Photosensitive resin composition

Abstract

To provide a polyolefin resin composition, a polyolefin resin molded article, a polypropylene resin composition and a polypropylene resin molded article that exhibit high antiviral activity through the use of only a small amount of an antiviral agent.SOLUTION: A polyolefin resin composition comprises 95 pts.wt. or more and less than 100 pts.wt. of a hydroxyl-group-modified polyolefin (A1) and more than 0 pt.wt. and 5 pts.wt. or less of an antiviral agent (C), the total of (A1) and (C) being 100 pts.wt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyolefin resin composition, a polyolefin resin molded article, a polypropylene resin composition, and a polypropylene resin molded article. [Background technology]

[0002] Infectious diseases caused by viruses such as new strains of influenza, avian influenza, and norovirus, especially the recent SARS and COVID-19 infections, are contracted through aerosol infection (droplet infection) caused by droplets from phlegm and coughs, or through contact. However, in normal social activities, there are many opportunities to come into contact with large numbers of people, for example, at the counters of financial institutions, eating and drinking at restaurants, and even at convenience stores, supermarkets, public institutions, etc. Therefore, in order to prevent the spread of infection in such places, there is a demand for antiviral materials that can be used for, for example, product display shelves installed in stores, equipment and tools that may come into contact with the human body, such as key chains, as well as splash guards (hereinafter referred to as "droplet guards, etc.") to prevent the spread of droplets, toilet seats, handrails, hanging straps, miscellaneous goods, home appliances, etc. For example, Patent Document 1 proposes an "antibacterial and antiviral resin composition containing a transparent resin (A) and an antibacterial and antiviral agent (B), wherein the antibacterial and antiviral agent (B) is a cationic amphiphilic substance" as an antiviral material, and also proposes a "resin molded product obtained by molding or processing the antibacterial and antiviral resin composition" as a resin molded product that can be suitably used for a face-to-face counter. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-176949 Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, in order to impart antiviral properties to splash prevention boards and the like, it is usually necessary to set the weight ratio of the antiviral agent relatively high, although this depends on the type of antiviral agent, and there is a demand to reduce the weight ratio of the antiviral agent from the viewpoints of increased costs and further discoloration, etc. However, reducing the weight ratio of the antiviral agent generally reduces the antiviral properties, and in some cases, the desired antiviral properties may not be achieved. On the other hand, Patent Document 1 does not use a hydroxyl group-modified polyolefin as the resin, nor does it use a combination of a polypropylene resin and a hydrophilic resin with a specific molecular weight. Under these circumstances, an object of the present invention is to provide a polyolefin resin composition, a polyolefin resin molded article, a polypropylene resin composition, and a polypropylene resin molded article that exhibit high antiviral activity with the use of a small amount of an antiviral agent. [Means for solving the problem]

[0005] The present inventors have conducted extensive research in light of the above background and have completed the present invention. That is, the present invention and its preferred aspects or embodiments are as follows [1] to

[11] .

[0006] Invention 1 [1] A polyolefin resin composition comprising 95 to less than 100 parts by weight of a hydroxyl group-modified polyolefin (A1) and more than 0 to 5 parts by weight of an antiviral agent (C), wherein the total of (A1) and (C) is 100 parts by weight. [2] The polyolefin resin composition according to [1], wherein the hydroxyl-modified polyolefin (A1) is a hydroxyl-modified polypropylene. [3] The polyolefin resin composition according to [1] or [2], wherein the hydroxyl group-modified polyolefin (A1) is a terminal hydroxyl group-modified polypropylene. [4] The polyolefin resin composition according to any one of [1] to [3], wherein the hydroxyl-modified polyolefin (A1) is a polypropylene modified with a hydroxyl group at one end. [5] The polyolefin resin composition according to any one of [1] to [4], wherein the antiviral agent (C) is a silver and / or zinc compound. [6] The polyolefin resin composition according to any one of [1] to [5], wherein the antiviral agent (C) has a median diameter of 2 to 15 μm. [7] A polyolefin resin molded article comprising the polyolefin resin composition according to any one of [1] to [6]. Invention 2 [8] A polypropylene-based resin composition comprising 65 parts by weight or more and less than 100 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B) having a weight-average molecular weight (Mw) of 1,000 to 300,000, and more than 0 parts by weight and 5 parts by weight or less of an antiviral agent (C), wherein the total of (A2), (B), and (C) is 100 parts by weight. [9] The polypropylene resin composition according to [8], wherein the hydrophilic resin (B) is at least one selected from the group consisting of thermoplastic polyethylene oxide, polyvinyl alcohol, and resins having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is at least one selected from the group consisting of a block copolymer of polypropylene oxide and polyethylene oxide, partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, and a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[10] The polypropylene resin composition according to [8] or [9], wherein the antiviral agent (C) is a silver and / or zinc compound.

[11] A polypropylene resin molded article comprising the polyolefin resin composition according to any one of [8] to

[10] . [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polyolefin resin composition, a polyolefin resin molded article, a polypropylene resin composition, and a polypropylene resin molded article that exhibit high antiviral activity using a small amount of an antiviral agent. These and other features and advantages of the present invention will become more apparent from the following description. DETAILED DESCRIPTION OF THE INVENTION

[0008] Invention 1 Polyolefin resin composition The polyolefin resin composition of the present invention is as follows. A polyolefin resin composition comprising 95 to less than 100 parts by weight of a hydroxyl group-modified polyolefin (A1) and more than 0 to 5 parts by weight of an antiviral agent (C), wherein the total of (A1) and (C) is 100 parts by weight. Invention 2 Polypropylene resin composition A polypropylene-based resin composition comprising 65 parts by weight or more and less than 100 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B) having a weight-average molecular weight (Mw) of 1,000 to 300,000, and more than 0 parts by weight and 5 parts by weight or less of an antiviral agent (C), wherein the total of (A2), (B), and (C) is 100 parts by weight. Hydroxyl-modified polyolefin (A1) The hydroxyl-modified polyolefin (A1) is preferably a hydroxyl-modified polypropylene, a terminal hydroxyl-modified polypropylene, or a one-terminal hydroxyl-modified polypropylene.

[0009] [Method for producing hydroxyl group-modified polyolefin (A1)] The hydroxyl group-modified polyolefin (A1) of the present invention can be produced, for example, by the following production method: A method for producing a modified polyolefin, comprising step (1) of treating an olefin polymer having an organometallic-containing terminal group with a mixed gas containing a reactive gas compound and an inert gas, wherein the volume fraction of the reactive gas compound in the mixed gas is 0.01 to 15 vol%. <Process (1)> <Olefin polymer having organometallic terminal groups> Examples of the organometallic compound include residues of organozinc compounds, organoaluminum compounds, and organomagnesium compounds, which will be described in the section "Organozinc Compounds" below. The metal in the olefin polymer having an organometallic-containing terminal group is preferably a zinc atom. Various examples of organometallic end groups can be given, such as the -ZnEt group, -ZnMe group, -ZniPr group, -ZnnBu group, and -ZniBu group shown in the following chemical formulas: The olefin polymer having an organometallic end group used in the production method of the present invention and the modified polyolefin produced therefrom can be given, for example, as organometallic end group polypropylene and modified polypropylene, respectively, shown in the following chemical formulas: [ka] The olefin polymer having an organometallic end group is preferably one obtained by polymerizing an olefin in the presence of a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound. The method for producing an olefin polymer having an organometallic end group is not particularly limited, but for example, an olefin polymer having an organometallic end group can be produced by the following method for producing a propylene polymer material. a continuous supply step of continuously supplying propylene, a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound to a reactor; and a continuous removing step of continuously removing a portion of the propylene polymer material obtained in the reactor from the reactor.

[0010] <Solid catalyst component for olefin polymerization> The solid catalyst component for olefin polymerization used preferably contains titanium atoms and magnesium atoms. Examples of methods for preparing the solid catalyst component for olefin polymerization include the following methods (1) to (5): (1) A method of contacting a magnesium halide compound with a titanium compound; (2) A method of contacting a magnesium halide compound, an internal electron donor and a titanium compound; (3) A method in which a magnesium halide compound and a titanium compound are dissolved in an electron-donating solvent to obtain a solution, and then the solution is impregnated into a support material; (4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound and an internal electron donor; (5) A method of contacting a solid component containing magnesium atoms, titanium atoms and hydrocarbon oxy groups with a halogenated compound and an internal electron donor and / or an organic acid halide.

[0011] Among these, the solid catalyst component obtained by the method (4) or (5) is preferred, and a solid catalyst component containing at least one compound selected from the group consisting of a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, or a β-alkoxy ester compound as an internal electron donor is more preferred. Examples of the monoester compound, dicarboxylic acid ester compound, diol diester compound, diether compound, and β-alkoxy ester compound include the compounds described in Patent Document (Japanese Patent Application No. 2018-531923) and combinations of two or more of these. Examples of the solid catalyst component for olefin polymerization include those described in JP-A-63-142008, JP-A-4-227604, JP-A-5-339319, JP-A-6-179720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-80234, JP-A-11-322833, Japanese Patent Application No. 2018-531923, JP-A-2021-161216, JP-A-2022-31142, etc. When using this solid catalyst component for olefin polymerization, it is preferable to use an organoaluminum compound in combination, and if necessary, an external electron donor compound is used in combination.

[0012] <Organoaluminum compounds> Examples of the organic aluminum compound that can be used include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide; alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane, and methylisobutylalumoxane; and combinations of two or more thereof.Among these, trialkylaluminums are preferred, and triethylaluminum is more preferred.

[0013] <External electron donor compound> In the process for producing olefin polymers having organometallic end groups, an optional external electron donor compound (external electron donor) can also be continuously fed to the reactor. The external electron donor compound is a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, a β-alkoxy ester compound, or a silicon compound represented by the following formula [7], which is listed as the internal electron donor, and is preferably a silicon compound represented by the following formula [7]: R 7 r Si(OR 8 ) 4-r [7] In the formula, R 7 represents a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a group containing a heteroatom; R 7 If there are multiple, they are the same or different; R 8 represents a hydrocarbyl group having 1 to 20 carbon atoms, and R 8 When there are a plurality of , they may be the same or different; and r represents an integer of 0 to 3.

[0014] R 7 and R 8 Examples of the hydrocarbyl group having 1 to 20 carbon atoms include linear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, and pentyl groups; branched alkyl groups having 3 to 20 carbon atoms, such as isopropyl, sec-butyl, tert-butyl, and tert-amyl groups; cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups having 3 to 20 carbon atoms, such as cyclopentenyl groups; and aryl groups having 6 to 20 carbon atoms, such as phenyl and tolyl groups.

[0015] R 7Examples of groups containing a hetero atom include groups containing an oxygen atom such as a furyl group, a pyranyl group, and a perhydrofuryl group; groups containing a nitrogen atom such as a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl-n-propylamino group, a di-n-propylamino group, a pyrrolyl group, a pyridyl group, a pyrrolidinyl group, a piperidyl group, a perhydroindolyl group, a perhydroisoindolyl group, a perhydroquinolyl group, a perhydroisoquinolyl group, a perhydrocarbazolyl group, and a perhydroacridinyl group; groups containing a sulfur atom such as a thienyl group; and groups containing a phosphorus atom. Among these, the heteroatom is preferably a group capable of directly chemically bonding to the silicon atom of the silicon compound, and more preferably a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl-n-propylamino group, or a di-n-propylamino group.

[0016] As external electron donor compounds, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyl Dimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane Silane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxy Silane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,Cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis(perhydroquinolino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)methyldimethoxysilane, (perhydroisoquinolino)methyldimethoxysilane, (perhydroquinolino) Examples include (perhydroquinolino)(n-propyl)dimethoxysilane, (perhydroisoquinolino)(n-propyl)dimethoxysilane, (perhydroquinolino)(tert-butyl)dimethoxysilane, (perhydroisoquinolino)(tert-butyl)dimethoxysilane, and diethylaminotriethoxysilane, as well as combinations of two or more thereof.

[0017] <Organic zinc compounds> Examples of organozinc compounds used in the method for producing an olefin polymer having an organometallic end group include dialkylzincs such as dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, and di-n-hexylzinc; diarylzincs such as diphenylzinc and dinaphthylzinc; bis(cyclopentadienyl)zinc; and dialkenylzincs such as diallylzinc. Among these, dialkylzincs are preferred, more preferably dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, or di-n-hexylzinc, even more preferably dimethylzinc or diethylzinc, and particularly preferably diethylzinc.

[0018] <Monomers other than propylene> In the method for producing an olefin polymer having an organometallic end group, other olefins can be used as monomers in addition to propylene. Examples of such olefins include linear olefins such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene; branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; alicyclic olefins such as vinylcyclohexane; and combinations of two or more thereof.

[0019] The olefin polymer having an organometallic end group is preferably a propylene homopolymer or a copolymer of propylene and another olefin, such as a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-1-hexene copolymer. The intrinsic viscosity of the polymer is usually 0.5 to 15 dL / g, preferably 0.8 to 10 dL / g. The weight ratio of the other olefin units in the copolymer is usually 0.01 to 50 wt%, preferably 0.1 to 40 wt%, based on 100 wt% of the copolymer.

[0020] <Continuous supply process> and <Continuous removal process> The reactor used in the continuous feeding step and continuous withdrawing step of the method for producing an olefin polymer having an organometallic end group is a reactor in which internal homogeneity is maintained by stirring or the like in the liquid phase and by gas flow or the like in the gas phase. The reactor may be constructed as a single reactor, or may be constructed by connecting multiple reactors. When multiple reactors are connected, they are preferably connected in series. When constructed with multiple reactors connected in series, at least propylene, the solid catalyst component for olefin polymerization, and the organoaluminum compound are supplied to the most upstream reactor, and the reactor to which the organozinc compound is supplied may be continuously supplied as a polymer-containing material from the previous reactor. Furthermore, the organozinc compound is supplied to at least one reactor, but may also be supplied to multiple reactors. In the continuous supply step, it is preferable to continuously supply the organoaluminum compound and the organozinc compound to the reactor using separate lines. That is, when impurities (e.g., AlHEt2) contained in the organoaluminum compound (e.g., AlEt3) react with the organozinc compound, the organozinc compound is reduced to zinc. Since zinc is gray, the produced propylene polymer material becomes discolored. If the organoaluminum compound and the organozinc compound are supplied to the reactor through separate lines, such discoloration can be avoided. A propylene polymer material is obtained through a step (polymerization step) in which propylene continuously fed in the continuous feeding step is polymerized in the reactor, and then the propylene polymer material obtained in the reactor is continuously removed from the reactor.

[0021] The supply rate of the organozinc compound in the continuous supply step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 20 to 1000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP). In the continuous supply step, the supply rate of the organozinc compound relative to the supply rate of the organoaluminum compound is preferably 1.1 to 15 (mol-Zn / mol-Al), more preferably 1.2 to 10 (mol-Zn / mol-Al). The supply rate of the organoaluminum compound in the continuous supply step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0022] In the continuous supply step, it is preferable to further continuously supply hydrogen gas to the reactor.

[0023] The number of polymerization steps in the method for producing an olefin polymer having an organometallic terminal group is one or more. When the number of steps is two or more, the type and amount of monomer polymerized in each step and the polymerization conditions for each step may be different from each other. The olefin polymer discharged from the final step is essentially a mixture of the polymers produced in each step.

[0024] The polymerization step in the method for producing an olefin polymer having an organometallic end group preferably comprises the following step (I): (I) A step of homopolymerizing propylene in the presence of an olefin polymerization catalyst (a catalyst containing a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound) to produce a propylene homopolymer (referred to as polymer portion (1)).

[0025] The polymer portion (1) may be a propylene-ethylene copolymer containing 5% by weight or less of ethylene units (where the total weight of the copolymer is taken as 100% by weight). The intrinsic viscosity of the polymer portion (1) is preferably 0.5 to 4 dL / g, more preferably 0.6 to 3 dL / g.

[0026] The contact of the organozinc compound, the solid catalyst component, the organoaluminum compound, and the external electron donor compound is carried out in a reactor or outside the reactor, with or without diluting these compounds or components with a solvent. The order of contacting these compounds and components is not particularly limited, but an example method is to supply the organoaluminum compound and the external electron donor compound to a reactor, and then supply the contact product of the organozinc compound and the solid catalyst component to the reactor. The supply to the reactor is preferably carried out in an inert gas such as nitrogen or argon in a moisture-free state.

[0027] In the polymerization step (hereinafter referred to as "main polymerization") in the method for producing an olefin polymer having an organometallic terminal group, the amount of the organoaluminum compound used is usually 1 to 1,000 mol, preferably 5 to 600 mol, per mol of titanium atom in the solid catalyst component. The amount of the external electron donor compound used in the main polymerization is usually 0.1 to 2,000 mol, preferably 0.3 to 1,000 mol, more preferably 0.5 to 800 mol, per mol of titanium atom contained in the solid catalyst component, and is usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, relative to the organoaluminum compound.

[0028] The polymerization temperature for the main polymerization is usually −30 to 300° C., preferably 20 to 180° C., and more preferably 40 to 100° C. The polymerization pressure is usually normal pressure to 10 MPa, and preferably 200 kPa to 5 MPa.

[0029] The polymerization may be carried out batchwise, continuously, or in combination by a slurry polymerization method or a solution polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane; a bulk polymerization method using an olefin that is liquid at the polymerization temperature; a gas-phase polymerization method; or a combination of two or more of these methods. The polymerization may be carried out using multiple polymerization reactors arranged in series, each with different polymerization conditions. The polymerization conditions may also be changed continuously within a single reactor. A chain transfer agent such as hydrogen may be used to control the molecular weight of the olefin polymer obtained by the polymerization.

[0030] In the main polymerization, in order to improve the particle properties of the resulting olefin polymer powder, a prepolymerized solid catalyst component as described below may be used in place of the solid catalyst component. When a prepolymerized solid catalyst component is used in the main polymerization, the organoaluminum compound is not essential in the main polymerization.

[0031] The prepolymerization is usually preferably carried out by slurry polymerization of a small amount of olefin (the same or different from the olefin used in the main polymerization) in the presence of a solid catalyst component and an organoaluminum compound. Examples of the solvent used for slurrying include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Part or all of the solvent can be replaced with a liquid olefin.

[0032] The amount of the organoaluminum compound used in the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, and more preferably 1 to 200 mol per mol of titanium atoms in the solid catalyst component.

[0033] The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, and more preferably 0.1 to 200 g per 1 g of the solid catalyst component.

[0034] The slurry concentration in the prepolymerization is preferably 1 to 500 g of solid catalyst component / liter of solvent, more preferably 3 to 300 g of solid catalyst component / liter of solvent. The temperature in the prepolymerization is preferably -20 to 100°C, more preferably 0 to 80°C. The polymerization time of the prepolymerization is usually 30 seconds to 15 hours. The partial pressure of the olefin in the gas phase during the prepolymerization is preferably 1 kPa to 2 MPa, more preferably 10 kPa to 1 MPa, although this does not apply to olefins that are liquid under the pressure and temperature during the prepolymerization.

[0035] In the prepolymerization, examples of methods for feeding a solid catalyst component, an organoaluminum compound, and an olefin to a prepolymerization vessel include (1) a method in which the solid catalyst component is contacted with an organoaluminum compound and then the contact product and the olefin are fed, and (2) a method in which the solid catalyst component is contacted with an olefin and then the contact product and the organoaluminum compound are fed. Examples of methods for feeding the olefin include (1) a method in which the olefin is fed sequentially so as to maintain a predetermined pressure inside the prepolymerization vessel, and (2) a method in which the entire predetermined amount of the olefin is fed initially. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the olefin polymer to be prepolymerized. In the prepolymerization, an organozinc compound or an external electron donor compound may be used in addition to the solid catalyst component and the organoaluminum compound. The amount of the external electron donor compound used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, and more preferably 0.03 to 100 mol, per mol of titanium atom contained in the solid catalyst component, and usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and more preferably 0.01 to 2 mol, per mol of the organoaluminum compound.

[0036] In the prepolymerization, examples of the method for supplying the external electron donor compound to the prepolymerization tank include (1) a method for supplying the external electron donor compound separately from the organoaluminum compound, and (2) a method for supplying a contact product of the external electron donor compound and the organoaluminum compound. In the production of propylene polymer materials, preactivation may be performed by known methods. Preactivation can be carried out instead of or before prepolymerization. Known preactivation methods include, for example, contacting a solid catalyst component with an organoaluminum in a solvent in the absence of an olefin. Examples of the solvent include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene. Preactivation may also involve the use of an organozinc compound or an external electron donor compound in addition to the solid catalyst component and the organoaluminum compound. The preactivated catalyst exhibits a significantly lower tendency to form deposits, and the degree of preactivation can be established in a stable manner over a relatively long storage period, allowing for reproducible production conditions to be established over a long period of time. The resulting preactivated catalyst can be metered into a continuously operated stirred reactor. Preactivation can also be carried out in the presence of a viscous substance, such as an olefin wax, to obtain a preactivated catalyst that is stable during storage and handling. The mode of preactivation is not particularly limited, and preactivation can be carried out in any of batch, semi-batch, and continuous modes.

[0037] <Mixed gas containing reactive gas compound and inert gas> Examples of reactive gas compounds include oxygen gas, carbon dioxide gas, carbon monoxide gas, ozone gas, fluorine gas, chlorine gas, bromine gas, iodine gas, ethylene oxide gas, propylene oxide gas, methyl acrylate gas, methyl methacrylate gas, acrylonitrile gas, hydrogen cyanide gas, formaldehyde gas, methyl isocyanate gas, carbon disulfide gas, etc. The reactive gas compound is preferably at least one gas selected from the group consisting of oxygen gas and carbon dioxide gas. Examples of the inert gas include nitrogen gas and argon gas. The volume fraction of the reactive gas compound in the mixed gas is 0.01 to 15 vol%. The volume fraction is preferably 0.05 to 15 vol%, more preferably 1 to 10 vol%, even more preferably 1 to 5 vol%, and most preferably 1 to 3 vol%. When the reactive gas compound is oxygen gas, the mixed gas preferably contains an oxygen gas at a concentration lower than that of air, and when the reactive gas compound is carbon dioxide gas, the mixed gas preferably contains a carbon dioxide gas at a concentration higher than that of the atmosphere.

[0038] Step (1) is preferably carried out under conditions of a total pressure of 3 MPa or less. Carrying out the reaction under high-pressure conditions requires an expensive reaction vessel that can withstand high pressures, which is undesirable from an economic standpoint. It is more preferably carried out under conditions of a total pressure of 0.1 MPa or more. Even more preferably, the total pressure is 0.1 to 1 MPa, and most preferably, the total pressure is 0.1 to 0.2 MPa. When the molar amount of the reactive gas compound used is A and the molar amount of the organometallic used is B, the value of A / B is preferably 1 to 100,000. The value of A / B is more preferably 1 to 10,000, even more preferably 1 to 1,000, particularly preferably 1 to 100, and most preferably 1 to 50. The time for step (1) is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0039] <Process (2)> In the present invention, the method for producing the hydroxyl group-modified polyolefin (A1) preferably further comprises a step (2) of treating the modified polyolefin obtained in the step (1) with an active proton compound. <Active proton compounds> Examples of active proton compounds include water (including, for example, atmospheric moisture, hydrated nitrogen gas, boiled water, etc.), alcohol (ethanol, boiled ethanol, methanol, boiled methanol, isopropyl alcohol, boiled isopropyl alcohol, etc.), hydrocarbons having active protons (toluene, etc.), carboxylic acids (acetic acid, etc.), inorganic acids (for example, concentrated hydrochloric acid, carbonic acid, etc.), etc. Preferred active proton compounds are water, ethanol, methanol, etc. The time for step (2) is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0040] <Process (3)> In the present invention, the method for producing the hydroxyl group-modified polyolefin (A1) preferably further comprises a step (3) of removing volatile compounds from the modified polyolefin obtained in the step (1) or (2). Specific examples of step (3) include a method of reducing the pressure while heating the modified polyolefin; Examples of such a method include a method in which nitrogen gas is passed through while the modified polyolefin is heated, and a method in which volatile compounds are continuously extracted and removed from the modified polyolefin with heated water or heated alcohol, followed by reducing the pressure or passing nitrogen gas through. Possible volatile compounds include (a) dilution solvents such as propylene, hydrogen gas, hexane, and heptane, (b) ethanol produced from unreacted diethylzinc compounds or triethylaluminum and oxygen gas, and low-molecular-weight (oligomer) PPOH (2-methyl-1-butanol, 2-methyl-1-pentanol, etc.). If (b) remains in the modified polyolefin, it may interfere with the expression of the modified polyolefin's functions or may give the modified polyolefin an odor. The time for step (3) is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0041] <Process (4)> In the present invention, the method for producing the hydroxyl group-modified polyolefin (A1) may include the following step (4): A method for producing a modified polyolefin, comprising step (4) treating an olefin polymer having an organometallic end group with a mixture of a reactive gas compound and an active proton compound. That is, step (4) is a step of treating an olefin polymer having an organometallic end group using a reactive gas compound and an active proton compound in combination, and is an efficient and economical method in which the reaction between the reactive gas compound and the active proton compound is combined into a single step by selecting the reaction conditions. In step (4), all raw materials and steps, such as the organometallic, organometallic-containing terminal group, olefin polymer having an organometallic-containing terminal group, method for producing the olefin polymer, reactive gas compound, active proton compound, mixture, and treatment step, can be the same as those exemplified in the above items <Step (1)> to <Step (3)>. Please do so. Typical reaction conditions for the treatment step (4) include dispensing the olefin polymer having organometallic end groups into a flask whose internal gas has been replaced with nitrogen gas, passing a mixed gas of oxygen gas and nitrogen gas (oxygen gas: 5.25 vol%, nitrogen gas: 94.75 vol%, dew point: -50.8°C) through the bottom of the olefin polymer having organometallic end groups at a flow rate of 200 mL / min, and reacting the olefin polymer having organometallic end groups with the oxygen gas at 66°C for 30 minutes. The mixture of reactive gas compound and active protons used in step (4) is, for example, an oxygen gas having a water content (dew point) of -80°C to 40°C. The gas composition (dew point) of the mixture is, for example, -80 to 0°C, more preferably -80 to -10°C, and even more preferably -80 to -20°C.

[0042] In the present invention, examples of the olefin polymer having an organometallic end group used in the above production method include the following propylene polymer materials: A propylene polymer material that satisfies the following requirements (a) and (b): (a) The ratio of zinc atoms to aluminum atoms in the propylene polymer material is 1.1 to 15 (mol-Zn / mol-Al). (b) Mw / Mn is 2.5 to 4.5. The zinc atoms and aluminum atoms in the propylene polymer material exist in two forms: one incorporated in the propylene polymer, and the other as a composition of the propylene polymer and catalyst residue. The ratio of zinc atoms to aluminum atoms in the (a) propylene polymer material is preferably 1.2 to 10 (mol-Zn / mol-Al), and the (b) Mw / Mn is preferably 2.6 to 4.4. The propylene polymer material preferably contains zinc atoms in the propylene polymer (c) at a concentration of 20 to 1000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP). The propylene polymer material (d) preferably contains aluminum atoms in a concentration of 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0043] The propylene polymer material may be a propylene polymer composition of a propylene polymer and a catalyst residue.

[0044] The propylene polymer material comprises: (f) L * a * b * Color difference ΔE between propylene polymer material and standard white board in color space * It is preferable that ab is 0 to 10, and it is more preferable that the color difference ΔE*ab is 0 to 6. The propylene polymer material comprises (g)L * a * b * Saturation C in color space * The value of chroma C* is preferably 0 to 4.0, and the value of chroma C* is more preferably 0 to 3.0. The propylene polymer material comprises (h) L * a* b * Coordinate b in color space * The value of the coordinate b* is preferably in the range of -1.0 to 3.0, and the value of the coordinate b* is more preferably in the range of -1.0 to 2.0. Color difference ΔE between propylene polymer material and standard white plate * ab and saturation C * In other words, the color difference ΔE*ab and saturation C * The smaller the absolute value of , the more difficult it is to visually distinguish the color difference from the standard white board, which is preferable. The larger the absolute value, the more easily it becomes distinguishable, which is not preferable.

[0045] The method for producing the propylene polymer material is not particularly limited, but it can be produced by the production method mentioned above in <Olefin polymer having organometallic terminal group>.

[0046] Polyolefin In the present invention, the polyolefin used in producing the hydroxyl group-modified polyolefin (A1) may be, for example, the following heterophasic propylene polymer material.

[0047] Heterophasic propylene polymer materials In the present invention, a heterophasic propylene polymerization material having a propylene polymer portion (A1) and a propylene-α-olefin copolymer portion (A2) can be produced, for example, by a method including a first polymerization step in which propylene is polymerized in the presence of a polymerization catalyst to produce a propylene polymer portion (A1) (hereinafter also referred to as "polymer (I)"), and a second polymerization step in which propylene and an olefin are copolymerized to produce a propylene-α-olefin copolymer portion (A2) (hereinafter also referred to as "polymer (II)"). Examples of the polymerization catalyst, polymerization method, and polymerization system used in these polymerization steps are described below.

[0048] Preferably, the heterophasic propylene polymeric material is A polymer (I) containing 80% by mass or more of structural units derived from propylene and having an intrinsic viscosity of 2.0 dL / g or less; The polymer (II) contains structural units derived from at least one selected from the group consisting of an α-olefin having 2 carbon atoms (ethylene) and an α-olefin having 4 to 12 carbon atoms, and structural units derived from propylene, and has an intrinsic viscosity of 1.5 to 8.0 dL / g. More preferably, the weight ratio of the polymer (I) is 40 to 99% by mass, and the weight ratio of the polymer (II) is 1 to 60% by mass.

[0049] The polymer (I) may be, for example, a propylene homopolymer, or may contain structural units derived from a monomer other than propylene. When the polymer (I) contains structural units derived from a monomer other than propylene, the weight ratio of the structural units may be, for example, 0.01% by mass or more and less than 10% by mass based on the total mass of the polymer (I).

[0050] Examples of the monomer other than propylene include ethylene and α-olefins having 4 or more carbon atoms. Among them, at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms is preferred, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene is more preferred, and at least one selected from the group consisting of ethylene and 1-butene is even more preferred.

[0051] Examples of polymers containing structural units derived from monomers other than propylene include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, and propylene-ethylene-1-octene copolymers.

[0052] From the viewpoint of dimensional stability of the molded article, the polymer (I) is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

[0053] The weight ratio of polymer (I) is preferably 40 to 99 mass %, more preferably 45 to 95 mass %, and even more preferably 50 to 92 mass %, based on the total mass of the heterophasic propylene polymerization material.

[0054] Polymer (II) preferably contains 10% by mass or more of structural units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms, and also contains structural units derived from propylene.

[0055] In polymer (II), the weight ratio of structural units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms may be 20 to 80 mass %, or may be 25 to 60 mass %.

[0056] In polymer (II), the at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0057] Examples of the polymer (II) include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-1-decene copolymer. Among them, propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer are preferred, and propylene-ethylene copolymer is more preferred.

[0058] The weight ratio of the polymer (II) is preferably from 1 to 60 mass %, more preferably from 5 to 55 mass %, and even more preferably from 8 to 50 mass %, based on the total mass of the heterophasic propylene polymerization material.

[0059] The weight ratio of the xylene-insoluble (CXIS) component in the heterophasic propylene polymerization material is preferably 40 to 99 mass %, more preferably 45 to 95 mass %, based on the total mass of the heterophasic propylene polymerization material. The weight ratio of xylene solubles (CXS components) in the heterophasic propylene polymer material is preferably 1 to 60 mass %, more preferably 5 to 55 mass %, based on the total mass of the heterophasic propylene polymer material.

[0060] In this embodiment, it is considered that the CXIS component in the heterophasic propylene polymerization material is mainly composed of polymer (I), and the CXS component in the heterophasic propylene polymerization material is mainly composed of polymer (II).

[0061] Examples of heterophasic propylene polymer materials include (propylene)-(propylene-ethylene) polymer materials, (propylene)-(propylene-ethylene-1-butene) polymer materials, (propylene)-(propylene-ethylene-1-hexene) polymer materials, (propylene)-(propylene-ethylene-1-octene) polymer materials, (propylene)-(propylene-1-butene) polymer materials, (propylene)-(propylene-1-hexene) polymer materials, (propylene)-(propylene-1-octene) polymer materials, and (propylene)-(propylene-1-decene) polymer materials. materials, (propylene-ethylene)-(propylene-ethylene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-ethylene)-(propylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-1-hexene) polymerization materials, (propylene-ethylene) (propylene)-(propylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-( (propylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-1-decene) polymerization materials, (propylene-1-hexene)-(propylene-1-hexene) polymerization materials, (propylene-1-hexene)-(propylene-1-octene) polymerization materials, (propylene-1-hexene)-(propylene-1-decene) polymerization materials, (propylene-1-octene)-(propylene-1-octene) polymerization materials,and (propylene-1-octene)-(propylene-1-decene) polymeric materials.

[0062] Here, the expression "(propylene)-(propylene-ethylene) polymer material" means "a heterophasic propylene polymer material in which polymer (I) is a propylene homopolymer and polymer (II) is a propylene-ethylene copolymer." The same applies to other similar expressions.

[0063] As the heterophasic propylene polymeric material, a (propylene)-(propylene-ethylene) polymeric material, a (propylene)-(propylene-ethylene-1-butene) polymeric material, a (propylene-ethylene)-(propylene-ethylene) polymeric material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymeric material, or a (propylene-1-butene)-(propylene-1-butene) polymeric material is preferred, and a (propylene)-(propylene-ethylene) polymeric material is more preferred.

[0064] The intrinsic viscosity ([η]I) of the polymer (I) is preferably from 0.10 to 3.00 dL / g, more preferably from 0.50 to 2.0 dL / g, and even more preferably from 0.70 to 1.50 dL / g.

[0065] The intrinsic viscosity ([η]II) of the polymer (II) is preferably from 1.50 to 8.00 dL / g, more preferably from 2.00 to 8.00 dL / g, and even more preferably from 2.50 to 8.00 dL / g.

[0066] Furthermore, the ratio ([η]II / [η]I) of the intrinsic viscosity number ([η]II) of polymer (II) to the intrinsic viscosity number ([η]I) of polymer (I) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 9.

[0067] The intrinsic viscosity ([η]I) of the polymer (I) can be measured, for example, by forming the polymer (I) and then measuring the intrinsic viscosity of the polymer.

[0068] The intrinsic viscosity number ([η]II) of polymer (II) can be calculated, for example, by the following formula (6) using the intrinsic viscosity number ([η]whole) of the heterophasic propylene polymerization material, the intrinsic viscosity number ([η]I) of polymer (I), and the weight ratio of polymer (II) to polymer (I).

[0069] [η]II=([η]whole-[η]I×XI) / XII ···(6) [η]whole: Intrinsic viscosity number (dL / g) of heterophasic propylene polymerized material [η]I: Intrinsic viscosity number of polymer (I) (dL / g) XI: Ratio of the mass of polymer (I) to the total mass of the heterophasic propylene polymer material (mass of polymer (I) / mass of heterophasic propylene polymer material) XII: Ratio of the mass of polymer (II) to the total mass of heterophasic propylene polymer material (mass of polymer (II) / mass of heterophasic propylene polymer material)

[0070] Here, XII was calculated using the following formula by measuring the heat of fusion of the heterophasic propylene polymer material. A sample (approximately 5 mg) of the heterophasic propylene polymer material was placed in an aluminum pan and placed in a DSC8500 differential scanning calorimeter (PerkinElmer). The pan was heated to 230°C, held at 230°C for 5 minutes, cooled to 0°C at a rate of 5°C / min, held at 0°C for 5 minutes, and then heated to 200°C at a rate of 5°C / min to measure a melting curve. The temperature was corrected using the melting point of indium as 156.6°C. The heat of fusion (unit: J / g) was calculated from the melting peak area in the melting curve, and XII was then calculated using the following formula. XII = (1 - (heat of fusion of heterophasic propylene polymer material) / 105) × 100

[0071] XI and XII may be calculated from the material balance during polymerization.

[0072] The intrinsic viscosity number ([η]CXIS) of the CXIS component is preferably 0.10 to 3.00 dL / g, more preferably 0.50 to 2.00 dL / g, and even more preferably 0.70 to 1.50 dL / g.

[0073] The intrinsic viscosity number ([η]CXS) of the CXS component is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0074] The ratio ([η]CXS / [η]CXIS) of the intrinsic viscosity number of the CXS component ([η]CXS) to the intrinsic viscosity number of the CXIS component ([η]CXIS) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 9.

[0075] The isotactic pentad fraction (also referred to as the [mmmm] fraction) of the polymer (I) is preferably 0.950 or more, more preferably 0.970 or more, from the viewpoint of rigidity and dimensional stability of a molded article made from the resin composition. The isotactic pentad fraction of the polymer (I) may be, for example, less than 1.000.

[0076] The isotactic pentad fraction refers to the isotactic fraction in pentad units. In other words, the isotactic pentad fraction indicates the content of structures in which five consecutive propylene-derived structural units are meso-bonded when viewed in pentad units. When the target component is a copolymer, the isotactic pentad fraction refers to a value measured for a chain of propylene-derived structural units.

[0077] In this specification, the isotactic pentad fraction is 13 This refers to the value measured by C-NMR spectroscopy. 13 The ratio of the area of ​​the mmmm peak to the area of ​​all absorption peaks in the methyl carbon region obtained by C-NMR spectroscopy is defined as the isotactic pentad fraction. 13The method for measuring the isotactic pentad fraction by C-NMR spectroscopy is described, for example, in Macromolecules, 6, 925 (1973) by A. Zambelli et al., where: 13 The assignment of absorption peaks obtained by C-spectrometry is based on the description in Macromolecules, 8, 687 (1975).

[0078] In this specification, the melt flow rate of polymer (I) at a temperature of 230°C and a load of 2.16 kgf refers to a value measured at 230°C under a load of 2.16 kgf in accordance with JIS K6758. The melt flow rate may also be referred to as MFR hereinafter. From the viewpoint of molding processability of the resin composition, the melt flow rate of polymer (I) is preferably 3 g / 10 min or more, and more preferably 10 g / 10 min to 500 g / 10 min.

[0079] The melt flow rate of polymer (II) at a temperature of 230°C and a load of 2.16 kgf refers to a value measured at 230°C and under a load of 2.16 kgf in accordance with JIS K 6758. From the viewpoint of molding processability of the resin composition, the melt flow rate of polymer (II) is preferably 0.01 g / 10 min or more, and more preferably 0.02 g / 10 min to 20 g / 10 min.

[0080] In producing polymer (I) and polymer (II), fossil resource-derived monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), plant-derived monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), chemically recycled monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), etc. can be used, and two or more of these may be used in combination. Specific monomer combinations include, for example, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene / fossil resource-derived 1-butene / plant-derived 1-butene / chemically recycled 1-butene, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene / fossil resource-derived 1-hexene / plant-derived 1-hexene / chemically recycled 1-hexene, fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene, fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene / fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene, and fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene / fossil resource-derived 1-butene / plant-derived 1-butene / chemically recycled 1-butene.

[0081] Fossil resource-derived monomers are derived from underground carbon resources such as petroleum, coal, and natural gas, and generally contain very little carbon-14 (14C). Methods for producing fossil resource-derived monomers include well-known methods, such as cracking petroleum-derived naphtha and ethane, and producing olefins by dehydrogenating ethane and propane.

[0082] Plant-derived monomers are derived from carbon circulating on the earth's surface as plants and animals, and generally contain a certain percentage of carbon-14 (14C). Examples of methods for producing plant-derived monomers include known methods, such as cracking bionaphtha, vegetable oil, or animal oil; dehydrogenating biopropane; separating alcohol from fermented sugars extracted from plant materials such as sugarcane or corn and then subjecting it to a dehydration reaction (JP Patent Publication Nos. 2010-511634, 2011-506628, and 2013-503647, etc.); and subjecting ethylene obtained from plant-derived ethanol to a metathesis reaction with n-butene (WO 2007 / 055361, etc.).

[0083] Chemically recycled monomers are derived from carbon generated by the decomposition or combustion of waste, and their carbon-14 (14C) weight ratio varies depending on the waste. Methods for producing chemically recycled monomers include known methods, such as thermal decomposition of waste plastics (e.g., JP 2017-512246), cracking of waste vegetable oil, waste animal oil, etc. (e.g., JP 2018-522087), and gasification, alcohol conversion, and dehydration of waste materials such as food waste, biomass waste, food waste, waste oil, waste wood, waste paper, and waste plastics (e.g., JP 2019-167424, WO 2021 / 006245).

[0084] When two or more of fossil resource-derived olefins, plant-derived olefins, and chemically recycled olefins are used, the olefins produced individually may be mixed and used in combinations such as fossil resource-derived olefins / plant-derived olefins, fossil resource-derived olefins / chemically recycled olefins, plant-derived olefins / chemically recycled olefins, or fossil resource-derived olefins / plant-derived olefins / chemically recycled olefins. Furthermore, a mixture of the above olefin combinations may be produced by using a mixture of combinations such as fossil resource-derived compounds / plant-derived compounds, fossil resource-derived compounds / chemically recycled compounds, plant-derived compounds / chemically recycled compounds, or fossil resource-derived compounds / plant-derived compounds / chemically recycled compounds as raw materials or intermediates in the olefin production process.

[0085] From the viewpoint of reducing the environmental load, the carbon-14 (C) concentration of polymer (I) and polymer (II) is preferably 0.2 pMC(%) or more, more preferably 0.5 pMC(%) or more, even more preferably 1 pMC(%) or more, still more preferably 5 pMC(%) or more, and particularly preferably 10 pMC(%) or more. From the viewpoint of cost, the C concentration is preferably 99 pMC(%) or less, more preferably 95 pMC(%) or less, even more preferably 90 pMC(%) or less, still more preferably 70 pMC(%) or less, and particularly preferably 50 pMC(%) or less.

[0086] The carbon-14 (14C) concentration of polymer (I) and polymer (II) can be adjusted by changing the ratio of fossil resource-derived olefin, plant-derived olefin, and chemically recycled olefin used in the production of the polyolefin resin.

[0087] <Solid catalyst component for olefin polymerization> The solid catalyst component for olefin polymerization used in the production method of the present invention preferably contains titanium atoms and magnesium atoms. Examples of methods for preparing the solid catalyst component for olefin polymerization used in the production method of the present invention include the following methods (1) to (5): (1) A method of contacting a magnesium halide compound with a titanium compound; (2) A method of contacting a magnesium halide compound, an internal electron donor and a titanium compound; (3) A method in which a magnesium halide compound and a titanium compound are dissolved in an electron-donating solvent to obtain a solution, and then the solution is impregnated into a support material; (4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound and an internal electron donor; (5) A method of contacting a solid component containing magnesium atoms, titanium atoms and hydrocarbon oxy groups with a halogenated compound and an internal electron donor and / or an organic acid halide.

[0088] Among these, the solid catalyst component obtained by the method (4) or (5) is preferred, and a solid catalyst component containing at least one compound selected from the group consisting of a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, or a β-alkoxy ester compound as an internal electron donor is more preferred. Examples of the monoester compound, dicarboxylic acid ester compound, diol diester compound, diether compound, and β-alkoxy ester compound include the compounds described in Patent Document (Japanese Patent Application No. 2018-531923) and combinations of two or more of these. Examples of the solid catalyst component for olefin polymerization include those described in JP-A-63-142008, JP-A-4-227604, JP-A-5-339319, JP-A-6-179720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-80234, JP-A-11-322833, Japanese Patent Application No. 2018-531923, JP-A-2021-161216, JP-A-2022-31142, etc. When using this solid catalyst component for olefin polymerization, it is preferable to use an organoaluminum compound in combination, and if necessary, an external electron donor compound is used in combination.

[0089] <Organoaluminum compounds> The organoaluminum compounds used in the production method of the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide; alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane, and methylisobutylalumoxane; and combinations of two or more thereof.Among these, trialkylaluminums are preferred, and triethylaluminum is more preferred.

[0090] <External electron donor compound> In the production method of the present invention, an external electron donor compound (external electron donor) can also be continuously fed to the reactor as an optional component. The external electron donor compound is a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, a β-alkoxy ester compound, or a silicon compound represented by the following formula [7], which is listed as the internal electron donor, and is preferably a silicon compound represented by the following formula [7]: R 7 r Si(OR 8 ) 4-r [7] In the formula, R 7 represents a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a group containing a heteroatom; R 7 If there are multiple, they are the same or different; R 8 represents a hydrocarbyl group having 1 to 20 carbon atoms, and R 8 When there are a plurality of r's, they may be the same or different; and r represents an integer of 0 to 3. r is preferably 1 or 2, and more preferably 2.

[0091] R 7 and R 8 Examples of the hydrocarbyl group having 1 to 20 carbon atoms include linear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, and pentyl groups; branched alkyl groups having 3 to 20 carbon atoms, such as isopropyl, sec-butyl, tert-butyl, and tert-amyl groups; cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups having 3 to 20 carbon atoms, such as cyclopentenyl groups; and aryl groups having 6 to 20 carbon atoms, such as phenyl and tolyl groups. R 7 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a tert-amyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a diethylamino group; More preferred are a methyl group, an ethyl group, an n-propyl group, a tert-butyl group, a cyclohexyl group, and a diethylamino group. R 8 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0092] R 7 Examples of groups containing a hetero atom include groups containing an oxygen atom such as a furyl group, a pyranyl group, and a perhydrofuryl group; groups containing a nitrogen atom such as a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl-n-propylamino group, a di-n-propylamino group, a pyrrolyl group, a pyridyl group, a pyrrolidinyl group, a piperidyl group, a perhydroindolyl group, a perhydroisoindolyl group, a perhydroquinolyl group, a perhydroisoquinolyl group, a perhydrocarbazolyl group, and a perhydroacridinyl group; groups containing a sulfur atom such as a thienyl group; and groups containing a phosphorus atom. Among these, the heteroatom is preferably a group capable of directly chemically bonding to the silicon atom of the silicon compound, and more preferably a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl-n-propylamino group, or a di-n-propylamino group.

[0093] As external electron donor compounds, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyl Dimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane Silane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxy Silane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,Cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis(perhydroquinolino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)methyldimethoxysilane, (perhydroisoquinolino)methyldimethoxysilane, (perhydroquinolino) Examples include (perhydroquinolino)(n-propyl)dimethoxysilane, (perhydroisoquinolino)(n-propyl)dimethoxysilane, (perhydroquinolino)(tert-butyl)dimethoxysilane, (perhydroisoquinolino)(tert-butyl)dimethoxysilane, and diethylaminotriethoxysilane, as well as combinations of two or more thereof.

[0094] <Organic zinc compounds> Examples of the organozinc compound used in the production method of the present invention include dialkylzincs such as dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, and di-n-hexylzinc; diarylzincs such as diphenylzinc and dinaphthylzinc; bis(cyclopentadienyl)zinc; and dialkenylzincs such as diallylzinc. Among these, dialkylzincs are preferred, more preferably dimethylzinc, diethylzinc, di-n-propylzinc, di-n-butylzinc, diisobutylzinc, or di-n-hexylzinc, even more preferably dimethylzinc or diethylzinc, and particularly preferably diethylzinc.

[0095] The number of polymerization steps in the production method of the present invention is one or more. The type and amount of monomer polymerized in each step and the polymerization conditions in each step may be different from each other, but propylene is polymerized in at least one step. The olefin polymer discharged from the final step is essentially a mixture of polymers produced in each step.

[0096] The contact of the organozinc compound, the solid catalyst component, the organoaluminum compound, and the external electron donor compound is carried out in a reactor or outside the reactor, with or without diluting these compounds or components with a solvent. The order of contacting these compounds and components is not particularly limited, but an example method is to supply the organoaluminum compound and the external electron donor compound to a reactor, and then supply the contact product of the organozinc compound and the solid catalyst component to the reactor. The supply to the reactor is preferably carried out in an inert gas such as nitrogen or argon in a moisture-free state.

[0097] In the polymerization step (hereinafter referred to as "main polymerization") in the production method of the present invention, the amount of the organoaluminum compound used is usually 1 to 1000 mol, preferably 5 to 600 mol, per mol of titanium atom in the solid catalyst component. The amount of the external electron donor compound used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, more preferably 0.5 to 800 mol, per mol of titanium atom contained in the solid catalyst component, and is usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, relative to the organoaluminum compound.

[0098] The polymerization temperature for this polymerization is usually -30 to 300°C, preferably 20 to 180°C, and more preferably 40 to 100°C. The polymerization pressure is usually atmospheric pressure to 10 MPa, and preferably 200 kPa to 5 MPa. The polymerization time is usually 0.2 to 10 hours, and preferably 0.5 to 6 hours. When multiple reactors are used, the average residence time in each reactor is 0.05 to 5 hours, and preferably 0.1 to 3 hours. Examples of polymerization reactors include loop reactors, continuous stirred tank reactors, fluidized bed reactors, and spouted bed reactors.

[0099] The polymerization may be carried out by a slurry polymerization method or a solution polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane; a bulk polymerization method using an olefin that is liquid at the polymerization temperature; a gas-phase polymerization method; or a combination of two or more of these methods. Among these, at least bulk polymerization is preferred. The polymerization may also be carried out in a batch mode, at least a continuous mode, or a combination of these. The polymerization may also be carried out using multiple polymerization reactors arranged in series and each having different polymerization conditions. The polymerization conditions may also be continuously changed within a single reactor. A chain transfer agent such as hydrogen may also be used to adjust the molecular weight of the propylene polymer material obtained by the polymerization.

[0100] In the main polymerization, a prepolymerized solid catalyst component described below may be used in place of the solid catalyst component in order to improve the particle properties of the resulting propylene polymer material powder. When a prepolymerized solid catalyst component is used in the main polymerization, the organoaluminum compound is not essential in the main polymerization.

[0101] In the production of propylene polymer materials, prepolymerization may be performed by a known method before the main polymerization. Known prepolymerization methods include, for example, a method in which a small amount of olefin (the same or different from the olefin used in the main polymerization) is supplied to a solid catalyst component and an organoaluminum compound, and polymerization is carried out in a slurry state using a solvent. Examples of the solvent used for slurrying include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene. A liquid olefin can be used in place of a part or all of the solvent. Alternatively, prepolymerization can be carried out in the presence of a viscous substance such as an olefin wax to obtain a prepolymerization catalyst that is stable during storage and handling. The prepolymerization method is not particularly limited, and can be performed in any of batch, semi-batch, and continuous modes.

[0102] The amount of the organoaluminum compound used in the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, and more preferably 1 to 200 mol per mol of titanium atoms in the solid catalyst component.

[0103] The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, and more preferably 0.1 to 200 g per 1 g of the solid catalyst component.

[0104] The slurry concentration in the prepolymerization is preferably 1 to 500 g of solid catalyst component / liter of solvent, more preferably 3 to 300 g of solid catalyst component / liter of solvent. The temperature in the prepolymerization is preferably -20 to 100°C, more preferably 0 to 80°C. The polymerization time of the prepolymerization is usually 30 seconds to 15 hours. The partial pressure of the olefin in the gas phase during the prepolymerization is preferably 1 kPa to 2 MPa, more preferably 10 kPa to 1 MPa, although this does not apply to olefins that are liquid under the pressure and temperature during the prepolymerization.

[0105] In the prepolymerization, examples of methods for feeding a solid catalyst component, an organoaluminum compound, and an olefin to a prepolymerization vessel include (1) a method in which the solid catalyst component is contacted with an organoaluminum compound and then the contact product and the olefin are fed, and (2) a method in which the solid catalyst component is contacted with an olefin and then the contact product and the organoaluminum compound are fed. Examples of methods for feeding the olefin include (1) a method in which the olefin is fed sequentially so as to maintain a predetermined pressure inside the prepolymerization vessel, and (2) a method in which the entire predetermined amount of the olefin is fed initially. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the olefin polymer to be prepolymerized. In the prepolymerization, an organozinc compound or an external electron donor compound may be used in addition to the solid catalyst component and the organoaluminum compound. The amount of the external electron donor compound used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, and more preferably 0.03 to 100 mol, per mol of titanium atom contained in the solid catalyst component, and usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and more preferably 0.01 to 2 mol, per mol of the organoaluminum compound.

[0106] In the prepolymerization, examples of the method for supplying the external electron donor compound to the prepolymerization tank include (1) a method for supplying the external electron donor compound separately from the organoaluminum compound, and (2) a method for supplying a contact product of the external electron donor compound and the organoaluminum compound. In the production of propylene polymer materials, preactivation may be performed by known methods. Preactivation can be carried out instead of or before prepolymerization. Known preactivation methods include, for example, contacting a solid catalyst component with an organoaluminum in a solvent in the absence of an olefin. Examples of the solvent include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene. Preactivation may also involve the use of an organozinc compound or an external electron donor compound in addition to the solid catalyst component and the organoaluminum compound. The preactivated catalyst exhibits a significantly lower tendency to form deposits, and the degree of preactivation can be established in a stable manner over a relatively long storage period, allowing for reproducible production conditions to be established over a long period of time. The resulting preactivated catalyst can be metered into a continuously operated stirred reactor. Preactivation can also be carried out in the presence of a viscous substance, such as an olefin wax, to obtain a preactivated catalyst that is stable during storage and handling. The mode of preactivation is not particularly limited, and preactivation can be carried out in any of batch, semi-batch, and continuous modes.

[0107] The heterophasic propylene polymer material obtained in the polymerization process of the present invention has organozinc-containing end groups at at least some of its polymer chain ends. In the case of linear polymer chains, the organometallic end group is usually present at only one end. The organometallic end groups are generally highly reactive and can be modified with hydroxyl groups in any non-polymerization reaction process with reactive gas compounds, such as oxygen gas, air, water vapor containing oxygen gas or air, or alcohol containing oxygen gas or air. The heterophasic propylene polymer material of the present invention may be a heterophasic propylene polymer material having an organometallic end group, a heterophasic propylene polymer material modified with a hydroxyl group, or a polymer material containing the polymer produced by combining the polymerization process of the present invention with another polymerization process.

[0108] Method for producing heterophasic propylene polymerized materials The method for producing the heterophasic propylene polymer material of the present invention is, for example, as follows: a first polymerization step of polymerizing propylene to form a polymer (I) in the presence of an olefin polymerization catalyst obtained by contacting an aluminum compound with a solid olefin polymerization catalyst component containing a titanium atom, a magnesium atom, a halogen atom, and an internal electron donor; a second polymerization step of copolymerizing propylene and at least one member selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms in the presence of the polymer (I) and the contact product described below to form a polymer (II); A method for producing a heterophasic propylene polymerization material, comprising:

[0109] In the method for producing a heterophasic propylene polymerization material of the present invention, propylene or the like is polymerized in the presence of the above-mentioned olefin polymerization catalyst.

[0110] An example of a method for producing the heterophasic propylene polymer material will be described. (Step 1) Propylene polymerization step (Step 2) Copolymerization of propylene and α-olefin (Step 3) Reactive gas compound treatment step Includes.

[0111] (Step 1) Propylene polymerization step: Step 1-a of polymerizing a propylene-containing monomer in a liquid phase in the presence of a specified amount of diethyl zinc under conditions of an appropriate hydrogen / propylene ratio to obtain at least a propylene-based polymer (a); and Step 1-b: polymerizing a monomer containing propylene in a gas phase in the presence of a specified amount of diethylzinc under conditions of an appropriate hydrogen / propylene ratio to obtain at least a portion of a propylene-based polymer (a); At least one step selected from the group consisting of: (Step 2) Copolymerization step of propylene and α-olefin: A step of polymerizing a monomer containing propylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms in the presence of a specified amount of diethyl zinc under conditions of an appropriate hydrogen / propylene ratio to obtain a propylene-based copolymer (b). (Step 3) Reactive gas compound treatment step: The propylene polymer (b) obtained through (Step 1) and (Step 2) is treated with a reactive gas compound, A step of obtaining a heterophasic propylene polymer modified with hydroxyl groups.

[0112] In this specification, the hydrogen / propylene ratio is defined as follows: In the case of polymerization in a liquid phase, the hydrogen / propylene ratio refers to the ratio of the amounts of hydrogen in the gaseous state to propylene in the liquid state in the reactor supply section. In the case of gas phase polymerization, the hydrogen / propylene ratio refers to the ratio of the amounts of gaseous hydrogen to gaseous propylene at the reactor outlet. In this specification, for example, the description "the hydrogen / propylene ratio is 1 mol ppm" means "the hydrogen / propylene ratio is 1×10 -6 mol / mol" and 1 mol of propylene is equivalent to 1 x 10 hydrogen.-6 This means that it is a mol. The hydrogen / propylene ratio is usually 0.00001 to 10 mol / mol, preferably 0.0001 to 1 mol / mol, and more preferably 0.001 to 0.5 mol / mol.

[0113] [Step 1-a] In step 1-a, for example, a liquid-phase polymerization reactor is used to polymerize a monomer containing propylene in the presence of a polymerization catalyst, hydrogen, and diethyl zinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the types and weight ratios of the structural units constituting the propylene polymer (a). The weight ratio of propylene in the monomers may be, for example, 80% by mass or more, 90% by mass or more, or even 100% by mass, based on the total mass of the monomers.

[0114] Examples of the liquid phase polymerization reactor include a loop type liquid phase reactor and a vessel type liquid phase reactor.

[0115] Examples of polymerization catalysts include Ziegler-Natta catalysts and metallocene catalysts, with Ziegler-Natta catalysts being preferred. Examples of Ziegler-Natta catalysts include those containing the above-mentioned solid catalyst component for olefin polymerization, an aluminum compound, and an electron donor compound. Pre-activated catalysts can also be used as polymerization catalysts by contacting them with a small amount of olefin.

[0116] As the polymerization catalyst, a prepolymerization catalyst component obtained by prepolymerizing an olefin in the presence of the above-mentioned solid catalyst component for olefin polymerization, normal hexane, triethylaluminum, diethylzinc, cyclohexylethyldimethoxysilane, etc. The olefin used for prepolymerization is preferably any one of the olefins constituting the heterophasic propylene polymerization material.

[0117] The polymerization temperature can be, for example, 0 to 120° C. The polymerization pressure can be, for example, normal pressure to 10 MPaG.

[0118] Step 1-a may be carried out continuously in multiple stages using a plurality of reactors in series.

[0119] [Step 1-b] In step 1-b, for example, a gas-phase polymerization reactor is used to polymerize a monomer containing propylene in the presence of a polymerization catalyst, hydrogen, and diethyl zinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the types and weight ratios of the structural units constituting the propylene polymer (a). The weight ratio of propylene in the monomers may be, for example, 80% by mass or more, 90% by mass or more, or even 100% by mass, based on the total mass of the monomers.

[0120] Examples of gas phase polymerization reactors include vessel type reactors, fluidized bed type reactors, and spouted bed type reactors.

[0121] The gas-phase polymerization reactor may be a multistage gas-phase polymerization reactor having a plurality of reaction zones connected in series. The multistage gas-phase polymerization reactor may be a multistage gas-phase polymerization reactor having a plurality of polymerization vessels connected in series. It is considered that such an apparatus makes it easy to adjust the intrinsic viscosity of the propylene polymer (a) to the above range.

[0122] The multistage gas phase polymerization reactor may comprise, for example, a cylindrical section extending in the vertical direction, and a tapered section formed in the cylindrical section, the inner diameter of which decreases downward and which has a gas inlet opening at its lower end, and may comprise a spouted bed type olefin polymerization reaction region surrounded by the inner surface of the tapered section and the inner surface of the cylindrical section above the tapered section, within which a spouted bed is formed, and a fluidized bed type olefin polymerization reaction region.

[0123] The multistage gas-phase polymerization reactor preferably has multiple reaction zones in the vertical direction. From the viewpoint of the intrinsic viscosity of the propylene polymer (a), the multistage gas-phase polymerization reactor preferably has multiple reaction zones in the vertical direction, of which the uppermost one is a fluidized-bed olefin polymerization reaction zone and the remaining ones are multiple spouted-bed olefin polymerization reaction zones. In such an apparatus, for example, a fluidized bed or spouted bed is formed in the reaction zone by supplying a solid component from the top of the apparatus and a gas component from the bottom of the apparatus. The gas component may contain an inert gas such as nitrogen in addition to a monomer containing propylene and hydrogen. In such an apparatus, the number of spouted-bed olefin polymerization reaction zones is preferably 3 or more.

[0124] When multiple reaction zones are arranged vertically, the lower reaction zone may be disposed diagonally below the upper reaction zone. In such an apparatus, for example, the solid component obtained in the upper reaction zone is discharged diagonally downward, and the discharged solid component is supplied to the lower reaction zone from diagonally above. In this case, the gas component is, for example, discharged from the top of the lower reaction zone and supplied from the bottom of the upper reaction zone.

[0125] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0126] The polymerization temperature may be, for example, 0 to 120° C., 20 to 100° C., or 40 to 100° C. The polymerization pressure may be, for example, normal pressure to 10 MPaG, or 1 to 5 MPaG.

[0127] [Second polymerization step] The second polymerization step may be carried out in a liquid phase or a gas phase, for example, in a gas phase. When carried out in a liquid phase, a liquid phase reactor such as a loop type or a vessel type can be used. When carried out in a gas phase, a gas phase reactor such as a vessel type reactor, a fluidized bed type reactor, or a spouted bed type reactor can be used.

[0128] In the second polymerization step, for example, a monomer containing propylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms is polymerized in the presence of a polymerization catalyst, hydrogen, and diethyl zinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the type and weight ratio of the structural units constituting the propylene copolymer (b). The weight ratio of the at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms in the monomers used in the polymerization may be, for example, 30 to 55 mass% or 35 to 50 mass% based on the total mass of the monomers.

[0129] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0130] When polymerizing in a liquid phase, the polymerization temperature is, for example, 40 to 100° C., and the polymerization pressure is, for example, normal pressure to 5 MPaG. When polymerizing in a gas phase, the polymerization temperature is, for example, 40 to 100° C., and the polymerization pressure is, for example, 0.5 to 5 MPaG.

[0131] The propylene polymer (a) and the propylene copolymer (b) may be produced in separate steps, and the polymerization catalyst may be deactivated before they are mixed in a solution state, a melt state, or the like. Alternatively, the polymer may be continuously produced by supplying the resulting polymer to the next step without deactivating the catalyst. When continuous polymerization is carried out without deactivating the catalyst, the polymerization catalyst in the previous step also acts as a polymerization catalyst in the subsequent step.

[0132] The order of the first polymerization step and the second polymerization step is not particularly limited. The first polymerization step can include step 1-a and step 1-b.

[0133] The production method according to this embodiment may include, for example, step 1-a, step 1-b, and the second polymerization step in this order, or may not include step 1-b.

[0134] The order of steps 1 and 2 and step 3 can be selected as follows: (a) Step 3 is performed after Steps 1 and 2 are completed. (b) Step 3 is carried out simultaneously with Step 1 (c) Step 3 is carried out simultaneously with Step 2 (d) Step 3 is carried out simultaneously with step 1, and step 3 is carried out simultaneously with step 2. (a) can be achieved by carrying out step 3 before the deactivation treatment after the polymerization step or simultaneously with the deactivation treatment. (b), (c), and (d) can be carried out by allowing an organozinc compound such as diethylzinc and a reactive gas such as oxygen gas to coexist during the polymerization step of step 1 or step 2.

[0135] Hydroxyl-modified heterophasic propylene polymeric materials. Preferably, the hydroxyl-modified heterophasic propylene polymeric material of the present invention is: A heterophasic propylene polymer material having a propylene polymer portion (A1) and a propylene and α-olefin copolymer portion (A2), A heterophasic propylene polymer material in which a portion of (A1) and / or (A2) is modified with a hydroxyl group. The amount of —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably 0.01×10 -3 wt%~100×10 -3 wt%, more preferably 0.03×10 -3 wt%~50×10 -3 wt%, more preferably 0.05 × 10 -3 wt%~10×10 -3 The amount of -OH (hydroxyl group) is 0.01×10 -3 If the content is less than 100×10 wt%, the coating properties of the resulting heterophasic propylene polymer material modified with hydroxyl groups may be insufficient. -3 If it exceeds 50 wt %, the impact strength of the resulting hydroxyl-modified heterophasic propylene polymer material may be insufficient. Preferably, the propylene polymer portion (A1) is a propylene homopolymer portion.

[0136] The modification site by the hydroxyl group may be (A1) only, (A2) only, or both (A1) and (A2). The case of only (A2) or both (A1) and (A2) is preferred, The most preferable case is (A2) only.

[0137] The bonding site in the polymer chain of the -OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably at a terminal of the polymer chain, and particularly preferably at only one terminal (single terminal). Since the polymer chain end has higher mobility than the polymer chain itself, the hydroxyl group bonded to the polymer chain end can effectively contribute to reaction and interaction with fillers such as polar resins and inorganic compounds. Furthermore, because the site of modification by hydroxyl groups is limited to one end of the polymer chain, the number of hydroxyl groups per polymer chain is 1 or less. Therefore, when reacting or interacting with polar resins or inorganic fillers, gelation due to crosslinking reactions does not occur in principle, and there is no deterioration in appearance or mechanical properties. Furthermore, since the hydroxyl group is bonded to only one end of the polymer chain, the movement and crystallization of the polymer chain are not hindered, and the inherent physical properties of the polymer chain are not deteriorated, allowing the effects of the hydroxyl group to be utilized.

[0138] The ratio (A) of the number of hydroxyl group terminals to the number of initiation terminals of the propylene polymer material having a hydroxyl group is preferably 0.01 to 0.90, more preferably 0.02 to 0.70, even more preferably 0.03 to 0.50, particularly preferably 0.04 to 0.30, and most preferably 0.05 to 0.25.

[0139] Method for producing hydroxyl-modified heterophasic propylene polymer materials In the present invention, the method for producing a hydroxyl-modified heterophasic propylene polymer material is as follows: In the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, 1. A method for producing a heterophasic propylene polymerization material, comprising: The method is characterized by comprising the following steps (1) to (3) and satisfying condition (i): A method for producing the heterophasic propylene polymerization material described above: (1) Propylene polymerization step (A), (2) copolymerization step (B) of propylene and α-olefins; (3) reactive gas compound treatment step (C); (i) carrying out (A) and / or (B) in the presence of an organozinc compound.

[0140] In the present invention, the propylene polymer material obtained in the polymerization step has organometallic end groups containing organozinc at at least a portion of the polymer chain ends. In the case of a linear polymer chain, an organometallic end group is usually present at only one end. The organometallic end group is generally highly reactive and can be stabilized in any non-polymerization reaction process with, for example, an active proton compound such as water, alcohols, or carboxylic acids, or a reactive gas compound such as oxygen or carbon dioxide. Examples of the stabilized end group include a hydroxyl group and a carboxyl group. The propylene polymer material of the present invention may be a polymer material having an organometallic end group, or a terminally stabilized polymer material that has undergone any non-polymerization reaction process. It may also be a polymer material containing the polymer produced by combining the polymerization process of the present invention with another polymerization process.

[0141] Examples of active proton compounds that can be used in any non-polymerization reaction step include water (including, for example, atmospheric moisture, hydrated nitrogen gas, boiled water, etc.), alcohols (ethanol, boiled ethanol, methanol, boiled methanol, isopropyl alcohol, boiled isopropyl alcohol, etc.), hydrocarbons having active protons (toluene, etc.), carboxylic acids (acetic acid, etc.), inorganic acids (concentrated hydrochloric acid, carbonic acid, etc.), etc. Preferred active proton compounds are water, methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol. More preferred are water, methyl alcohol, and ethyl alcohol. More preferably, it is water.

[0142] In the present invention, the solid catalyst component for olefin polymerization and the organoaluminum compound used in the above production method can be the same as the above-mentioned solid catalyst component for olefin polymerization and the aluminum compound. In the present invention, the polymerization step 1) (propylene polymerization step) in the above production method can be the same as the first polymerization step described above. In the present invention, the polymerization step 2) (copolymerization step of propylene and α-olefin) in the above production method can be the same as the second polymerization step described above.

[0143] In the present invention, the above-mentioned production method can also employ a continuous supply step and a continuous withdrawal step. The reactor used in these steps is a reactor in which internal homogeneity is maintained by stirring or the like in the liquid phase and by gas flow or the like in the gas phase. The reactor may have a fractional structure in the polymerization region therein, but it is preferable that each fractional structure is as homogeneous as possible. The reactor may be constructed as a single unit, or it can be constructed by connecting multiple reactors. When multiple reactors are connected, they are preferably connected in series. When multiple reactors are connected in series, at least propylene, the solid catalyst component for olefin polymerization, and the organoaluminum compound are supplied to the most upstream reactor, and the reactor to which the organozinc compound is supplied may be continuously supplied as a polymer-containing material from the previous reactor. Furthermore, the organozinc compound is supplied to at least one reactor, but it may also be supplied to multiple reactors. In the present invention, in the above-mentioned production method, for example, in the continuous supply step, it is preferable to continuously supply the organoaluminum compound and the organozinc compound to the reactor using separate lines. That is, when impurities (e.g., AlHEt2) contained in the organoaluminum compound (e.g., AlEt3) react with the organozinc compound, the organozinc compound is reduced to zinc. Since zinc is gray, the produced propylene polymer material is discolored. If the organoaluminum compound and the organozinc compound are supplied to the reactor through separate lines, such discoloration can be avoided. In the present invention, in the above-mentioned production method, for example, a propylene polymer material is obtained through a step (polymerization step) in which propylene continuously supplied in a continuous supply step is polymerized in a reactor, and then the propylene polymer material obtained in the reactor is continuously removed from the reactor. In this continuous removal step, a part of the propylene, the solid catalyst component for olefin polymerization, the organoaluminum compound, and the organozinc compound supplied in the continuous supply step are also removed, and their concentrations in the reactor are maintained within a certain range. In particular, it is important to maintain the concentration of the organozinc compound consumed during the polymerization reaction within a certain range in order to maintain a constant structure of the hydroxyl group-modified heterophasic propylene polymer material. In batch polymerization, the organozinc compound is consumed as the polymerization reaction progresses, and the concentration of the organozinc compound in the polymerization system decreases. Therefore, the structure (molecular weight and amount of hydroxyl group modification) of the resulting hydroxyl-modified heterophasic propylene polymer material differs between the early and late stages of the polymerization. The feed rate of each component in the continuous feed step and the withdrawal rate in the continuous withdrawal step can be changed within a range that maintains a constant concentration of each component in the reactor. The concentration of each component in the reactor is preferably maintained within ±30% of the target concentration, more preferably within ±10%. It is preferable that at least a part of the continuous supplying step and at least a part of the continuous removing step are carried out simultaneously.

[0144] The supply rate of the organozinc compound in the continuous supply step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 20 to 1000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP).

[0145] In the continuous supply step, the supply rate of the organozinc compound relative to the supply rate of the organoaluminum compound is preferably 1.1 to 15 (mol-Zn / mol-Al), more preferably 1.2 to 10 (mol-Zn / mol-Al).

[0146] The supply rate of the organoaluminum compound in the continuous supply step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0147] In the continuous supply step, it is preferable to further continuously supply hydrogen gas to the reactor.

[0148] The number of polymerization steps in the production method of the present invention is one or two or more. When the number of steps is two or more, the type and amount of monomer polymerized in each step and the polymerization conditions in each step may be different from one another, but propylene is polymerized in at least one step. The olefin polymer discharged from the final step is essentially a mixture of polymers produced in each step.

[0149] The contact of the organozinc compound, the solid catalyst component, the organoaluminum compound, and the external electron donor compound is carried out in a reactor or outside the reactor, with or without diluting these compounds or components with a solvent. The order of contacting these compounds and components is not particularly limited, but an example method is to supply the organoaluminum compound and the external electron donor compound to a reactor, and then supply the contact product of the organozinc compound and the solid catalyst component to the reactor. The supply to the reactor is preferably carried out in an inert gas such as nitrogen or argon in a moisture-free state.

[0150] Reactive Gas Compounds Examples of reactive gas compounds used in the production method of the present invention include oxygen gas, air, water vapor containing oxygen gas or air, ozone gas, ethylene oxide gas, propylene oxide gas, and formaldehyde gas. For example, the reactive gas compound is preferably at least one gas selected from the group consisting of oxygen gas, air, and ozone gas. The reactive gas compound can be diluted with nitrogen gas or the like before use. When diluted, the volume fraction of the reactive gas compound after dilution is preferably 0.05 to 15 vol%, more preferably 1 to 10 vol%, further preferably 1 to 5 vol%, and most preferably 1 to 3 vol%. When the reactive gas compound is oxygen gas, a mixed gas containing oxygen gas at a concentration lower than that of air is preferred.

[0151] Reactive gas compound treatment process The reactive gas compound treatment step can be carried out, for example, under a total pressure of 3 MPa or less. Carrying out the reaction under high-pressure conditions requires an expensive reaction vessel capable of withstanding high pressures, which is undesirable from an economic standpoint. It is preferable to carry out the reaction under a total pressure of 0.1 MPa or more. A total pressure of 0.1 to 1 MPa is more preferred, and a total pressure of 0.1 to 0.2 MPa is most preferred. When the molar amount of the reactive gas compound used is A and the molar amount of the organozinc compound used is B, the value of A / B is preferably 1 to 100,000. The value of A / B is more preferably 1 to 10,000, even more preferably 1 to 1,000, particularly preferably 1 to 100, and most preferably 1 to 50. The duration of the reactive gas compound treatment step is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0152] If the polymeric material having organometallic end groups has been treated with a reactive gaseous compound in any non-polymerization reaction step, it is preferred that it be further treated with an active proton compound. The time for treatment with the active proton compound is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes. In a non-polymerization reaction process in which the polymeric material having organometallic end groups is an optional reaction, treatment with a reactive gas compound and treatment with an active proton compound may be carried out simultaneously. That is, the polymeric material having organometallic end groups may be treated with a mixture of a reactive gas compound and an active proton compound. In this case, the number of treatments can be reduced, which is advantageous in terms of efficiency and economy.

[0153] Preferably, the end-capped polymeric material that has undergone any non-polymerization reaction step is further treated with a step to remove volatile compounds. Specific examples of the step of removing volatile compounds include a method of reducing the pressure while heating, a method of passing nitrogen gas through while heating, and a method of continuously extracting and removing volatile compounds with heated water or heated alcohol, followed by reducing the pressure or passing nitrogen gas through. Possible volatile compounds include (a) dilution solvents such as propylene, hydrogen gas, hexane, and heptane; (b) ethanol and low-molecular-weight (oligomeric) alcohols (such as 2-methyl-1-butanol and 2-methyl-1-pentanol) produced from unreacted diethylzinc compounds or triethylaluminum and oxygen gas; and (c) active proton compounds such as water and ethanol added in the non-polymerization reaction step. If (b) remains in the propylene polymer material, it may hinder the function of the propylene polymer material and may give the propylene polymer material an odor. The time for the step of removing the volatile compounds is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0154] In the present invention, the melting point (Tm) of the propylene polymer material is preferably 150 to 170°C, more preferably 158 to 170°C, further preferably 160 to 168°C, and most preferably 161 to 168°C.

[0155] In the present invention, the heat of fusion (ΔH) of the propylene polymer material is preferably 80-150, more preferably 100-135.

[0156] Polypropylene composition In the present invention, the polypropylene composition can be: A polypropylene composition comprising the heterophasic propylene polymer material and a polymer having a polar group.

[0157] Polymers with polar groups The polar group of the polar group-containing polymer is a functional group that can react with or interact with a hydroxyl group. Specific functional groups may be carboxyl groups, carbonyl groups, isocyanate groups, epoxy groups, carbodiimide groups, oxazoline groups, or amino groups. The polymer containing a carboxyl group may be a polymer having an unsaturated carboxylic acid or a derivative of an unsaturated carboxylic acid. Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid. Furthermore, examples of the derivatives of unsaturated carboxylic acids include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts, and the like derived from the unsaturated carboxylic acids. Specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, and sodium methacrylate. Furthermore, compounds such as citric acid and malic acid that are dehydrated to produce unsaturated carboxylic acids in the process of graft polymerization onto polypropylene may also be used. The polymer used in the polymer having a polar group is not particularly limited, and examples thereof include homopolymers, copolymers, and terpolymers of olefins, etc.

[0158] Examples of polymers having a polar group include maleic anhydride-modified polypropylene, polyamide, nylon 4, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, polymethyl methacrylate, polymethyl acrylate, polyacrylic acid, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate polylactic acid, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, polyurethane, polycarbodiimide, and polyimide.

[0159] When maleic anhydride-modified polypropylene is used as the polymer having a polar group, the intrinsic viscosity ([η]II) of the polymer (II) in the heterophasic propylene polymerization material is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0160] When nylon is used as the polymer having a polar group, the intrinsic viscosity ([η]II) of the polymer (II) in the heterophasic propylene polymerization material is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0161] <<Coupling body>> In the present invention, the heterophasic propylene polymer material may be such that the heterophasic propylene polymer material and the polymer having a polar group are bonded together by a covalent bond. It is preferred that the hydroxyl group of the heterophasic propylene polymer material and the carboxylic acid anhydride residue or the residue of the carboxylic acid anhydride derivative of the polymer having a polar group are bonded by a covalent bond. The covalent bond is preferably an ester bond.

[0162] <<Method of manufacturing the coupling body>> The coupling product can be produced by, for example, melt-kneading the heterophasic propylene polymerization material and the polymer having a polar group in an extruder, or by heating the heterophasic propylene polymerization material and the polymer having a polar group in a solvent. The coupling product may be in the form of either a graft modified product or a block modified product. The coupling modified product is a graft modified product and / or a block modified product containing the following segment (I) and the following segment (II). Segment (I): A propylene polymerized segment, which contains 90% by weight or more of structural units derived from propylene, relative to 100% by weight of the total weight of the propylene polymerized segment. Segment (II): at least one segment selected from the group consisting of an ethylene-α-olefin copolymer segment and a hydrogenated conjugated diene copolymer segment, The ethylene-α-olefin copolymer segment contains structural units derived from ethylene and structural units derived from an α-olefin having 3 to 10 carbon atoms, and contains more than 10 wt % and 99 wt % or less of structural units derived from ethylene, relative to 100 wt % of the total weight of the ethylene-α-olefin copolymer segment. A coupling catalyst may be added during the production of the coupling product.

[0163] <<Coupling catalyst>> By adding a coupling catalyst, the hydroxyl groups and polar groups in the heterophasic propylene polymer material are covalently bonded to each other, forming a coupling product in which the heterophasic propylene polymer material and the polymer having the polar group are covalently bonded. The coupling product can be either a graft type or a block type. By adding a coupling catalyst to form a coupling product, toughness such as impact resistance and tensile elongation can be imparted. The coupling catalyst may include a metal compound, a nitrogen-containing compound, or a Bronsted acid. Preferably, the metal compound is an inorganic metal compound such as a metal oxide, a metal hydroxide, a metal alkoxide, a metal carboxylate, a metal enolate, or a metal carbonate. More preferred are inorganic transition metal compounds such as transition metal oxides, transition metal hydroxides, transition metal alkoxides, transition metal carboxylates, transition metal enolates, and transition metal carbonates. Specific examples of metal oxides include: Examples of the oxide include lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, titanium oxide, zirconium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, aluminum oxide, and tin oxide. Specific examples of metal hydroxides include: Examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and tin hydroxide. Specific examples of metal alkoxides include: Examples of the alkoxide include lithium alkoxide, sodium alkoxide, potassium alkoxide, magnesium alkoxide, calcium alkoxide, titanium alkoxide, zirconium alkoxide, iron alkoxide, cobalt alkoxide, nickel alkoxide, copper alkoxide, zinc alkoxide, aluminum alkoxide, and tin alkoxide. Specific examples of metal carboxylates include: Examples of the carboxylate include lithium carboxylate, sodium carboxylate, potassium carboxylate, magnesium carboxylate, calcium carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, zinc carboxylate, aluminum carboxylate, and tin carboxylate. Specific examples of metal enolates include: Examples of the enolate include lithium enolate, sodium enolate, potassium enolate, magnesium enolate, calcium enolate, titanium enolate, zirconium enolate, iron enolate, cobalt enolate, nickel enolate, copper enolate, zinc enolate, aluminum enolate, and tin enolate. Specific examples of metal carbonates include: Examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, titanium carbonate, zirconium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, zinc carbonate, aluminum carbonate, and tin carbonate. The inorganic metal compound is preferably an inorganic transition metal compound. Specific examples of transition metal oxides include: Examples of the oxide include titanium oxide, zirconium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. Specific examples of transition metal hydroxides include: Examples include titanium hydroxide, zirconium hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, and zinc hydroxide. Specific examples of transition metal alkoxides include: Examples of the alkoxide include titanium alkoxide, zirconium alkoxide, iron alkoxide, cobalt alkoxide, nickel alkoxide, copper alkoxide, and zinc alkoxide. The transition metal alkoxide is preferably tetraalkyl titanates such as tetrastearyl titanate, tetraisopropyl titanate, and tetranormalbutyl titanate; Examples include tetraalkyl zirconates such as tetrastearyl zirconate, tetraisopropyl zirconate, and tetra-n-butyl zirconate. Specific examples of transition metal carboxylates include: Examples of the carboxylate include titanium carboxylate, zirconium carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, and zinc carboxylate. The transition metal carboxylate is preferably Titanium carboxylates such as titanium stearate and titanium octanoate, Examples include zirconium carboxylates such as zirconium stearate and zirconium octanoate. Specific examples of transition metal enolates include: Examples of the enolate include titanium enolate, zirconium enolate, iron enolate, cobalt enolate, nickel enolate, copper enolate, and zinc enolate. The transition metal enolate is preferably Examples include titanium enolates derived from 1,3-diketones, such as titanium tetraacetylacetonate, and zirconium enolates derived from 1,3-diketones, such as zirconium tetraacetylacetonate. Specific examples of transition metal carbonates include: Examples of the carbonate include titanium carbonate, zirconium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, and zinc carbonate. The inorganic transition metal compound is preferably a transition metal oxide, a transition metal hydroxide, a transition metal alkoxide, or a transition metal enolate.

[0164] Thermoplastic elastomer In the present invention, the heterophasic propylene polymer material and polypropylene composition can be mixed with known thermoplastic elastomers in powder or molten state. Specific examples of thermoplastic elastomers include styrene-based thermoplastic elastomers (TPS) such as styrene-ethylene-butene-styrene (SEBS), olefin-based thermoplastic elastomers (TPO) such as ethylene-propylene copolymers (EPR), ethylene-butene copolymers (EBR), and ethylene-octene copolymers (EOR), vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers (TPU), ester-based thermoplastic elastomers (TPC), amide-based thermoplastic elastomers (TPA), and butadiene-based thermoplastic elastomers.

[0165] Filler In the present invention, the heterophasic propylene polymer material and polypropylene composition described above can be mixed with known fillers in a powder or molten state. Specific examples of fillers include glass fiber, carbon fiber, mica, talc, clay, alumina, silica, wolsenite, kaolin, bentonite, calcium silicate, aluminum silicate, sand, diatomaceous earth, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, dolomite, dawsonite, calcium sulfate, magnesium sulfate, calcium sulfite, carbon black, molybdenum sulfide, magnet powder, cadmium sulfide, whiskers, wood flour, wood fiber, bamboo powder, melamine, and cellulose. Fillers may be used alone or in combination of at least two or more.

[0166] Other ingredients In the present invention, the heterophasic propylene polymer material and polypropylene composition described above can be mixed with known additives in a powder state or a hot-melt state. Examples of additives include neutralizers, antioxidants, UV absorbers, light stabilizers, antistatic agents, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.), foaming agents, foam nucleating agents, plasticizers, flame retardants, crosslinking aids, brightness enhancers, light diffusing agents, and scratch resistance inhibitors. These additives may be mixed alone or in combination of two or more.

[0167] Hydrophilic resin (B) The hydrophilic resin (B) used in invention 2 has a weight average molecular weight (Mw) in terms of polystyrene of 1,000 to 300,000, and preferably a weight average molecular weight (Mw) in terms of polystyrene of 1,500 to 290,000. The hydrophilic resin (B) used in Invention 2 is contained in an amount of more than 0 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 2 to 20 parts by weight. The polyolefin resin composition of Invention 1 may further contain, for example, 0.1 part by weight or more and less than 50 parts by weight of the hydrophilic resin (B). The hydrophilic resin (B) is preferably a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 g / g or more and less than 10 g / g. More preferably, the water absorption capacity is 0.02 to 9.5 g / g. The hydrophilic resin (B) is preferably a thermoplastic polyethylene oxide, polyvinyl alcohol, or a resin having a hydrophilic portion and a hydrophobic portion. The hydrophilic resin (B) is preferably a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bond of polypropylene oxide and polyethylene oxide, or a block copolymer such as a triblock copolymer or diblock copolymer of polypropylene oxide and polyethylene oxide, or partially saponified polyvinyl alcohol, or a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, or a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[0168] Examples of the hydrophilic resin (B) in the present invention include polyethylene oxide, polyalkylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, cellulose, and starch. Polymers or copolymers of acrylates or methacrylates having a hydroxyl group, such as polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate, and polyhydroxybutyl acrylate, may also be used. These are preferably thermoplastic from the viewpoint of dispersibility. Multiple types may also be used.

[0169] The polyvinyl alcohol that can be used as the hydrophilic resin (B) in the present invention is preferably a heat-meltable polyvinyl alcohol, such as JMR "H type," "M type," "L type," "JL-05E," or "JR-05," each of which has a saponification degree of 90 mol% or less, manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.

[0170] In addition, the hydrophilic resin (B) in the present invention preferably has a hydrophobic moiety therein. By having a hydrophobic moiety, compatibility with polypropylene is improved, resulting in a preferable dispersion state. As the hydrophobic moiety, one having high compatibility with polypropylene is more preferred.

[0171] Examples of the hydrophobic moiety in the hydrophilic resin (B) include polyolefins such as polypropylene, polypropylene oxide, and unsaponified acetyl groups in partially saponified polyvinyl alcohol. These may be bonded to either the end or the chain of the hydrophilic resin, and multiple types or multiple units may be bonded. The bonding mode is not important. For example, resins having a hydrophilic portion and a hydrophobic portion include a reaction bond of polypropylene oxide and polyethylene oxide, a triblock copolymer of polypropylene oxide and polyethylene oxide (ADEKA Pluronic (registered trademark) (manufactured by ADEKA Corporation), Newpol (manufactured by Sanyo Chemical Industries, Ltd.)), partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, and a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin. Multiple types of these may be used.

[0172] The polyethylene oxide usable as the hydrophilic resin (B) in the present invention has a polystyrene-equivalent weight-average molecular weight of 1,000 to 300,000, preferably 1,500 to 250,000. Thermoplastic polyethylene oxide and block copolymers of polypropylene oxide and polyethylene oxide are particularly preferred, and the polystyrene-equivalent weight-average molecular weight is more preferably 3,000 or more, more preferably 10,000 or more, and particularly preferably 50,000 or more, and is more preferably 200,000 or less, and even more preferably 150,000 or less.

[0173] The flow initiation temperature of the thermoplastic polyethylene oxide is preferably 40°C or higher, more preferably 50°C or higher, in order to maintain the properties of the molded product, and is preferably 200°C or lower, more preferably 160°C or lower in terms of moldability.

[0174] Specific examples of the thermoplastic polyethylene oxide include "ALKOX E-30" and "ALKOX R-1000" (both trade names) manufactured by Meisei Chemical Industry Co., Ltd. (both are linear polyethylene oxides obtained by ring-opening polymerization of ethylene oxide, with polystyrene-equivalent molecular weights of approximately 300,000 to 300,000 and 250,000 to 300,000, respectively).

[0175] The thermoplastic polyethylene oxide may be partially crosslinked with, for example, a diisocyanate compound or a triisocyanate compound. Crosslinking can further improve durability without impairing hydrophilicity. However, if the degree of crosslinking is too high, the fluidity during molding decreases, so it is preferable to adjust the degree of crosslinking in addition to the molecular weight.

[0176] The above-mentioned partial crosslinking refers to a crosslinking that has properties that do not adversely affect molding processability, such as maintaining fluidity during spinning and spinnability while maintaining properties such as hydrophilicity and durability such as washing resistance in a resin composition obtained by heat-melting and mixing the crosslinked thermoplastic polyethylene oxide with a polyolefin and a surfactant, or by heat-melting and mixing the polyolefin, a surfactant and a compatibilizer.The degree of crosslinking is preferably about one bond involved in crosslinking (two bonds are crosslinked) per 100,000 to 200,000 weight average molecular weight in terms of polystyrene.

[0177] In the present invention, the hydrophilic resin (B) may be a mixture of 100 parts by weight of highly hydrophilic polyethylene oxide and 1 to 30 parts by weight of more hydrophobic polypropylene oxide or ethylene oxide-propylene oxide copolymer as the polyalkylene oxide.

[0178] As the hydrophilic resin (B), a thermoplastic water-absorbing resin can also be used, which is obtained by reacting a polyalkylene oxide obtained by mixing 100 parts by weight of polyethylene oxide having a weight-average molecular weight of 10,000 to 500,000 in terms of polystyrene with 1 to 30 parts by weight of polypropylene oxide having a weight-average molecular weight of 500 to 50,000 in terms of polystyrene or an ethylene oxide-propylene oxide copolymer having a weight-average molecular weight of 500 to 50,000, with a diisocyanate compound and a low-molecular-weight diol having a molecular weight of 500 or less.

[0179] That is, in order to obtain the thermoplastic water-absorbing resin as the hydrophilic resin (B), a mixture of 100 parts by weight of highly hydrophilic polyethylene oxide and 1 to 30 parts by weight of more hydrophobic polypropylene oxide or ethylene oxide-propylene oxide copolymer can be used as the polyalkylene oxide.

[0180] The polyethylene oxide used has, for example, a weight average molecular weight of 10,000 to 500,000, preferably 20,000 to 200,000.

[0181] The polystyrene-equivalent weight average molecular weight of the polypropylene oxide or ethylene oxide-propylene oxide copolymer is, for example, within the range of 500 to 50,000, preferably 1,000 to 30,000.

[0182] The mixing ratio of the mixture of polyethylene oxide and polypropylene oxide or ethylene oxide-propylene oxide copolymer used as the polyalkylene oxide is, for example, 100 parts by weight of polyethylene oxide to 1 to 30 parts by weight of polypropylene oxide or ethylene oxide-propylene oxide copolymer, preferably 3 to 20 parts by weight. If the amount of polypropylene oxide or ethylene oxide-propylene oxide copolymer added is less than 1 part by weight, excellent compatibility will not be achieved, while if it is more than 30 parts by weight, it will be difficult to impart hydrophilic properties to the hydrophobic resin, which is undesirable.

[0183] Examples of low-molecular-weight diols having a polystyrene-equivalent molecular weight of 500 or less include aliphatic or aromatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, glyceryl monoacetate, glyceryl monobutyrate, 1,6-hexanediol, 1,9-nonanediol, and 1,4-bishydroxyethylbenzene, with 1,4-butanediol being preferred. These low-molecular-weight diols can be used alone or as a mixture of two or more.

[0184] Examples of the diisocyanate compound include aliphatic or aromatic diisocyanates such as 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,8-dimethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,2'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)benzene, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate. 4,4'-diphenylmethane diisocyanate and 2,4-tolylene diisocyanate are preferred. These diisocyanate compounds can be used alone or in combination.

[0185] In the present invention, for example, the proportions of polyalkylene oxide, low molecular weight diol, and diisocyanate compound used are selected so that the ratio (R value) of the sum of the number of terminal hydroxyl groups of the polyalkylene oxide and the number of active hydrogens in the low molecular weight diol to the number of isocyanate groups in the diisocyanate compound is 0.5 to 2.0, preferably 0.8 to 1.8. If the R value is less than 0.5, the resulting resin will be water-soluble. On the other hand, if the R value exceeds 2.0, a chemical crosslinking reaction will proceed, making the resin insoluble in organic solvents or impairing thermoplasticity, which is undesirable. The number of moles of polyalkylene oxide can be calculated by dividing the weight by the average molecular weight.

[0186] The method of reacting a polyalkylene oxide and a low molecular weight diol with a diisocyanate compound is generally a method of reacting them in a solution state using an appropriate solvent. It is also possible to react them in a dispersed state, or to mix them uniformly in a powder or solid state and then heat them to a predetermined temperature to react them, but from the viewpoint of industrial implementation, it is preferable to continuously feed each raw material in a molten state and mix and react them in a multi-screw extruder.

[0187] The reaction temperature for the above reaction is usually 50 to 210°C. The reaction can also be accelerated by adding a small amount of triethylamine, triethanolamine, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, triethylenediamine, etc. to the reaction system. The polypropylene resin composition of the present invention can also contain additives such as plasticizers, stabilizers, fillers, lubricants, and pigments.

[0188] Thus, by reacting a polyalkylene oxide and a low-molecular-weight diol with a diisocyanate compound, a thermoplastic water-absorbing resin having excellent compatibility with hydrophobic general-purpose resins can be obtained. The resin has excellent compatibility with polyolefin resins and exhibits excellent processability when molded into films, sheets, fibers, etc.

[0189] The polystyrene-equivalent weight average molecular weight of polypropylene oxide or ethylene oxide-propylene oxide triblock copolymer that can be used as the hydrophilic resin (B) in the present invention is desirably in the range of 500 to 300,000, preferably 1,000 to 150,000.

[0190] In the present invention, the following can also be used as the hydrophilic resin (B): ADEKA PLURONIC® L·P·F series (nonionic surfactants in which polypropylene glycol serves as the hydrophobic group and is rendered hydrophilic by the addition of ethylene oxide: for example, ADEKA PLURONIC® F-38, L-44, L-62, L-64, F-68, F-108, F-127, 25R-1, 25R-2, 17R-2, 17R-3, 17R-4, etc.) Adeka Pluronic® TR series (ethylenediamine-based, slightly cationic: e.g., Adeka Pluronic® TR-913R) Adeka Pluronic (registered trademark) reverse type. -New Pole series manufactured by Sanyo Chemical Industries, Ltd.

[0191] Polypropylene resin (A2) In Invention 2, the polypropylene resin (A2) used in the polypropylene resin composition of the present invention is preferably a homopolypropylene, a random polypropylene, or a block polypropylene. The polypropylene-based resin (A2) can be the same as the polypropylene or heterophasic propylene polymer material exemplified as a raw material for producing the hydroxyl group-modified polyolefin (A1) used in the above-mentioned Invention 1. The polypropylene or heterophasic propylene polymer material can be produced by the same production method as exemplified in the above-mentioned Invention 1. The polyolefin resin composition of Invention 1 may further contain, for example, 5 parts by weight or more and less than 90 parts by weight of the polypropylene resin (A2).

[0192] Antiviral Agents (C) The antiviral agent (C) used in the present invention may be any compound having antiviral properties, and examples thereof include various known compounds, usually inorganic compounds. In particular, if the antiviral agent (C) is a silver and / or zinc-based compound, it is preferred because it is less likely to decompose during molding, does not impair the antiviral properties, and can suppress discoloration due to decomposition products. The polyolefin resin composition and polypropylene resin composition of the present invention may contain one or more types of antiviral agent (C). Depending on the type of antiviral compound, the polyolefin resin composition and polypropylene resin composition of the present invention may exhibit antibacterial activity in addition to antiviral activity. The weight ratio of the antiviral agent (C) is more than 0 part by weight and not more than 5 parts by weight, preferably not less than 0.01 part by weight and not more than 4.5 parts by weight, more preferably not less than 0.02 parts by weight and not more than 4 parts by weight, and even more preferably not less than 0.03 parts by weight and not more than 3.5 parts by weight, per 100 parts by weight of the resin composition of the present invention. In particular, the weight ratio of the antiviral agent (C) can be reduced while maintaining excellent antiviral properties, and in some cases, discoloration can be suppressed at the same time, so that the weight ratio of the antiviral agent (C) can be set to not more than 3 parts by weight within the above range.

[0193] The antiviral agent (C) may be any salt of silver, zinc or copper, but is preferably a silver salt and / or a zinc salt.

[0194] A preferred particle size (median size) is 20 μm or less, particularly 2 to 15 μm, in view of the effect on the physical properties of the object to which antiviral properties are imparted, or the antiviral properties themselves. <Median diameter measurement> A volume-based particle size cumulative distribution curve was measured using a laser diffraction particle size distribution analyzer (SALD-2300) (Shimadzu Corporation), and the median diameter, which is the 50% diameter, was calculated from the particle size cumulative distribution curve. Measurement conditions (Batch cell, dispersion solvent: water, refractive index: 1.70-0.20i, absorbance: approximately 0.3-1.5, number of measurements: 9, stirring time: approximately 3 minutes) The sample was placed in the dispersion solvent (water) so that the absorbance was approximately 0.3 to 1.5, and measurements were performed three times after approximately three minutes had passed until the absorbance had stabilized. The above procedure, from sample preparation to measurement, was repeated three times to obtain a total of nine data points. The median diameter was calculated from each data point, and the average value of the nine median diameters was determined.

[0195] The salts as the antiviral agent (C) can be dispersed in water, an organic solvent, or the like using a dispersant such as an inorganic extender or a surfactant, and a viscosity modifier, an antioxidant, a rust inhibitor, a metal sequestering agent, or the like can be blended therewith, or other antibacterial compositions can be blended therewith.

[0196] In the present invention, "antiviral activity" refers to the property of inactivating a virus and eliminating its infectivity. The antiviral properties of the polyolefin resin composition, polyolefin resin molded article, polypropylene resin composition, and polypropylene resin molded article of the present invention are specifically expressed as "antiviral activity values" (log 10 The composition and molded article of the present invention can exhibit high antiviral properties, and for example, the "antiviral activity value" can preferably be 1.1 or more, and more preferably 1.2 or more.

[0197] Compatibilizer (D) The polyolefin resin composition and polypropylene resin composition of the present invention may further contain a compatibilizer (D). The compatibilizer (D) is preferably a modified polyolefin. The compatibilizer (D) is preferably a modified polyolefin, and the modifying group of the modified polyolefin is one type of modifying group selected from maleic anhydride and a hydroxyl group. The compatibilizer (D) is preferably a modified polypropylene, and the modifying group of the modified polypropylene is one type of modifying group selected from maleic anhydride and a hydroxyl group. As the compatibilizer (D), the same hydroxyl group-modified polyolefin (A1) as described in the above invention 1 can also be used.

[0198] The compatibilizer may be one that is compatible with both components to be mixed, such as maleic anhydride-grafted polyolefin, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, etc. Among these, maleic anhydride-grafted polyolefin is preferred because of its high compatibilizing ability and ease of handling.

[0199] The maleic anhydride grafted polyolefin is a polyolefin obtained by graft copolymerizing 100 parts of maleic anhydride with 100 parts of polyolefin, and has an intrinsic viscosity of 0.4 dL / g or more and 3.0 dL / g or less, preferably 0.5 dL / g or more and 1.0 dL / g or less.

[0200] The compatibilizer (D) can be a modified polypropylene, and the modified polypropylene can be a polypropylene modified by modification with maleic anhydride. Compared to unmodified polypropylene, the modified polypropylene has excellent dispersibility of the hydrophilic resin (B), and the addition of the hydrophilic resin (B) can improve the antiviral properties.

[0201] In the maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride may be 0.01 to 2.50% by mass. The graft modification rate of maleic anhydride is the weight ratio of maleic anhydride in the maleic anhydride-modified polypropylene. When the graft modification rate is within this range, the polypropylene can exhibit excellent antiviral properties while satisfying its properties. If the modification rate of maleic anhydride is low, the antiviral properties may not be satisfactory. If the modification rate is high, there is a risk of incompatibility with unmodified PP. If the graft modification rate is 0.01 to 1.00% by mass, compatibility with unmodified PP can be satisfied. The amount of succinic anhydride residues may be considered as the graft modification rate of maleic anhydride.

[0202] <Other resins> The resin composition of the present invention may contain a resin other than the above-mentioned resins and other than the at least one resin described above (hereinafter referred to as "other resin").

[0203] <Other ingredients> The resin composition of the present invention may further contain other components that can be generally used in resin compositions, as long as the effects of the present invention are not impaired. The other components are not particularly limited, and examples thereof include rubber particles, ultraviolet absorbers, slip agents, antioxidants, release agents, antistatic agents, flame retardants, neutralizing agents, and pigments.

[0204] Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxalanilide-based ultraviolet absorbers. Examples of the slipping agent include silicone oil and polysiloxane compounds. Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Examples of the release agent include higher fatty acid esters, higher fatty alcohols, higher fatty acids, higher fatty acid amides, higher fatty acid metal salts, and fatty acid derivatives. Examples of antistatic agents include conductive inorganic particles, tertiary amines, quaternary ammonium salts, cationic acrylic acid ester derivatives, and cationic vinyl ether derivatives.

[0205] The weight ratio of the other resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, relative to 100 parts by weight of the resin composition of the present invention. The weight ratio of the other components is not particularly limited and may be appropriately determined depending on the intended use.

[0206] <Method of manufacturing resin composition> The resin composition of the present invention can be produced (prepared) by carrying out a kneading step using any suitable conventionally known equipment and conditions to mix at least one necessary resin component and the antiviral agent (C), and optionally other resins or components.

[0207] In the present invention, the temperature conditions in the (melt) kneading step are not particularly limited. The temperature conditions can be any suitable conditions taking into consideration the selected components, their weight ratios, properties, etc. In the melt kneading step, for example, the temperature from the raw material inlet to the outlet of the extruder may be set to 50 to 260°C.

[0208] Any suitable conventional mixer or kneader can be used as the equipment used in the kneading step. Specific examples of such equipment include a single-screw kneader, a twin-screw kneader, a multi-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. Furthermore, when a higher rotation speed is required in the kneading step, for example, a high-shear processing device may be used.

[0209] The composition of the present invention can be formed into a molded article having a desired shape and dimensions and is suitable for use in various applications described below, particularly applications requiring antiviral properties.

[0210] <Formed body (material)> The resin composition (raw material) of the present invention can be molded into a preform (molded article) having a desired shape and dimensions by any suitable conventional molding method.

[0211] The preform of the present invention maintains the excellent antiviral properties exhibited by the resin composition of the present invention, and furthermore, can suppress discoloration. In the present invention, the term "formed material" refers to a part, member, or final product itself that has been given a predetermined shape by applying a predetermined heat and force to a material such as a resin composition, rubber, glass, or metal. In other words, the antiviral formed material of the present invention is a molded article having a predetermined shape and dimensions obtained by molding the thermoplastic resin composition of the present invention. The shape, thickness, and other dimensions of the preform are appropriately determined depending on the intended use and are not particularly limited.

[0212] (Method for manufacturing molded body (raw material)) The method for producing the molded article (formed material) of the present invention is not particularly limited. Examples of the method for producing the molded material of the present invention include a method of molding the resin composition of the present invention using any suitable conventional molding machine.

[0213] Examples of methods for producing the preform of the present invention include extrusion molding and injection molding. When the preform is to be formed into a preform having a more complex shape, for example, an injection molding method may be used in which the resin composition of the present invention is injected into a mold of an injection molding machine.

[0214] When a sheet or a laminated sheet is produced, it is preferable to form it by extrusion molding.

[0215] The method for producing the preform of the present invention will be explained below by taking the extrusion molding method as an example. The method for producing a preform of the present invention includes the steps of preparing a resin composition of the present invention (sometimes simply referred to as a resin composition) and extruding the prepared resin composition to produce a preform. Each step will be described in detail below.

[0216] (1) Step of preparing a resin composition This step is a step of preparing a resin composition to be fed to an extruder. In the present invention, the properties of the resin composition to be fed to the extruder are not particularly limited. The shape, size, etc. of the resin composition to be fed to the extruder may be set within any suitable range, taking into consideration the extruder to be used, the conditions to be applied, etc.

[0217] (2) A step of extruding the resin composition to form a base material. This step is a step in which the resin composition is molded by an extrusion molding machine to form a preform. Specifically, a sheet, which is an example of the preform of the present invention, can be produced by extruding a molten resin composition through the die of an extruder and molding it with the die lip in accordance with a conventional method.

[0218] A laminate sheet, which is an example of the base material of the present invention, has a two-kind, three-layer structure in which the above-mentioned sheets are used as layers of resin composition and are arranged on both the first and second main surfaces, which are opposed in the thickness direction of the base layer, so as to sandwich the base layer (a laminate sheet laminated in the order of resin composition layer (first surface sheet) / base layer (intermediate sheet) / resin composition layer (second surface sheet)). This laminate sheet can be produced, for example, as follows.

[0219] First, a melt of the resin composition of the present invention and a melt of the resin composition that is the material for the substrate layer are prepared.

[0220] Next, for example, using an extrusion molding machine equipped with a multi-manifold die, a resin composition that is the material for the molten base layer is extruded from the middle die lip, and simultaneously, molten resin composition is extruded from the upper and lower die lips.If necessary, the extruded molded product can be cooled using any suitable cooling roll known in the art, or further molded using other rolls such as conveying rolls, to produce a laminate sheet that is a laminate having a two-type, three-layer structure, including layers (sheets) of the resin composition on both the first and second main surfaces of the base layer molded in the middle, sandwiching the base layer.

[0221] In producing a laminate sheet, the temperature conditions for molding a layer of a resin composition by extrusion molding can be appropriately selected taking into consideration the composition of the resin composition, the required thickness of the layer of the resin composition, etc. The temperature conditions for molding a layer of the resin composition are, for example, preferably 180 to 300°C, more preferably 200 to 290°C, and even more preferably 220 to 280°C. The temperature is the temperature of the molten resin composition at the die lip of the die (or immediately after extrusion).

[0222] The melt of the resin composition for forming the substrate layer can be extruded through the die in a heated state as needed. When producing the laminate sheet of the present invention, the temperature conditions for molding the substrate layer by extrusion molding can be appropriately selected taking into consideration the components and blending ratio of the resin composition material, the required thickness of the substrate layer, and the like. When the substrate layer is formed from a resin composition, the temperature conditions for molding the substrate layer are, for example, preferably 180 to 300°C, more preferably 200 to 290°C, and even more preferably 220 to 280°C. The temperature is the temperature of the melt of the resin composition at the die lip of the die (or immediately after extrusion).

[0223] (Purpose of the sheet) The sheet of the present invention is suitable for applications requiring antiviral properties, and can be particularly suitable for use in equipment, tools, etc. that may come into contact with the human body, or as a shaped material contained in such equipment, tools, etc. Examples include handrails, door handles, containers, container lids, wall materials, and other components that inevitably come into contact with the human body when used. Other examples include screens (that can be placed on desks) used to separate adjacent or facing customers in stores, or adjacent or facing attendees in meetings, partitions (splash prevention panels), covers for product samples in vending machines, product display shelves in stores, covers for lighting, and even display panel components such as protective sheets placed on the outermost surface of touch sensor panels, meter panel components for vehicles such as automobiles and motorcycles, and key chains.

[0224] Fiber manufacturing method The polyolefin-based resin molded article and polypropylene-based resin molded article of the present invention may be in the form of fibers, and the method for producing the fibers may be as follows. A method for producing a polypropylene fiber by melt-spinning the resin composition of the present invention into a fiber shape. After spinning, the fiber is dyed with a dye using water as a medium.

[0225] <Polyolefin-based fibers and polypropylene-based fibers> The polyolefin-based fibers and polypropylene-based fibers of the present embodiment can be formed from the above-mentioned polyolefin-based resin composition and polypropylene-based resin composition by a conventionally known method, for example, melt spinning.

[0226] The tensile strength of the fiber of this embodiment is preferably 2.0 to 7.0 cN / dtex, and more preferably 3.0 to 6.0 cN / dtex.

[0227] The fiber of this embodiment can be applied to textile products such as clothing, bedding coverings, blankets, throws, carpets, etc. Examples of clothing include underwear, undergarments, shirts, jumpers, sweaters, pants, training wear, sportswear, tights, belly warmers, scarves, hats, gloves, socks, earmuffs, and cold weather clothing. Furthermore, the fabric surface may be brushed like fleece.

[0228] The fibers of this embodiment can be produced by feeding pellets of the above-mentioned resin composition into an extruder with a cylinder temperature set to 180 to 250°C, melting them, discharging them from a multi-hole nozzle also set to 180 to 250°C, and further heating and drawing them with a roll, thereby producing fibers such as FDY (fully drawn yarn) and POY (pre-sawn yarn).

[0229] The method for producing a molded article from the resin composition described above may include other steps in addition to the steps of producing a melt of the resin composition, molding, cooling and solidifying, and dyeing. For example, it may include a processing step of processing the molded article into a predetermined shape after the cooling and solidifying step.

[0230] Specifically, when a thread is produced from the resin composition, the steps include a drawing step in which the thread after the cooling and solidifying step is heated again and stretched, a heat treatment step in which distortion of the thread is removed by heat treatment, a cutting step in which the thread is cut to a predetermined length, and a winding step in which the thread is wound onto a bobbin or the like.

[0231] In addition, when producing a film, the film after the cooling and solidifying step may be subjected to a stretching step in which the film is stretched lengthwise or widthwise, a corona treatment step for improving the adhesion of ink or adhesive, a flame treatment step, a chemical treatment step, a winding step in which the film is wound up on a winder, etc., and the like.

[0232] As described above, the present invention can also provide a polypropylene resin composition, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article that are particularly suitable for general clothing applications.

[0233] The fiber of the present invention can be obtained by spinning the resin composition into fibers according to a known melt spinning method. The melt spinning method is not limited to a method using a winder, and air spinning methods such as spunbonding and meltblowing can also be used.

[0234] The fibers of the present invention can be processed into nonwoven fabrics, which can be produced using the dyed polypropylene-based fibers of the present invention. Here, nonwoven fabric literally means "non-woven fabric," and is a sheet made by bonding fibers together, rather than a knitted fabric, paper, or film. There are no particular restrictions on the method for bonding fibers together, and any known appropriate method may be selected depending on the purpose and application.

[0235] The fibers of the present invention are not limited to polyolefin-based fibers and polypropylene-based fibers, but may also include fibers formed into threads by melting a resin and extruding it through pores using various combinations of components included in the present invention, or composite fibers in which the resin is exposed on all or part of the fiber surface, such as core-sheath structures and side-by-side structures. [Example]

[0236] The present invention will be specifically described below, but the present invention is not limited in any way by the following examples.

[0237] Invention 1 Materials used In the examples and comparative examples, the following materials were used to prepare polypropylene resin compositions.

[0238] 1. Hydroxyl group-modified polyolefin (A1) <Synthesis of Polypropylene-1 Modified with One End Hydroxyl Group> (PPOH-1) MFR (230°C, load 21.2N): 150g / 10min Terminated terminal OH conversion rate: 12% [Preparation of solid catalyst component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP-A-2009-173870. [Prepolymerization] A 2-L stainless steel autoclave equipped with a stirrer was charged with 1.5 L of thoroughly dehydrated and degassed n-hexane, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution). 13 g of the solid catalyst component for olefin polymerization prepared above was added, and 46 g of propylene was continuously fed over approximately 30 minutes while maintaining the temperature inside the autoclave at approximately 3 to 10°C to carry out prepolymerization. The prepolymerized slurry was then transferred to a 160-L stainless steel autoclave equipped with a stirrer, and 130 L of fully purified liquid butane was added to form a prepolymerized catalyst component slurry. This was then stored at a temperature below 10°C. [First stage propylene polymerization (liquid phase polymerization reaction)] Propylene homopolymerization was carried out using a 42 L stirred vessel-type slurry polymerization reactor. The liquid level in the slurry polymerization reactor was adjusted to 18 L, and propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the prepolymerized catalyst component slurry prepared above were continuously fed into the reactor for polymerization. The reaction conditions were: polymerization temperature: 70°C, pressure: 3.87 MPaG, propylene feed rate: 26 kg / h, hydrogen feed rate: 130.1 nL / h, triethylaluminum feed rate: 28.8 mmol / h (hexane solution), cyclohexylethyldimethoxysilane feed rate: 4.1 mmol / h (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.51 g / h. The amount of propylene polymer component (A) continuously discharged from the reactor was 2.5 kg / h. The resulting slurry containing the propylene polymer component (A) was continuously transferred to the reactor for the second step without being deactivated. [Second-stage propylene polymerization (gas-phase polymerization reaction)] Propylene homopolymerization was carried out using a 1.4 m3 gas-phase fluidized-bed reactor equipped with an agitator. The fluidized bed held 25.5 kg of propylene polymer material, the polymerization temperature was 83°C, the polymerization pressure was 1.6 MPaG, the reactor gas superficial velocity was 0.128 m / s, and propylene, hydrogen, and nitrogen were supplied so that the hydrogen concentration in the gas phase was 0.06 mol% and the propylene concentration was maintained at 98.7 mol%. Diethylzinc was also supplied at a rate of 300.1 mmol / h (hexane solution). A separate supply line was used to supply diethylzinc to the reactor. The propylene polymer material continuously discharged from the reactor was 7.6 kg / h, which was then continuously transferred to a post-treatment process. Propylene, hydrogen, and nitrogen were supplied to the reactor at a rate of 0.06 mol% and 98.7 mol%. The obtained propylene polymer material was continuously received while nitrogen at 60°C was passed through for 1 hour at a flow rate of 20 Nm / h, and then dried by passing nitrogen at 60°C for another 1 hour at a flow rate of 20 Nm / h. Thereafter, the propylene polymer material was brought into contact with dry air for 1 hour, and then with air containing water for 1 hour.

[0239] <Calculation method for terminal OH termination rate> The rate of hydroxyl terminated terminals in the modified propylene polymer was measured by the following method. Model: Bruker AVANCE600 Probe: 10mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4 = 75 / 25 (volume ratio) mixture Measurement temperature: 135℃ Pulse repetition time: 4 seconds Pulse width: 45° Accumulation count: 5120 times Magnetic field strength: 600MHz (1H) Measurement standard: tetramethylsilane Measured nuclide: 13C The integral values ​​of the following peaks (a1 to a5) were calculated when the integral value of all peaks present at 50 to 10 ppm was set to 1,000,000. These values ​​were substituted into the following formula to calculate the initiation end integral value and OH end integral value of the modified propylene polymer. A1(68.39ppm): C H2OH a2(45.25ppm):CH3CH2CH(CH3) C H2 A3(41.74ppm): C H2CH(CH3)CH2OH A4(39.48ppm): C H2CH2CH3 A5(29.36ppm): C H2CH3 Initiation end integral value of propylene polymer material = a4 + (a2 + a5) / 2 OH terminal integral value = (a1 + a3) / 2 End OH conversion rate = [OH terminal integral value] / [initial terminal integral value of propylene polymer material] × 100 (%)

[0240] <Median diameter measurement> A volume-based particle size cumulative distribution curve was measured using a laser diffraction particle size distribution analyzer (SALD-2300) (Shimadzu Corporation), and the median diameter, which is the 50% diameter, was calculated from the particle size cumulative distribution curve. Measurement conditions (Batch cell, dispersion solvent: water, refractive index: 1.70-0.20i, absorbance: approximately 0.3-1.5, number of measurements: 9, stirring time: approximately 3 minutes) The sample was placed in the dispersion solvent (water) so that the absorbance was approximately 0.3 to 1.5, and measurements were performed three times after approximately three minutes had passed until the absorbance had stabilized. The above procedure, from sample preparation to measurement, was repeated three times to obtain a total of nine data points. The median diameter was calculated from each data point, and the average value of the nine median diameters was determined.

[0241] <Measurement of antiviral activity value of press sheet> The antiviral activity value of the press sheet is the result of testing using the ISO21702 "Measurement of antiviral activity on plastics and other non-porous surface" method at the Japan Textile Products Quality Technology Center, a general incorporated foundation.

[0242] For the test virus, influenza A virus (H3N2, A / Hong Kong / 8 / 68; TC adapted ATCC1679) was used, and the host cell was MDCK (dog kidney-derived cells). A virus suspension of a predetermined concentration was prepared by infecting the host cells with the virus and culturing them. In a petri dish, a press sheet sample cut into 5 cm × 5 cm was placed, 0.4 mL of the virus suspension was placed on it, and it was covered with a polyethylene film cut into 4 cm × 4 cm so as to cover the whole. This petri dish was stored in a thermo-hygrostat (temperature 25°C, humidity 90RH%) for 24 hours, washed out with SCDLP medium, the washout liquid was serially diluted with EMEM medium, and the virus infectivity titer of these diluted liquids was measured by the plaque assay method.

[0243] <Measurement of discoloration of press sheet> The discoloration of the press sheet was measured in the reflection mode for whiteness (W(Lab)) using a color difference meter ("Color Meter SM-P45", manufactured by Suga Test Instruments Co., Ltd.).

[0244] <Measurement of MFR> MFR was measured based on JIS K7210-1:2014 and K7210-2:2014.

[0245] Polyolefin resin (A2) Homopolypropylene 1 (hPP-1, Noblen U501E1 manufactured by Sumitomo Chemical Co., Ltd.) MFR (230°C, load 21.2 N): 100 g / 10 min

[0246] Antiviral agent 1 (C1) (Bactekiller BM-102SD, a silver-zinc antiviral agent manufactured by Fuji Chemical Co., Ltd.) Particle size (median diameter): 11.6 μm

[0247] Other ingredients Antioxidant 1: Irganox 1010 manufactured by BASF Japan Ltd. Antioxidant 2: Irgafos 168 manufactured by BASF Japan Ltd. Neutralizer: Calcium stearate manufactured by Sun Ace Co., Ltd.

[0248] ---The following provides an example of Invention 1. <Production of Polypropylene Resin Composition> (Example 1 (Synthesis Example 1)) A mixture was obtained by mixing 100 parts by mass of the above PPOH-1, 0.2 parts by mass of antioxidant 1, 0.2 parts by mass of antioxidant 2, and 0.05 parts by mass of neutralizer. The mixture was melt-kneaded in a 40 mm single-screw extruder (VS40-28 vented extruder, manufactured by Tanabe Plastics Co., Ltd.) at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm, and pelletized. A mixture of 99 parts by weight of the obtained pellets and 1 part by weight of antiviral agent 1 was melt-kneaded in a small kneader (Labo Plastomill, manufactured by Toyo Seiki Seisaku-sho, kneading temperature 180°C, screw rotation speed 80 rpm, kneading time 5 minutes) to obtain a polyolefin resin composition (C-1).

[0249] (Comparative Example 1 (Synthesis Example 2)) A polyolefin resin composition (C-2) was obtained in the same manner as in Synthesis Example 1, except that 99 parts by weight of hPP-1 and 1 part by weight of antiviral agent 1 were uniformly mixed together. That is, in Comparative Example 1, no hydroxyl group-modified polyolefin (A1) was used, and instead a polyolefin resin (homopolypropylene) was used.

[0250] Example 2 (Synthesis Example 3) A mixture was obtained by mixing 100 parts by mass of the above PPOH-1, 0.2 parts by mass of antioxidant 1, 0.2 parts by mass of antioxidant 2, and 0.05 parts by mass of neutralizer. The mixture was melt-kneaded and pelletized in a 40 mm single-screw extruder (VS40-28 vented extruder, manufactured by Tanabe Plastics Co., Ltd.) at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm. A polyolefin resin composition (C-3) was obtained in the same manner as in Synthesis Example 1, except that 97 parts by weight of the obtained pellets and 3 parts by weight of antiviral agent 1 were uniformly mixed.

[0251] Using the above materials, a press plate was produced as follows to obtain a resin composition. <Production of polyolefin-based pressed plates> Example 1 The polyolefin resin composition (C-1) was sandwiched between iron plates with 2 mm spacers, preheated to 180°C for 5 minutes in a compression molding machine, and then compressed at 180°C and 50 kgf / cm 2 After pressing at 30℃ and 50kgf / cm, 2 The mixture was cooled under pressure at 400° C. to obtain a pressed plate (D-1) of the polyolefin resin composition.

[0252] (Comparative Example 1) Except for using the polyolefin resin composition (C-2), a pressed plate (D-2) of the polyolefin resin composition was obtained in the same manner as in Example 1. That is, in Comparative Example 1, the hydroxyl group-modified polyolefin (A1) was not used, and instead a polyolefin resin (homopolypropylene) was used.

[0253] Example 2 A pressed plate (D-3) of a polypropylene resin composition was obtained in the same manner as in Example 1, except that the polyolefin resin composition was changed to (C-3).

[0254] The antiviral activity value and whiteness of the press plate of the polyolefin resin composition thus prepared are shown in Table 1. The results shown in Table 1 reveal the following: That is, in Example 1, when a hydroxyl group-modified polyolefin (A1) was used, high antiviral activity was exhibited with an antiviral activity value (common logarithm) of 3.1 while maintaining high whiteness. On the other hand, in Comparative Example 1, when a polyolefin resin (homopolypropylene) was used instead of using a hydroxyl group-modified polyolefin (A1), the antiviral activity value (common logarithm) was extremely low at 0.2, and almost no antiviral activity was exhibited.

[0255] [Table 1]

[0256] Invention 2 Materials used In the examples and comparative examples, the following materials were used to prepare polypropylene resin compositions.

[0257] Polypropylene resin (A2) Homopolypropylene 1 (hPP-1, Noblen R101 manufactured by Sumitomo Chemical Co., Ltd.) MFR (230℃, load 21.2N): 16g / 10 minutes

[0258] Hydrophilic resin (B) Hydrophilic resin 1 (ADEKA Corporation Pluronic F108) Molecular weight (Mw): 72,000 (polystyrene equivalent) Hydrophilic resin 2 (ADEKA Corporation Pluronic F68) Molecular weight (Mw): 91,000 (polystyrene equivalent) The molecular weight of the hydrophilic resin was measured under the following conditions. (Measurement conditions) The molecular weight of the sample was measured by gel permeation chromatography (GPC) under the following conditions. Sample preparation The sample solution was adjusted to a concentration of 1 mg / mL using dimethylformamide as the solvent, and then filtered using a 0.45 μm diameter PTFE syringe filter. GPC measurement device The measurement was performed using an apparatus consisting of the following equipment: (i) Liquid transfer pump: LC-20AD (Shimadzu Corporation) (ii) Degasser: DG-2080-53 (JASCO) (iii) Autosampler: SIL-20A (Shimadzu Corporation) (iv) Column oven: CTO-20A (Shimadzu Corporation) (v) Refractive index detector (RID): RID-10A (Shimadzu Corporation) (vi) System controller: CBM-20A (Shimadzu Corporation) GPC columns Two Plus Pore series Poly Pore 7.5 mm ID x 300 mm (Agilent Technologies) tubes were connected in series. Measurement conditions The mobile phase was dimethylformamide, and the flow rate was 0.8 mL / min. The column oven temperature was set to 35°C, and a differential refractive index detector was used (RID cell temperature: 35°C). The sample solution injection volume was 100 μL. PStQuick Kit-H (Tosoh Corporation) was used as the calibration standard for the GPC column, and the molecular weight was calculated in terms of polystyrene.

[0259] Antiviral Agents (C) Bactekiller BM102SD (Fuji Chemical Co., Ltd., silver-zinc antiviral agent) Particle size (median diameter): 11.6 μm <Median diameter measurement> Using a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation), the volume-based particle size cumulative distribution curve was measured, and the median diameter, which is the 50% diameter, was calculated from the particle size cumulative distribution curve. Measurement conditions (Batch cell, dispersion solvent: water, refractive index: 1.70 - 0.20i, absorbance: approximately 0.3 - 1.5, number of measurements: 9 times, stirring time: approximately 3 minutes) The sample was introduced into the dispersion solvent (water) so that the absorbance was about 0.3 - 1.5. After about 3 minutes when the absorbance became stable, the measurement was performed 3 times. By repeating the above operations from sample preparation to measurement 3 times, a total of 9 data points were collected, and the average of the 9 data points was calculated to obtain the average median diameter.

[0260] <Measurement of MFR> MFR was measured based on JIS K7210-1:2014 and K7210-2:2014.

[0261] Additives Antioxidant 1 (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GP) Antioxidant 2 (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GA80)

[0262] <Measurement of antiviral activity value of injection molded plate> The antiviral activity value of the injection molded plate was tested at the Japan Textile Products Quality Technology Center, using the method of ISO21702 "Measurement of antiviral activity on plastics and other non-porous surface".

[0263] The test virus was influenza A virus (H3N2, A / Hong Kong / 8 / 68; TC adapted ATCC1679), and the host cells were MDCK (canine kidney-derived cells). The host cells were infected with the virus and cultured to prepare a virus suspension of the desired concentration. A 5cm x 5cm injection-molded plate sample was placed in a Petri dish, and 0.4mL of the virus suspension was placed on top. The dish was then covered with a 4cm x 4cm piece of polyethylene film to ensure even coverage. The Petri dish was stored in a thermo-hygrostat (25°C, 90% RH) for 24 hours. The washed solution was then washed with SCDLP medium. Serial dilutions of the washed solution were made with EMEM medium, and the virus infectivity titers (common logarithm) of these dilutions were measured using the plaque assay.

[0264] <Manufacturing of injection molded plates> (Example A1) A homogeneous mixture of 94 parts by weight of hPP-1, 5 parts by weight of hydrophilic resin 1, 1 part by weight of antiviral agent, 0.2 phr of antioxidant 1, and 0.2 phr of antioxidant 2 was melt-kneaded in a twin-screw extruder (Technovel Corporation, KZW-15, screw diameter 15 mm, L / D = 45, temperature 200 °C, rotation speed 500 rpm, output 4 kg / hr) while purging with nitrogen to obtain polypropylene resin composition (D-1). The MFR of polypropylene resin composition (D-1) was 21.5 g / 10 min (230 °C, load 21.2 N). The resin composition (D-1) was injection molded using an injection molding machine (SE130DU-C360 manufactured by Sumitomo Heavy Industries, Ltd., temperature 220°C, mold temperature 50°C, injection speed 30 mm / sec) to obtain an injection-molded plate (E-1) measuring 150 mm x 90 mm x 3 mm thick.

[0265] (Example A2) A polypropylene resin composition (D-2) was obtained in the same manner as in Example A1, except that a uniform mixture was prepared by mixing 94 parts by weight of hPP-1, 5 parts by weight of hydrophilic resin 2, 1 part by weight of antiviral agent, 0.2 phr of antioxidant 1, and 0.2 phr of antioxidant 2. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (D-2) was 29.4 g / 10 min. An injection-molded plate (E-2) was obtained in the same manner as in Example A1, except that resin composition (D-2) was used.

[0266] (Comparative Example A1) A polypropylene resin composition (D-3) was obtained in the same manner as in Example A1, except that 99 parts by weight of hPP-1, 1 part by weight of an antiviral agent, 0.2 phr of antioxidant 1, and 0.2 phr of antioxidant 2 were uniformly mixed. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (D-3) was 13.9 g / 10 min. In Comparative Example A1, no hydrophilic resin was used. An injection-molded plate (E-3) was obtained in the same manner as in Example A1, except that resin composition (D-3) was used.

[0267] Table 2 shows the flowability (MFR) of the prepared polypropylene resin composition and the antiviral activity value of each injection-molded plate. The results shown in Table 2 reveal the following: That is, in Examples A1 and A2, when hydrophilic resin (B) was used, high antiviral activity was exhibited with an antiviral activity value (common logarithm) of 1.2 to 1.3 while maintaining an appropriate fluidity (MFR). On the other hand, in Comparative Example A1, when hydrophilic resin (B) was not used, the antiviral activity value (common logarithm) was an extremely low 0.7.

[0268] [Table 2] [Industrial Applicability]

[0269] Applications of the polyolefin-based resin composition, polyolefin-based resin molded article, polypropylene-based resin composition, and polypropylene-based resin molded article of the present invention include antiviral applications, and specific examples thereof include toilet seats, home appliances, miscellaneous goods, automobile parts, handrails, hanging straps, clothing, bedding coverings, blankets, lap blankets, car seats, and carpets. Additionally, they can be molded into components for products such as electrical appliances and automobiles by molding processes such as injection molding, injection compression molding, gas assist molding, and extrusion molding. Furthermore, the material can be suitably used for various automobile interior and exterior parts, including injection molding materials, such as instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, and back doors, as well as various parts for home appliances, various housing equipment parts, various industrial parts, and various building material parts, and is highly applicable in various industrial fields, such as the transportation machinery industry, the electrical and electronics industry, and the building and construction industry.

Claims

1. A polyolefin-based resin composition comprising 95 parts by weight or more and less than 100 parts by weight of a hydroxyl group-modified polyolefin (A1) and more than 0 part by weight and 5 parts by weight or less of an antiviral agent (C), wherein the total of (A1) and (C) is 100 parts by weight.

2. The polyolefin resin composition according to claim 1, wherein the hydroxyl-modified polyolefin (A1) is a hydroxyl-modified polypropylene.

3. The polyolefin resin composition according to claim 1, wherein the hydroxyl-modified polyolefin (A1) is a terminal hydroxyl-modified polypropylene.

4. The polyolefin resin composition according to claim 1, wherein the hydroxyl-modified polyolefin (A1) is a polypropylene modified with a hydroxyl group at one end.

5. 2. The polyolefin resin composition according to claim 1, wherein the antiviral agent (C) is a silver and / or zinc compound.

6. The polyolefin resin composition according to claim 1, wherein the antiviral agent (C) has a median diameter of 2 to 15 μm.

7. A polyolefin resin molded article comprising the polyolefin resin composition according to any one of claims 1 to 6.

8. A polypropylene-based resin composition comprising: 65 parts by weight or more and less than 100 parts by weight of a polypropylene-based resin (A2); more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B) having a weight-average molecular weight (Mw) of 1,000 to 300,000; and more than 0 parts by weight and 5 parts by weight or less of an antiviral agent (C), wherein the total of (A2), (B), and (C) is 100 parts by weight.

9. 9. The polypropylene resin composition according to claim 8, wherein the hydrophilic resin (B) is at least one selected from the group consisting of thermoplastic polyethylene oxide, polyvinyl alcohol, and resins having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is at least one selected from the group consisting of a block copolymer of polypropylene oxide and polyethylene oxide, partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to a polyolefin terminal or in its chain, a polymer in which polyvinyl alcohol is bonded to a polyolefin terminal or in its chain, and a polymer in which partially saponified polyvinyl alcohol is bonded to a polyolefin terminal or in its chain.

10. 9. The polypropylene resin composition according to claim 8, wherein the antiviral agent (C) is a silver and / or zinc compound.

11. A polypropylene resin molded article comprising the polyolefin resin composition according to any one of claims 8 to 10.

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