Adhesion of different materials with polypropylene, which has good adhesive properties

Abstract

By using a hydroxyl-modified polypropylene polymer whose terminals are modified with hydroxyl groups, an adhesive body can be provided which has an improved vapor deposition strength of the adherend. The present invention provides an adhesive body in which a polypropylene composition containing 1 to 100 wt% of a hydroxyl-modified polypropylene polymer (A) whose molecular chain terminals are modified with hydroxyl groups and 0 to 99 wt% of a polypropylene polymer (B) is adhered to an adherend, the adhesive body comprising: The above adhesive body, wherein the hydroxyl group content of the hydroxyl group-modified polypropylene polymer (A) is 0.001 to 3 wt %.

Description

[Technical Field]

[0001] The present invention relates to an adherend in which a polypropylene composition containing a hydroxyl group-modified polypropylene polymer is adhered to an adherend. [Background technology]

[0002] A polypropylene polymer modified at one end with a hydroxyl group and a method for producing the same are already known techniques (e.g., Patent Document 1). Also, a polypropylene polymer modified with a hydroxyl group and having an OH value of 100 or more and a method for producing the same are already known techniques (e.g., Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2023 / 190469 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-70390 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, an adhesive comprising a polypropylene polymer modified with terminal hydroxyl groups and an adherend is not known. The inventors have discovered that when homopolypropylene or a combination of homopolypropylene and a polymer having a polar group (such as maleic anhydride-modified polypropylene (MAH-PP)) is used as the resin contained in the adhesive, the deposition strength of the adherend may be insufficient. Under these circumstances, the problem that the present invention aims to solve is to improve the adhesive strength, such as the vapor deposition strength, of the adherend in an adhesive body containing a polypropylene polymer and an adherend. According to the present invention, by using a hydroxyl-modified polypropylene polymer whose terminals are modified with hydroxyl groups as the polypropylene polymer, an adhesive body can be obtained in which the adhesive strength of the adherend (between different materials) is significantly improved. [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 relates to the following [1] to [7]. [1] An adhesive obtained by adhering a polypropylene composition containing 1 to 100 wt% of a hydroxyl-modified polypropylene polymer (A) whose molecular chain terminals are modified with hydroxyl groups and 0 to 99 wt% of a polypropylene polymer (B) to an adherend, The above adhesive body, wherein the hydroxyl group content of the hydroxyl group-modified polypropylene polymer (A) is 0.001 to 3 wt %. [2] The adhesive body according to [1], wherein the adherend is a metal, a polymer having a polar group, a paint, or a coating agent. [3] The adhesive described in [2], characterized in that the metal is a metal layer and is a single element selected from Al, Fe, Ni, Cr, Sn, Mg, Zn, Mn, Co, Ti, Cu, Ag, Mo, and W, or an alloy containing two or more of these elements. [4] The adhesive according to [2] or [3], wherein the polar group of the polymer having a polar group is a functional group capable of reacting with or interacting with a hydroxyl group. [5] The adhesive body according to any one of [2] to [4], wherein the paint is a urethane paint, a melamine paint, an acrylic paint, an epoxy paint, a polyester paint, a urethane paint, and / or an alkyd paint. [6] The adhesive body according to any one of [2] to [5], wherein the coating agent is a urethane-based hard coating agent, an acrylic resin, an epoxy resin, an acrylic urethane-based resin, a polyester-based polyurethane resin, and / or a polyether-based polyurethane resin coating agent. [7] The adhesive body according to any one of [1] to [6], wherein the hydroxyl-modified polypropylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups is a propylene polymer material produced by a method for producing a propylene polymer material, the method comprising: a continuous supplying 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 unloading step of continuously unloading a portion of the propylene polymer material obtained in the reactor from the reactor. [Effects of the Invention]

[0006] According to the present invention, by using a hydroxyl-modified polypropylene polymer whose terminals are modified with hydroxyl groups as the polypropylene polymer, an adhesive body can be obtained in which the adhesive strength, such as the vapor deposition strength of the adherends (between different materials), is significantly improved. DETAILED DESCRIPTION OF THE INVENTION

[0007] Adhesive body The adhesive of the present invention is: An adhesive obtained by adhering a polypropylene composition containing 1 to 100 wt% of a hydroxyl-modified polypropylene polymer (A) whose molecular chain terminals are modified with hydroxyl groups and 0 to 99 wt% of a polypropylene polymer (B) to an adherend, The above adhesive body, wherein the hydroxyl group content of the hydroxyl group-modified polypropylene polymer (A) is 0.001 to 3 wt %.

[0008] Hydroxyl-modified polypropylene polymer (A) in which the ends of the molecular chain are modified with hydroxyl groups In the present invention, examples of the polypropylene polymer include polypropylene homopolymer, copolymers (random or block copolymers, etc.) of propylene as the main component with an α-olefin (an α-olefin having 2 or 4 to 12 carbon atoms, etc.), terpolymers of propylene as the main component with two types of α-olefins (an α-olefin having 2 or 4 to 12 carbon atoms, etc.), and heterophasic propylene polymerization materials.

[0009] [Method for producing hydroxyl-modified polypropylene polymer (A) whose molecular chain ends are modified with hydroxyl groups] The hydroxyl-modified polypropylene polymer (A), in which the terminals of the molecular chains are modified with hydroxyl groups, is preferably produced by a method for producing a propylene polymer material, which includes 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 withdrawal step of continuously withdrawing a portion of the propylene polymer material obtained in the reactor from the reactor. In the present invention, the hydroxyl group-modified propylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups can also 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 8When 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 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.

[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, a propylene-1-hexene copolymer, a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, or a propylene-ethylene-1-octene 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 a hydroxyl-modified polypropylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups 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 a hydroxyl-modified polypropylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups 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 a hydroxyl group-modified polypropylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups may include the following step (4): A method for producing a modified polyolefin, comprising the step (4) of 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-modified polypropylene polymer (A) in which the molecular chain terminals are modified with hydroxyl groups 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 1 to 60 mass %, more preferably 5 to 55 mass %, and even more preferably 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 diethyl zinc 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 4 to 12 carbon atoms inclusive, 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] [Process 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 gas 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 any non-polymerization reaction step of a polymeric material having an organometallic end group, treatment with a reactive gas compound and treatment with an active proton compound may be carried out simultaneously. That is, the polymeric material having an organometallic end group 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 to 150 (kJ / mol), more preferably 100 to 135 (kJ / mol).

[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] Polypropylene polymer (B) In the present invention, the polypropylene polymer (B) can typically be a homopolypropylene polymer, and can be produced by a known method.

[0168] Adherent material In the present invention, the adherend is preferably a metal or a polymer having a polar group, or a paint or coating agent. The metal is preferably a metal layer, and more preferably a simple substance selected from Al, Fe, Ni, Cr, Sn, Mg, Zn, Mn, Co, Ti, Cu, Ag, Mo, and W, or an alloy containing two or more of these components. The polar group of the polymer having a polar group is preferably a functional group capable of reacting with or interacting 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 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. The paint is preferably a urethane-based paint, a melamine-based paint, an acrylic-based paint, an epoxy-based paint, a polyester-based paint, a urethane-based paint, and / or an alkyd-based paint. The coating agent is preferably a urethane-based hard coating agent, an acrylic resin, an epoxy resin, an acrylic urethane-based resin, a polyester-based polyurethane resin, and / or a polyether-based polyurethane resin coating agent.

[0169] Molded body The adhesive article of the present invention can be used to produce a molded article by, for example, injection molding, press molding, extrusion molding, sheet molding, blow molding, vacuum molding, inflation molding, or the like. [Example]

[0170] The present invention will be specifically described below, but the present invention is not limited in any way by the following examples.

[0171] Materials used In the examples and comparative examples, the following materials were used to prepare adhesive bodies of different materials and polypropylene resin compositions.

[0172] 1. Hydroxyl-modified polypropylene (A) One-terminal hydroxyl group modified polypropylene-1 (PPOH-1) <Synthesis of Polypropylene-1 Modified with One End Hydroxyl Group> MFR (230℃, load 21.2N): 120g / 10min Terminated terminal OH conversion rate: 8% Hydroxyl group content: 0.0045wt% The hydroxyl group content was calculated from the terminal hydroxylation rate of 8% and the number average molecular weight data. [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 1.53 L of thoroughly dehydrated and degassed n-hexane, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution). 13.2 g of the solid catalyst component for olefin polymerization prepared above was added, and 46.2 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 130.5 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 30 L loop-type slurry polymerization reactor. The liquid level in the slurry polymerization reactor was adjusted to 30 L, and polymerization was carried out by continuously feeding propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the prepolymerized catalyst component slurry prepared above into the reactor. The reaction conditions were: polymerization temperature: 70°C, pressure: 4.41 MPaG, propylene feed rate: 78.0 kg / h, hydrogen feed rate: 50.8 NL / h, triethylaluminum feed rate: 38.4 mmol / h (hexane solution), cyclohexylethyldimethoxysilane feed rate: 5.7 mmol / h (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.602 g / h. The amount of propylene polymer component (A) continuously discharged from the reactor was 3.54 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)] Internal volume 1.4m 3 Propylene homopolymerization was carried out using a gas-phase fluidized-bed reactor equipped with a stirrer. Propylene, hydrogen, and nitrogen were supplied so that the fluidized-bed propylene polymer material load was 22.7 kg, the polymerization temperature was 83°C, the polymerization pressure was 1.95 MPaG, the superficial gas velocity inside the reactor was 0.186 m / s, the hydrogen concentration in the gas phase was 0.19 mol%, and the propylene concentration was maintained at 95.7 mol%. Diethylzinc was also supplied at 199.9 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 10.6 kg / h, and was continuously transferred to a post-treatment process. While continuously receiving the resulting propylene polymer material 1, nitrogen at 60°C was supplied for 1 hour at a flow rate of 20 Nm. 3 / h, and then nitrogen at 60°C was passed for 1 hour at a flow rate of 20 Nm 3The propylene polymer material was dried by flowing it through at a rate of 1 / h. Then, the propylene polymer material was placed in a flask under nitrogen and the pressure was reduced at room temperature using a vacuum pump. Dry oxygen was introduced into the flask until the pressure inside the flask reached atmospheric pressure, and the flask was left standing at room temperature for 3 hours. Then, the material was exposed to air containing water for 1 hour. <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 (%)

[0173] <Measurement of number average molecular weight> The number average molecular weight was measured by the following method. [Measurement conditions] Model: HLC-8321GPC / HT (Tosoh Corporation) GPC column: TSKgel GMHHR-H(S)HT 7.8mm ID x 300mm (Tosoh Corporation), 3 columns Mobile phase: Orthodichlorobenzene (special grade) with BHT added (0.1 w / V%) Flow rate: 1mL / min Column oven temperature: 145°C Autosampler temperature: 145℃ System oven temperature: 40°C Detector: Refractive index detector (RID) RID cell temperature: 145℃ Sample solution injection volume: 300 μL GPC column calibration standard: Tosoh standard polystyrene [Sample solution preparation conditions] Solvent: Orthodichlorobenzene (special grade) with 0.12 w / V% BHT added Sample solution concentration: 1 mg / mL Automatic dissolution shaker: DF-8020 (Tosoh) Dissolution conditions: 5 mg of sample was sealed in a 1000 mesh SUS wire bag, the wire bag containing the sample was placed in a test tube, 5 mL of solvent was added to the test tube, the test tube was covered with aluminum foil, the test tube was placed in a shaker, and the mixture was stirred at 140°C for 120 minutes at a stirring speed of 60 strokes per minute. [Analysis method] Complies with JIS K 7252-1. The measured value obtained as the average extended chain length (unit: Å) equivalent to polystyrene was multiplied by the Q factor value of 26.4 to obtain the polypropylene-equivalent molecular weight.

[0174] Maleic anhydride modified polypropylene-1 (MAH-PP-1) Maleic anhydride-modified polypropylene-1 was produced using Synthesis Example 2 described in WO2020 / 009090. MFR (230°C, load 21.2N): 199g / 10min MAH content in maleic anhydride modified polypropylene: 0.3% by mass

[0175] 2. Polypropylene resin (B) Homopolypropylene 1 (hPP-1, Noblen U501E1 manufactured by Sumitomo Chemical Co., Ltd.) MFR (230℃, load 21.2N): 120g / 10min Homopolypropylene 2 (hPP-2, Noblen R101 manufactured by Sumitomo Chemical Co., Ltd.) MFR (230℃, load 21.2N): 16g / 10 minutes

[0176] 3. Additives 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.

[0177] <Production of Polypropylene Resin Composition> Synthesis Example 1 A homogeneous mixture of 100 parts by weight of PPOH-1, 0.2 phr of antioxidant 1, 0.2 phr of antioxidant 2, and 0.05 phr of neutralizer was melt-mixed in a 20 mm single-screw extruder (VS20-14 manufactured by Tanabe Plastics Co., Ltd., screw diameter 20 mm, L / D = 26, temperature 200 °C, rotation speed 60 rpm) while purging with nitrogen to obtain polypropylene resin composition (C-1). The MFR of polypropylene resin composition (C-1) was 120 g / 10 min (230 °C, load 21.2 N).

[0178] Synthesis Examples 2-3 Polypropylene compositions of Synthesis Examples 2 and 3 were synthesized in the same manner as in Synthesis Example 1, except that the materials shown in Table 1 were used. [Table 1]

[0179] <Production of Adhesive of Aluminum and Polypropylene Composition> Example 1 The polypropylene resin composition (C-1) was extrusion molded using a 20 mm single-screw extruder (VS20-14 manufactured by Tanabe Plastics Co., Ltd., screw diameter 20 mm, L / D = 26, temperature 190 °C, rotation speed 60 rpm) using a T-die while purging with nitrogen to obtain a film with a thickness of 100 μm. One side of the resulting 100 μm-thick film was subjected to a corona discharge treatment, and then aluminum was vapor-deposited onto the corona-treated surface using a vacuum vapor deposition device (manufactured by Sato Vacuum Machinery Co., Ltd.) to obtain an aluminum-deposited film. The vapor deposition strength of the resulting film is shown in Table 2.

[0180] Evaluation of physical properties 1. Vapor deposition strength (unit: N / 15mm) An adhesive solution was prepared by mixing ethyl acetate, the base agent of an ester-based adhesive (Takelac A-310; Takeda Pharmaceuticals), and a curing agent (Takenate A-3; Takeda Pharmaceuticals) in a mass ratio of 36:12:1. The adhesive solution was applied to a 15 μm-thick stretched nylon substrate film (Unitika Emblem) using a Yasui Seiki benchtop test coater and then dried at 85°C. The dry mass of the adhesive present on the nylon substrate film was 3.7 g / m². The vapor-deposited surface of an aluminum vapor-deposited film was placed on one side of the nylon substrate film, and the adhesive-coated surface was brought into contact with the vapor-deposited surface of the nylon substrate film, and the film was pressed at 40°C and 3 kg / cm². The pressed film was then heat-aged at 40°C for two days to obtain a dry lamination film. The dry lamination film was cut into a piece 15 mm wide x 80 mm long (with the film formation direction and the long side direction aligned), and a tensile test was performed using an Autograph AGS-X manufactured by Shimadzu Corporation at a tensile speed of 300 mm / min. The tensile load during peeling was taken as the deposition strength. 2. Melt mass flow rate (unit: g / 10 min) The melt mass-flow rate was measured according to the method specified in JIS K 7210 at a measurement temperature of 230°C and a load of 2.16 kg.

[0181] Comparative Examples 1 and 2 Polypropylene compositions of Comparative Examples 1 and 2 were synthesized in the same manner as in Example 1, except that the materials shown in Table 2 were used. [Table 2] [Industrial Applicability]

[0182] The adhesive of the present invention can be used as a compatibilizer for fillers or other resins (for example, to improve strength, heat resistance, paintability, adhesion, printability, etc.), as a raw material for synthesizing graft polymers or block polymers with other resins (for example, to be used as a compatibilizer after grafting or blocking, to improve strength, heat resistance, paintability, adhesion, printability, etc.), etc. The adhesive bond of the present invention can also be molded into parts for products such as electrical appliances and automobiles by molding methods such as injection molding, injection compression molding, gas-assisted molding, and extrusion molding, with particular preference given to automobile parts such as door trims, pillars, instrument panels, and bumpers. The adhesive bond of the present invention is suitable for use in a variety of automobile interior and exterior parts, including instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, and back doors, including injection molding materials, 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. An adhesive body obtained by adhering a polypropylene composition containing 1 to 100 wt % of a hydroxyl group-modified polypropylene polymer (A) whose molecular chain terminals are modified with hydroxyl groups and 0 to 99 wt % of a polypropylene polymer (B) to an adherend, The adhesive body as described above, wherein the hydroxyl group content of the hydroxyl group-modified polypropylene polymer (A) is 0.001 to 3 wt %.

2. 2. The adhesive structure according to claim 1, wherein the adherend is a metal, a polymer having a polar group, a paint, or a coating agent.

3. The adhesive body according to claim 2, characterized in that the metal is a metal layer and is a single element selected from Al, Fe, Ni, Cr, Sn, Mg, Zn, Mn, Co, Ti, Cu, Ag, Mo, and W, or an alloy containing two or more of these elements.

4. 3. The adhesive structure according to claim 2, wherein the polar group of the polymer having a polar group is a functional group capable of reacting with or interacting with a hydroxyl group.

5. 3. The adhesive structure according to claim 2, wherein the paint is a urethane paint, a melamine paint, an acrylic paint, an epoxy paint, a polyester paint, a urethane paint, and / or an alkyd paint.

6. 3. The adhesive structure according to claim 2, wherein the coating agent is a urethane-based hard coating agent, an acrylic resin, an epoxy resin, an acrylic urethane-based resin, a polyester-based polyurethane resin, and / or a polyether-based polyurethane resin coating agent.

7. 3. The adhesive body according to claim 1 or 2, wherein the hydroxyl-modified polypropylene polymer (A) in which the terminals of the molecular chains are modified with hydroxyl groups is a propylene polymer material produced by a method for producing a propylene polymer material, the method comprising: a continuous supplying 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 unloading step of continuously unloading a portion of the propylene polymer material obtained in the reactor from the reactor.

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