Solid composition and method for producing the same

Abstract

The solid composition of 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°C. Requirement (3): The crystal orientation degree 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-peak 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-based polymer B relative to the azimuth angle obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition].

Description

Technical Field

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

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

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

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 5020524 Summary of the invention

[0007] However, there is a demand for a solid composition mainly comprising a propylene-based polymer to have further improved impact resistance at low temperatures.

[0008] The present invention has been made in view of the above-mentioned 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.

[0009] The solid composition of 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).

[0010] Requirement (1): The propylene-based polymer B forms a continuous phase, and the polymer A forms a dispersed phase.

[0011] Requirement (2): The glass transition temperature (Tg) of the polymer A is lower than 0°C.

[0012] Requirement (3): The degree of crystal orientation of the solid composition represented by the following formula is 60 to 80%.

[0013] Crystal orientation degree (%) = {(180-hw040) / 180}×100…(1)

[0014] [In formula (1), hw040 is the half-peak 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-based polymer B with respect to the azimuth angle obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition]

[0015] 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 account for 50.1 to 99.9 parts by weight, and the polymer A may account for 0.1 to 49.9 parts by weight.

[0016] Furthermore, the glass transition temperature (Tg) of the polymer A may be -30°C or lower.

[0017] The polymer A may be an ethylene-based copolymer.

[0018] In addition, the ethylene-based 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.

[0019] In addition, the melt mass flow rate of the polymer A may be 0.01 to 35 g / 10 min under the conditions of a temperature of 190° C. and a load of 2.16 kgf.

[0020] The method for producing a solid composition of the present invention comprises the step of applying pressure to a solid raw material containing a thermoplastic resin and a polymer A at a temperature below the melting point (°C) of the thermoplastic resin + 10°C to make it flow to obtain a solid composition,

[0021] In the solid composition, the thermoplastic resin forms a continuous phase, and the polymer A forms a dispersed phase.

[0022] The glass transition temperature (Tg) of the polymer A is less than 0°C,

[0023] The solid composition has a crystal orientation degree represented by the following formula of 60 to 80%.

[0024] Crystal orientation degree (%) = {(180-hw040) / 180}×100…(1)

[0025] [In formula (1), hw040 is the half-peak width (degrees) of the maximum peak in the distribution curve of the scattering intensity at a scattering angle 2θ' with respect to the azimuth angle β obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the above-mentioned solid composition, and the scattering angle 2θ' is the angle that gives the maximum peak in the range of the scattering angle 2θ = 16° to 18°]

[0026] According to the present invention, a solid composition having excellent impact resistance at low temperatures and a method for producing the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 (a) and (b) are schematic diagrams for sequentially explaining a method for producing a solid composition according to an embodiment of the present invention, Figure 1 (c) is a side view of the obtained solid composition, Figure 1 (d) is a top view of the obtained solid composition. DETAILED DESCRIPTION

[0028] Several embodiments of the present invention are described in detail below, but the present invention is not limited to the following embodiments.

[0029] The solid composition of the present embodiment is a solid composition containing a propylene-based polymer B and a polymer A, and satisfies the following requirements (1) to (3).

[0030] Requirement (1): The propylene-based polymer B forms a continuous phase, and the polymer A forms a dispersed phase.

[0031] Requirement (2): The glass transition temperature (Tg) of polymer A is lower than 0°C.

[0032] Requirement (3): The degree of crystal orientation of the solid composition determined by the following formula (1) is 60 to 80%.

[0033] Formula (1) ... Crystal orientation degree (%) = {(180-hw040) / 180}×100

[0034] [In formula (1), hw040 is the half-peak width (degrees) of the maximum peak in the azimuthal distribution curve of the scattering intensity of the (040) plane of the propylene polymer B obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition]

[0035] (Propylene polymer B)

[0036] 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 polymer material (a multiphase propylene polymer material). The propylene polymer B can be one of these or a mixture of two or more. It should be noted that in this specification, "structural unit" can be referred to as "monomer unit".

[0037] <(1) Propylene homopolymer>

[0038] The propylene homopolymer is a polymer consisting only of structural units derived from propylene.

[0039] <(2) Propylene random copolymer>

[0040] Propylene random copolymers are:

[0041] (2-1) a random copolymer comprising a structural unit derived from propylene and a structural unit derived from ethylene,

[0042] (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

[0043] (2-3) A random copolymer comprising a structural unit derived from propylene, a structural unit derived from ethylene, and a structural unit derived from an α-olefin having 4 to 10 carbon atoms.

[0044] 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, 1-decene, etc., and 1-butene, 1-hexene, and 1-octene are preferred.

[0045] Examples of the random copolymer (2-2) include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, a propylene-1-octene random copolymer, and a propylene-1-decene random copolymer.

[0046] Examples of the random copolymer (2-3) include propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, propylene-ethylene-1-octene copolymers, and propylene-ethylene-1-decene copolymers.

[0047] The content of the structural unit 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 further preferably 0.1 to 10% by weight. Furthermore, the content of the structural unit 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 further preferably 99.9 to 90% by weight. (The total weight of the random copolymer (2-1) is set to 100% by weight)

[0048] The content of the structural unit derived from an α-olefin having 4 to 10 carbon atoms 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. Furthermore, the content of the structural unit derived from propylene 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. (The total weight of the random copolymer (2-2) is 100% by weight.)

[0049] The total content of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 4 to 10 carbon atoms in the random copolymer (2-3) is preferably 0.1 to 49% by weight, more preferably 0.1 to 40% by weight, and further preferably 0.1 to 30% by weight. Furthermore, the content of the structural unit derived from propylene in the random copolymer (2-3) is preferably 99.9 to 51% by weight, more preferably 99.9 to 60% by weight, and further preferably 99.9 to 70% by weight. (The total weight of the random copolymer (2-3) is 100% by weight.)

[0050] <(3) Propylene multi-stage polymer material>

[0051] The propylene multi-stage polymer material is:

[0052] (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

[0053] (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 the propylene copolymer component (I-2) and the propylene copolymer component (II)).

[0054] Here, the propylene homopolymer component (I-1) and the propylene copolymer component (I-2) are collectively referred to as a polymer component (I).

[0055] The propylene homopolymer component (I-1) is a homopolymer component consisting only of structural units derived from propylene.

[0056] The propylene copolymer component (I-2) 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, and the content of the structural unit derived from the olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms is 0.1 wt% or more and less than 20 wt%, preferably 0.1 to 15 wt%, and more preferably 0.1 to 10 wt%. (The total weight of the propylene copolymer component (I-2) is 100 wt%)

[0057] The content of the structural unit derived from propylene in the propylene copolymer component (I-2) is more than 80% by weight and not more than 99.9% by weight, preferably 85 to 99.9% by weight, more preferably 90 to 99.9% by weight.

[0058] 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, and the content of the structural unit derived from the 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. (The total weight of the propylene copolymer component (II) is 100% by weight)

[0059] The content of the structural unit derived from propylene is 20 to 80% by weight, preferably 40 to 80% by weight, and more preferably 40 to 70% by weight.

[0060] 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, 1-decene and the like, preferably 1-butene, 1-hexene, 1-octene, and more preferably 1-butene.

[0061] Examples of the propylene copolymer component (I-2) include 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, and propylene-ethylene-1-octene copolymer components. Preferred are propylene-ethylene copolymer components, propylene-1-butene copolymer components, and propylene-ethylene-1-butene copolymer components.

[0062] Examples of the propylene copolymer component (II) include propylene-ethylene copolymer components, propylene-ethylene-1-butene copolymer components, propylene-ethylene-1-hexene copolymer components, propylene-ethylene-1-octene copolymer components, propylene-ethylene-1-decene copolymer components, propylene-1-butene copolymer components, propylene-1-hexene copolymer components, propylene-1-octene copolymer components, and propylene-1-decene copolymer components. Preferred are propylene-ethylene copolymer components, propylene-1-butene copolymer components, and propylene-ethylene-1-butene copolymer components. More preferred are propylene-ethylene copolymer components.

[0063] Examples of the propylene multi-stage polymer material (3-1) include (propylene)-(propylene-ethylene) multi-stage polymer material, (propylene)-(propylene-ethylene-1-butene) multi-stage polymer material, (propylene)-(propylene-ethylene-1-hexene) multi-stage polymer material, (propylene)-(propylene-ethylene-1-octene) multi-stage polymer material, (propylene)-(propylene-1-butene) multi-stage polymer material, (propylene)-(propylene-1-hexene) multi-stage polymer material, (propylene)-(propylene-1-octene) multi-stage polymer material, and (propylene)-(propylene-1-decene) multi-stage polymer material.

[0064] Preferred are (propylene)-(propylene-ethylene) multi-stage polymer materials and (propylene)-(propylene-ethylene-1-butene) multi-stage polymer materials, and more preferred are (propylene)-(propylene-ethylene) multi-stage polymer materials.

[0065] Examples of the propylene multi-stage polymer material (3-2) include a (propylene-ethylene)-(propylene-ethylene) multi-stage polymer material, a (propylene-ethylene)-(propylene-ethylene-1-butene) multi-stage polymer material, a (propylene-ethylene)-(propylene-ethylene-1-hexene) multi-stage polymer material, a (propylene-ethylene)-(propylene-ethylene-1-octene) multi-stage polymer material, a (propylene-ethylene)-(propylene-ethylene-1-decene) multi-stage polymer material, a (propylene-ethylene)-(propylene-1-butene) multi-stage polymer material, a (propylene-ethylene)-(propylene-1-hexene) multi-stage polymer material, a (propylene-ethylene)-(propylene-1-octene) multi-stage polymer material, a (propylene-ethylene)-(propylene-1-decene) multi-stage polymer material, a (propylene-1-butene)-(propylene-ethylene) multi-stage polymer material, a (propylene-1-butene)-(propylene-ethylene-1-butene) multi-stage polymer material, and a (propylene-1-butene)-(propylene-ethylene-1-butene) multi-stage polymer material. (Propylene-ethylene-1-hexene) multi-stage polymer material, (propylene-1-butene)-(propylene-ethylene-1-octene) multi-stage polymer material, (propylene-1-butene)-(propylene-ethylene-1-decene) multi-stage polymer material, (propylene-1-butene)-(propylene-1-butene) multi-stage polymer material, (propylene-1-butene)-(propylene-1-hexene) multi-stage polymer material, (propylene-1-butene)-(propylene-1-octene) multi-stage polymer material, ( Propylene-1-butene)-(propylene-1-decene) multi-stage polymer material, (propylene-1-hexene)-(propylene-1-hexene) multi-stage polymer material, (propylene-1-hexene)-(propylene-1-octene) multi-stage polymer material, (propylene-1-hexene)-(propylene-1-decene) multi-stage polymer material, (propylene-1-octene)-(propylene-1-octene) multi-stage polymer material, (propylene-1-octene)-(propylene-1-decene) multi-stage polymer material, and the like.

[0066] Preferred are (propylene-ethylene)-(propylene-ethylene) multi-stage polymer materials, (propylene-ethylene)-(propylene-ethylene-1-butene) multi-stage polymer materials, and (propylene-1-butene)-(propylene-1-butene) multi-stage polymer materials.

[0067] The content of the copolymer component (II) contained in the multi-stage polymer material comprising the polymer component (I) and the copolymer component (II) is preferably 1 to 49 weight %, more preferably 1 to 40 weight %, further preferably 1 to 30 weight %, and further preferably 1 to 20 weight % (wherein the weight of the entire multi-stage polymer material is set to 100 weight %).

[0068] The content of polymer component (I) contained in the multi-stage polymer material comprising polymer component (I) and copolymer component (II) is preferably 51 to 99 weight %, more preferably 60 to 99 weight %, further preferably 70 to 99 weight %, and further preferably 80 to 99 weight % (wherein the weight of the entire multi-stage polymer material is set to 100 weight %).

[0069] (MFR of propylene polymer B)

[0070] The melt mass flow rate (MFR) of the propylene polymer B measured under the 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, further preferably 0.01 to 5 g / 10 min, and may be 0.01 to 2 g / 10 min. If the value of the melt mass flow rate of the propylene polymer B is within the above range, there is a tendency that the impact resistance of the solid composition is excellent.

[0071] In this specification, the melt mass flow rate refers to a value measured in accordance with JIS K6758.

[0072] (Tg of propylene polymer B)

[0073] 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, further preferably -10°C or higher, and further preferably 0°C or higher. The Tg is measured in accordance with JIS K7121.

[0074] The glass transition temperature (PP: Tg) of the propylene polymer B is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0075] (Tm of propylene polymer B)

[0076] The melting point (Tm) of the propylene polymer B may be 100 to 180°C.

[0077] The melting point of the propylene-based polymer B is determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0078] <Method for producing propylene-based polymer B>

[0079] The propylene-based polymer B can be obtained by homopolymerizing propylene using a polymerization catalyst or by copolymerizing propylene and other olefins using a polymerization catalyst.

[0080] <Polymerization Catalyst>

[0081] Examples of the polymerization catalyst include:

[0082] (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 organic aluminum compound and (1-iii) an electron donor component,

[0083] (2) a catalyst system consisting of (2-i) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and (2-ii) an alkylaluminoxane,

[0084] (3) a catalyst system consisting of (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 transition metal compound to form an ionic complex, and (3-iii) an organoaluminum compound,

[0085] (4) A catalyst system in which a catalyst component composed 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 organic aluminum compound is supported on inorganic particles such as silica and clay minerals to modify them.

[0086] Furthermore, a prepolymerized catalyst prepared by prepolymerizing ethylene, propylene or α-olefin in the presence of the above-mentioned catalyst system may also be used.

[0087] Examples of the catalyst system include catalyst systems described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, and JP-A-2004-182981.

[0088] <Polymerization method>

[0089] As the polymerization method, for example, bulk polymerization, solution polymerization, slurry polymerization or gas phase polymerization can be cited. These polymerization methods can be any of batch type or continuous type. Moreover, it can be any of a single-stage type using a single polymerization reaction tank or a multi-stage type in which a plurality of polymerization reaction tanks are connected in series, and these polymerization methods can also be arbitrarily combined. For example, in the case of a propylene multi-stage polymer material, the propylene homopolymer component (I-1) or the propylene copolymer component (I-2) can be polymerized in the front stage, and the propylene copolymer component (II) can be polymerized in the back stage.

[0090] It should be noted that various conditions in the polymerization step (polymerization temperature, polymerization pressure, monomer concentration, catalyst charge amount, polymerization time, etc.) may be appropriately determined depending on the (1) propylene homopolymer, (2) propylene random copolymer, and (3) propylene multi-stage polymer material to be produced.

[0091] In addition, as a method for producing (1) a propylene homopolymer, (2) a propylene random copolymer, or (3) a propylene multistage polymerized material, there can be mentioned a method in which a propylene homopolymer or a copolymer of propylene and other olefins obtained by the above-mentioned polymerization method using the above-mentioned polymerization catalyst is subjected to an extraction operation using 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 multistage polymerized material is recovered as a component insoluble in boiling octane.

[0092] The method for recovering the components insoluble in boiling octane includes, for example, the following method: using a Soxhlet extraction tube, adding a homopolymer of propylene obtained by polymerization or a copolymer of propylene and other olefins to a filter paper for Soxhlet extraction, refluxing with boiling octane for 5 hours, extracting and removing the components soluble in boiling octane from the homopolymer or copolymer, and recovering the components insoluble in boiling octane remaining on the filter paper for Soxhlet extraction.

[0093] The amount of octane used in the extraction operation was 0.1 L based on 20 g of the homopolymer or copolymer obtained by polymerization.

[0094] (Polymer A)

[0095] Polymer A and propylene polymer B are incompatible.

[0096] (Tg of polymer A)

[0097] From the viewpoint of impact resistance, the glass transition temperature (Tg) of polymer A is lower than 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.

[0098] The glass transition temperature (Tg) of the polymer A is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0099] (MFR of polymer A)

[0100] The melt mass flow rate (MFR) of polymer A measured under the conditions of temperature 190°C and load 2.16 kgf may be 0.01 g / 10 min or more, and may be 35 g / 10 min or less. The upper limit of 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. There is a tendency that the smaller the melt mass flow rate of polymer A, the better the impact resistance of the solid composition.

[0101] (Tm of polymer A)

[0102] From the viewpoint of processability, the melting point of the polymer A determined by DSC is preferably lower than 200°C, more preferably lower than 180°C, and still more preferably lower than 150°C.

[0103] The melting point (Tm) of the polymer A determined by DSC is the melting temperature of the crystal phase contained in the polymer A, specifically, the peak top temperature of the endothermic peak on the highest temperature side in the DSC curve obtained when the temperature of the polymer A is increased.

[0104] The melting point is measured under the following conditions: (i) About 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 temperature drop rate of 10°C / min. (ii) Next, the temperature is maintained at 50°C for 1 minute, and then heated from 50°C to 180°C at a temperature rise rate of 10°C / min.

[0105] The polymer A of the present invention is preferably a thermoplastic resin. Examples of thermoplastic resins include olefin polymers, styrene polymers, methacrylic resins, acrylic resins, ester resins, amide resins, vinyl polymers, and fluorine resins. The polymer A may be a single resin or a mixture of two or more resins.

[0106] <Olefin polymers>

[0107] 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 (the total amount of the olefin polymer is 100% by weight). Examples of the 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, and the like, and any plurality of olefins may be included.

[0108] In addition, the olefin polymer may contain a structural unit derived from a monomer other than an olefin having 2 to 10 carbon atoms excluding 3 carbon atoms. Examples of the monomer other than the olefin 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.

[0109] The olefin polymer is preferably a thermoplastic elastomer, and examples thereof include ethylene copolymers, butene copolymers, and octene copolymers.

[0110] <Ethylene copolymer>

[0111] Examples of ethylene copolymers include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-propylene-1-butene copolymers, ethylene-isobutylene copolymers, ethylene-1-pentene copolymers, ethylene-2-methyl-1-butene copolymers, ethylene-3-methyl-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-2-methyl-1-pentene copolymers, ethylene-3-1-pentene copolymers, ethylene-1-octene copolymers, ethylene-1-nonene copolymers, and ethylene-1-decene copolymers. The ethylene copolymers are preferably ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-propylene-1-butene copolymers, and ethylene-1-octene copolymers, more preferably ethylene-propylene copolymers or ethylene-1-butene copolymers and ethylene-1-octene copolymers, and even more preferably ethylene-propylene copolymers and ethylene-1-butene copolymers.

[0112] In addition to the structural units derived from ethylene and olefins other than ethylene, the ethylene copolymer may also have structural units derived from other monomers. Examples of the 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. As the other monomer, 5-ethylidene-2-norbornene, dicyclopentadiene, or styrene is preferred.

[0113] The ethylene copolymer may also be a SEBS (styrene-ethylene-butylene-styrene) block copolymer. In SEBS, when the total amount of the polymer is 100 wt %, the structural units derived from olefins (ethylene and butene) other than propylene are 51 wt % or more, and therefore the structural units derived from styrene are 49 wt % or less.

[0114] The content of the structural unit derived from ethylene in the ethylene-based copolymer is preferably 30% by weight to 95% by weight, more preferably 40% by weight to 80% by weight.

[0115] When the ethylene-based 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 the structural units derived from the other monomers is preferably 1 to 40 parts by weight, more preferably 5 to 25 parts by weight. The total content of the structural units derived from ethylene and the content of the structural units derived from propylene or an α-olefin having 4 to 10 carbon atoms is set to 100 parts by weight.

[0116] The olefin-based polymer may have two or more structural units derived from other monomers.

[0117] <Styrene polymer>

[0118] Styrene polymers are polymers containing 51% by weight 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 polymers may also contain structural units derived from monomers other than styrene or styrene derivatives, such as 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; 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.

[0119] <Methacrylic resin>

[0120] The methacrylic resin is a polymer containing 51% by weight or more of a structural unit derived from methacrylate, and examples thereof include poly(methyl methacrylate), poly(ethyl methacrylate), poly(butyl methacrylate), and poly(2-ethylhexyl methacrylate).

[0121] <Acrylic resin>

[0122] The acrylic resin is a polymer containing 51% by weight or more of a structural unit derived from acrylic acid ester, and examples thereof include poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), and poly(2-ethylhexyl acrylate).

[0123] <Ester resin>

[0124] The ester resin is a polymer containing 51% by weight or more of a structural unit derived from an ester of a polycarboxylic acid and a polyol, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate.

[0125] <Amide resin>

[0126] Amide resins are polymers containing more than 51% by weight of structural units repeating with amide bonds, and examples thereof include poly(ε-caprolactam), polydodecamide, poly(hexamethylene adipamide), poly(hexamethylene dodecamide), poly(p-phenylene terephthalamide), and poly(p-phenylene isophthalamide).

[0127] <Vinyl polymer>

[0128] 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 thereof include polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinylidene chloride, and the like.

[0129] <Fluorine-based resin>

[0130] The fluorine-based resin of the present invention is a polymer containing 51% by weight or more of a structural unit containing a fluorine atom, 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,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.

[0131] As a method for producing the above-mentioned polymer A, a known polymerization method using a known polymerization catalyst can be adopted.

[0132] <Composition of solid composition>

[0133] The solid composition of the present invention contains a propylene-based polymer (B) and a polymer (A).

[0134] As described in the above 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 incompatible, and the solid composition has a sea-island structure in which the polymer A is a continuous phase (sea part) and the propylene polymer B is a dispersed phase (island part). The average circle equivalent diameter of the dispersed phase (island part) can be 10nm to 200μm.

[0135] In the solid composition, when the total of the propylene polymer B and the polymer A is 100 parts by weight, it is preferred that 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. In the solid composition, it is more preferred that the propylene polymer B accounts for 70 to 99.9 parts by weight, and the polymer A accounts for 0.1 to 30 parts by weight, and it is further preferred that the propylene polymer B accounts for 80 to 99.9% by weight, and the polymer A accounts for 0.1 to 20% by weight, and it is further preferred that the propylene polymer B accounts for 90 to 99.9% by weight, and the polymer A accounts for 0.1 to 10% by weight.

[0136] If the amount of polymer A is too large, the low-temperature impact resistance tends to decrease.

[0137] The total amount of the propylene-based polymer B and the polymer A may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more in the entire solid composition.

[0138] <Degree of crystal orientation in the central portion of the solid composition (Requirement 3)>

[0139] As described in requirement (3), the crystal orientation degree of the solid composition is 60 to 80%. The lower limit of the crystal orientation degree may be 62%, 63%, or 65%. In addition, the upper limit of the crystal orientation degree may be 79%, 78%, 77%, 76%, or 75%.

[0140] If the orientation is too high or too low, the low-temperature impact resistance tends to decrease.

[0141] The degree of crystal orientation of a solid composition can be measured as follows. First, a two-dimensional wide-angle X-ray scattering image of the central portion of the solid composition is obtained by a wide-angle X-ray scattering (WAXS) method. Next, based on the scattering image, a distribution curve of the scattering intensity of the (040) plane of the α crystal of the propylene-based polymer B relative to the azimuth angle β is obtained. When obtaining the distribution curve of the scattering intensity relative to the azimuth angle β, the width of the circular integral of the scattering angle 2θ is in the range of ±0.5° from the scattering peak position from the (040) plane. Next, the half-width hw040 (in degrees) of the maximum peak in the distribution curve of the scattering intensity relative to the azimuth angle β is obtained. Then, the half-width hw040 is substituted into formula (1).

[0142] Crystal orientation degree (%) = {(180-hw040) / 180}×100…(1)

[0143] The α crystal of the propylene-based polymer B refers to an orthorhombic crystal containing chains (molecular chains) of structures derived from propylene. In a two-dimensional wide-angle X-ray scattering image, the peak of the (040) plane of the α crystal usually exists in the range of a scattering angle 2θ=16 to 18°.

[0144] The central part of the solid composition refers to the part of the solid composition other than the surface part, and is any place in the range of 5% to 95% in the thickness direction when the distance from one surface to the other surface of the solid composition (for example, 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 them, the place of 20% to 80% is preferred.

[0145] In order to obtain the XRD of the central portion, it is sufficient to obtain a cross section of the solid composition and then irradiate the central portion of the cross section with X-rays.

[0146] The two-dimensional wide-angle X-ray scattering image is obtained by irradiating the sample with X-rays from one direction. If the irradiation direction of the X-rays is parallel to the orientation direction of the propylene polymer B, no scattering peak can be obtained. Therefore, X-rays are irradiated in a direction that intersects (preferably orthogonal) with the orientation direction of the propylene polymer B, that is, in a direction that intersects (preferably orthogonal) with the direction in which the polymer flows during extrusion during the manufacturing process. In the case where the orientation direction of the propylene polymer B in the sample is unknown, it is sufficient to irradiate X-rays from various directions to obtain multiple scattering images, obtain a distribution curve of the scattering intensity from the (040) plane relative to the azimuth angle based on each scattering image, and calculate hw040 based on the distribution curve with the highest maximum peak.

[0147] For example, when the direction of extrusion during manufacturing (thickness direction) is known, it is preferred to obtain X-ray scattering images for three directions: a first direction orthogonal to the thickness direction, a second direction orthogonal to the thickness direction and to the first direction, and a third direction orthogonal to the thickness direction and at an angle of 45 degrees to the first direction, and calculate hw040 based on a distribution curve with the highest maximum peak of the scattering intensity from the (040) plane.

[0148] The solid composition may also contain additives as required. Examples of additives include stabilizers, antibacterial agents, mildewproofing 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 passivators, ultraviolet absorbers, light stabilizers, and copper corrosion inhibitors. As lightfast agents, hindered amine lightfast agents can be cited, as colorants, for example, titanium oxide, carbon black and organic pigments can be cited, as metal powders, ferrites can be cited, as inorganic fibers, glass fibers and metal fibers can be cited, as organic fibers, carbon fibers and aramid fibers can be cited, as inorganic whiskers, potassium titanate whiskers can be cited, and as fillers, glass beads, glass microspheres, glass fragments, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, hard rubber powder, cotton wool, cork powder, barium sulfate, fluororesin, cellulose powder, wood powder can be cited. The additives may contain only one kind or two or more kinds. The additives may be contained in the propylene polymer B, i.e., the continuous phase, or in the dispersed phase of the polymer A, or may form a dispersed phase different from the polymer A.

[0149] The solid composition may contain a component with low wettability from the viewpoint of improving antifouling properties, low icing properties and skiing properties. These components with low wettability may form a dispersed phase different from the polymer A in the continuous phase of the propylene polymer B.

[0150] (Mechanism of Action)

[0151] Such a solid composition has improved impact resistance at low temperatures and can also have sufficient values ​​of impact resistance and flexural modulus at room temperature.

[0152] (Method for producing solid composition)

[0153] The method for producing a solid composition according to the present embodiment includes a step of applying pressure to a solid raw material including a thermoplastic resin and a polymer A at a predetermined temperature to cause the solid raw material to flow, thereby obtaining a solid composition.

[0154] Furthermore, in the solid composition, the thermoplastic resin forms a continuous phase, and the polymer A forms a dispersed phase.

[0155] The glass transition temperature (Tg) of polymer A is less than 0°C,

[0156] The above-mentioned crystal orientation degree of the solid composition is 60 to 80%.

[0157] The thermoplastic resin may be the above-mentioned propylene polymer B, or may be a thermoplastic resin other than the propylene polymer B. Examples of thermoplastic resins other than the propylene polymer B include ethylene polymers, butene polymers, amide polymers, methacrylic polymers, acrylic polymers, and styrene polymers.

[0158] In the case where the thermoplastic resin does not contain the propylene polymer B, in the calculation of the above-mentioned crystal orientation degree, instead of the distribution curve of the scattering intensity of the (040) plane of the α crystal of the propylene polymer B with respect to the azimuth angle β, the distribution curve of the scattering intensity with respect to the azimuth angle β at the scattering angle 2θ' of the maximum peak observed in the range of the scattering angle 2θ=16 to 18° in the two-dimensional wide-angle X-ray scattering image can be used to calculate the half-peak width (degrees) of the maximum peak. When there are multiple maximum peaks of the same height at different scattering angles 2θ' within the above-mentioned range of the scattering angle 2θ=16 to 18°, the distribution curve is obtained by using the peak with the larger value of the scattering angle 2θ'. The width of the circular integral when calculating the distribution curve of the scattering intensity at the scattering angle 2θ' with respect to the azimuth angle β is in the range of ±0.5° from 2θ'.

[0159] The solid raw material includes a thermoplastic resin such as the above-mentioned propylene polymer B and the above-mentioned polymer A. The solid raw material may be a molded product of a mixture obtained by melt-kneading a thermoplastic resin such as a propylene polymer B and a polymer A by a known method to prepare a composite raw material, and molding the above-mentioned composite raw material by a known method, or may be a laminated material obtained by molding a thermoplastic resin such as a propylene polymer B and a polymer A into a film or the like by a known method, and laminating the molded product of the thermoplastic resin and the molded product of the polymer A. It should be noted that in the case of the laminated material, the molded product of the thermoplastic resin and the molded product of the polymer A may be melt-bonded or may not be melt-bonded.

[0160] The solid raw material is preferably a mixture of a thermoplastic resin and a polymer A. It is preferred that the thermoplastic resin such as the propylene polymer B forms a continuous phase and the polymer A forms a dispersed phase.

[0161] From the viewpoint of processability and impact resistance, the specified temperature is the melting point (°C) of the thermoplastic resin such as the propylene polymer B + 10°C or less, preferably the melting point of the thermoplastic resin + 5°C or less, further preferably a temperature below the melting point of the thermoplastic resin, and further preferably a temperature below the melting point of the thermoplastic resin -5°C or less.

[0162] By applying pressure to the solid raw material at such a temperature to make it flow, the molecules of the polymer are oriented in the direction of flow. Therefore, the orientation of the molecules in the crystal of the propylene-based polymer B can be sufficiently improved.

[0163] Specifically, for example, Figure 1 As shown in (a), a pair of plate-shaped molds 10 are used to uniaxially pressurize the solid raw material 20 in the direction of the thick arrow, thereby Figure 1 As shown in (b), the polymer of the solid raw material flows in a direction intersecting the pressurization direction (the direction of the thin arrow). As the flow progresses, the thickness decreases, while the length (width) in the direction intersecting the thickness increases. Figure 1 (c) side view and Figure 1 As shown in the top view of (d), in the obtained solid composition 30, the polymer molecules of the continuous phase are oriented along the flow direction as indicated by the arrows.

[0164] Furthermore, by rolling the sheet-shaped solid raw material between a pair of rolls, the polymer in the solid raw material can also be caused to flow in a direction intersecting with the pressing direction of the sheet.

[0165] The mold and the roller are preferably kept at the above-mentioned predetermined temperature, but the solid raw material may be kept at a predetermined temperature separately from them by using an infrared heater or the like before being pressurized and flowed.

[0166] The shape of the solid raw material is not limited, and may be a sheet, a disk, or the like.

[0167] Lubricants may be applied to the portions of the mold and roller that are in contact with the solid raw material. Examples of lubricants include silicone oils. Applying lubricants can reduce the frictional resistance between the solid raw material and the mold / roller, and can make the solid raw material flow more smoothly based on pressure, thereby improving the molding cycle and reducing the load on the heating and compressing device.

[0168] The solid composition obtained by the above-mentioned production method can be further molded into a desired shape by a known method such as vacuum molding, pressure molding, press molding, etc.

[0169] The solid composition of the present invention can be bonded to other resins, metals, paper, or leather to form a multilayer structure for use.

[0170] The surface of the solid composition of the present invention may be subjected to a surface treatment. Examples of the surface treatment method include embossing treatment, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.

[0171] As the use of the solid composition of the present invention, outdoor equipment components, furniture and interior decoration components, household appliance components, toy components, gardening components, automobile components, and packaging materials can be cited. As outdoor equipment components, for example, carport components, fence components, door components, doorpost components, column components, bicycle shed components, deck components, sunroom components, roof components, balcony components, railing components, blackout curtain components, awning components, etc. can be cited; as furniture and interior decoration components, for example, sofa components, table components, chair components, bed components, wardrobe components, cabinet components, dressing table components, etc. can be cited; as household appliance components, for example, clock components, mobile phone components, white appliance components, etc. can be cited; as toy components, for example, plastic model components, three-dimensional model components, video game main body components, etc. can be cited; as gardening components, for example, flower stand components, vase components, flower pot components, etc. can be cited; as automobile components, for example, bumper materials, instrument panel materials, etc. can be cited; as packaging materials, for example, food packaging materials, fiber packaging materials, and sundries packaging materials can be cited. Furthermore, as other uses, for example, there can be mentioned monitor parts, office automation (OA) machine parts, medical parts, drain pans, toiletry parts, bottles, containers, snow removal parts, various building parts, and the like.

[0172] Example

[0173] The present invention will be described below using examples and comparative examples. The propylene polymer B and polymer A used in the examples and comparative examples are shown below.

[0174] (1) Propylene polymer B

[0175] The following propylene homopolymer was obtained by a gas phase polymerization method using the catalyst described in Japanese Patent Application Laid-Open No. 10-2123219 and by controlling the hydrogen concentration and polymerization temperature in the polymerization reactor.

[0176] (PP-1) Propylene homopolymer

[0177] MFR (230°C, 2.16kg load): 0.5g / 10min

[0178] Glass transition temperature (PP: Tg): 0℃

[0179] Melting point (Tm): 163°C

[0180] (2) Polymer A

[0181] (A1-1) Ethylene-propylene copolymer (trade name) TAFMER P0775: Mitsui Chemicals, Inc.

[0182] MFR (190°C, 2.16kg load): 0.5g / 10min

[0183] Glass transition temperature (Tg): -48°C

[0184] (A1-2) Ethylene-propylene copolymer (trade name) TAFMER P0275: Mitsui Chemicals, Inc.

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

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

[0187] (A2-1) Ethylene-1-butene copolymer (trade name) TAFMER A0250: Mitsui Chemicals, Inc.

[0188] MFR (190°C, 2.16kg load): 0.2g / 10min

[0189] Glass transition temperature (Tg): -57°C

[0190] (A3-1) Ethylene-1-octene copolymer (trade name) ENGAGE Engage 8100: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 0.5 g / 10 min

[0191] Glass transition temperature (Tg): -52°C

[0192] (A3-2) Ethylene-1-octene copolymer (trade name) ENGAGE Engage 8200: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 4.9 g / 10 min

[0193] Glass transition temperature (Tg): -54°C

[0194] (A3-3) Ethylene-1-octene copolymer (trade name) ENGAGE Engage 8407: Dow Elastomers Japan Co., Ltd. MFR (190°C, 2.16 kg load): 34 g / 10 min

[0195] Glass transition temperature (Tg): -53°C

[0196] (A4-1) Styrene-ethylene-1-butene-styrene copolymer

[0197] (Trade name) Tuftec H1062: Asahi Kasei Co., Ltd.

[0198] MFR (190°C, 2.16kg load): 1g / 10min

[0199] Glass transition temperature (Tg): -47°C

[0200] (A5-1) Ethylene-methyl methacrylate copolymer

[0201] (Trade name) Acryft WH102: Sumitomo Chemical Co., Ltd.

[0202] MFR (190°C, 2.16kg load): 0.25g / 10min

[0203] Glass transition temperature (Tg): -40°C

[0204] (A6-1) Polyvinylidene fluoride

[0205] (Trade name) KF polymer #1300: KUREHA Co., Ltd.

[0206] MFR (190°C, 2.16kg load): 0.19g / 10min

[0207] Glass transition temperature (Tg): -31°C

[0208] The physical properties of the raw material components and the solid composition were measured according to the methods shown below.

[0209] (1) Melt flow rate (MFR, unit: g / 10 minutes)

[0210] The measurement was carried out according to the method specified in JIS K6758. The measurement was carried out at a measurement temperature of 230°C or 190°C and a load of 2.16 kg.

[0211] (2) Glass transition temperature (Tg, unit: °C)

[0212] The measurement was performed according to the method specified in JIS K7121. The measurement temperature was -60°C to 250°C and the temperature increase rate was 10°C / min.

[0213] (3) Wide-angle X-ray scattering (WAXS)

[0214] The wide-angle X-ray scattering of the central portion of the solid composition was measured under the following conditions.

[0215] <Measurement conditions>

[0216] Machine model: Rigaku ultraX18

[0217] X-ray source: CuKα rays

[0218] Voltage: 40kV

[0219] Current: 200mA

[0220] Detector: X-ray photon counting type two-dimensional detector PILATUS

[0221] Determination method: transmission method

[0222] <Measurement method>

[0223] The solid composition is cut parallel to the direction in which pressure is applied to the solid composition during manufacture (thickness direction) and the direction in which the resin flows under pressure (flow direction) which is orthogonal to the thickness direction to form a cut surface. The wide-angle X-ray scattering curve is measured by irradiating X-rays at depth positions equidistant from the two surfaces in the thickness direction of the solid composition of the cut surface. That is, when the thickness of the solid composition is set to 100%, the measurement is performed at a measurement position of 50% in the thickness direction.

[0224] (4) Crystal orientation degree (unit: %)

[0225] Based on the obtained wide-angle X-ray scattering (WAXS) curve, the intensity distribution curve of the (040) plane of the α crystal of polypropylene with respect to the azimuth angle was obtained, and the half-value width hw040 of the maximum peak was obtained and calculated using formula (1).

[0226] Crystal orientation degree (%) = {(180-hw040) / 180}×100…Formula (1)

[0227] (5) Room temperature Charpy impact strength (unit: kJ / m 2 )

[0228] A test piece having a size of 10 mm in width and 80 mm in length was cut out from the solid composition and used for measurement. The measurement was performed at a temperature of 23° C. in accordance with JIS K7111-1 (ISO 0179-1).

[0229] (6) Low temperature Charpy impact strength (unit: kJ / m 2 )

[0230] A test piece having a size of 10 mm in width and 80 mm in length was cut out from the solid composition and used for measurement. The measurement was performed at a temperature of -30°C in accordance with JIS K7111-1 (ISO 0179-1).

[0231] (7) Flexural modulus (unit: MPa)

[0232] A test piece having a size of 10 mm in width and 80 mm in length was cut out from the solid composition and used for measurement. The measurement conditions were in accordance with JIS-K-7171, and the flexural modulus at 23° C. was measured.

[0233] (Example 1)

[0234] (Preparation of solid raw materials)

[0235] 99 wt% of the propylene polymer (PP-1) and 1 wt% of the polymer (A1-1) were uniformly mixed in advance and then used. The raw material of the composition was obtained by melt kneading in a single-screw extruder (VS40-28, manufactured by TANABE PLASTICS Machinery Co., Ltd., with a full-length screw) at a barrel setting temperature of 220° C. and a screw speed of 105 rpm. The raw material of the composition was molded using a 220-ton injection molding machine (IS220EN, manufactured by Toshiba Machine Co., Ltd.) at a barrel setting 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.

[0236] (Preparation of Solid Composition)

[0237] The solid raw material was placed in a hot press molding machine with a platen temperature of 160°C, and the pressure was applied to 100t in the thickness direction to make it flow in a direction perpendicular to the thickness direction. The pressure was maintained for 5 minutes, and the pressure was released after cooling to 80°C while maintaining the pressure to obtain a solid composition with a thickness of 4 mm. The physical properties of the obtained solid composition are shown in Table 1.

[0238] (Example 2)

[0239] 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 physical properties of the obtained solid composition are shown in Table 1.

[0240] (Example 3)

[0241] 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 physical properties of the obtained solid composition are shown in Table 1.

[0242] (Example 4)

[0243] 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 physical properties of the obtained solid composition are shown in Table 1.

[0244] (Example 5)

[0245] 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 physical properties of the obtained solid composition are shown in Table 1.

[0246] (Example 6)

[0247] 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 physical properties of the obtained solid composition are shown in Table 1.

[0248] (Example 7)

[0249] 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 physical properties of the obtained solid composition are shown in Table 1.

[0250] (Example 8)

[0251] 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 physical properties of the obtained solid composition are shown in Table 1.

[0252] (Example 9)

[0253] 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 physical properties of the obtained solid composition are shown in Table 1.

[0254] (Example 10)

[0255] 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 physical properties of the obtained solid composition are shown in Table 1.

[0256] (Comparative Example 1)

[0257] (Preparation of solid raw materials)

[0258] 95 wt% of the propylene polymer (PP-1) and 5 wt% of the polymer (A1-2) were uniformly mixed in advance and then mixed with The single-screw extruder (VS40-28, manufactured by TANABE PLASTICS Machinery Co., Ltd., with a full-length screw) was melt-kneaded under the conditions of a barrel setting temperature of 220° C. and a screw speed of 105 rpm to obtain a composition raw material. A 150-ton injection molding machine (J150EV-C5, manufactured by Nippon Steel Works, Ltd.) was used to mold the composition raw material under the conditions of a barrel setting 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.

[0259] (Preparation of Solid Composition)

[0260] The solid raw material was placed in a hot press molding machine with a platen temperature of 160°C, and pressure was applied to 100t in the thickness direction to make it flow in a direction perpendicular to the thickness direction, and the pressure was maintained for 5 minutes. After cooling to 80°C while maintaining the pressure, 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 2.

[0261] (Comparative Example 2)

[0262] 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. Table 2 shows the properties of the obtained solid composition.

[0263] (Comparative Example 3)

[0264] A solid composition was prepared by the same method as in Example 4 except that the thickness of the solid raw material was 4.8 mm. Table 2 shows the physical properties of the obtained solid composition.

[0265] (Example 11)

[0266] 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 physical properties of the obtained solid composition are shown in Table 1.

[0267] (Example 12)

[0268] 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 physical properties of the obtained solid composition are shown in Table 1.

[0269] (Example 13)

[0270] 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 physical properties of the obtained solid composition are shown in Table 1.

[0271] [Table 1]

[0272]

[0273] [Table 2]

[0274]

[0275] It was confirmed that the solid composition of the embodiment had high impact resistance, especially at low temperatures. In addition, the solid composition of the embodiment also maintained sufficiently high impact resistance and bending modulus at room temperature. In addition, according to the transmission electron microscope photograph, it was confirmed that the polymer A in each embodiment and comparative example was dispersed in the continuous layer of the propylene polymer B. The average equivalent circle diameter of the dispersed phase was approximately 0.2 to 14 μm.

[0276] Explanation of symbols

[0277] 10…mold, 20…solid raw material, 30…solid composition.

Claims

1. A solid composition comprising a propylene polymer B and a polymer A, Satisfy the following requirements (1) to (3), Requirement (1): The propylene polymer B forms a continuous phase, and the polymer A forms a dispersed phase; when the total of the propylene polymer B and the polymer A is 100 parts by weight, the propylene polymer B accounts for 90 to 99.9 parts by weight, and the polymer A accounts for 0.1 to 10 parts by weight; and the polymer A 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; 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%, Crystal orientation degree (%) = {(180-hw040) / 180}×100…(1) In formula (1), hw040 is the half-width of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α crystal of the propylene-based polymer B relative to the azimuth angle obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition, and the unit of the half-width is degree.

2. The solid composition according to claim 1, wherein The glass transition temperature (Tg) of the polymer A is -30°C or lower.

3. The solid composition according to claim 1 or 2, wherein The melt mass flow rate of the polymer A is 0.01 to 35 g / 10 min under the conditions of a temperature of 190° C. and a load of 2.16 kgf.

4. A method for producing a solid composition, comprising the step of applying pressure to a solid raw material comprising a thermoplastic resin and a polymer A at a temperature below the melting point (°C) of the thermoplastic resin + 10°C to make it flow to obtain a solid composition, In the solid composition, the thermoplastic resin forms a continuous phase, the polymer A forms a dispersed phase, the thermoplastic resin is a propylene polymer B, when the total of the propylene polymer B and the polymer A is 100 parts by weight, the propylene polymer B accounts for 90 to 99.9 parts by weight, the polymer A accounts for 0.1 to 10 parts by weight, and the polymer A is at least one selected from ethylene-propylene copolymers, ethylene-1-butene copolymers and ethylene-1-octene copolymers. The glass transition temperature (Tg) of the polymer A is less than 0°C, The solid composition has a crystal orientation degree represented by the following formula of 60 to 80%, Crystal orientation degree (%) = {(180-hw040) / 180}×100…(1) In formula (1), hw040 is the half-width of the maximum peak in the distribution curve of the scattering intensity of the (040) plane of the α crystal of the propylene-based polymer B relative to the azimuth angle obtained from the two-dimensional wide-angle X-ray scattering image of the central part of the solid composition, and the unit of the half-width is degree.

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