Olefin resin composition and use thereof

Abstract

An olefin-based resin composition comprising: 9.7-36 parts by mass of an unmodified olefin-based polymer (A); 0.3-15 parts by mass of an acid-modified propylene polymer (B); 54-90 parts by mass of metal oxide (C) (provided that the total amount of the unmodified olefin polymer (A), the acid-modified propylene polymer (B), and the metal oxide (C) is 100 parts by mass) ; and 0.1-10 parts by mass of an unmodified polyolefin wax (D) per 100 parts by mass of the total of the unmodified olefin polymer (A), the acid-modified propylene polymer (B), and the metal oxide (C).

Description

TECHNICAL FIELD

[0001] The present application relates to an olefin resin composition containing a metal oxide and use thereof. BACKGROUND

[0002] Olefin polymers are molded using various methods and are put to a wide variety of uses. On the other hand, polyolefins such as polypropylene have poor mechanical properties such as heat resistance, rigidity, tensile strength, etc. compared to engineering plastics such as polyamides, polycarbonates, etc., and thus, inorganic fillers such as talc, heat-resistant fibers such as glass fibers, carbon fibers, etc. are added as reinforcing materials depending on the use.

[0003] For example, in Patent Literature 1, a polyolefin composition containing a large amount of 20 to 80 parts by weight of an inorganic filler formed of an inorganic compound is proposed, and it is taught that the moldability can be improved and the effect of preventing sheet sagging can be obtained by adding a silane-modified polyolefin.

[0004] On the other hand, it has been found that when a large amount of an inorganic compound such as a metal oxide is added, the mixing properties with a polyolefin are poor, and in order to improve the mixing properties, for example, in Patent Literature 2, a proposal is made to add 0.1 to 20 parts by mass of a modified polyolefin wax in a composition containing 10 to 50 parts by mass of a thermoplastic resin and 50 to 90 parts by mass of a metal oxide.

[0005] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: Japanese Patent Application Laid-Open No. 52-15542 Patent Literature 2: International Publication No. 2017 / 209215 Patent Literature 3: International Publication No. 2023 / 282327 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION However, it has been found that, in the case of an olefin resin composition obtained by adding a modified polyolefin wax, there is a tendency for the hydroxyl density of the surface of the molded body obtained to become relatively high and for the hydrophilicity to increase, becoming a moist feel, and in addition, there are cases in which the inorganic compound is eluted under certain conditions (acid solution, etc.) and the feel is degraded.

[0007] In such a case, the present applicant has found that a resin composition containing a thermoplastic resin such as a polyolefin and a metal oxide and an unmodified polyolefin wax is excellent in non-water absorption and hard feel, and has proposed a proposal thereof (see Patent Literature 3). However, further improvement in strength is desired in applications to a variety of uses.

[0008] An object of the present application is to provide an olefin resin composition suitable for obtaining a molded body which does not cause an increase in hydrophilicity (low water absorption), has a hard feel, has a texture closer to that of a ceramic and has a high-class feel, and which is excellent in strength, and a molded body containing the same.

[0009] Means for solving the problem The present application relates to matters such as the following items [1] to

[15] .

[0010] [1] An olefin resin composition comprising: 9.7 to 36 parts by mass of an unmodified olefin polymer (A); 0.3 to 15 parts by mass of an acid-modified propylene polymer (B); 54 to 90 parts by mass of a metal oxide (C) (wherein the total amount of the unmodified olefin polymer (A), the acid-modified propylene polymer (B) and the metal oxide (C) is 100 parts by mass); and an unmodified polyolefin wax (D) in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the aforementioned unmodified olefin polymer (A), the aforementioned acid-modified propylene polymer (B) and the aforementioned metal oxide (C).

[0011] [2] The olefin resin composition according to [1], wherein the aforementioned unmodified olefin polymer (A) is one or more selected from the group consisting of an ethylene polymer, a propylene polymer, a 1-butene polymer and a 4-methyl-1-pentene polymer.

[0012] [3] The olefin resin composition according to [1] or [2], wherein the aforementioned metal oxide (C) comprises magnesium oxide.

[0013] [4] The olefin resin composition according to any one of [1] to [3], wherein the thermal conductivity of the aforementioned metal oxide (C) is in the range of 10 to 300 W / mK.

[0014] [5] The olefin resin composition according to any one of [1] to [4], wherein the thermal conductivity of the aforementioned olefin resin composition is in the range of 0.5 to 5 W / mK.

[0015] [6] The olefin resin composition according to any one of [1] to [5], wherein the specific gravity of the aforementioned olefin resin composition is in the range of 1.2 to 5.0.

[0016] 〔7〕 The olefin resin composition according to any one of <1> to <6>, wherein the unsaturated carboxylic acid content in the aforementioned olefin resin composition is in the range of 0.002 to 0.42 parts by mass relative to 100 parts by mass of the total of the aforementioned unmodified olefin polymer (A), the aforementioned acid-modified propylene polymer (B), the aforementioned metal oxide (C), and the aforementioned unmodified polyolefin wax (D).

[0017] 〔8〕 A molded body comprising the olefin resin composition according to any one of <1> to <7>.

[0018] 〔9〕 A door handle, a door knob, a handrail, or a switch comprising the olefin resin composition according to any one of <1> to <7>.

[0019] 〔10〕 A housing comprising the olefin resin composition according to any one of <1> to <7>.

[0020] 〔11〕 An electrical storage device comprising the olefin resin composition according to any one of <1> to <7>.

[0021] 〔12〕 An accessory for clothing comprising the olefin resin composition according to any one of <1> to <7>.

[0022] 〔13〕 Stationery comprising the olefin resin composition according to any one of <1> to <7>.

[0023] 〔14〕 A container, tableware, or wine ware comprising the olefin resin composition according to any one of <1> to <7>.

[0024] 〔15〕 A mouse or a keyboard comprising the olefin resin composition according to any one of <1> to <7>.

[0025] Effects of the Invention The olefin-based resin composition of the present application has an extremely low water absorption and excellent non-water absorption, has a thermal conductivity equivalent to that of pottery, and is thus suitable for obtaining a molded body having a cool touch and a texture close to that of pottery, and having a high-grade feel, and excellent in surface hardness, tensile strength, impact strength, bending strength, and the like. The molded body of the present application can be suitably used for various applications such as door handles, spherical door pulls, handrails or switches, housings of household electric appliances, power storage devices, accessories for clothing, containers, stationery, tableware, wine sets, mice or keyboards, and the like, has an extremely low water absorption and excellent non-water absorption, has a cool touch and a texture close to that of pottery, and can be suitably used for applications in which the molded body is touched by hand. DETAILED DESCRIPTION

[0026] Hereinafter, the present application will be specifically described.

[0027] In the present specification, the case where described as "polymer" includes homopolymers and copolymers unless otherwise specified.

[0028] [Olefin-based resin composition] The olefin-based resin composition of the present application contains an unmodified olefin-based polymer (A), an acid-modified propylene-based polymer (B), a metal oxide (C), and an unmodified polyolefin-based wax (D) as essential components.

[0029] [Unmodified olefin-based polymer (A)] The unmodified olefin-based polymer (A) constituting the olefin-based resin composition of the present application (hereinafter, also simply referred to as "olefin-based polymer (A)") is an olefin-based polymer which has not been subjected to acid modification or graft modification, and is a homopolymer of an α-olefin (including ethylene) such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, a copolymer of an α-olefin and another α-olefin, and a copolymer of an α-olefin and a monomer other than an α-olefin, and is a polymer in which an α-olefin is a main component.

[0030] The monomer constituting the olefin-based polymer (A) (for example, an α-olefin such as propylene) can use any of a monomer from fossil fuels, a monomer from biomass, and a monomer from chemical recycling.

[0031] In addition, as the raw material monomer of the olefin-based polymer (A), a raw material from fossil fuels and a raw material from biomass can be used in combination, a raw material from fossil fuels and a raw material from chemical recycling can be used in combination, a raw material from biomass and a raw material from chemical recycling can be used in combination, a raw material from fossil fuels, a raw material from biomass, and a raw material from chemical recycling can be used in combination.

[0032] As an olefin polymer (A) involved in this invention, examples of the following polymers (A1) to (A4) are specifically cited.

[0033] <Ethylene polymers (A1)> Ethylene-based polymers (A1) are homopolymers of ethylene, copolymers of ethylene and α-olefins with 3 to 20 carbon atoms. Examples commonly include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene-α-olefin copolymers, polymers whose main component is structural units derived from ethylene (containing ethylene at 51 to 100 mol%). Specific examples of α-olefins with 3 to 20 carbon atoms copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, and 3,5,5-trimethyl-1-hexene. Preferably, the α-olefin has 3 to 10 carbon atoms, more preferably α-olefin has 3 to 8 carbon atoms, and even more preferably ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The molar ratio of ethylene to α-olefin (ethylene / α-olefin) is preferably 99 / 1 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 60 / 25.

[0034] Preferred examples of ethylene-α-olefin copolymers include ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-octene copolymers, ethylene-propylene-1-butene copolymers, and ethylene-propylene-1-octene copolymers. Among these, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-1-octene copolymers are preferred, and ethylene-1-butene copolymers are more preferred.

[0035] The density of the ethylene-based polymer (A1) (determined according to JIS K7112) is preferably 850~980 kg / m³. 3 More preferably, it is 855~978 kg / m 3 Further preferred is 860~976 kg / m 3 The preferred strength is 862~973 kg / m³. 3 .

[0036] When the olefin-based resin composition of the present invention contains an ethylene-based polymer (A1), the molded articles obtained from the olefin-based resin composition tend to have higher thermal conductivity and better temperature sensitivity compared to the case containing a propylene-based polymer (A2), which will be described later. Furthermore, they produce a higher sound when struck. Such molded articles can be suitably used in a variety of applications without limitation, for example, they can be suitably used as a base raw material for surface modification in metal vapor deposition.

[0037] <Propylene polymers (A2)> Propylene polymers (A2) are polymers whose main component is a structural unit derived from propylene (containing propylene: 51 to 100 mol%), such as homopolymers of propylene (propylene homopolymer: homopolymer PP), copolymers of propylene with ethylene and / or α-olefins having 4 to 20 carbon atoms (random copolymer: random copolymer: random copolymer PP), and compositions of homopolymers of propylene with ethylene-propylene copolymers (block copolymer: block copolymer PP). Specific examples of α-olefins in propylene-α-olefin copolymers include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-hexene, and 3,5,5-trimethyl-1-hexene. Preferably, ethylene and α-olefins having 4 to 10 carbon atoms are used; more preferably, ethylene and α-olefins having 4 to 8 carbon atoms are used; even more preferably, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are used; and particularly preferably, ethylene is used. The molar ratio of propylene to α-olefins (propylene / α-olefin) is preferably 99 / 1 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 70 / 30.

[0038] Preferred examples of propylene-α-olefin copolymers (random PP) include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1-octene copolymers, and propylene-ethylene-1-butene copolymers. Among these, propylene-ethylene copolymers and propylene-1-butene copolymers are preferred, and propylene-ethylene copolymers are particularly preferred.

[0039] In the case of a propylene homopolymer, the preferred melting point is 155~170℃, and more preferably 158~165℃.

[0040] In the case of a propylene-ethylene random copolymer, the ethylene content of the propylene-ethylene random copolymer is preferably 1.9 to 5.4% by mass, more preferably 2.0 to 4.8% by mass. In addition, the crystal melting point of the propylene-ethylene random copolymer, as determined by differential scanning calorimetry (DSC) according to JIS K7121, is generally preferably 130 to 150°C, more preferably 130 to 145°C, and particularly preferably 135 to 145°C.

[0041] The density of the propylene polymer (A2) (determined according to JIS K7112) is preferably 850~910 kg / m³. 3 More preferably, it is 875~909 kg / m 3 Further preferred is 890~908 kg / m 3 .

[0042] As a propylene-based polymer (A2), one of propylene-ethylene block copolymers and propylene-ethylene random copolymers can be used alone, or two or more copolymers can be used in combination. For example, two or more copolymers can be mixed to adjust the MFR.

[0043] When the olefin-based resin composition of the present invention contains a propylene polymer (A2) as the olefin polymer (A), the molded articles obtained from the olefin-based resin composition of the present invention can be used in various applications without limitation. Since it has a thermal conductivity similar to that of pottery and a specific gravity similar to that of pottery, and on the other hand, it will not break like pottery due to impacts such as falling, it has excellent safety. Therefore, it can be suitable for applications such as tableware such as cups, containers, door handles, etc., which are touched by hand.

[0044] <1-Butene polymers (A3)> 1-Butene polymers (A3) are homopolymers of 1-butene (polybutene) and copolymers of 1-butene with ethylene, propylene and α-olefins with 5 to 20 carbon atoms (1-butene-α-olefin copolymers), etc., with structural units derived from 1-butene as the main component (containing 1-butene: 51 to 100 mol%).

[0045] <4-Methyl-1-pentene polymers (A4)> 4-Methyl-1-pentene polymers (A4) are homopolymers of 4-methyl-1-pentene and copolymers of 4-methyl-1-pentene with α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (4-methyl-1-pentene·α-olefin copolymers), etc., with structural units derived from 4-methyl-1-pentene as the main component (containing 4-methyl-1-pentene: 51 to 100 mol%).

[0046] Specific examples of α-olefins in 4-methyl-1-pentene α-olefin copolymers include linear α-olefins with 2 to 20 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms) such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, as well as branched α-olefins with 5 to 20 carbon atoms (preferably 5 to 15 carbon atoms) such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, with ethylene and propylene being particularly preferred. α-olefins can be derived from one or more of these compounds.

[0047] The molar ratio of 4-methyl-1-pentene to α-olefin (4-methyl-1-pentene / α-olefin) is preferably 55 / 45 to 90 / 10, more preferably 60 / 40 to 86 / 14, and even more preferably 68 / 32 to 85 / 15.

[0048] In one embodiment, for the 4-methyl-1-pentene polymer (A4), the temperature at which the loss tangent (tanδ) peaks, obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C, is 0°C to 60°C, preferably 10°C to 50°C, more preferably 20°C to 45°C, and particularly preferably 25°C to 44°C.

[0049] The peak value of the tanδ of the 4-methyl-1-pentene polymer (A4) is 0.6 or more and 5.0 or less. The peak value of this tanδ is preferably 0.7 or more and 4.5 or less, more preferably 0.8 or more and 3.5 or less.

[0050] For tanδ, the storage elastic modulus (G') and loss elastic modulus (G'') obtained during the dynamic viscoelasticity measurement can be used as the ratio of storage elastic modulus (G') to loss elastic modulus (G'') (G'' / G': loss tangent) to calculate it.

[0051] In this invention, the temperature at which tanδ reaches its peak value (maximum value) within the range of -40 to 150°C is taken as the temperature at which tanδ reaches its peak value (hereinafter referred to as the "tanδ peak temperature"), and the value of tanδ at this temperature is taken as the peak value of tanδ (hereinafter referred to as the "tanδ peak value"). It should be noted that the peak is considered to originate from the glass transition temperature of the 4-methyl-1-pentene polymer (A4).

[0052] In another embodiment, for the 4-methyl-1-pentene polymer (A4), the tanδ peak temperature obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C is preferably 15°C to 45°C and below. Here, regarding the lower limit of the aforementioned tanδ peak temperature, it is more preferably 20°C or above, and even more preferably 25°C or above. Furthermore, in the exemplary embodiment of the present invention, the aforementioned tanδ peak temperature is 40°C or below, but it may exceed 40°C as long as the purpose of this application is achieved. In a typical embodiment of the present invention, the aforementioned tanδ peak temperature is more preferably 20°C to 45°C and even more preferably 25°C to 43°C and below. By setting the tanδ peak temperature to the above-mentioned temperature range, the tanδ value at room temperature can be further improved.

[0053] For the 4-methyl-1-pentene polymer (A4), the tanδ peak value obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) within a temperature range of -40 to 150°C is preferably 0.6 to 5.0, more preferably 1.0 to 4.8, even more preferably 1.3 to 4.5, and particularly preferably 1.8 to 4.0. By setting the tanδ peak value within the above range, vibration absorption, material hardness, and conformability can be varied according to the speed of stretching and deformation.

[0054] The melting point (Tm) of the 4-methyl-1-pentene polymer (A4), as determined by differential scanning calorimetry (DSC), is preferably below 160°C or not observable, more preferably below 140°C or not observable, and even more preferably not observable. By satisfying this requirement, the compatibility with inorganic substances such as metal oxides (C) in the resin composition of the present invention is improved, thereby enhancing vibration absorption and stress mitigation.

[0055] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A4) measured in decahydronaphthalene at 135°C is preferably 0.1 dL / g or more and 5.0 dL / g or less, more preferably 0.5 dL / g or more and 4.0 dL / g or less, and even more preferably 0.5 dL / g or more and 3.5 dL / g or less. If the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A4) is within the above range, it is easy to manufacture molded articles.

[0056] The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (A4) can be adjusted to the above range by adding hydrogen in the polymerization-based manufacturing process to control the molecular weight and polymerization activity.

[0057] For the aforementioned intrinsic viscosity [η], the viscosity increase rate ηsp (i.e. ηsp / c) of each polymer, calculated per unit concentration c, when different amounts of olefin resin compositions are dissolved in decahydronaphthalene at 135°C can be obtained as the reducing viscosity ηred. ηred is then extrapolated to the condition that the unit concentration c of the polymer is zero.

[0058] The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of the 4-methyl-1-pentene polymer (A4), as determined by gel permeation chromatography (GPC) (molecular weight distribution: Mw / Mn), is preferably 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 2.8. If the Mw / Mn of the 4-methyl-1-pentene polymer (A4) is within the above range, the reduction in moldability caused by low molecular weight, low cubicity polymers is less likely to occur, and molding is easier.

[0059] Furthermore, the weight-average molecular weight (Mw) of the 4-methyl-1-pentene polymer (A4), as determined by gel permeation chromatography (GPC), is preferably 500 to 10,000,000 when converted to polystyrene, more preferably 1,000 to 5,000,000, and even more preferably 1,000 to 2,500,000.

[0060] The Mw / Mn and Mw of the 4-methyl-1-pentene polymer (A4) can be adjusted to the above range, for example, by using a metallocene catalyst.

[0061] For the aforementioned Mw and Mw / Mn, for example, a Waters ALC / GPC 150-C plus (differential refractometer detector integrated type) can be used as a liquid chromatograph, with two Tosoh GMH6-HT columns and two GMH6-HTL columns connected in series, using o-dichlorobenzene as the mobile phase medium, and analyzing the chromatogram obtained under the conditions of a flow rate of 1.0 ml / min and 140 °C using a standard curve with a standard polystyrene sample to determine the Mw / Mn ratio.

[0062] The density of the 4-methyl-1-pentene polymer (A4) (determined according to JIS K7112) is preferably 870~830 kg / m³. 3 More preferably, it is 865~830 kg / m 3 Further preferred values ​​are 855~830 kg / m³. 3 .

[0063] The density can be suitably changed by the proportion of comonomers in the 4-methyl-1-pentene polymer (A4), and polymers (A4) with densities within the above range are advantageous from the perspective of manufacturing molded articles.

[0064] When the olefin resin composition of the present invention contains a 4-methyl-1-pentene polymer (A4), the molded articles obtained from the olefin resin composition can be suitably used in a variety of applications without limitation. Compared with the case containing a propylene polymer (A2), such molded articles have excellent softness, impart a characteristic of easy heat transfer, and thus have the properties of being easy to bend upon touch and easily maintaining their shape at room temperature.

[0065] In the olefin-based resin composition of the present invention, the unmodified olefin polymer (A) is preferably one or more polymers selected from the group consisting of (A1) to (A4) described above, and more preferably the unmodified olefin polymer (A) includes one or more of an ethylene polymer (A1) and a propylene polymer (A2). Furthermore, when the unmodified olefin polymer (A) includes both an ethylene polymer (A1) and a propylene polymer (A2), the resulting molded article exhibits excellent balance in mechanical properties, and is therefore preferred. When the unmodified olefin polymer (A) is composed of a propylene polymer (A2), the resulting molded article exhibits excellent heat resistance, and is therefore preferred.

[0066] The MFR (ASTM D1238, 230°C, 2.16 kg load) of the olefin polymer (A) is preferably 9 to 300 g / 10 minutes, more preferably 10 to 200 g / 10 minutes. Olefin polymers (A) with MFR in the above range have good moldability, such as injection molding properties, and the resulting molded articles also have good mechanical properties.

[0067] When the olefin polymer (A) is an ethylene polymer (A1), the MFR (ASTM D1238, 190°C, 2.16 kg load) is preferably 6 to 100 g / 10 minutes. Here, considering the lower limit of the MFR, it is preferably 8 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and even more preferably 11 g / 10 minutes or more. Furthermore, considering the upper limit of the MFR, it is preferably 80 g / 10 minutes or less, more preferably 60 g / 10 minutes or less, and even more preferably 50 g / 10 minutes or less.

[0068] When the olefin polymer (A) is an ethylene polymer (A1), a propylene polymer (A2), or a 1-butene polymer (A3), the MFR (ASTM D1238, 230°C, 2.16 kg load) is preferably 20-150 g / 10 min, more preferably 30-100 g / 10 min, and even more preferably 40-80 g / 10 min.

[0069] When the olefin polymer (A) is a 4-methyl-1-pentene polymer (A4), the upper limit of the MFR (ASTM D1238, 230°C, 2.16 kg load) is preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, further preferably 15 g / 10 min or less, and particularly preferably 13 g / 10 min or less.

[0070] <Acid-Modified Propylene Polymers (B)> The acid-modified propylene polymer (B), as one of the components included in the olefin-based resin composition of the present invention, improves the compatibility and adhesion between the unmodified olefin polymer (A) and the metal oxide (C). By improving their compatibility, the acid-modified propylene polymer (B) facilitates the micro-dispersion of the metal oxide (C), thereby improving the processability, heat resistance, mechanical strength, and appearance of the molded article.

[0071] Acid-modified propylene polymers (B) can be obtained by modifying unmodified propylene polymers using known methods.

[0072] There is no particular limitation on the type of unmodified propylene polymer used as a raw material for acid-modified propylene polymers. Unmodified propylene polymers are polymers containing 51 to 100 mol% of structural units derived from propylene; examples include propylene homopolymers and propylene-α-olefin copolymers. Specific examples of α-olefins in propylene-α-olefin copolymers include ethylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. Preferred examples of unmodified propylene polymers include propylene homopolymers, propylene-ethylene random copolymers, propylene-1-butene random copolymers, and propylene-ethylene random-1-butene copolymers, with propylene homopolymers being more preferred.

[0073] The unsaturated carboxylic acids used in the modification of unmodified propylene polymers can be unsaturated compounds with one or more carboxylic acid groups (unsaturated carboxylic acids in the narrow sense), or derivatives of unsaturated carboxylic acids such as esters of unsaturated carboxylic acids and alkyl alcohols, and anhydrides of unsaturated carboxylic acids containing carboxylic anhydrides. The unsaturated groups in these unsaturated carboxylic acids can be vinyl, vinylidene, and unsaturated cyclic hydrocarbon groups. Examples of unsaturated carboxylic acids in the narrow sense include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, nadic acid, and cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid. Examples of derivatives of unsaturated carboxylic acids include anhydrides such as maleic anhydride and citraconic anhydride, and acyl halides, amidates, imides, and esters of unsaturated carboxylic acids such as maleyl chloride, maleimide, monomethyl maleate, and dimethyl maleate (in the narrow sense). The unsaturated carboxylic acids are preferably maleic acid, nadic acid, or their anhydrides, and more preferably maleic anhydride. Only one type of these unsaturated carboxylic acids may be used, or two or more may be used.

[0074] The monomers constituting the acid-modified propylene polymer (B) (propylene, other α-olefins besides propylene, unsaturated carboxylic acids) can be any monomers from fossil fuels, biomass, and chemical recycling.

[0075] Furthermore, as a monomer constituting acid-modified propylene polymer (B), it can be derived from both fossil fuel and biomass feedstocks. It can also combine feedstocks from fossil fuels and feedstocks from chemical recycling. It is also possible to use raw materials from biomass and raw materials from chemical recycling. It is also possible to use feedstocks from fossil fuels, biomass, and chemical recycling.

[0076] When modifying unmodified propylene polymers using the aforementioned unsaturated carboxylic acids, organic peroxides are typically used as free radical initiators. Examples of such organic peroxides include di-n-propyl peroxide, diisopropyl peroxide, disec-butyl peroxide, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-pentyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-butyl peroxide neopentanoate, tert-hexyl peroxide neopentanoate, tert-butyl peroxide neopentanoate, tert-hexyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-pentyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-isobutyrate, and 1,1-di(tert-butylperoxide)-2-methyl Cyclohexane, 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, 1,1-di(tert-butylperoxide)cyclohexane, 1,1-di(tert-pentylperoxide)cyclohexane, 2,2-di(4,4-di(tert-butylperoxide)cyclohexyl)propane, tert-pentyl peroxide isononanoate, tert-hexyl peroxide isopropyl monocarbonate, tert-pentyl peroxide n-octanoate, tert-butyl peroxide maleate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide laurate, iso... tert-amyl propyl monocarbonate, tert-butyl isopropyl monocarbonate peroxide, tert-amyl 2-ethylhexyl monocarbonate peroxide, tert-butyl 2-ethylhexyl monocarbonate peroxide, tert-hexyl benzoate peroxide, tert-butyl acetate peroxide, tert-amyl acetate peroxide, 2,2-di(tert-butylperoxide)butane, tert-butyl isononanoate peroxide, tert-amyl benzoate peroxide, tert-butyl benzoate peroxide, n-butyl 4,4-di(tert-butylperoxide)valerate, methyl ethyl ketone peroxide, di(2-tert-butylperoxide isopropyl)benzene, 3,3-di(tert-butylperoxide) Ethyl butyrate, di-tert-hexyl peroxide, 1,3-bis(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-pentyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, tert-pentyl hydrogen peroxide, tert-butyl hydrogen peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, etc. Among these, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, di-tert-butylperoxide, tert-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hex-3-yne, dicumyl peroxide, and tert-butyl peroxybenzoate are preferred. Only one of these organic peroxy acids may be used, or two or more may be used.

[0077] The amount of organic peroxide used in modification can be set to 0.01 parts by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of unmodified propylene polymer.

[0078] The amount of unsaturated carboxylic acid contained in the acid-modified propylene polymer (B) relative to the total mass of the acid-modified propylene polymer (B) is preferably 0.005% by mass or more than 10% by mass, more preferably 0.01% by mass or more than 5% by mass, and even more preferably 0.02% by mass or more than 3% by mass.

[0079] Regarding the amount of unsaturated carboxylic acid, in the olefin resin composition of the present invention, it is desirable to be within the range of preferably 0.002 to 0.42 parts by mass, more preferably 0.005 to 0.35 parts by mass, and even more preferably 0.01 to 0.1 parts by mass, relative to a total of 100 parts by mass of the aforementioned unmodified olefin polymer (A), the aforementioned acid-modified propylene polymer (B), the aforementioned metal oxide (C), and the aforementioned unmodified polyolefin wax (D). Here, the amount of unsaturated carboxylic acid generally refers to the amount of unsaturated carboxylic acid contained in the acid-modified propylene polymer (B). That is, the olefin resin composition of the present invention preferably contains the aforementioned acid-modified propylene polymer (B) in an amount of unsaturated carboxylic acid as described above. If the content of unsaturated carboxylic acid in the olefin resin composition of the present invention is within the aforementioned range, the compatibility and adhesion between the unmodified olefin polymer (A) and the metal oxide (C) in the resin composition are improved, and it is easy to obtain a molded article with excellent texture and strength from the resin composition, which is therefore preferred.

[0080] The density (determined according to JIS K7112) of acid-modified propylene polymer (B) is preferably 860~930 kg / m³. 3 More preferably, it is 880~925 kg / m 3 Further preferred is 890~920 kg / m 3 .

[0081] The number-average molecular weight (Mn) of the acid-modified propylene polymer (B), as determined by gel permeation chromatography (GPC), is preferably 2,000 to 60,000 (converted to polystyrene), more preferably 7,000 to 50,000, and even more preferably 10,000 to 45,000. Acid-modified propylene polymers (B) with a number-average molecular weight (Mn) within the above range can better improve the dispersibility of metal oxides (C) in the resin composition, and can further improve the appearance, heat resistance, and mechanical strength of the molded article. In addition, the processability and composability of the resin composition are also improved.

[0082] <Metal Oxides (C)> The metal oxide (C), which is one of the components included in the olefin-based resin composition of the present invention, is not particularly limited in type as long as it is a metal oxide, and it is acceptable to use a metal oxide that has a higher thermal conductivity than the olefin-based polymer (A). For example, magnesium oxide (45~60 W / mK), aluminum oxide (17~36.0 W / mK), zinc oxide (25~54 W / mK), titanium oxide (8.4 W / mK), etc., can be used. Two or more metal oxides can also be used together. It should be noted that the value in parentheses after the substance name indicates the thermal conductivity value at 300 K.

[0083] The metal oxide (C) involved in this invention is preferably a metal oxide with a thermal conductivity in the range of 10 to 300 W / mK. The lower limit of thermal conductivity is more preferably 15 W / mK, further preferably 20 W / mK, particularly preferably 30 W / mK, and most preferably 40 W / mK.

[0084] Furthermore, the upper limit of thermal conductivity is more preferably 250 W / mK, further preferably 200 W / mK, and particularly preferably 100 W / mK.

[0085] By using a metal oxide (C) with thermal conductivity within the above range, the olefin resin composition obtained by mixing with the above-mentioned unmodified olefin polymer (A) and acid-modified propylene polymer (B) has a suitable thermal conductivity. Therefore, it is possible to obtain molded articles such as containers that feel cool to the touch and warm when filled with hot objects.

[0086] In addition, unlike the use of titanium dioxide as a photocatalyst, for metal oxides (C), magnesium oxide and zinc oxide are preferred in applications where light irradiation is not required and antibacterial and / or antiviral properties are required. Furthermore, magnesium oxide is more preferred from the perspective of its white color, ease of coloring, and low cost.

[0087] The metal oxide (C) involved in this invention can be in the shape of spheres, cubic shapes, plates, columns, hexagonal plates, etc., with spherical metal oxides being preferred. Alternatively, pulverized metal oxides (C) can also be used.

[0088] The average particle size of the metal oxide (C) involved in this invention is preferably in the range of 0.1 to 110 μm. The lower limit of the average particle size is more preferably 0.5 μm, further preferably 1 μm, and particularly preferably 3 μm. The particle size (average particle size) of the metal oxide (C) is the 50% particle size (d50) obtained from the cumulative % distribution curve measured using a laser diffraction particle size distribution measuring device.

[0089] Furthermore, the upper limit of the average particle size is more preferably 80 μm, further preferably 70 μm, and particularly preferably 60 μm.

[0090] If the average particle size is too small, there are concerns that it is easy to agglomerate, the workability is reduced, and it is difficult to mix it uniformly with the olefin polymer (A). On the other hand, if the average particle size is too large, there are concerns that the thermal conductivity of the obtained olefin resin composition becomes too low, and there are also concerns that the mechanical properties of the obtained molded article are reduced.

[0091] Using a metal oxide (c1) with a small average particle size as the metal oxide (C) is further preferred from the perspective of the mechanical properties of the resulting resin composition and molded article. The average particle size of the metal oxide (c1) is 0.1 μm or more and less than 10 μm, preferably 0.5 μm or more and less than 10 μm, more preferably 1 μm or more and less than 10 μm, and even more preferably 3 μm or more and less than 10 μm. The metal oxide (c1) is preferably a metal oxide that has been pulverized to this average particle size.

[0092] Using a metal oxide (c2) with a large average particle size as the metal oxide (C) is further preferred in terms of the flowability and moldability of the resulting resin composition. The average particle size of the metal oxide (c2) is 10 μm or more and 110 μm or less, preferably 10 μm or more and 80 μm or less, more preferably 10 μm or more and 70 μm or less, and even more preferably 10 μm or more and 60 μm or less. Spherical metal oxides (c2) are preferred.

[0093] In applications requiring higher thermal conductivity, it is preferable to use, for example, metal oxides (c1) with an average particle size of 0.1 μm or more and less than 10 μm and metal oxides (c2) with an average particle size of 10 μm or more and less than 110 μm. In this case, the mixing ratio (mass ratio) is preferably (c1) / (c2) = 1 / 99 to 49 / 51, more preferably 5 / 95 to 45 / 55, and even more preferably 10 / 90 to 40 / 60.

[0094] By combining metal oxides (c1) with small average particle size and metal oxides (c2) with large average particle size, metal oxides (c1) can be filled in the gaps between metal oxides (c2), increasing the filling density and thus improving the thermal conductivity of the resulting olefin resin composition.

[0095] Furthermore, for metal oxides (C), a small aspect ratio is preferred from the viewpoint of uniform heat conduction. Specifically, the aspect ratio is preferably less than 1.2, and more preferably less than 1.1.

[0096] The metal oxide (C) involved in this invention is preferably a water-resistant metal oxide. Preferably, the metal oxide (C) does not substantially contain metal hydroxides and their hydrates, or hydrates of metal oxides. Specifically, the content of metal hydroxides and their hydrates, or hydrates of metal oxides in 100% by mass of the total metal oxide (C) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0097] <Unmodified polyolefin wax (D)> The unmodified polyolefin wax (D), which is one of the components included in the olefin resin composition of the present invention, is a low molecular weight polymer. It can be any unmodified wax formed from polyolefins, such as polyethylene wax or polypropylene wax, and is not particularly limited, but is preferably polyethylene wax or polypropylene wax, and more preferably polyethylene wax.

[0098] It should be noted that the unmodified polyolefin wax (D) involved in this invention has not been oxidized or modified by unsaturated carboxylic acids, and is therefore unmodified.

[0099] Furthermore, the acid value of the unmodified polyolefin wax (D) of the present invention, as determined according to JIS K0070, is preferably 0.01 mg KOH / g or less, and more preferably 0 mg KOH / g.

[0100] The monomers constituting unmodified polyolefin waxes (D) can be any monomers from fossil fuels, biomass, and chemical recycling.

[0101] Furthermore, as a raw material monomer for unmodified polyolefin waxes (D), it can be derived from both fossil fuels and biomass. It can also combine feedstocks from fossil fuels and feedstocks from chemical recycling. It is also possible to use raw materials from biomass and raw materials from chemical recycling. It is also possible to use feedstocks from fossil fuels, biomass, and chemical recycling.

[0102] Polyethylene-based waxes The polyethylene wax used as the unmodified polyolefin wax (D) of this invention is a wax formed from a homopolymer of ethylene or a copolymer of ethylene and an α-olefin. The α-olefin is preferably an α-olefin with 3 to 10 carbon atoms, more preferably an α-olefin with 3 to 8 carbon atoms, and even more preferably 1-butene. Examples of polyethylene waxes include polymers or copolymers whose main component is a structural unit derived from ethylene (containing ethylene: 51 to 100 mol%).

[0103] For the polyethylene-based waxes involved in this invention, the density, preferably measured according to the density gradient tube method of JIS K7112 (1999), is between 890 and 980 kg / m³. 3 More preferably, it is within the range of 895~975 kg / m 3 Within this range. If the density of polyethylene wax is within this range, the dispersibility of polyethylene wax in the olefin resin composition is improved.

[0104] For the polyethylene-based waxes involved in this invention, the number-average molecular weight (Mn) calculated based on standard polyethylene by gel permeation chromatography is preferably 700 to 4000, more preferably 1500 to 3800.

[0105] Polyethylene-based waxes with a number-average molecular weight (Mn) of 700-4000 can be appropriately dispersed in the unmodified olefin polymer (A) when preparing the olefin resin composition of the present invention, and also contribute to the dispersibility of the metal oxide (C). Furthermore, they can reduce the extrusion load during molding extrusion. As a result, the productivity of molded articles can be further improved.

[0106] For the polyethylene-based waxes involved in this invention, the weight-average molecular weight (Mw) calculated based on standard polyethylene by gel permeation chromatography is preferably 1000-9000, more preferably 1500-8000, and even more preferably 2000-7000.

[0107] The melting point of the polyethylene-based wax involved in this invention is preferably 70~130℃, more preferably 80~129℃.

[0108] The melting point of polyethylene wax was determined using a differential scanning calorimeter (DSC) in accordance with JIS K7121.

[0109] <Polypropylene Wax> The polypropylene wax used as the unmodified polyolefin wax (D) of this invention is a wax formed from a homopolymer of propylene or a copolymer of propylene with ethylene or an α-olefin. The α-olefin is preferably an α-olefin with 4 to 10 carbon atoms, more preferably an α-olefin with 4 to 8 carbon atoms, and even more preferably 1-butene. Examples of polypropylene waxes include polymers or copolymers whose main component is a structural unit derived from propylene (containing propylene: 51 to 100 mol%).

[0110] The polypropylene waxes involved in this invention do not have particularly limited properties in terms of density, number-average molecular weight (Mn), weight-average molecular weight (Mw), and melting point (Tm), but it is desirable that each of these properties be within the same range as the preferred properties of the polyethylene waxes described above.

[0111] <Olefin-based resin compositions> The olefin resin composition of the present invention comprises: 9.7 to 36 parts by weight of the above-mentioned unmodified olefin polymer (A); 0.3 to 15 parts by weight of an acid-modified propylene polymer (B); 54 to 90 parts by weight of a metal oxide (C) (wherein the total amount of the unmodified olefin polymer (A), the acid-modified propylene polymer (B), and the metal oxide (C) is set to 100 parts by weight); and unmodified polyolefin wax (D) in the range of 0.1 to 10 parts by weight relative to the total of 100 parts by weight of (A) + (B) + (C).

[0112] In the olefin-based resin composition of the present invention, the lower limit of the content of unmodified olefin polymer (A) when the total amount of (A) + (B) + (C) is set to 100 parts by mass is preferably 11.5 parts by mass, more preferably 13.3 parts by mass, further preferably 15.1 parts by mass, and even more preferably 21.1 parts by mass. If the content of olefin polymer (A) in the olefin-based resin composition is a certain amount or more, conventional molding methods such as injection molding can be implemented.

[0113] The upper limit of the content of unmodified olefin polymer (A) is preferably 35 parts by mass, more preferably 33 parts by mass, further preferably 32 parts by mass, and particularly preferably 26 parts by mass.

[0114] If the content of unmodified olefin polymer (A) in the olefin resin composition of the present invention is below a certain amount, the thermal conductivity of the obtained olefin resin composition can be fully utilized, and the obtained molded body can feel weight and texture.

[0115] In the olefin-based resin composition of the present invention, the lower limit of the content of acid-modified propylene polymer (B) when the total amount of (A) + (B) + (C) is set to 100 parts by mass is preferably 0.3 parts by mass, more preferably 0.5 parts by mass, further preferably 0.7 parts by mass, and even more preferably 0.9 parts by mass. If the content of acid-modified propylene polymer (B) in the olefin-based resin composition is a certain amount or more, the dispersibility of metal oxide (C) in the resin composition can be improved more effectively, and the appearance, heat resistance, surface hardness, and mechanical strength of the molded article can be further improved.

[0116] The maximum content of acid-modified propylene polymer (B) is 15 parts by mass, preferably 12 parts by mass, more preferably 10 parts by mass, even more preferably 8 parts by mass, even more preferably 7 parts by mass, and particularly preferably 5 parts by mass.

[0117] If the content of acid-modified propylene polymer (B) in the olefinic resin composition of the thermoplastic resin composition of the present invention is below a certain amount, the dispersibility of metal oxide (C) in the resin composition can be improved more effectively, and the appearance, heat resistance, surface hardness and mechanical strength of the molded article can be further improved. In addition, the processability and mixing properties of the resin composition are also improved.

[0118] Furthermore, in the olefin resin composition of the present invention, regarding the content of the acid-modified propylene polymer (B) when the total amount of (A) + (B) + (C) + (D) is set to 100 parts by mass, it is desirable that the amount of unsaturated carboxylic acid contained in the acid-modified propylene polymer (B) is preferably 0.002 to 0.42 parts by mass, more preferably 0.005 to 0.35 parts by mass, and even more preferably 0.01 to 0.1 parts by mass. If the content of unsaturated carboxylic acid is within the aforementioned range, the compatibility and adhesion between the unmodified olefin polymer (A) and the metal oxide (C) in the olefin resin composition of the present invention are improved, and it is easy to obtain a molded article with excellent texture and strength from the resin composition, which is therefore preferred.

[0119] On the other hand, when the total amount of (A) + (B) + (C) is set to 100 parts by mass, the lower limit of the content of metal oxide (C) is preferably 57 parts by mass, more preferably 60 parts by mass, further preferably 63 parts by mass, and even more preferably 69 parts by mass.

[0120] In addition, the upper limit of the content of metal oxide (C) is preferably 88 parts by mass, more preferably 86 parts by mass, even more preferably 84 parts by mass, and even more preferably 78 parts by mass.

[0121] The olefin-based resin composition of the present invention contains 0.1 to 10 parts by weight of unmodified polyolefin wax (D) relative to 100 parts by weight of the total of unmodified olefin polymer (A), acid-modified propylene polymer (B), and metal oxide (C) (total of (A) + (B) + (C)). The lower limit of the content of unmodified polyolefin wax (D) is preferably 0.2 parts by weight, more preferably 0.4 parts by weight, and even more preferably 0.5 parts by weight.

[0122] Furthermore, the upper limit of the content of unmodified polyolefin wax (D) is preferably 8 parts by mass, more preferably 6 parts by mass, and even more preferably 4 parts by mass.

[0123] In the olefin-based resin composition of the present invention, by including unmodified polyolefin wax (D) within the above-mentioned range, the molding torque during molding when obtaining the olefin-based resin composition and during molding processing using the olefin-based resin composition can be reduced, thereby improving the composability. In addition, since the melting temperature is lower than that of the olefin-based polymer (A), it functions as a lubricant, preventing wear on the screw and barrel.

[0124] On the other hand, since the olefin resin composition of the present invention does not contain modified polyolefin wax, there is no concern about generating an unpleasant odor during molding and processing.

[0125] Furthermore, the molded body obtained from the olefin resin composition of the present invention containing unmodified polyolefin wax (D) has a hard texture, a texture closer to that of ceramics, compared to the molded body obtained from the composition containing modified polyolefin wax, and there is no change in hydrophilicity. Therefore, there is no concern about the dissolution of metal oxides or the reduction of texture.

[0126] The specific gravity of the olefin-based resin composition of the present invention is preferably in the range of 1.2 to 5.0. The lower limit of the specific gravity of the olefin-based resin composition of the present invention is more preferably 1.4, further preferably 1.6, and particularly preferably 1.7. Furthermore, the upper limit of the specific gravity is more preferably 4.0, further preferably 3.0, and particularly preferably 2.5.

[0127] By ensuring the specific gravity falls within the aforementioned range, a molded object with better texture can be obtained.

[0128] The thermal conductivity of the olefin-based resin composition of the present invention is preferably in the range of 0.5 to 5 W / mK. The lower limit of the thermal conductivity of the olefin-based resin composition of the present invention is more preferably 0.6 W / mK, further preferably 0.65 W / mK, and particularly preferably 0.7 W / mK. Furthermore, the upper limit of the thermal conductivity is more preferably 4.5 W / mK, further preferably 4.0 W / mK, and particularly preferably 3.6 W / mK.

[0129] By ensuring that the thermal conductivity meets the above-mentioned range, molded objects such as containers can be obtained that feel cool to the touch and have a better texture.

[0130] For the olefin-based resin composition of the present invention, it is preferable to use an antibacterial activity value (water resistance category 0 and light resistance category 0) of 2.0 or higher for *Escherichia coli* or *Staphylococcus aureus*, and more preferably, an antibacterial activity value of 2.0 or higher for both *Escherichia coli* and *Staphylococcus aureus*. The antibacterial activity value of the olefin-based resin composition of the present invention can be increased, for example, by increasing the content of metal oxide (C) (e.g., magnesium oxide). It should be noted that an antibacterial activity value of 2.0 or higher is considered to have an antibacterial effect. A higher antibacterial activity value (water resistance category 0 and light resistance category 0) indicates a higher antibacterial effect, and is therefore preferred; however, there is no particular upper limit.

[0131] The antibacterial activity values ​​(water resistance category 0 and light resistance category 0) in this invention are index values ​​obtained according to the test methods in JIS Z 2801:2012 "Membrane sealing method".

[0132] The so-called water resistance category 0 refers to category 0 in the "Antibacterial Products Technical Association Test Method Continuous Test Method (2021 Edition) (1) Water Resistance Test" (conditions without water resistance pretreatment). Similarly, the so-called lightfastness category 0 refers to category 0 in the "Antibacterial Products Technical Association Test Method Continuous Test Method (2021 Edition) (2) Lightfastness Test" (conditions without lightfastness pretreatment).

[0133] For the olefin-based resin composition of the present invention, it is preferable to use a feline calicivirus with an antiviral activity value of 2.0 or higher. It should be noted that an antiviral activity value of 2.0 or higher is considered to indicate an antiviral effect. A higher antiviral activity value indicates a higher antiviral effect, and is therefore preferred; however, there is no particular upper limit.

[0134] The antiviral activity value in this invention is an index value obtained according to the test method in ISO 21702:2019 "Determination of antiviral activity of plastics and other non-porous surfaces".

[0135] The olefin-based resin compositions of the present invention may also include various known additives, such as plasticizers, lubricants, antioxidants, ultraviolet absorbers, heat stabilizers, pigments, pigment masterbatches, dyes, antistatic agents, flame retardants, coupling agents, and dispersants, depending on the application and without prejudice to the purpose of the present invention.

[0136] <Method for manufacturing olefin-based resin compositions> The olefin-based resin composition of the present invention can be obtained by mixing the above components using a dry mixer, Henschel mixer, Banbury mixer, kneader, etc., or by melt mixing using a single-screw extruder, twin-screw extruder, high-speed twin-screw extruder, etc.

[0137] <Molded Body> The olefin-based resin composition of the present invention exhibits excellent moldability and can therefore be used in various molding methods. Specific examples of molded articles obtained from the olefin-based resin composition of the present invention include injection molded articles, foamed articles, injection-foamed articles, extruded articles, hollow articles, vacuum-molded articles, calendered articles, three-dimensional laminated articles, microwave molded articles, stretch films, blown films, etc.

[0138] More specifically, examples include containers for holding food, forks, knives, spoons, plates, small teapots, teacups, and other tableware; wine vessels such as wine jugs or bottles; and cutlery rests such as chopstick rests. Considering their ease of injection molding, the ability to easily feel the temperature of their contents, and the sense of weight, they are very useful as alternatives to ceramic tableware, wine vessels, containers, and cutlery. Furthermore, their use can be extended to other applications of ceramics, such as lampshades, vases, and other everyday items; housings and structural materials for specific audio speakers (high-end speakers, etc.); bathroom products such as washbasins and toilets; and vases and flowerpots for holding plants. Beyond its applications in ceramics, its weight and stability can be effectively utilized to expand into various uses, such as model making and toys (e.g., plastic models), furniture (e.g., tables, chairs), home appliances (e.g., refrigerators, rice cookers, vacuum cleaners), musical instruments (e.g., piano keyboards), construction materials (e.g., tiles, artificial marble substitutes), and clothing (e.g., buttons). Furthermore, its temperature sensitivity and moldability make it potentially suitable as filaments for 3D printers.

[0139] In addition to the molded articles of the present invention, examples of other products that effectively utilize features such as design, stability, antibacterial properties, and tactile feel include various bottles, kettles, and other containers; steering wheels, gear shift levers, door handles, spherical door handles, various switches, railings, mice, keyboards, controllers, remote controls, decorative accessories, stationery (mechanical pencils, ballpoint pens, fountain pens, etc.); smartphone covers; tablet computer protective cases; personal computer, tablet computer, and smartphone cases; various household appliance cases; beauty appliance cases; household appliance cases; energy storage devices (battery cases, etc.); book covers; wallpaper; wall materials; flooring materials; building materials; toilets; and toilet supplies, etc., which can be appropriately used in everyday situations involving hand contact.

[0140] Among containers, preferred examples are containers for beauty-related products such as cosmetics (lotions, creams, etc.), detergents (including shower gels, etc.), and conditioners, whose properties tend to have a high impact on the value of the product. More specifically, containers in the shape of lidded containers (including vacuum containers, etc.), small cosmetic boxes, cosmetic palettes, bottles, etc., can be cited.

[0141] In such applications, containers made of lightweight and impact-resistant plastics such as polyolefins have been widely used in recent years. However, these are not suitable materials for conveying a sense of luxury in terms of visual appeal and tactile feel (including thermal conductivity and weight). Containers such as ceramics are suitable for conveying a sense of luxury, but they have significant drawbacks such as limitations in design and mass production, and low impact resistance.

[0142] The container of the present invention can be molded using the same methods as conventional plastic products. Therefore, it not only has excellent productivity and design, but also has superior impact resistance compared to ceramics, and has the same weight and thermal conductivity as ceramics. Thus, it can be considered suitable for the aforementioned applications.

[0143] Furthermore, the molded articles obtained from the olefin-based resin composition of the present invention are also useful as heat dissipation components for applications requiring high thermal conductivity. For example, they are very useful as heat dissipation components such as heat sinks in various electronic devices such as electronic components requiring high thermal conductivity, laptops, and mobile devices. In addition, if the olefin-based resin composition of the present invention is applied to part or all of the housing of various electronic devices such as laptops and mobile devices and used in combination with heat sinks, it is expected that the heat dissipation performance of electronic devices can be further improved. Furthermore, the olefin-based resin composition of the present invention can be used in part of the housing of various electronic devices such as laptops and mobile devices, while materials with reduced metal oxide content or materials without metal oxides are used in other parts, such as parts that are frequently touched by hands during operation, thereby creating a housing that can reduce the possibility of low-temperature burns during prolonged operation. Such a housing can be manufactured, for example, by providing multiple resin injection gates on a mold for molding the housing and injecting resins of different compositions into each gate.

[0144] As for other applications, its excellent thermal conductivity, freedom of shape during molding, and high impact strength make it useful as a substitute material for metal casings. For example, it can also be expected to be used in the casings and straps of clocks and watches, furniture parts (such as metal handles), and exterior decorative materials for household appliances such as washing machines and refrigerators.

[0145] Example The present invention will be described in more detail below with reference to embodiments, but the present invention is not limited to the following embodiments, as long as they do not depart from its spirit. The materials used in the embodiments are described below. The methods for evaluating the properties of each material are described later.

[0146] (1) Unmodified olefin polymer (A) The following shows the olefin polymers (A) used in the examples and comparative examples.

[0147] (1-1) Propylene-based polymers (A2-1): Propylene-ethylene block copolymer (manufactured by Prime Polymer Co., Ltd., trade name J-6083HP, MFR (230℃, load 2.16kg) = 60g / 10min, density = 900kg / m³) 3 ) (1-2) Ethylene-based polymers (A1-1): Ethylene-1-butene copolymer (manufactured by Mitsui Chemicals, Ltd., TAFMER (registered trademark), trade name A-35070S, MFR (190℃, 2.16kg load) = 35g / 10min, MFR (230℃, 2.16kg load) = 65g / 10min, density = 870kg / m³ 3 ) (2) Acid-modified propylene polymers (B) The acid-modified propylene polymer (B) used in the examples and comparative examples is a substance manufactured by the method described below.

[0148] (2-1) Acid-modified propylene polymers (B-1) To 100 parts by weight of polypropylene (manufactured by Prime Polymer Co., Ltd., Prime Polypro (trade name) grade E-200 GP), 1 part by weight of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.25 parts by weight of 2,5-dimethyl-2,5-bis(tert-butylperoxide)hex-3-yne (manufactured by Nippon Oil Co., Ltd., trade name PERHEXYNE 25B) were mixed, and extruded using a twin-screw mixer (manufactured by Nippon Steel Co., Ltd., TEX-30, L / D=40, using a vacuum exhaust port) at a barrel temperature of 220°C, a screw speed of 200 rpm, and an extrusion rate of 80 g / min, an acid-modified propylene polymer (B-1) containing maleic acid-modified polypropylene and unreacted maleic anhydride was obtained. The obtained polymer (B-1) was dissolved in xylene and purified by redeposition in acetone. The grafting amount of maleic anhydride was determined by IR, and the result was 0.7% by mass. The number-average molecular weight (Mn) was determined by GPC, and the result was 28,000. The density was 910 kg / m³. 3 .

[0149] (2-2) Acid-modified propylene polymers (B-2) 15 parts by mass of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.5 parts by mass of dicumyl peroxide (manufactured by Nippon Oil Co., Ltd., trade name PERCUMYL D) were mixed with 100 parts by mass of polypropylene (manufactured by Prime Polymer Co., Ltd., Prime Polypro (trade name) grade J106G) and reacted in toluene solution for 5 hours to obtain an acid-modified propylene polymer (B-2) containing maleic acid-modified polypropylene and unreacted maleic anhydride. The obtained polymer (B-2) was dissolved in xylene and purified by redeposition in acetone. The grafting amount of maleic anhydride was determined by IR, and the result was 2.8% by mass. The number-average molecular weight (Mn) was determined by GPC, and the result was Mn was 18,000. The density was 910 kg / m³. 3 .

[0150] (3) Metal oxides (C) The following shows the metal oxides (C) used in the examples and comparative examples.

[0151] (3-1) Magnesium oxide (C1-1): MgO (manufactured by Kyowa Chemical Industry Co., Ltd., PYROKISUMA 3320, average particle size = 20μm) (3-2) Magnesium oxide (C1-2): MgO (manufactured by Ube Material Industries, Ltd., RF-10CS, average particle size = 5.0 μm) (3-3) Alumina (C2-1): Alumina (Denka Corporation, DENKA spherical alumina DAM-45, average particle size = 42.8 μm) (4) Unmodified polyolefin wax (D) The following shows the unmodified polyolefin wax (D) used in the examples and comparative examples.

[0152] (4-1) Unmodified polyolefin wax (D-1): Ethylene-1-butene copolymer (manufactured by Mitsui Chemicals, Ltd., trade name EXCEREX 30050B, density = 907 kg / m³) 3 Acid value = 0 mg KOH / g, melting point = 91℃, weight-average molecular weight = 5100, molecular weight distribution Mw / Mn = 2.6) (5) Modified polyolefin waxes (5-1) Modified polyolefin wax: Modified polyolefin polymer (manufactured by Mitsui Chemicals, Ltd., trade name EXCEREX 15341PA, density = 930 kg / m³) 3(Acid value = 14 mg KOH / g, melting point = 89℃) • Determination and evaluation methods of physical properties The physical properties of the olefin-based resin compositions obtained in the examples and comparative examples were determined by the following methods. It should be noted that the specific gravity and melt flow rate (MFR) were determined using resin composition granules, while other physical properties were determined using samples for physical property testing.

[0153] 〔proportion〕 The specific gravity was determined by comparing it with the density of water at 4°C using the water displacement method.

[0154] [Mel flow rate (MFR) (g / 10 min)] According to ASTM D1238, the tests were conducted using TESTER SANGYO CO., LTD.'s AUTO MELT INDEXER TP-407 at a temperature of 230°C and a load of 2.16 kg, and at a temperature of 230°C and a load of 5 kg.

[0155] [Tensile strength, elongation at break] According to JIS K6251, a tensile testing machine (Strograph) VG1F from Toyo Seiki Co., Ltd. was used, with specimen shape JIS 3, and the test was conducted at a test speed of 500 mm / min, a fixture distance of 55 mm, a mark distance of 20 mm, and a test temperature of 23°C.

[0156] Regarding the determination of tensile elongation at break, when measuring tensile strength, a marking tracking device is installed on the test piece to measure the elongation at break.

[0157] [IZOD Impact Strength] According to ASTM D256, the test was conducted using a Toyo Seiki Co., Ltd. digital impact testing machine DG-IB, with a test piece (63mm × 13mm × 2mm thickness with a notch), under the conditions of an impact capacity of 3.92J, a swing angle of 148.9°, and a test temperature of 23°C.

[0158] Rockwell hardness According to JIS K7202-2 (ISO2039-2), the test was performed using a Mitutoyo HR-523 automatic Rockwell hardness tester from Mitutoyo Corporation, using test pieces (three overlapping 2mm pressure sheets) under the conditions of HRR scale, test pressure of 588.4N, and test temperature of 23°C.

[0159] [Shabby Impact] According to JIS K7111-1, the test was conducted using the DG-UB digital impact testing machine of Toyo Seiki Co., Ltd., with a test piece (80mm×10mm×2mm thickness, no notch), under the conditions of an impact capacity of 2J, a swing angle of 148.9°, and a test temperature of 23°C.

[0160] [Bending strength, bending stress, bending modulus of elasticity] According to ASTM D790, using the Shimadzu Corporation AG-1kNX plus 5-strand bending tester, with test pieces (65mm × 14mm × 2mm thickness), the bending strength, bending stress and bending modulus were measured under the following conditions: the distance between the supports was 32mm (16 times the span thickness), the test speed was 5mm / min, and the test temperature was 23°C.

[0161] [Pencil Hardness] According to JIS K5600-56, the pencil scratch hardness tester SH-V of Toyo Seiki Co., Ltd. was used to determine the hardness under a load of 750g.

[0162] [Coefficient of linear expansion] According to JIS K 7197, using SII Nano Technology Inc. TMA-SS7100, under compression expansion mode, TMA method (without annealing), measurement temperature range: 23℃~60℃, test load: 26mN, heating rate: 5℃ / min.

[0163] [Load flexural temperature measurement (°C)] According to ISO 75-2 Method A, the test was conducted using a fully automatic HDT testing machine 6A-2 from Toyo Seiki Co., Ltd., with a test piece (80mm × 10mm × 2mm thickness) and under the following conditions: heating rate of 120℃ / hour, test start temperature of 35℃, and bending stress of 1.80MPa.

[0164] Thermal conductivity (W / m·K) According to ASTM E1530, the thermal conductivity was measured using the ULVAC-RIKO Corporation steady-state thermal conductivity measuring apparatus GH-1, with a sample (50 mm in diameter × 2 mm in thickness), under the conditions of a sample holding air pressure of 0.3 MPa and a set temperature of 30 °C.

[0165] [Water absorption rate (by weight)] The water absorption rate was measured at 23℃ for 24 hours.

[0166] [Examples 1-3] Propylene polymer (A2-1), ethylene polymer (A1-1), acid-modified propylene polymer (B-1), magnesium oxide (C1-1), and unmodified polyolefin wax (D-1) were introduced as raw materials into a mixing apparatus (a benchtop kneader manufactured by Irie & Co., Ltd.) in the manner described in Table 1, and mixed at 200°C and 15-35 rpm to obtain granules of a thermoplastic resin composition. Using a manual hydraulic heating and pressurizing device (manufactured by Imoto Manufacturing Co., Ltd.), the obtained thermoplastic resin composition granules were formed into pressurized sheets of a specified thickness at 200°C, and cut into specified shapes to obtain samples for physical property testing. The physical properties of the obtained sheets were measured using the methods described above. The results are shown in Table 1.

[0167] [Examples 4-6] As raw materials, propylene polymer (A2-1), ethylene polymer (A1-1), acid-modified propylene polymer (B-2), magnesium oxide (C1-1), and unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)) in the manner described in Table 1. Otherwise, the process was the same as in Example 1 to produce granules of the thermoplastic resin composition and test samples. The physical properties of each component were determined using the methods described above. The results are shown in Table 1.

[0168] [Comparative Example 1] As raw materials, 68 parts by weight of propylene polymer (A2-1), 2.0 parts by weight of ethylene polymer (A1-1), 30 parts by weight of magnesium oxide (C-1), and 0.6 parts by weight of unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)). Otherwise, the process was the same as in Example 1 to produce granules of the thermoplastic resin composition and test samples. The physical properties were determined using the methods described above. The results are shown in Table 1.

[0169] The composition obtained from Comparative Example 1 has low thermal conductivity, making it difficult to conduct heat and thus failing to achieve the texture and high-end feel of ceramics. Moreover, due to the low content of metal oxides (C), the surface hardness and load flexural temperature (1.80 MPa) are significantly reduced, making it unsuitable for everyday use.

[0170] [Comparative Example 2] As raw materials, 23 parts by mass of propylene polymer (A2-1), 2.0 parts by mass of ethylene polymer (A1-1), 75 parts by mass of magnesium oxide (C-1), and 0.6 parts by mass of modified polyolefin wax were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)). Otherwise, the process was the same as in Example 1 to produce granules of the thermoplastic resin composition and test samples. The physical properties were determined using the methods described above. The results are shown in Table 1.

[0171] The composition obtained from Comparative Example 2 exhibited a lower load flexural temperature and reduced physical properties. This is believed to be because the modified polyolefin wax had a low acid value, resulting in weak hydrogen bonds with the metal oxide (hereinafter also referred to as filler), and uneven dispersion of the filler in the resin. On the other hand, it is believed that although the unmodified polyolefin wax (D) used in the examples had weaker hydrogen bonds with the filler due to its 0 acid value, its interaction with the small amount of acid-modified propylene polymer (B) acting as a binder was stronger, thus resulting in a composition with good load flexural temperature and physical properties.

[0172] [Comparative Example 3] As raw materials, 23 parts by mass of propylene polymer (A2-1), 2.0 parts by mass of ethylene polymer (A1-1), and 75 parts by mass of magnesium oxide (C-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)). Otherwise, the same procedure as in Example 1 was followed to produce granules of the thermoplastic resin composition and test samples. The physical properties were determined by the methods described above. The results are shown in Table 1.

[0173] The composition obtained from Comparative Example 3, lacking the addition of acid-modified propylene polymer (B) and unmodified polyolefin wax (D), resulted in filler agglomeration and difficulty in uniform dispersion, making it difficult to manufacture and prone to unevenness, poor compatibility, and reduced resin flowability (MFR).

[0174] [Example 7] As raw materials, propylene polymer (A2-1), ethylene polymer (A1-1), acid-modified propylene polymer (B-1), alumina (C2-1), and unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)) in the manner described in Table 1. Otherwise, the same procedure as in Example 1 was followed to produce granules of the thermoplastic resin composition and test samples. The physical properties of each component were determined using the methods described above. The results are shown in Table 1.

[0175] [Example 8] As raw materials, propylene polymer (A2-1), ethylene polymer (A1-1), acid-modified propylene polymer (B-2), alumina (C2-1), and unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)) in the manner described in Table 1. Otherwise, the process was the same as in Example 1 to produce granules of the thermoplastic resin composition and test samples. The physical properties of each component were determined using the methods described above. The results are shown in Table 1.

[0176] [Comparative Example 4] As raw materials, propylene polymer (A2-1), ethylene polymer (A1-1), alumina (C2-1), and unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)) in the manner described in Table 1. Otherwise, the process was the same as in Example 1 to produce granules of the thermoplastic resin composition and test samples. The physical properties of each component were determined using the methods described above. The results are shown in Table 1.

[0177] It is speculated that the composition obtained in Comparative Example 4, due to the absence of acid-modified propylene polymer (B), has lower affinity between the metal oxide and resin components, lower strength and hardness, poorer mechanical properties, lower load flexural temperature, and poorer heat resistance compared to the composition of Example 8.

[0178] [Example 9] As raw materials, propylene polymer (A2-1), acid-modified propylene polymer (B-1), magnesium oxide (C1-2), and unmodified polyolefin wax (D-1) were introduced into a mixing apparatus (a benchtop kneader (manufactured by Irie & Co.)) in the manner described in Table 1. Otherwise, the same procedure as in Example 1 was followed to produce granules of the thermoplastic resin composition and test samples. The physical properties of each component were determined using the methods described above. The results are shown in Table 1.

[0179] [Table 1]

Claims

1. An olefin-based resin composition comprising: 9.7 to 36 parts by weight of unmodified olefin polymer (A); 0.3~15 parts by weight of acid-modified propylene polymer (B); 54-90 parts by mass of metal oxide (C) (in, The total amount of unmodified olefin polymer (A), acid-modified propylene polymer (B), and metal oxide (C) is set at 100 parts by mass; and, Unmodified polyolefin wax (D) in the range of 0.1 to 10 parts by mass relative to a total of 100 parts by mass of the unmodified olefin polymer (A), the acid-modified propylene polymer (B), and the metal oxide (C).

2. The olefin-based resin composition according to claim 1, wherein, The unmodified olefin polymer (A) is selected from one or more of the group consisting of ethylene polymers, propylene polymers, 1-butene polymers, and 4-methyl-1-pentene polymers.

3. The olefin-based resin composition according to claim 1, wherein, The metal oxide (C) comprises magnesium oxide.

4. The olefin-based resin composition according to claim 1, wherein, The thermal conductivity of the metal oxide (C) is in the range of 10~300 W / mK.

5. The olefin-based resin composition according to claim 1, wherein, The thermal conductivity of the olefin-based resin composition is in the range of 0.5~5 W / mK.

6. The olefin-based resin composition according to claim 1, wherein, The specific gravity of the olefin-based resin composition is in the range of 1.2 to 5.

0.

7. The olefin-based resin composition according to claim 1, wherein, The content of unsaturated carboxylic acids in the olefin resin composition is in the range of 0.002 to 0.42 parts by mass relative to a total of 100 parts by mass of the unmodified olefin polymer (A), the acid-modified propylene polymer (B), the metal oxide (C), and the unmodified polyolefin wax (D).

8. A molded article comprising the olefinic resin composition according to any one of claims 1 to 7.

9. A door handle, spherical door handle, handrail, or switch comprising an olefinic resin composition according to any one of claims 1 to 7.

10. A housing comprising the olefinic resin composition according to any one of claims 1 to 7.

11. An energy storage device comprising the olefinic resin composition according to any one of claims 1 to 7.

12. Apparel accessories comprising the olefinic resin composition according to any one of claims 1 to 7.

13. Stationery comprising the olefinic resin composition according to any one of claims 1 to 7.

14. A container, tableware or wine vessel comprising an olefinic resin composition according to any one of claims 1 to 7.

15. A mouse or keyboard comprising the olefinic resin composition according to any one of claims 1 to 7.

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