Solid composition and method of manufacturing the same

Abstract

The solid composition according to the present invention is a solid composition comprising a propylene-based 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 less than 0 ℃. Requirement (3): The degree of crystal orientation of the solid composition represented by the following formula is 60 to 80%. Crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1) [In Equation (1), hw040 is the full width at half maximum (degrees) of the maximum peak in the distribution curve of the scattering intensity of the α-defined (040) plane of the propylene-based polymer B with respect to the azimuthal angle, obtained from the two-dimensional wide-angle X-ray scattering phase of the central part of the solid composition.]

Description

Technology Field

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

[0002] Conventionally, solid compositions obtained by molding a resin composition containing a propylene-based polymer are used in automotive parts or home appliance parts. Such solid compositions contain not only propylene-based polymers but also copolymers of ethylene and α-olefins having three or more carbon atoms, and inorganic fillers.

[0003] For example, Patent Document 1 describes a resin composition comprising an isotactic propylene-based polymer containing a structural unit derived from propylene in an amount of 84 to 50 mol%, a structural unit derived from ethylene in an amount of 15 to 30 mol%, and a structural unit derived from an α-olefin having 4 to 20 carbon atoms in an amount of 1 to 20 mol%, wherein the isotactic triad fraction (mm) calculated by 13C-NMR is 85% or more and no melting point is observed in DSC, and a propylene-ethylene-α-olefin copolymer. Prior art literature

[0004] Japanese Patent Publication No. 5020524 The problem to be solved

[0005] However, in solid compositions mainly comprising propylene-based polymers, it is required to further improve impact resistance at low temperatures.

[0006] The present invention has been made in consideration of the above problem and aims to provide a solid composition having excellent impact resistance at low temperatures and a method for manufacturing the same. means of solving the problem

[0007] The solid composition according to the present invention is a solid composition comprising a propylene-based polymer B and a polymer A, and satisfies the following requirements (1) to (3).

[0008] Requirement (1): The above propylene-based polymer B forms a continuous phase, and the above polymer A forms a dispersed phase.

[0009] Requirement (2): The glass transition temperature (Tg) of the above polymer A is less than 0 ℃.

[0010] Requirement (3): The degree of crystal orientation of the solid composition represented by the following formula is 60 to 80 percent.

[0011] Crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1)

[0012] [In Equation (1), hw040 is the full width at half maximum (degrees) of the maximum peak in the distribution curve of the scattering intensity of the α-defined (040) plane of the propylene-based polymer B with respect to the azimuthal angle, obtained from the two-dimensional wide-angle X-ray scattering phase of the central part of the solid composition.]

[0013] Here, when the total of the propylene-based polymer B and the polymer A is 100 parts by weight, the propylene-based polymer B may occupy 50.1 to 99.9 parts by weight and the polymer A may occupy 0.1 to 49.9 parts by weight.

[0014] In addition, the glass transition temperature (Tg) of the above polymer A may be -30 ℃ or lower.

[0015] The above polymer A may be an ethylene copolymer.

[0016] In addition, the ethylene copolymer may be at least one selected from the group consisting of ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene copolymer.

[0017] In addition, the solid composition may have a melt mass flow rate of polymer A of 0.01 to 35 g / 10 min under conditions of a temperature of 190 ℃ and a load of 2.16 kgf.

[0018] A method for manufacturing a solid composition according to the present invention comprises a process of obtaining a solid composition by flowing a solid raw material comprising a thermoplastic resin and polymer A under pressure at a temperature of the melting point (°C) of the thermoplastic resin + 10°C or lower.

[0019] In the above solid composition, the thermoplastic resin forms a continuous phase, and the polymer A forms a dispersed phase, and

[0020] The glass transition temperature (Tg) of the above polymer A is less than 0 ℃, and

[0021] A method for preparing a solid composition having a crystal orientation degree represented by the following formula in the above solid composition of 60 to 80 percent.

[0022] Crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1)

[0023] [(1) In the formula, hw040 is the full width at half maximum (degrees) of the maximum peak in the distribution curve of scattering intensity at scattering angle 2θ' with respect to azimuth β, obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition, and scattering angle 2θ' is the angle that gives the maximum peak in the range of scattering angle 2θ = 16° to 18°.] Effects of the invention

[0024] According to the present invention, a solid composition having excellent impact resistance at low temperatures and a method for manufacturing the same are provided. Brief explanation of the drawing

[0025] FIGS. 1(a) and FIGS. 1(b) are schematic diagrams illustrating, in sequence, a method for manufacturing a solid composition related to an embodiment of the present invention, 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. Specific details for implementing the invention

[0026] Several embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0027] The solid composition of the present embodiment is a solid composition comprising a propylene-based polymer B and a polymer A, satisfying the following requirements (1) to (3).

[0028] Requirement (1): Propylene-based polymer B forms a continuous phase, and polymer A forms a dispersed phase.

[0029] Requirement (2): The glass transition temperature (Tg) of polymer A is less than 0 ℃.

[0030] Requirement (3): The degree of crystal orientation of the solid composition obtained by the following formula (1) is 60 to 80 percent.

[0031] Equation (1) … Crystal orientation (%) = {(180 ― hw040) / 180} × 100

[0032] [In Equation (1), hw040 is the full width at half maximum (degrees) of the maximum peak in the azimuthal distribution curve of the scattering intensity of the (040) plane of the propylene-based polymer B, obtained from the two-dimensional wide-angle X-ray scattering phase of the central part of the solid composition.]

[0033] (Propylene-based polymer B)

[0034] The propylene-based polymer B of the present invention is a polymer comprising a structural unit derived from propylene, and may be (1) a propylene homopolymer, (2) a propylene random copolymer, or (3) a propylene multistage polymerization material (heterophasic propylene polymerization material). The propylene-based polymer B may be one of these, but may also be a mixture of two or more types. Furthermore, in this specification, "structural unit" may be replaced with "monomer unit."

[0035] <(1) Propylene homopolymer>

[0036] Propylene homopolymer is a polymer composed solely of structural units derived from propylene.

[0037] <(2) Propylene Random Copolymer>

[0038] Propylene random copolymer is,

[0039] (2-1) A random copolymer comprising structural units derived from propylene and structural units derived from ethylene,

[0040] (2-2) A random copolymer comprising a structural unit derived from propylene and a structural unit derived from an α-olefin having 4 to 10 carbon atoms, or,

[0041] (2-3) It is a random copolymer containing structural units derived from propylene, structural units derived from ethylene, and structural units derived from α-olefins with 4 to 10 carbon atoms.

[0042] Examples of α-olefins having 4 to 10 carbon atoms used in random copolymer (2-2) or (2-3) include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc., preferably 1-butene, 1-hexene, 1-octene.

[0043] Examples of random copolymers (2-2) include, for instance, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-1-decene random copolymer, etc.

[0044] Examples of the above random copolymers (2-3) include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, etc.

[0045] The content of structural units derived from ethylene contained in the random copolymer (2-1) is preferably 0.1 to 30 weight%, more preferably 0.1 to 20 weight%, and even more preferably 0.1 to 10 weight%. In addition, the content of structural units derived from propylene contained in the random copolymer (2-1) is preferably 99.9 to 70 weight%, more preferably 99.9 to 80 weight%, and even more preferably 99.9 to 90 weight% (provided that the total weight of the random copolymer (2-1) is 100 weight%).

[0046] The content of structural units derived from α-olefins having 4 to 10 carbon atoms contained in the random copolymer (2-2) is preferably 0.1 to 30 weight%, more preferably 0.1 to 20 weight%, and even more preferably 0.1 to 10 weight%. In addition, the content of structural units derived from propylene contained in the random copolymer (2-2) is preferably 99.9 to 70 weight%, more preferably 99.9 to 80 weight%, and even more preferably 99.9 to 90 weight% (provided that the total weight of the random copolymer (2-2) is 100 weight%).

[0047] The sum of the content of structural units derived from ethylene and the content of structural units derived from α-olefins having 4 to 10 carbon atoms contained in the random copolymer (2-3) is preferably 0.1 to 49 weight%, more preferably 0.1 to 40 weight%, and even more preferably 0.1 to 30 weight%. In addition, the content of structural units derived from propylene contained in the random copolymer (2-3) is preferably 99.9 to 51 weight%, more preferably 99.9 to 60 weight%, and even more preferably 99.9 to 70 weight% (provided that the total weight of the random copolymer (2-3) is 100 weight%).

[0048] <(3) Propylene Multi-stage Polymerization Material>

[0049] Propylene multi-stage polymerization material is,

[0050] (3-1) A propylene multi-stage polymer material comprising 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,

[0051] (3-2) A propylene multi-stage polymer material comprising 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)).

[0052] Here, the propylene homopolymer component (I-1) and the propylene copolymer component (I-2) are collectively referred to as polymer component (I).

[0053] The propylene homopolymer component (I-1) is a homopolymer component consisting only of structural units derived from propylene.

[0054] The propylene copolymer component (I-2) is a copolymer component comprising a structural unit derived from propylene and a structural unit derived from ethylene and an olefin selected from α-olefins having 4 to 10 carbon atoms, wherein the content of the structural unit derived from ethylene and an olefin selected from α-olefins having 4 to 10 carbon atoms is 0.1 weight% or more and less than 20 weight%, preferably 0.1 to 15 weight%, more preferably 0.1 to 10 weight% (provided that the total weight of the propylene copolymer component (I-2) is 100 weight%).

[0055] In the propylene copolymer component (I-2), the content of structural units derived from propylene is greater than 80 weight% and less than or equal to 99.9 weight%, preferably 85 to 99.9 weight%, and more preferably 90 to 99.9 weight%.

[0056] The propylene copolymer component (II) is a copolymer component comprising a structural unit derived from propylene and a structural unit derived from an olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms, wherein the content of the structural unit derived from ethylene and an olefin selected from an α-olefin having 4 to 10 carbon atoms is 20 to 80 weight%, preferably 20 to 60 weight%, more preferably 30 to 60 weight% (provided that the total weight of the propylene copolymer component (II) is 100 weight%).

[0057] The content of structural units derived from propylene is 20 to 80 weight%, preferably 40 to 80 weight%, and more preferably 40 to 70 weight%.

[0058] Examples of α-olefins having 4 to 10 carbon atoms used in the propylene copolymer component (I-2) or propylene copolymer component (II) include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc., preferably 1-butene, 1-hexene, 1-octene, and more preferably 1-butene.

[0059] Examples of propylene copolymer components (I-2) include, for instance, propylene-ethylene copolymer components, propylene-1-butene copolymer components, propylene-1-hexene copolymer components, propylene-1-octene copolymer components, propylene-ethylene-1-butene copolymer components, propylene-ethylene-1-hexene copolymer components, propylene-ethylene-1-octene copolymer components, etc., and preferably, propylene-ethylene copolymer components, propylene-1-butene copolymer components, and propylene-ethylene-1-butene copolymer components.

[0060] The propylene copolymer component (II) may include, for example, 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, a propylene-1-decene copolymer component, and preferably a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-ethylene-1-butene copolymer component, and more preferably a propylene-ethylene copolymer component.

[0061] Examples of propylene multi-stage polymerization materials (3-1) include, for instance, (propylene)-(propylene-ethylene) multi-stage polymerization materials, (propylene)-(propylene-ethylene-1-butene) multi-stage polymerization materials, (propylene)-(propylene-ethylene-1-hexene) multi-stage polymerization materials, (propylene)-(propylene-ethylene-1-octene) multi-stage polymerization materials, (propylene)-(propylene-1-butene) multi-stage polymerization materials, (propylene)-(propylene-1-hexene) multi-stage polymerization materials, (propylene)-(propylene-1-octene) multi-stage polymerization materials, (propylene)-(propylene-1-decene) multi-stage polymerization materials.

[0062] Preferably, it is a (propylene)-(propylene-ethylene) multistage polymerization material, a (propylene)-(propylene-ethylene-1-butene) multistage polymerization material, and more preferably, a (propylene)-(propylene-ethylene) multistage polymerization material.

[0063] Propylene multi-stage polymerization material (3-2) is, for example, (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-ethylene)-(propylene-1-butene) multi-stage polymerization material, (propylene-ethylene)-(propylene-1-hexene) multi-stage polymerization material, (propylene-ethylene)-(propylene-1-octene) multi-stage polymerization material, (propylene-ethylene)-(propylene-1-decene) multi-stage polymerization material, (propylene-1-butene)-(propylene-ethylene) multi-stage polymerization material, (Propylene-1-butene)-(Propylene-ethylene-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-1-butene)-(Propylene-1-decene) multistage polymerization material, (Propylene-1-hexene)-(Propylene-1-hexene) multistage polymerization material, Examples include (propylene-1-hexene)-(propylene-1-octene) multi-stage polymerization materials, (propylene-1-hexene)-(propylene-1-decene) multi-stage polymerization materials, (propylene-1-octene)-(propylene-1-octene) multi-stage polymerization materials, and (propylene-1-octene)-(propylene-1-decene) multi-stage polymerization materials.

[0064] Preferably, it is a (propylene-ethylene)-(propylene-ethylene) multistage polymerization material, a (propylene-ethylene)-(propylene-ethylene-1-butene) multistage polymerization material, or a (propylene-1-butene)-(propylene-1-butene) multistage polymerization material.

[0065] The content of copolymer component (II) contained in the multistage polymerization material comprising polymer component (I) and copolymer component (II) is preferably 1 to 49 weight%, more preferably 1 to 40 weight%, even more preferably 1 to 30 weight%, and even more preferably 1 to 20 weight% (provided that the total weight of the multistage polymerization material is 100 weight%).

[0066] The content of polymer component (I) contained in the multistage polymerization material comprising polymer component (I) and copolymer component (II) is preferably 51 to 99 weight%, more preferably 60 to 99 weight%, even more preferably 70 to 99 weight%, and even more preferably 80 to 99 weight% (provided that the total weight of the multistage polymerization material is 100 weight%).

[0067] (MFR of propylene-based polymer B)

[0068] The melt mass flow rate (MFR) of the above-described propylene-based 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, even more preferably 0.01 to 5 g / 10 min, and may also be 0.01 to 2 g / 10 min. When the value of the melt mass flow rate of the propylene-based polymer B is within the above range, the impact resistance of the solid composition tends to be excellent.

[0069] In this specification, the melt mass flow rate refers to a value measured according to JIS K6758.

[0070] (Tg of propylene-based polymer B)

[0071] The glass transition temperature (PP:Tg) of propylene-based polymer B is, in terms of impact resistance, 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. In addition, the Tg is measured according to JIS K7121.

[0072] The glass transition temperature (PP:Tg) of propylene-based polymer B is a value obtained by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0073] (Tm of propylene-based polymer B)

[0074] The melting point (Tm) of propylene-based polymer B can be 100 to 180 °C.

[0075] The melting point of propylene-based polymer B can be determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0076] Method for manufacturing propylene-based polymer B

[0077] The above-mentioned propylene-based polymer B can be obtained by homopolymerizing propylene using a polymerization catalyst, or by copolymerizing propylene with other olefins using a polymerization catalyst.

[0078] Polymerization Catalyst

[0079] As polymerization catalysts, for example,

[0080] (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,

[0081] (2) A catalyst system comprising (2-i) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and (2-ii) an alkylaluminoxane,

[0082] (3) A catalytic 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 it to form an ionic complex, and (3-iii) an organoaluminum compound,

[0083] (4) Examples of catalyst systems include a catalyst system in which a catalyst component consisting of (4-i) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, (4-ii) a compound forming an ionic complex, and (4-iii) an organoaluminum compound is supported on inorganic particles such as silica or clay minerals and modified.

[0084] In addition, a pre-polymerization completed catalyst prepared by pre-polymerizing ethylene, propylene, or α-olefin in the presence of the above catalyst system may be used.

[0085] Examples of the above-mentioned catalyst systems include the catalyst systems described in Japanese Patent Publication No. Sho 61-218606, Japanese Patent Publication No. Hei 5-194685, Japanese Patent Publication No. Hei 7-216017, Japanese Patent Publication No. Hei 9-316147, Japanese Patent Publication No. Hei 10-212319, and Japanese Patent Publication No. 2004-182981.

[0086] Polymerization Method

[0087] Polymerization methods may include, for example, bulk polymerization, solution polymerization, slurry polymerization, or gas phase polymerization. These polymerization methods may be either batch or continuous. Furthermore, they may be either a single-stage method using a single polymerization reactor or a multi-stage method in which multiple polymerization reactors are connected in series, and these polymerization methods may be arbitrarily combined. 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) may be polymerized in the first stage, and a propylene copolymer component (II) may be polymerized in the second stage.

[0088] In addition, various conditions in the polymerization process (polymerization temperature, polymerization pressure, monomer concentration, amount of catalyst input, polymerization time, etc.) can be appropriately determined according to the (1) propylene homopolymer, (2) propylene random copolymer, and (3) propylene multistage polymerization material being manufactured.

[0089] In addition, as a method for manufacturing (1) a propylene homopolymer, (2) a propylene random copolymer, and (3) a propylene multi-stage polymerization material, a method may be used in which a propylene homopolymer or a copolymer of propylene and other olefins obtained by the above polymerization method is subjected to an extraction operation with boiling octane to remove components soluble in boiling octane, and (1) a propylene homopolymer, (2) a propylene random copolymer, (3) a propylene block copolymer, or (4) a propylene multi-stage polymerization material is recovered as components insoluble in boiling octane.

[0090] A method for recovering components insoluble in boiling octane is, for example, to use a Soxhlet extraction tube to add a homopolymer of propylene obtained by polymerization or a copolymer of propylene and another olefin to a Soxhlet extraction filter paper, and to reflux in boiling octane for 5 hours to extract and remove components soluble in boiling octane from the homopolymer or copolymer, and to recover components insoluble in boiling octane remaining on the Soxhlet extraction filter paper.

[0091] The octane used in the extraction operation is 0.1 L per 20 g of homopolymer or copolymer obtained by polymerization.

[0092] (Polymer A)

[0093] Polymer A is incompatible with propylene-based polymer B.

[0094] (Tg of Polymer A)

[0095] The glass transition temperature (Tg) of polymer A is less than 0°C [Requirement (2)] in terms of impact resistance, preferably -30°C or less, and more preferably -40°C or less. The smaller the glass transition temperature (Tg), the better the impact resistance of the solid composition tends to be.

[0096] The glass transition temperature (Tg) of polymer A is a value obtained by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0097] (MFR of Polymer A)

[0098] 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, may be 0.01 g / 10 min or higher and 35 g / 10 min or lower. The upper limits of the MFR may be 20 g / 10 min, 10 g / 10 min, 5 g / 10 min, 2.0 g / 10 min, and 1.0 g / 10 min. As the melt mass flow rate of polymer A decreases, the impact resistance of the solid composition tends to be superior.

[0099] (Tm of Polymer A)

[0100] The melting point of polymer A obtained by DSC is, in terms of processability, preferably less than 200°C, more preferably less than 180°C, and even more preferably less than 150°C.

[0101] The melting point (Tm) obtained by DSC of polymer A is the melting temperature of the crystalline phase contained in polymer A, and specifically, it is the peak top temperature at the highest temperature endothermic peak in the DSC curve obtained when polymer A is heated.

[0102] In addition, this melting point is measured under the following conditions: (i) Approximately 10 mg of polymer A is heat-treated at 220 °C for 5 minutes under a nitrogen atmosphere, and then cooled to 50 °C at a cooling rate of 10 °C / min. (ii) Subsequently, the temperature is held at 50 °C for 1 minute, and then heated from 50 °C to 180 °C at a heating rate of 10 °C / min.

[0103] Polymer A of the present invention is preferably a thermoplastic resin. Examples of thermoplastic resins include olefin-based polymers, styrene-based polymers, methacrylic resins, acrylic resins, ester-based resins, amide-based resins, vinyl-based polymers, and fluorine-based resins. Polymer A may be a single resin or a mixture of two or more resins.

[0104] Olefin Polymers

[0105] The olefin-based 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 (provided that the total amount of the olefin-based polymer is 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, 1-decene, etc., and may include any multiple types.

[0106] In addition, the olefin-based polymer may contain structural units derived from monomers other than olefins having 2 to 10 carbon atoms, excluding 3 carbon atoms. Examples of monomers other than olefins having 2 to 10 carbon atoms, excluding 3 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.

[0107] The above olefin-based polymer is preferably a thermoplastic elastomer, and examples include ethylene copolymers, butene copolymers, octene copolymers, etc.

[0108] < Ethylene-based copolymer >

[0109] Examples of ethylene copolymers are 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-3-1-pentene copolymer, ethylene-1-octene copolymer, ethylene-1-nonene copolymer, and ethylene-1-decene copolymer. The ethylene copolymer is preferably an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-propylene-1-butene copolymer, or an ethylene-1-octene copolymer, more preferably an ethylene-propylene copolymer, or an ethylene-1-butene copolymer, and an ethylene-1-octene copolymer, and even more preferably an ethylene-propylene copolymer or an ethylene-1-butene copolymer.

[0110] Ethylene-based copolymers may have structural units derived from other monomers in addition to structural units derived from ethylene and olefins other than ethylene. 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; Examples include 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. Other monomers are preferably 5-ethylidene-2-norbornene, dicyclopentadiene, or styrene.

[0111] The ethylene copolymer may be a SEBS (styrene-ethylene-butylene-styrene) block copolymer. However, even in the case of SEBS, when the total amount of the polymer is 100 weight%, the structural units derived from olefins other than propylene (ethylene and butylene) are 51 weight% or more, and the structural units derived from styrene are 49 weight% or less.

[0112] The content of structural units derived from ethylene in the ethylene copolymer is preferably 30 weight% or more and 95 weight% or less, and more preferably 40 weight% or more and 80 weight% or less.

[0113] In the case where the ethylene copolymer has structural units derived from other monomers in addition to structural units derived from propylene or α-olefins having 4 to 10 carbon atoms or 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, and more preferably 5 parts by weight or more and 25 parts by weight or less. However, the sum of the content of structural units derived from ethylene and the content of structural units derived from propylene or α-olefins having 4 to 10 carbon atoms is 100 parts by weight.

[0114] Olefin polymers may have two or more types of structural units derived from other monomers.

[0115] Styrene-based polymers

[0116] A styrene-based polymer is a polymer containing 51 weight percent or more of structural units derived from styrene or styrene derivatives. Examples of styrene derivatives include p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, and p-methoxystyrene. Styrene-based polymers may contain structural units derived from monomers other than styrene or styrene derivatives, such as, for example, olefins 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; and conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene). Examples of non-conjugated dienes include dicyclopentadiene and 5-ethylidene-2-norbornene.

[0117] Methacrylic resin

[0118] Methacryl resin is a polymer containing 51% by weight or more of structural units derived from methacrylic acid esters, and examples include poly(methyl methacrylate), poly(ethyl methacrylate), poly(butyl methacrylate), poly(2-ethylhexyl methacrylate), etc.

[0119] Acrylic Resin

[0120] Acrylic resin is a polymer containing 51% by weight or more of structural units derived from acrylic acid esters, and examples include poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), poly(2-ethylhexyl acrylate), etc.

[0121] Ester resins

[0122] Ester resin is a polymer containing 51% by weight or more of structural units derived from esters of polycarboxylic acids and polyhydric alcohols, and examples include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc.

[0123] <Amid-based Resin>

[0124] An amide resin is a polymer containing 51% by weight or more of structural units that are repeated by amide bonds, and examples include poly(ε-caprolactam), polydodecaneamide, poly(hexamethyleneadipamide), poly(hexamethylenedodecanamide), poly(p-phenyleneterephthalamide), poly(m-phenyleneterephthalamide), etc.

[0125] Vinyl polymers

[0126] The vinyl polymer of the present invention is a polymer containing 51% by weight or more of a structural unit derived from a monomer having a vinyl group, and examples include polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinylidene chloride, etc.

[0127] Fluorine-based resin

[0128] The fluorine-based resin of the present invention is a polymer containing 51 weight% or more of structural units containing fluorine atoms, and, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyfluoropolymer, tetrafluoroethylene·hexafluoropropylene copolymer, ethylene·tetrafluoroethylene copolymer, ethylene·chlorotrifluoroethylene copolymer, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, ethylene-1H,1H,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, Examples include ethylene-2-hydroxy-3-((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)oxy)propyl methacrylate-glycidyl methacrylate copolymer.

[0129] As a method for manufacturing the above polymer A, a known polymerization method using a known polymerization catalyst is used.

[0130] <Composition of Solid Composition>

[0131] The solid composition of the present invention contains propylene-based polymer B and polymer A.

[0132] As described in requirement (1) above, in the solid composition, the propylene-based polymer B forms a continuous phase and the polymer A forms a dispersed phase. In other words, in the solid composition, the propylene-based polymer B and the polymer A do not interact, and the solid composition has a sea island structure in which the polymer A is the continuous phase (decomposition) and the propylene-based polymer B is the dispersed phase (island). The average circular equivalent diameter of the dispersed phase (island) may be 10 nm to 200 μm.

[0133] In the solid composition, when the total of propylene-based polymer B and polymer A is 100 parts by weight, it is preferable that propylene-based polymer B occupies 50.1 to 99.9 parts by weight and polymer A occupies 0.1 to 49.9 parts by weight. In the solid composition, it is more preferable that propylene-based polymer B occupies 70 to 99.9 parts by weight and polymer A occupies 0.1 to 30 parts by weight, more preferably that propylene-based polymer B occupies 80 to 99.9% by weight and polymer A occupies 0.1 to 20% by weight, and even more preferable that propylene-based polymer B occupies 90 to 99.9% by weight and polymer A occupies 0.1 to 10% by weight.

[0134] If polymer A is excessively abundant, low-temperature impact resistance tends to decrease.

[0135] The ratio of the total of propylene-based polymer B and polymer A to the total of the solid composition may be 50 weight% or more, preferably 60 weight% or more, and more preferably 70 weight% or more.

[0136] <Crystal orientation of the central portion of the solid composition (Requirement 3)>

[0137] As stated above in requirement (3), the degree of crystal orientation of the solid composition is 60 to 80 percent. The lower limit of the degree of crystal orientation may be 62 percent, 63 percent, or 65 percent. Also, the upper limit of the degree of crystal orientation may be 79 percent, 78 percent, 77 percent, 76 percent, or 75 percent.

[0138] Whether the degree of orientation is excessively high or excessively low, low-temperature shock resistance tends to decrease.

[0139] The degree of crystal orientation of the solid composition is measured as follows. First, a two-dimensional wide-angle X-ray scattering image of the central part of the solid composition is obtained by the wide-angle X-ray scattering (WAXS) method. Next, based on the scattering image, a distribution curve for the scattering intensity of the α-defined (040) plane of the propylene-based polymer B with respect to the azimuth angle β is obtained. When obtaining the distribution curve of the scattering intensity with respect to the azimuth angle β, the width of the circular integral of the scattering angle 2θ is set to a range of ±0.5° from the position of the scattering peak originating from the (040) plane. Next, the full width at half maximum hw040 (in degrees) of the maximum peak in the distribution curve of the scattering intensity with respect to the azimuth angle β is obtained. Then, this full width at half maximum hw040 is substituted into Equation (1).

[0140] Crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1)

[0141] The α-type of the propylene-based polymer B is an orthorhombic structure 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-type typically exists in the range of a scattering angle 2θ = 16 to 18°.

[0142] The central part of the solid composition is a portion other than the surface layer of the solid composition, and is any location between 5% and 95% in the thickness direction when the distance from one surface of the solid composition to the other surface (e.g., the thickness from one end surface to the other end surface) is set to 100%, one surface is set to 0%, and the other surface is set to 100%. Among these, a location between 20% and 80% is preferred.

[0143] In addition, to obtain the XRD of the central part, a cross-section of the solid composition is obtained, and then X-rays are irradiated onto the central part of the cross-section.

[0144] A two-dimensional wide-angle X-ray scattering image is obtained by irradiating the sample with X-rays from one direction. If the direction of X-ray irradiation is parallel to the orientation direction of the propylene-based polymer B, no scattering peak is obtained. Therefore, X-rays are irradiated in a direction that intersects (preferably orthogonally) the orientation direction of the propylene-based polymer B, that is, in a direction that intersects (preferably orthogonally) the direction in which the polymer flowed during pressurization in the manufacturing process. If the orientation direction of the propylene-based polymer B in the sample is unknown, multiple scattering images are obtained by irradiating X-rays from various directions, and based on each scattering image, a distribution curve for the azimuth angle of scattering intensity originating from the (040) plane is obtained, and hw040 is determined based on the distribution curve with the highest maximum peak.

[0145] For example, if the direction of pressure applied during manufacturing (thickness direction) is known, it is preferable to obtain X-ray scattering images for each of the three directions: a first direction orthogonal to the thickness direction, a second direction orthogonal to the thickness direction and also orthogonal to the first direction, and a third direction orthogonal to the thickness direction and also at 45 degrees to the first direction, and to obtain hw040 based on the distribution curve in which the maximum peak of scattering intensity originating from the (040) plane is highest.

[0146] The solid composition may include additives as needed. Examples of 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, anti-aging agents, heat stabilizers, light-resistant agents, weather-resistant agents, metal inerts, ultraviolet absorbers, light stabilizers, and anti-freeze agents. Examples of light-retardant agents include hindered amine-based light-retardant agents, examples of coloring agents include titanium oxide, carbon black, and organic pigments, examples of metal powders include ferrite, examples of inorganic fibers include glass fibers and metal fibers, examples of organic fibers include carbon fibers and aramid fibers, 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, Evo powder, cotton flock, cork powder, barium sulfate, fluoropolymer, cellulose powder, and wood powder. The additive may include only one type or two or more types. The additive may be included in the propylene-based polymer B, that is, in the continuous phase, or may be included in the dispersed phase of polymer A, or may form a dispersed phase different from polymer A.

[0147] The solid composition may include a component with low wettability in order to increase antifouling, anti-icing, and anti-smoothing properties. These components with low wettability may form a dispersed phase different from polymer A within the continuous phase of the propylene-based polymer B.

[0148] (Mechanism of action)

[0149] Such a solid composition improves impact resistance at low temperatures. In addition, the impact resistance and bending modulus at room temperature can also have sufficient values.

[0150] (Method for manufacturing a solid composition)

[0151] The method for manufacturing a solid composition related to the present embodiment includes a process of obtaining a solid composition by flowing a solid raw material comprising a thermoplastic resin and polymer A under pressure at a predetermined temperature.

[0152] And, in the solid composition, the thermoplastic resin forms a continuous phase, and the polymer A forms a dispersed phase, and

[0153] The glass transition temperature (Tg) of polymer A is less than 0 ℃, and

[0154] The degree of crystal orientation in the solid composition is 60 to 80 percent.

[0155] The thermoplastic resin may be the above-mentioned propylene-based polymer B, but may also be any other thermoplastic resin. Examples of thermoplastic resins other than propylene-based polymer B are ethylene-based polymers, butene-based polymers, amide-based polymers, methacrylic-based polymers, acrylic-based polymers, and styrene-based polymers.

[0156] In cases where the thermoplastic resin does not contain propylene-based polymer B, in calculating the crystal orientation degree above, instead of using a distribution curve for azimuthal angle β for scattering intensity of the α definition (040) plane of propylene-based polymer B, a distribution curve for azimuthal angle β for scattering intensity at a scattering angle 2θ' where a maximum peak is observed in the range of scattering angle 2θ = 16 to 18° in the two-dimensional wide-angle X-ray scattering image is used to obtain the full width (degrees) of the maximum peak. If multiple maximum peaks of the same height exist at different scattering angles 2θ' in the range of scattering angle 2θ = 16 to 18°, the peak with a larger value of scattering angle 2θ' is adopted to obtain the distribution curve. When obtaining the distribution curve of the scattering intensity with respect to the azimuth angle β at the scattering angle 2θ', the width of the toroidal integral is set to a range of ±0.5° from 2θ'.

[0157] The solid raw material includes the thermoplastic resin such as the above-mentioned propylene-based polymer B and the above-mentioned polymer A. The solid raw material may be a molded body of a mixture formed by melt-kneading the thermoplastic resin such as the above-mentioned polymer B and polymer A by a known method to form a composition raw material, and molding the composition raw material by a known method; or it may be a laminated material formed by laminating the thermoplastic resin molded body and the polymer A molded body by separately molding the thermoplastic resin such as the above-mentioned polymer B and polymer A into a film, etc. by a known method. Furthermore, in the case of the laminated material, the thermoplastic resin molded body and the polymer A molded body may be melt-bonded or not melt-bonded.

[0158] 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.

[0159] In terms of processability and impact resistance, the specified temperature is the melting point (°C) of a thermoplastic resin such as propylene-based polymer B plus 10°C or lower, preferably the melting point of the thermoplastic resin plus 5°C or lower, more preferably the melting point of the thermoplastic resin or lower, and even more preferably the melting point of the thermoplastic resin minus 5°C or lower.

[0160] At such a temperature, by applying pressure to the solid raw material and causing it to flow, the molecules of the polymer are oriented along the direction of flow. Therefore, the orientation of the molecules in the crystallization of the propylene-based polymer B can be sufficiently improved.

[0161] Specifically, for example, as shown in FIG. 1(a), by applying uniaxial pressure to a solid raw material (20) in the direction of the thick arrow with a pair of, for example, plate-shaped molds (10), as shown in FIG. 1(b), the polymer of the solid raw material flows in a direction intersecting the direction of pressure (in the direction of the thin arrow). As the flow decreases, the length (width) in the direction intersecting the thickness increases. As shown in the side view of FIG. 1(c) and the top view of FIG. 1(d), in the obtained solid composition (30), the polymer molecules in the continuous phase are oriented along the direction of flow as indicated by the arrow.

[0162] In addition, by rolling the sheet-shaped solid raw material between a pair of rolls, the polymer in the solid raw material can be flowed in a direction intersecting the pressing direction of the sheet.

[0163] While it is suitable to set the mold and roll to the above-mentioned predetermined temperature, the solid raw material may also be heated to a predetermined temperature before flow by applying pressure using an infrared heater or the like, separately from these.

[0164] There is no limitation on the shape of the solid raw material, and it can be in the form of a sheet, a disc, etc.

[0165] It is possible to apply a lubricant to the parts of the mold and roll that come into contact with the solid material. Examples of lubricants include silicone oil. By applying the lubricant, the frictional resistance between the solid material and the mold / roll is reduced, allowing for smoother flow of the solid material under pressure. This leads to an improvement in the molding cycle and a reduction in the load on the heat-compressing device.

[0166] The solid composition obtained by the above manufacturing method can also be formed into a further required shape using known methods such as vacuum forming, compression forming, and press forming.

[0167] The solid composition of the present invention can be used as a multilayer structure by bonding it with other resins, metals, paper, or leather.

[0168] Surface treatment may be performed on the surface of the solid composition of the present invention. Examples of surface treatment methods include embossing, corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc.

[0169] Uses of the solid composition of the present invention include exterior components, furniture and interior decoration components, home appliance components, toy components, gardening components, automobile components, and packaging materials. Examples of external components include carport components, fence components, gate components, gate posts, posts, cycle ports, deck components, sunroom components, roof components, terrace components, railing components, shade components, awning components, etc. As furniture and interior decoration components, examples include sofa components, table components, chair components, bed components, wardrobe components, cabinet components, dresser components, etc. As home appliance components, examples include clock components, mobile phone components, white goods components, etc. As toy components, examples include plastic model components, diorama components, video game main components, etc. As gardening components, examples include planter components, vase components, flower pot components, etc. As automobile components, examples include bumper materials, instrument panel materials, etc. As packaging materials, examples include food packaging materials, textile packaging materials, general merchandise packaging materials, etc. In addition, other uses include, for example, components for monitors, components for office automation (OA) equipment, medical components, drainage fans, toilet components, bottles, containers, components for snow removal supplies, and various construction components.

[0170] Examples

[0171] The present invention will be explained below using examples and comparative examples. The propylene-based polymer B and polymer A used in the examples and comparative examples are shown below.

[0172] (1) Propylene-based polymer B

[0173] The following propylene homopolymer was obtained by using the catalyst described in Japanese Patent Publication No. Hei 10-2123219 and controlling the hydrogen concentration and polymerization temperature in the polymerization reactor by a vapor phase polymerization method.

[0174] (PP-1) Propylene Homopolymer

[0175] MFR (230 ℃, 2.16 kg load): 0.5 g / 10 min

[0176] Glass transition temperature (PP : Tg): 0 ℃

[0177] Melting point (Tm): 163 ℃

[0178] (2) Polymer A

[0179] (A1-1) Ethylene-propylene copolymer

[0180] (Product Name) Tafmer P0775 : Mitsui Chemical Co., Ltd.

[0181] MFR (190 ℃, 2.16 kg load): 0.5 g / 10 min

[0182] Glass transition temperature (Tg): -48 ℃

[0183] (A1-2) Ethylene-propylene copolymer

[0184] (Product Name) Tafmer P0275 : Mitsui Chemical Co., Ltd.

[0185] MFR (190 ℃, 2.16 kg load): 2.5 g / 10 min

[0186] Glass transition temperature (Tg): -47 ℃

[0187] (A2-1) Ethylene-1-butene copolymer

[0188] (Product Name) Tafmer A0250: Mitsui Chemical Co., Ltd.

[0189] MFR (190 ℃, 2.16 kg load): 0.2 g / 10 min

[0190] Glass transition temperature (Tg): -57 ℃

[0191] (A3-1) Ethylene-1-octene copolymer

[0192] (Product Name) Engage 8100: Dow Elastomer Japan Co., Ltd.

[0193] MFR (190 ℃, 2.16 kg load): 0.5 g / 10 min

[0194] Glass transition temperature (Tg): -52 ℃

[0195] (A3-2) Ethylene-1-octene copolymer

[0196] (Product Name) Engage 8200: Dow Elastomer Japan Co., Ltd.

[0197] MFR (190 ℃, 2.16 kg load): 4.9 g / 10 min

[0198] Glass transition temperature (Tg): -54 ℃

[0199] (A3-3) Ethylene-1-octene copolymer

[0200] (Product Name) Engage 8407 : Dow Elastomer Japan Co., Ltd.

[0201] MFR (190 ℃, 2.16 kg load): 34 g / 10 min

[0202] Glass transition temperature (Tg): -53 ℃

[0203] (A4-1) Styrene-ethylene-1-butene-styrene copolymer

[0204] (Product Name) Toughtec H1062 : Asahi Kasei Co., Ltd.

[0205] MFR (190 ℃, 2.16 kg load): 1 g / 10 min

[0206] Glass transition temperature (Tg): -47 ℃

[0207] (A5-1) Ethylene-methyl methacrylate copolymer

[0208] (Product Name) Arclift WH102 : Sumitomo Chemical Co., Ltd.

[0209] MFR (190 ℃, 2.16 kg load): 0.25 g / 10 min

[0210] Glass transition temperature (Tg): -40 ℃

[0211] (A6-1) Polyvinylidene Fluoride

[0212] (Product Name) KF Polymer #1300 : Kureha Co., Ltd.

[0213] MFR (190 ℃, 2.16 kg load): 0.19 g / 10 min

[0214] Glass transition temperature (Tg): -31 ℃

[0215] The physical properties of the raw material components and solid composition were measured according to the method shown below.

[0216] (1) Melt mass flow rate (MFR, unit: g / 10 min)

[0217] Measurements were taken according to the method specified in JIS K6758. Measurements were taken at a temperature of 230 ℃ or 190 ℃ with a load of 2.16 kg.

[0218] (2) Glass transition temperature (Tg, unit: ℃)

[0219] Measurements were taken according to the method specified in JIS K7121. The measurement temperature was -60 ℃ to 250 ℃, and the heating rate was 10 ℃ / min.

[0220] (3) Wide-angle X-ray scattering (WAXS)

[0221] Wide-angle X-ray scattering in the central part of the solid composition was measured under the following conditions.

[0222] < Measurement Conditions >

[0223] Model: Rigaku ultraX18

[0224] X-ray source: CuKα line

[0225] Voltage: 40 kV

[0226] Current: 200 mA

[0227] Detector: X-ray photon counting 2D detector PILATUS

[0228] Measurement method: Transmission method

[0229] <Measurement Method>

[0230] During manufacturing, the solid composition was cut in a direction in which pressure was applied (thickness direction) and in a direction perpendicular to the thickness direction and parallel to the direction in which the resin flowed due to pressure (flow direction) to form a cross-section. X-rays were irradiated at depths equidistant from both surfaces in the thickness direction of the solid composition on the cross-section to measure wide-angle X-ray scattering profiles. Specifically, measurements were taken at a measurement point at 50% in the thickness direction, where the thickness of the solid composition was set to 100%.

[0231] (4) Crystal orientation (Unit: %)

[0232] Based on the obtained wide-angle X-ray scattering (WAXS) profile, an intensity distribution curve for the azimuthal angle of the α-defined (040) plane of polypropylene was obtained, and the full width at half maximum hw040 of the maximum peak was calculated by Equation (1).

[0233] Crystal orientation (%) = {(180 ― hw040) / 180} × 100 … Equation (1)

[0234] (5) Room temperature Charpy impact strength (unit: kJ / m²)

[0235] A test specimen with a width of 10 mm and a length of 80 mm was cut from the solid composition and used for measurement. Measurements were taken at a temperature of 23 ℃ in accordance with JIS K7111-1 (ISO0179-1).

[0236] (6) Low-temperature Charpy impact strength (unit: kJ / m²)

[0237] A test specimen with a width of 10 mm and a length of 80 mm was cut from the solid composition and used for measurement. Measurements were taken at a temperature of -30 ℃ in accordance with JIS K7111-1 (ISO0179-1).

[0238] (7) Bending modulus (Unit: MPa)

[0239] A test specimen with a width of 10 mm and a length of 80 mm was cut from the solid composition and used for measurement. The bending modulus at 23 ℃ was measured according to JIS-K-7171.

[0240] (Example 1)

[0241] (Production of solid raw materials)

[0242] 99 wt% of propylene polymer (PP-1) and 1 wt% of polymer (A1-1) were uniformly mixed in advance, and a composition raw material was obtained by melt-kneading using a 40 mmφ single-screw extruder (VS40-28 type, manufactured by Tanabe Plastics Machinery Co., Ltd., equipped with a full-flight screw) under conditions of cylinder set temperature: 220 ℃ and screw rotation speed: 105 rpm. The composition raw material was molded using a 220 ton injection molding machine (IS220EN, manufactured by Toshiba Machinery Co., Ltd.) under conditions of cylinder set temperature: 220 ℃, injection speed: 31 mm / sec, thickness: 11 mm, length: 150 mm, and width: 150 mm to obtain a solid raw material.

[0243] (Preparation of solid compositions)

[0244] A solid raw material was placed into a hot press molding machine with the press plate temperature set to 160°C, pressed in the thickness direction up to 100°C, flowed in a direction perpendicular to the thickness direction, maintained the pressure for 5 minutes, cooled to 80°C while maintaining the pressure, and then depressurized to obtain a solid composition with a thickness of 4 mm. The physical properties of the obtained solid composition are shown in Table 1.

[0245] (Example 2)

[0246] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A1-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0247] (Example 3)

[0248] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 90 wt% and the polymer (A1-1) was 10 wt%. The properties of the obtained solid composition are shown in Table 1.

[0249] (Example 4)

[0250] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A1-2) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0251] (Example 5)

[0252] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A2-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0253] (Example 6)

[0254] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A3-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0255] (Example 7)

[0256] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A3-2) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0257] (Example 8)

[0258] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A3-3) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0259] (Example 9)

[0260] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A4-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0261] (Example 10)

[0262] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A5-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0263] (Comparative Example 1)

[0264] (Production of solid raw materials)

[0265] 95 wt% of propylene polymer (PP-1) and 5 wt% of polymer (A1-2) were uniformly mixed in advance, and a composition raw material was obtained by melt-kneading using a 40 mmφ single-screw extruder (VS40-28 type, manufactured by Tanabe Plastics Machinery Co., Ltd., equipped with a full-flight screw) under conditions of cylinder set temperature: 220 ℃ and screw rotation speed: 105 rpm. The composition raw material was molded using a 150 ton injection molding machine (J150EV-C5, manufactured by Nippon Steel Co., Ltd.) under conditions of cylinder set temperature: 220 ℃, injection speed: 31 mm / sec, thickness: 20 mm, length: 98 mm, and width: 98 mm to obtain a solid raw material.

[0266] (Preparation of solid compositions)

[0267] The above solid raw material was placed into a heat press molding machine with the press plate temperature set to 160 ℃, pressed in the thickness direction up to 100 t, flowed in a direction perpendicular to the thickness direction, maintained the pressure for 5 minutes, cooled to 80 ℃ while maintaining the pressure, and then depressurized to obtain a solid composition with a thickness of 4 mm. The physical properties of the obtained solid composition are shown in Table 2.

[0268] (Comparative Example 2)

[0269] 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 properties of the obtained solid composition are shown in Table 2.

[0270] (Comparative Example 3)

[0271] 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.

[0272] (Example 11)

[0273] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 99 wt% and the polymer (A6-1) was 1 wt%. The properties of the obtained solid composition are shown in Table 1.

[0274] (Example 12)

[0275] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 95 wt% and the polymer (A6-1) was 5 wt%. The properties of the obtained solid composition are shown in Table 1.

[0276] (Example 13)

[0277] A solid composition was prepared in the same manner as in Example 1, except that the propylene polymer (PP-1) was 98 wt%, the polymer (A1-1) was 1 wt%, and the polymer (A6-1) was 1 wt%. The properties of the obtained solid composition are shown in Table 1.

[0278]

[0279]

[0280] It was confirmed that the solid composition related to the examples exhibits high impact resistance, particularly at low temperatures. Furthermore, the solid composition related to the examples maintains sufficiently high impact resistance and bending modulus at room temperature. Additionally, transmission electron microscope images confirmed that in each example and comparative example, polymer A is dispersed within a continuous layer of propylene-based polymer B. The average circular equivalent diameter of the dispersed phase was generally about 0.2 to 14 μm. Explanation of the symbols

[0281] 10 : Mold 20: Solid raw materials 30: Solid composition

Claims

Claim 1 A solid composition comprising a propylene-based polymer B and a polymer A, satisfying 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 less than 0°C. Requirement (3): The degree of crystal orientation of the solid composition represented by the following formula is 60 to 80%. Degree of crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1) [In formula (1), hw040 is the full width at half maximum (°) of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α definition of the propylene-based polymer B with respect to the azimuthal angle, obtained from the two-dimensional wide-angle X-ray scattering phase of the central part of the solid composition.] Claim 2 A solid composition according to claim 1, wherein, when the total of the propylene-based polymer B and the polymer A is 100 parts by weight, the propylene-based polymer B occupies 50.1 to 99.9 parts by weight and the polymer A occupies 0.1 to 49.9 parts by weight. Claim 3 A solid composition according to claim 1 or 2, wherein the glass transition temperature (Tg) of the polymer A is -30°C or lower. Claim 4 A solid composition according to claim 1 or 2, wherein the polymer A is an ethylene-based copolymer. Claim 5 A solid composition wherein the ethylene-based copolymer is at least one selected from the group consisting of ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene copolymer. Claim 6 A solid composition according to claim 1 or 2, wherein, under conditions of a temperature of 190 ℃ and a load of 2.16 kgf, the melt mass flow rate of polymer A is 0.01 to 35 g / 10 min. Claim 7 A method for manufacturing a solid composition comprising a process of flowing a solid raw material containing a thermoplastic resin and polymer A under pressure at a temperature of the melting point (°C) of the thermoplastic resin + 10°C or lower to obtain a solid composition, wherein 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, and the degree of crystal orientation represented by the following formula in the solid composition is 60 to 80%. Degree of crystal orientation (%) = {(180 ― hw040) / 180} × 100 … (1) [(1) In the formula, hw040 is the full width at half maximum (degrees) of the maximum peak in the distribution curve of scattering intensity at scattering angle 2θ' with respect to azimuth β, obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition, and scattering angle 2θ' is the angle that gives the maximum peak in the range of scattering angle 2θ = 16° to 18°.]

Images