copolymer (2-2) is preferably 99.9 to 70% by weight, more preferably 99.9 to 80% by weight, and even more preferably 99.9 to 90% by weight (where the total weight of the random copolymer (2-2) is taken as 100% by weight).

[0026] The total content of structural units derived from ethylene and structural units derived from an α-olefin having 4 to 10 carbon atoms contained in the random copolymer (2-3) is preferably 0.1 to 49% by weight, more preferably 0.1 to 40% by weight, and even more preferably 0.1 to 30% by weight. The content of structural units derived from propylene contained in the random copolymer (2-3) is preferably 99.9 to 51% by weight, more preferably 99.9 to 60% by weight, and even more preferably 99.9 to 70% by weight (where the total weight of the random copolymer (2-3) is taken as 100% by weight).

[0027] <(3) Propylene multi-stage polymerization material> The propylene multi-stage polymerization material is (3-1) A propylene multi-stage polymerization material containing the following propylene homopolymer component (I-1) and the following propylene copolymer component (II) (i.e., a mixture of the propylene homopolymer component (I-1) and the propylene copolymer component (II)), or (3-2) A propylene multi-stage polymerization material containing the following propylene copolymer component (I-2) and the following propylene copolymer component (II) (i.e., a mixture of propylene copolymer component (I-2) and propylene copolymer component (II)). Here, the propylene homopolymer component (I-1) and the propylene copolymer component (I-2) are collectively referred to as polymer component (I).

[0028] The propylene homopolymer component (I-1) is a homopolymer component consisting only of structural units derived from propylene.

[0029] The propylene copolymer component (I-2) is a copolymer component containing structural units derived from propylene and structural units derived from an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms, and the content of structural units derived from an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms is 0.1% by weight or more but less than 20% by weight, preferably 0.1 to 15% by weight, and more preferably 0.1 to 10% by weight (where the total weight of the propylene copolymer component (I-2) is taken as 100% by weight). In the propylene copolymer component (I-2), the content of structural units derived from propylene is more than 80% by weight and not more than 99.9% by weight, preferably 85 to 99.9% by weight, and more preferably 90 to 99.9% by weight.

[0030] The propylene copolymer component (II) is a copolymer component containing structural units derived from propylene and structural units derived from an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms, and the content of structural units derived from an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms is 20 to 80% by weight, preferably 20 to 60% by weight, and more preferably 30 to 60% by weight (where the total weight of the propylene copolymer component (II) is taken as 100% by weight). The content of structural units derived from propylene is 20 to 80% by weight, preferably 40 to 80% by weight, and more preferably 40 to 70% by weight.

[0031] Examples of the α-olefin having 4 to 10 carbon atoms used in the propylene copolymer component (I-2) or the propylene copolymer component (II) include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and preferably 1-butene, 1-hexene, and 1-octene, and more preferably 1-butene.

[0032] Examples of the propylene copolymer component (I-2) include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, a propylene-1-octene copolymer component, a propylene-ethylene-1-butene copolymer component, a propylene-ethylene-1-hexene copolymer component, and a propylene-ethylene-1-octene copolymer component, and preferred are a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, and a propylene-ethylene-1-butene copolymer component.

[0033] Examples of the propylene copolymer component (II) include a propylene-ethylene copolymer component, a propylene-ethylene-1-butene copolymer component, a propylene-ethylene-1-hexene copolymer component, a propylene-ethylene-1-octene copolymer component, a propylene-ethylene-1-decene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, a propylene-1-octene copolymer component, and a propylene-1-decene copolymer component. Preferred are a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, and a propylene-ethylene-1-butene copolymer component, and more preferred is a propylene-ethylene copolymer component.

[0034] Examples of the propylene multistage polymerization material (3-1) include a (propylene)-(propylene-ethylene) multistage polymerization material, a (propylene)-(propylene-ethylene-1-butene) multistage polymerization material, a (propylene)-(propylene-ethylene-1-hexene) multistage polymerization material, a (propylene)-(propylene-ethylene-1-octene) multistage polymerization material, a (propylene)-(propylene-1-butene) multistage polymerization material, a (propylene)-(propylene-1-hexene) multistage polymerization material, a (propylene)-(propylene-1-octene) multistage polymerization material, and a (propylene)-(propylene-1-decene) multistage polymerization material. Preferred are (propylene)-(propylene-ethylene) multistage polymerization materials and (propylene)-(propylene-ethylene-1-butene) multistage polymerization materials, and more preferred are (propylene)-(propylene-ethylene) multistage polymerization materials.

[0035] Examples of the propylene multi-stage polymerization material (3-2) include (propylene-ethylene)-(propylene-ethylene) multi-stage polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) multi-stage polymerization material, (propylene-ethylene)-(propylene-ethylene-1-hexene) multi-stage polymerization material, (propylene-ethylene)-(propylene-ethylene-1-octene) multi-stage polymerization material, (propylene-ethylene)-(propylene-ethylene-1-decene) multi-stage polymerization material, (propylene (propylene-ethylene)-(propylene-1-butene) multistage polymerization material, (propylene-ethylene)-(propylene-1-hexene) multistage polymerization material, (propylene-ethylene)-(propylene-1-octene) multistage polymerization material, (propylene-ethylene)-(propylene-1-decene) multistage polymerization material, (propylene-1-butene)-(propylene-ethylene) multistage polymerization material, (propylene-1-butene)-(propylene-1-butene) multistage polymerization material, (propylene-1-butene) )-(propylene-ethylene-1-hexene) multistage polymerization material, (propylene-1-butene)-(propylene-ethylene-1-octene) multistage polymerization material, (propylene-1-butene)-(propylene-ethylene-1-decene) multistage polymerization material, (propylene-1-butene)-(propylene-1-butene) multistage polymerization material, (propylene-1-butene)-(propylene-1-hexene) multistage polymerization material, (propylene-1-butene)-(propylene-1-octene) multistage polymerization material, (propylene Examples of the polypropylene copolymer include (propylene-1-butene)-(propylene-1-decene) multistage polymerization materials, (propylene-1-hexene)-(propylene-1-hexene) multistage polymerization materials, (propylene-1-hexene)-(propylene-1-octene) multistage polymerization materials, (propylene-1-hexene)-(propylene-1-decene) multistage polymerization materials, (propylene-1-octene)-(propylene-1-octene) multistage polymerization materials, and (propylene-1-octene)-(propylene-1-decene) multistage polymerization materials. Preferred are (propylene-ethylene)-(propylene-ethylene) multistage polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-butene) multistage polymerization materials, and (propylene-1-butene)-(propylene-1-butene) multistage polymerization materials.

[0036] The content of copolymer component (II) contained in the multistage polymerization material containing polymer component (I) and copolymer component (II) is preferably 1 to 49% by weight, more preferably 1 to 40% by weight, even more preferably 1 to 30% by weight, and even more preferably 1 to 20% by weight (where the total weight of the multistage polymerization material is 100% by weight). The content of copolymer component (I) contained in the multistage polymerization material containing polymer component (I) and copolymer component (II) is preferably 51 to 99% by weight, more preferably 60 to 99% by weight, even more preferably 70 to 99% by weight, and even more preferably 80 to 99% by weight (where the total weight of the multistage polymerization material is 100% by weight).

[0037] (MFR of propylene polymer B) The melt mass-flow rate (MFR) of the propylene polymer B, measured under conditions of a temperature of 230°C and a load of 2.16 kgf, is preferably 0.01 to 20 g / 10 min, more preferably 0.01 to 10 g / 10 min, and even more preferably 0.01 to 5 g / 10 min, and may be 0.01 to 2 g / 10 min. When the melt mass-flow rate of the propylene polymer B is within the above range, the solid composition tends to have excellent impact resistance.

[0038] In this specification, the melt mass-flow rate refers to a value measured in accordance with JIS K6758.

[0039] (Tg of propylene polymer B) From the viewpoint of impact resistance, the glass transition temperature (PP:Tg) of the propylene polymer B is preferably −30° C. or higher, more preferably −20° C. or higher, even more preferably −10° C. or higher, and even more preferably 0° C. or higher. The Tg is measured in accordance with JIS K7121.

[0040] The glass transition temperature (PP:Tg) of the propylene polymer B is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0041] (Tm of propylene polymer B) The melting point (Tm) of the propylene polymer B can be 100 to 180°C. The melting point of the propylene polymer B can be determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0042] <Method for producing propylene polymer B> The propylene polymer B can be obtained by homopolymerizing propylene using a polymerization catalyst, or by copolymerizing propylene with another olefin using a polymerization catalyst.

[0043] <Polymerization catalyst> Examples of the polymerization catalyst include: (1) A catalyst system comprising (1-i) a solid catalyst component containing magnesium, titanium, a halogen, and an electron donor as essential components, (1-ii) an organoaluminum compound, and (1-iii) an electron donor component; (2) (2-i) a catalyst system comprising a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and (2-ii) an alkylaluminoxane; (3) A catalyst system comprising (3-i) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, (3-ii) a compound that reacts with the compound to form an ionic complex, and (3-iii) an organoaluminum compound. (4) Examples include a catalytic system in which catalyst components consisting of (4-i) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, (4-ii) a compound that forms an ionic complex, and (4-iii) an organoaluminum compound are supported on inorganic particles such as silica or clay minerals and modified. Alternatively, a prepolymerized catalyst prepared by prepolymerizing ethylene, propylene or an α-olefin in the presence of the above catalyst system may be used. Examples of the catalyst system include those described in JP-A Nos. 61-218606, 5-194685, 7-216017, 9-316147, 10-212319, and 2004-182981.

[0044] <Polymerization method> Examples of polymerization methods include bulk polymerization, solution polymerization, slurry polymerization, and gas-phase polymerization. These polymerization methods may be either batch or continuous. They may be either single-stage using a single polymerization reactor or multi-stage using multiple polymerization reactors connected in series, and these polymerization methods may be combined arbitrarily. For example, in the case of a propylene multi-stage polymerization material, a propylene homopolymer component (I-1) or a propylene copolymer component (I-2) can be polymerized in the first stage, and a propylene copolymer component (II) can be polymerized in the second stage.

[0045] The various conditions in the polymerization step (polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) may be appropriately determined depending on (1) propylene homopolymer, (2) propylene random copolymer, and (3) propylene multistage polymerization material to be produced.

[0046] Furthermore, examples of methods for producing (1) propylene homopolymers, (2) propylene random copolymers, and (3) propylene multi-stage polymerization materials include a method in which a propylene homopolymer or a copolymer of propylene and another olefin obtained by the above-mentioned polymerization method using the above-mentioned polymerization catalyst is subjected to an extraction operation with boiling octane to remove components soluble in boiling octane, and (1) propylene homopolymers, (2) propylene random copolymers, (3) propylene block copolymers, or (4) propylene multi-stage polymerization materials are recovered as components insoluble in boiling octane.

[0047] The method for recovering components insoluble in boiling octane is, for example, to use a Soxhlet extraction tube, add a propylene homopolymer or a copolymer of propylene and another olefin obtained by polymerization to a Soxhlet extraction filter paper, reflux with boiling octane for 5 hours, extract and remove components soluble in boiling octane from the homopolymer or copolymer, and recover the components insoluble in boiling octane remaining on the Soxhlet extraction filter paper. The amount of octane used in the extraction operation is 0.1 L per 20 g of the homopolymer or copolymer obtained by polymerization.

[0048] (Polymer A) The polymer A is incompatible with the propylene-based polymer B.

[0049] (Tg of polymer A) From the viewpoint of impact resistance, the glass transition temperature (Tg) of the polymer A is below 0° C. [requirement (2)], preferably −30° C. or lower, and more preferably −40° C. or lower. The lower the glass transition temperature (Tg), the better the impact resistance of the solid composition tends to be.

[0050] The glass transition temperature (Tg) of Polymer A is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0051] (MFR of polymer A) The melt mass-flow rate (MFR) of polymer A, measured under conditions of a temperature of 190°C and a load of 2.16 kgf, can be 0.01 g / 10 min or more and 35 g / 10 min or less. The upper limit of the MFR can be 20 g / 10 min, 10 g / 10 min, 5 g / 10 min, 2.0 g / 10 min, or 1.0 g / 10 min. The smaller the melt mass-flow rate of polymer A, the better the impact resistance of the solid composition tends to be.

[0052] (Tm of polymer A) The melting point of polymer A determined by DSC is preferably less than 200°C, more preferably less than 180°C, and even more preferably less than 150°C, from the viewpoint of processability. The melting point (Tm) of polymer A determined by DSC is the melting temperature of the crystalline phase contained in polymer A, and specifically, it is the peak-top temperature of the highest endothermic peak on the high-temperature side in the DSC curve obtained when polymer A is heated.

[0053] The melting point is measured under the following conditions: (i) Approximately 10 mg of polymer A is heat-treated at 220°C for 5 minutes in a nitrogen atmosphere, and then cooled to 50°C at a temperature decrease rate of 10°C / min. (ii) Next, the polymer is kept at 50°C for 1 minute, and then heated from 50°C to 180°C at a temperature increase rate of 10°C / min.

[0054] The polymer A of the present invention is preferably a thermoplastic resin. Examples of the thermoplastic resin include an olefin polymer, a styrene polymer, a methacrylic resin, an acrylic resin, an ester resin, an amide resin, a vinyl polymer, and a fluorine-containing resin. The polymer A may be a single resin or a mixture of two or more resins.

[0055] <Olefin polymer> The olefin polymer of the present invention is a polymer containing 51% by weight or more of structural units derived from olefins having 2 to 10 carbon atoms, excluding 3 carbon atoms (where the total amount of the olefin polymer is taken as 100% by weight). Examples of olefins having 2 to 10 carbon atoms, excluding 3 carbon atoms, include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene, and any two or more of these may be contained.

[0056] The olefin polymer may also contain structural units derived from a monomer other than an olefin having 2 to 10 carbon atoms, excluding 3 carbon atoms. Examples of the monomer other than an olefin having 2 to 10 carbon atoms include aromatic vinyl monomers such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene); non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene; and propylene.

[0057] The olefin polymer is preferably a thermoplastic elastomer, and examples thereof include an ethylene copolymer, a butene copolymer, and an octene copolymer.

[0058] <Ethylene copolymer> Examples of ethylene copolymers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-isobutene copolymer, ethylene-1-pentene copolymer, ethylene-2-methyl-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-2-methyl-1-pentene copolymer, ethylene-3-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-nonene copolymer, and ethylene-1-decene copolymer. The ethylene copolymer is preferably an ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, or ethylene-1-octene copolymer, more preferably an ethylene-propylene copolymer, ethylene-1-butene copolymer, or ethylene-1-octene copolymer, and even more preferably an ethylene-propylene copolymer or ethylene-1-butene copolymer.

[0059] The ethylene copolymer may contain structural units derived from other monomers in addition to structural units derived from ethylene and olefins other than ethylene. Examples of such other monomers include conjugated dienes having 4 to 8 carbon atoms, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene; non-conjugated dienes having 5 to 15 carbon atoms, such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, and 5-vinyl-2-norbornene; vinyl ester compounds, such as vinyl acetate; unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; and vinyl aromatic compounds, such as styrene. The other monomer is preferably 5-ethylidene-2-norbornene, dicyclopentadiene, or styrene.

[0060] The ethylene copolymer may be a SEBS (styrene-ethylene-butylene-styrene) block copolymer. However, even in SEBS, when the total amount of the polymer is taken as 100% by weight, structural units derived from olefins other than propylene (ethylene and butylene) account for 51% by mass or more, and structural units derived from styrene account for 49% by mass or less.

[0061] The content of structural units derived from ethylene in the ethylene copolymer is preferably 30% by weight or more and 95% by weight or less, and more preferably 40% by weight or more and 80% by weight or less.

[0062] When the ethylene copolymer has structural units derived from other monomers in addition to structural units derived from propylene or an α-olefin having 4 to 10 carbon atoms and structural units derived from ethylene, the content of structural units derived from other monomers is preferably 1 part by weight or more and 40 parts by weight or less, more preferably 5 parts by weight or more and 25 parts by weight or less, provided that the total content of structural units derived from ethylene and structural units derived from propylene or an α-olefin having 4 to 10 carbon atoms is 100 parts by weight.

[0063] The olefin polymer may have two or more types of structural units derived from other monomers.

[0064] <Styrene-based polymer> A styrene-based polymer is a polymer containing 51% by weight or more of structural units derived from styrene or a styrene derivative. Examples of styrene derivatives include p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, and p-methoxystyrene. The styrene polymer may contain structural units derived from a monomer other than styrene or a styrene derivative, such as an olefin having 2 to 10 carbon atoms; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene); and non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.

[0065] <Methacrylic resin> Methacrylic resins are polymers containing 51% by weight or more of structural units derived from methacrylic acid esters, and examples thereof include poly(methyl methacrylate), poly(ethyl methacrylate), poly(butyl methacrylate), and poly(2-ethylhexyl methacrylate).

[0066] <Acrylic resin> An acrylic resin is a polymer containing 51% by weight or more of structural units derived from acrylic esters, and examples thereof include poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), and poly(2-ethylhexyl acrylate).

[0067] <Ester resin> An ester resin is a polymer containing 51% by weight or more of structural units derived from an ester of a polycarboxylic acid and a polyhydric alcohol, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate.

[0068] <Amide resin> An amide resin is a polymer containing 51% by weight or more of structural units consisting of repeating amide bonds, and examples thereof include poly(ε-caprolactam), polydodecanamide, poly(hexamethylene adipamide), poly(hexamethylene dodecanamide), poly(p-phenylene terephthalamide), and poly(m-phenylene terephthalamide).

[0069] <Vinyl polymer> The vinyl polymer of the present invention is a polymer containing 51% by weight or more of structural units derived from a monomer having a vinyl group, and examples thereof include polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, and polyvinylidene chloride.

[0070] <Fluorine-based resin> The fluororesin of the present invention is a polymer containing 51% by weight or more of structural units containing fluorine atoms, and examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, ethylene-1H,1H, Examples thereof include 2H,2H-tridecafluoro-1-octyl acrylate-methyl acrylate copolymer, ethylene-2-hydroxy-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)amino)propyl methacrylate-glycidyl methacrylate copolymer, and ethylene-2-hydroxy-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)oxy)propyl methacrylate-glycidyl methacrylate copolymer.

[0071] The polymer A can be produced by a known polymerization method using a known polymerization catalyst.

[0072] <Composition of solid composition> The solid composition of the present invention contains a propylene-based polymer B and a polymer A. As described in the above-mentioned requirement (1), in the solid composition, the propylene polymer B forms a continuous phase, and the polymer A forms a dispersed phase. In other words, in the solid composition, the propylene polymer B and the polymer A are not compatible with each other, and the solid composition has a sea-island structure in which the polymer A forms the continuous phase (sea portion) and the propylene polymer B forms the dispersed phase (islands portion). The average equivalent circle diameter of the dispersed phase (islands portion) can be 10 nm to 200 μm.

[0073] In the solid composition, when the total of propylene polymer B and polymer A is 100 parts by weight, it is preferable that propylene polymer B accounts for 50.1 to 99.9 parts by weight and polymer A accounts for 0.1 to 49.9 parts by weight. It is more preferable that propylene polymer B accounts for 70 to 99.9 parts by weight and polymer A accounts for 0.1 to 30 parts by weight, it is even more preferable that propylene polymer B accounts for 80 to 99.9 parts by weight and polymer A accounts for 0.1 to 20% by weight, and it is even more preferable that propylene polymer B accounts for 90 to 99.9% by weight and polymer A accounts for 0.1 to 10% by weight. If the amount of polymer A is too large, the low-temperature impact resistance tends to decrease.

[0074] The total proportion of the propylene polymer B and the polymer A in the entire solid composition can be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more.

[0075] <Degree of crystalline orientation in the central portion of the solid composition (requirement 3)> As described above in requirement (2), the degree of crystalline orientation of the solid composition is 60 to 80%. The lower limit of the degree of crystalline orientation may be 62%, 63%, or 65%. The upper limit of the degree of crystalline orientation may be 79%, 78%, 77%, 76%, or 75%. If the degree of orientation is too high or too low, the low-temperature impact resistance tends to decrease.

[0076] The degree of crystalline orientation of a solid composition is measured as follows. First, a two-dimensional wide-angle X-ray scattering image of the center of the solid composition is obtained by wide-angle X-ray scattering (WAXD). Next, based on the scattering image, a distribution curve of the scattering intensity of the (040) plane of the α-crystal of propylene polymer B versus azimuth angle β is obtained. When obtaining the distribution curve of scattering intensity versus azimuth angle β, the width of the circular integral of the scattering angle 2θ is within a range of ±0.5° from the scattering peak position derived from the (040) plane. Next, the half-width hw040 (unit: degree) of the maximum peak in the distribution curve of the scattering intensity versus azimuth angle β is obtained. This half-width hw040 is then substituted into equation (1). Crystal orientation degree (%)={(180-hw040) / 180}×100...(1)

[0077] The α-crystal of the propylene polymer B is an orthorhombic crystal of a chain (molecular chain) containing a propylene-derived structure. In a two-dimensional wide-angle X-ray scattering image, the peak of the (040) plane of this α-crystal usually exists in the scattering angle 2θ range of 16 to 18°.

[0078] The central portion of the solid composition refers to the portion other than the surface layer of the solid composition, and is any location within 5% to 95% of the thickness when the distance from one surface to the other surface of the solid composition (for example, the thickness from one end face to the other end face) is taken as 100%, one surface is taken as 0%, and the other surface is taken as 100%. Of these, a location within 20% to 80% is preferred. In order to obtain the XRD of the central portion, a cross section of the solid composition may be obtained, and then the central portion of the cross section may be irradiated with X-rays.

[0079] A two-dimensional wide-angle X-ray scattering image can be obtained by irradiating a sample with X-rays from one direction. If the X-ray irradiation direction is parallel to the orientation direction of propylene polymer B, no scattering peak can be obtained. Therefore, X-rays are irradiated in a direction intersecting (preferably perpendicular to) the orientation direction of propylene polymer B, i.e., in a direction intersecting (preferably perpendicular to) the direction in which the polymer flows when pressed during the production process. When the orientation direction of propylene polymer B in a sample is unknown, multiple scattering images can be obtained by irradiating X-rays from various directions, and a distribution curve of the scattering intensity versus azimuth angle derived from the (040) plane can be obtained based on each scattering image, and hw040 can be determined based on the distribution curve with the highest maximum peak.

[0080] For example, if the direction of compression (thickness direction) during manufacturing is known, it is preferable to obtain X-ray scattering images in three directions: a first direction perpendicular to the thickness direction, a second direction perpendicular to the thickness direction and perpendicular to the first direction, and a third direction perpendicular to the thickness direction and at an angle of 45 degrees to the first direction, and determine hw040 based on the distribution curve with the highest maximum peak of scattering intensity originating from the (040) plane.

[0081] The solid composition may contain additives as needed. Examples of the additives include stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, inorganic fibers, organic fibers, composite fibers, inorganic whiskers, and fillers. Examples of the stabilizers include lubricants, antioxidants, heat stabilizers, light resistance agents, weather resistance agents, metal deactivators, ultraviolet absorbers, light stabilizers, and copper inhibitors. Examples of lightfasteners include hindered amine-based lightfasteners; examples of colorants include titanium oxide, carbon black, and organic pigments; examples of metal powders include ferrite; examples of inorganic fibers include glass fiber and metal fiber; examples of organic fibers include carbon fiber and aramid fiber; examples of inorganic whiskers include potassium titanate whiskers; and examples of fillers include glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, ebonized powder, cotton flock, cork powder, barium sulfate, fluororesin, cellulose powder, and wood flour. The additives may be contained alone or in combination. The additives may be contained in the propylene-based polymer B, i.e., the continuous phase, or in the dispersed phase of polymer A, or may form a dispersed phase separate from polymer A.

[0082] The solid composition may contain a component with low wettability from the viewpoint of improving antifouling properties, anti-icing properties, and snow sliding properties. The component with low wettability can form a dispersed phase different from the polymer A in the continuous phase of the propylene polymer B.

[0083] (Mechanism of action) Such a solid composition has improved impact resistance at low temperatures, and also has sufficient impact resistance and flexural modulus at room temperature.

[0084] (Method of producing solid composition) The method for producing a solid composition according to this embodiment includes a step of fluidizing a solid raw material containing a thermoplastic resin and a polymer A by applying pressure at a predetermined temperature to obtain a solid composition. In the solid composition, the thermoplastic resin forms a continuous phase and the polymer A forms a dispersed phase, The glass transition temperature (Tg) of polymer A is less than 0°C, The degree of crystal orientation in the solid composition is 60 to 80%. The thermoplastic resin may be the above-mentioned propylene polymer B, or may be any other thermoplastic resin. Examples of the thermoplastic resin other than the propylene polymer B include ethylene polymers, butene polymers, amide polymers, methacrylic polymers, acrylic polymers, and styrene polymers.

[0085] When the thermoplastic resin does not contain propylene polymer B, in calculating the degree of crystalline orientation, instead of the distribution curve of the scattering intensity of the (040) plane of the α-crystal of propylene polymer B versus the azimuth angle β, a distribution curve of the scattering intensity at a scattering angle 2θ' at which a maximum peak is observed in the scattering angle 2θ range of 16 to 18° in a two-dimensional wide-angle X-ray scattering image versus the azimuth angle β can be used to determine the half-width (degrees) of the maximum peak. If multiple maximum peaks of the same height exist at different scattering angles 2θ' within the scattering angle 2θ range of 16 to 18°, the peak with the larger scattering angle 2θ' is used to obtain the distribution curve. The width of the circular integral when determining the distribution curve of the scattering intensity at a scattering angle 2θ' versus the azimuth angle β is within the range of ±0.5° from 2θ'.

[0086] The solid raw material contains a thermoplastic resin such as the propylene polymer B and the polymer A. The solid raw material may be a molded product of a mixture obtained by melt-kneading a thermoplastic resin such as the propylene polymer B and the polymer A by a known method to prepare a raw material composition, and then molding the raw material composition by a known method, or a laminated material obtained by molding a thermoplastic resin such as the propylene polymer B and the polymer A into films or the like by a known method, and then laminating the molded product of the thermoplastic resin and the molded product of the polymer A. In the case of a laminated material, the molded product of the thermoplastic resin and the molded product of the polymer A may or may not be melt-bonded.

[0087] The solid raw material is preferably a mixture of a thermoplastic resin and polymer A, and it is preferable that the thermoplastic resin such as propylene-based polymer B forms a continuous phase and polymer A forms a dispersed phase.

[0088] From the viewpoint of processability and impact resistance, the predetermined temperature is not more than the melting point (°C) of the thermoplastic resin such as the propylene polymer B + 10°C, preferably not more than the melting point of the thermoplastic resin + 5°C, even more preferably not more than the melting point of the thermoplastic resin, and even more preferably not more than the melting point of the thermoplastic resin - 5°C.

[0089] By applying pressure to the solid raw material at such a temperature to cause it to flow, the polymer molecules are oriented in the direction of the flow, and therefore the molecular orientation in the crystals of the propylene-based polymer B can be sufficiently improved.

[0090] Specifically, as shown in Figure 1(a), for example, a pair of, for example, plate-shaped molds 10 uniaxially pressurize a solid raw material 20 in the direction of the thick arrow, causing the polymer of the solid raw material to flow in a direction intersecting the pressure direction (the direction of the thin arrow) as shown in Figure 1(b). While the thickness decreases due to the flow, the length (width) in the direction intersecting the thickness increases. As shown in the side view of Figure 1(c) and the top view of Figure 1(d), in the resulting solid composition 30, the polymer molecules of the continuous phase are oriented along the flow direction as indicated by the arrows.

[0091] Alternatively, the polymer in the solid raw material can be caused to flow in a direction perpendicular to the pressing direction of the sheet by rolling the sheet-like solid raw material between a pair of rolls.

[0092] It is preferable to bring the mold and rolls to the above-mentioned predetermined temperature, but separately from these, the solid raw material may be brought to the predetermined temperature by applying pressure using an infrared heater or the like before being fluidized.

[0093] There is no limitation on the shape of the solid raw material, and it can be in the form of a sheet, a disk, or the like.

[0094] It is possible to apply a lubricant to the parts of the mold and roll that come into contact with the solid raw material. Examples of lubricants include silicone oil. Applying a lubricant reduces the frictional resistance between the solid raw material and the mold / roll, allowing the solid raw material to flow more smoothly under pressure, which leads to an improvement in the molding cycle and a reduction in the load on the heating and compression equipment.

[0095] The solid composition obtained by the above-mentioned production method can be further molded into a desired shape using known methods such as vacuum molding, pressure molding, and press molding.

[0096] The solid composition of the present invention can be laminated with other resins, metals, paper, or leather to form a multi-layer structure.

[0097] The surface of the solid composition of the present invention may be subjected to a surface treatment, such as embossing, corona discharge treatment, flame treatment, plasma treatment, or ozone treatment.

[0098] The solid composition of the present invention can be used for exterior construction materials, furniture and interior decoration materials, house construction materials, toy construction materials, garden construction materials, automobile construction materials, and packaging materials. Examples of exterior construction materials include carport construction materials, fence construction materials, gate construction materials, gatepost construction materials, mailbox construction materials, cycle port construction materials, deck construction materials, sunroom construction materials, roof construction materials, terrace construction materials, handrail construction materials, shade construction materials, and awning construction materials. Examples of furniture and interior decoration materials include sofa construction materials, table construction materials, chair construction materials, bed construction materials, chest construction materials, cab net construction materials, and dresser construction materials. Examples of home appliance construction materials include clock construction materials, mobile phone construction materials, and white goods construction materials. Examples of toy construction materials include plastic model construction materials, diorama construction materials, and video game console construction materials. Examples of garden construction materials include planter construction materials, flower vase construction materials, and flower pot construction materials. Examples of automobile construction materials include bumper construction materials and instrument panel construction materials. Examples of packaging materials include food packaging materials, textile packaging materials, and miscellaneous goods packaging materials. Further, other applications include, for example, monitor components, office automation (OA) equipment components, medical components, drain pans, toiletry components, bottles, containers, snow removal equipment components, and various construction components. [Example]

[0099] The present invention will be described below with reference to examples and comparative examples. Propylene polymer B and polymer A used in the examples and comparative examples are shown below.

[0100] (1) Propylene Polymer B Using the catalyst described in JP-A-10-2123219, the following propylene homopolymer was obtained by gas phase polymerization by controlling the hydrogen concentration in a polymerization reactor and the polymerization temperature. (PP-1) Propylene homopolymer MFR (230°C, 2.16 kg load): 0.5 g / 10 min Glass transition temperature (PP: Tg): 0℃ Melting point (Tm): 163℃

[0101] (2) Polymer A (A1-1) Ethylene-propylene copolymer (Product name) Toughmer P0775: Mitsui Chemicals, Inc. MFR (190°C, 2.16 kg load): 0.5 g / 10 min Glass transition temperature (Tg): -48℃

[0102] (A1-2) Ethylene-propylene copolymer (Product name) Toughmer P0275: Mitsui Chemicals, Inc. MFR (190°C, 2.16 kg load): 2.5 g / 10 min Glass transition temperature (Tg): -47℃

[0103] (A2-1) Ethylene-1-butene copolymer (Product name) Toughmer A0250: Mitsui Chemicals, Inc. MFR (190°C, 2.16 kg load): 0.2 g / 10 min Glass transition temperature (Tg): -57℃

[0104] (A3-1) Ethylene-1-octene copolymer (Product name) Engage 8100: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 0.5 g / 10 min Glass transition temperature (Tg): -52℃

[0105] (A3-2) Ethylene-1-octene copolymer (Product name) Engage 8200: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 4.9 g / 10 min Glass transition temperature (Tg): -54℃

[0106] (A3-3) Ethylene-1-octene copolymer (Product name) Engage 8407: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 34 g / 10 min Glass transition temperature (Tg): -53℃

[0107] (A4-1) Styrene-ethylene-1-butene-styrene copolymer (Product name) Tuftec H1062: Asahi Kasei Corporation MFR (190°C, 2.16 kg load): 1 g / 10 min Glass transition temperature (Tg): -47℃

[0108] (A5-1) Ethylene-methyl methacrylate copolymer (Product name) Acryft WH102: Sumitomo Chemical Co., Ltd. MFR (190°C, 2.16 kg load): 0.25 g / 10 min Glass transition temperature (Tg): -40℃

[0109] (A6-1) Polyvinylidene fluoride (Product name) KF Polymer #1300: Kureha Corporation MFR (190°C, 2.16 kg load): 0.19 g / 10 min Glass transition temperature (Tg): -31℃

[0110] The physical properties of the raw material components and the solid composition were measured according to the methods shown below. (1) Melt mass-flow rate (MFR, unit: g / 10 min) Measurement was carried out in accordance with the method specified in JIS K6758, at a measurement temperature of 230°C or 190°C and a load of 2.16 kg.

[0111] (2) Glass transition temperature (Tg, unit: °C) Measurement was carried out in accordance with the method specified in JIS K7121. The measurement temperature was −60° C. to 250° C., and the temperature rise rate was 10° C. / min.

[0112] (3) Wide-angle X-ray scattering (WAXD) The wide-angle X-ray scattering of the central portion of the solid composition was measured under the following conditions. <Measurement conditions> Model: Rigaku UltraX18 X-ray source: CuKα ray Voltage: 40kV Current: 200mA Detector: X-ray photon counting two-dimensional detector PILATUS Measurement method: Transmission method <Measurement method> The solid composition was cut in both the direction in which pressure was applied to the solid composition during production (thickness direction) and the direction perpendicular to the thickness direction and parallel to the direction in which the resin flowed due to the pressure (flow direction) to form a cut surface. X-rays were irradiated to positions at a depth equidistant from both surfaces of the solid composition in the thickness direction on the cut surface, and the wide-angle X-ray scattering profile was measured. That is, the measurement was performed at a measurement point 50% in the thickness direction, assuming the thickness of the solid composition to be 100%.

[0113] (4) Crystal orientation (unit: %) Based on the obtained wide-angle X-ray scattering (WAXD) profile, the intensity distribution curve for the azimuth angle of the (040) plane of the α-crystal of polypropylene was obtained, and the half-width hw040 of the maximum peak was calculated using equation (1). Crystal orientation degree (%)={(180-hw040) / 180}×100...Equation (1)

[0114] (5) Room temperature Charpy impact strength (unit: kJ / m 2 ) A test piece measuring 10 mm in width and 80 mm in length was cut out from the solid composition and used for the measurement. The measurement was carried out at a temperature of 23°C in accordance with JIS K7111-1 (ISO0179-1).

[0115] (6) Low-temperature Charpy impact strength (unit: kJ / m 2 ) A test piece measuring 10 mm in width and 80 mm in length was cut out from the solid composition and used for the measurement. The measurement was carried out at a temperature of -30°C in accordance with JIS K7111-1 (ISO0179-1).

[0116] (7) Flexural modulus (unit: MPa) A test piece measuring 10 mm in width and 80 mm in length was cut out from the solid composition and used for the measurement. The measurement conditions were in accordance with JIS-K-7171, and the flexural modulus was measured at 23°C.

[0117] Example 1 (Preparation of solid raw materials) 99% by weight of propylene polymer (PP-1) and 1% by weight of polymer (A1-1) were uniformly mixed in advance and melt-kneaded using a 40 mmφ single-screw extruder (VS40-28 type, manufactured by Tanabe Plastics Machine Co., Ltd., with a full-flight screw) under conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 105 rpm to obtain a composition raw material. The composition raw material was molded using a 220 ton injection molding machine (IS220EN, manufactured by Toshiba Machine Co., Ltd.) under conditions of a cylinder temperature of 220 ° C., an injection speed of 31 mm / sec, a thickness of 11 mm, a length of 150 mm, and a width of 150 mm to obtain a solid raw material.

[0118] (Preparation of solid composition) The solid raw material was placed in a heat press molding machine with the press plate temperature set to 160°C, pressed in the thickness direction up to 100t, and flowed in the direction perpendicular to the thickness direction. The pressure was maintained for 5 minutes, and then cooled to 80°C while maintaining the pressure, and the pressure was released to obtain a solid composition with a thickness of 4 mm. The physical properties of the obtained solid composition are shown in Table 1.

[0119] Example 2 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A1-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0120] Example 3 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 90% by weight and the polymer (A1-1) was 10% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0121] Example 4 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A1-2) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0122] Example 5 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A2-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0123] Example 6 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A3-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0124] Example 7 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A3-2) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0125] Example 8 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A3-3) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0126] Example 9 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A4-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0127] Example 10 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A5-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0128] (Comparative Example 1) (Preparation of solid raw materials) 95% by weight of propylene polymer (PP-1) and 5% by weight of polymer (A1-2) were uniformly mixed in advance and melt-kneaded using a 40 mmφ single-screw extruder (VS40-28 model, manufactured by Tanabe Plastics Machine Co., Ltd., with a full-flight screw) under conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 105 rpm to obtain a composition raw material. The composition raw material was molded using a 150 ton injection molding machine (J150EV-C5, manufactured by The Japan Steel Works, Ltd.) under conditions of a cylinder temperature of 220 ° C., an injection speed of 31 mm / sec, a thickness of 20 mm, a length of 98 mm, and a width of 98 mm to obtain a solid raw material.

[0129] (Preparation of solid composition) The solid raw material was placed in a heat press molding machine with a press plate temperature of 160°C, pressed in the thickness direction up to 100t to cause flow in the direction perpendicular to the thickness direction, and held for 5 minutes. While maintaining the pressure, the raw material was cooled to 80°C and then released from the pressure to obtain a solid composition with a thickness of 4 mm. The physical properties of the resulting solid composition are shown in Table 2.

[0130] (Comparative Example 2) A solid composition was prepared in the same manner as in Comparative Example 1, except that only the propylene polymer (PP-1) was used and the polymer (A1-2) was not used. The physical properties of the obtained solid composition are shown in Table 2.

[0131] (Comparative Example 3) A solid composition was prepared in the same manner as in Example 4, except that the thickness of the solid raw material was 4.8 mm. The physical properties of the obtained solid composition are shown in Table 2.

[0132] Example 11 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 99% by weight and the polymer (A6-1) was 1% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0133] Example 12 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95% by weight and the polymer (A6-1) was 5% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0134] Example 13 A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 98% by weight, the polymer (A1-1) was 1% by weight, and the polymer (A6-1) was 1% by weight. The physical properties of the obtained solid composition are shown in Table 1.

[0135] [Table 1]

[0136] [Table 2]

[0137] The solid compositions according to the examples were confirmed to have high impact resistance, particularly at low temperatures. Furthermore, the solid compositions according to the examples maintained sufficiently high impact resistance and flexural modulus at room temperature. Transmission electron micrographs confirmed that polymer A was dispersed in the continuous phase of propylene polymer B in each of the examples and comparative examples. The average equivalent circle diameter of the dispersed phase was generally about 0.2 to 14 μm. [Explanation of symbols]

[0138] 10...mold, 20...solid raw material, 30...solid composition.

Claims

1. A solid composition comprising a propylene-based polymer B and a polymer A, A solid composition that satisfies the following requirements (1) to (3): Requirement (1): The propylene polymer B forms a continuous phase, and the polymer A forms a dispersed phase. Requirement (2): The glass transition temperature (Tg) of the polymer A is lower than 0°C. Requirement (3): The degree of crystalline orientation of the solid composition, represented by the following formula, is 60 to 80%. Crystal orientation degree (%) = {(180-hw040) / 180}×100...(1) [In formula (1), hw040 is the half-value width (degrees) of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α-crystal of the propylene polymer B versus the azimuth angle, obtained from a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition.]

2. 2. The solid composition according to claim 1, wherein, when the total amount of the propylene polymer B and the polymer A is 100 parts by weight, the propylene polymer B accounts for 50.1 to 99.9 parts by weight and the polymer A accounts for 0.1 to 49.9 parts by weight.

3. 3. The solid composition according to claim 1, wherein the polymer A has a glass transition temperature (Tg) of −30° C. or lower.

4. The solid composition according to any one of claims 1 to 3, wherein the polymer A is an ethylene copolymer.

5. 5. The solid composition according to claim 4, wherein the ethylene copolymer is at least one selected from the group consisting of an ethylene-propylene copolymer, an ethylene-1-butene copolymer, and an ethylene-1-octene copolymer.

6. The solid composition according to any one of claims 1 to 5, wherein the polymer A has a melt mass-flow rate of 0.01 to 35 g / 10 min under conditions of a temperature of 190°C and a load of 2.16 kgf.

7. A method for producing a solid composition, comprising: applying pressure to a solid raw material containing a propylene-based polymer B and a polymer A at a temperature equal to or lower than the melting point (°C) of the propylene-based polymer B plus 10°C to cause the raw material to flow; In the solid composition, the propylene-based polymer B forms a continuous phase, and the polymer A forms a dispersed phase, The glass transition temperature (Tg) of the polymer A is less than 0°C, The method for producing a solid composition, wherein the degree of crystalline orientation in the solid composition, as represented by the following formula, is 60 to 80%: Crystal orientation degree (%) = {(180-hw040) / 180}×100... (1) [In formula (1), hw040 is the half-value width (degrees) of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α-crystal of the propylene polymer B versus the azimuth angle, obtained from a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition.]

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